JP7396019B2 - Curable composition, cured product and laminate - Google Patents

Description

The present invention relates to a curable composition, a cured product, and a laminate.

The cured product obtained by curing the curable composition is (i) capable of forming cured products of various shapes from the curable composition in a short time by imprinting, cast molding, etc., and (ii) less susceptible to cracking than glass. (iii) It is lighter than glass. Therefore, the cured product is attracting attention as a material for optical members in place of glass.

Patent Document 1 discloses a curable composition containing an alicyclic epoxy compound, a cationic polymerization initiator, and an organopolysiloxane.

Japanese Patent Application Publication No. 2018-008518

However, as in Patent Document 1, curable compositions that are cured by cationic polymerization have inferior curability compared to curable compositions that are cured by radical polymerization, and the heat resistance of the resulting cured product is insufficient. It is. If a laminate in which the cured product is laminated with an inorganic base material such as a glass substrate or an inorganic compound layer such as a metal oxide film is used for a long period of time in a high temperature and high humidity environment, the adhesion between the layers will decrease and peeling will occur. Sometimes.

The present invention provides a cured product that has excellent curability, excellent heat resistance, and excellent adhesion to inorganic base materials and inorganic compound layers, and is resistant to peeling even when exposed to high temperature and high humidity environments for long periods of time. The object of the present invention is to provide a curable composition, a cured product using the curable composition, and a laminate.

One embodiment of the present invention includes metal oxide fine particles A that do not have an aromatic ring and have a median diameter of 5 to 20 nm, and a homopolymer glass that has an alicyclic condensed ring other than organopolysiloxane. An aromatic compound containing (meth)acrylate B having a transition temperature of 90 to 350°C, an antioxidant, an organopolysiloxane, and a radical polymerization initiator, but excluding the organopolysiloxane and the (meth)acrylate B. It may further contain epoxy (meth)acrylate C having no ring and having an ethylenically unsaturated group content of 0.1 to 3.0 mmol/g, and organopolysiloxane, the above (meth)acrylate B and urethane (meth)acrylate D that does not have an aromatic ring except for the epoxy (meth)acrylate C, and the antioxidant has a phenol moiety and the phenol This is a curable composition containing an antioxidant having a sulfide moiety but excluding an antioxidant having a sulfide moiety.

According to the present invention, the cured product has excellent curability, excellent heat resistance, excellent adhesion to an inorganic base material and an inorganic compound layer, and is resistant to peeling even when exposed to a high temperature and high humidity environment for a long period of time. It is possible to provide a curable composition, a cured product using the curable composition, and a laminate.

[Meaning of terms]
"(Meth)acryloyl group" is a general term for acryloyl group and methacryloyl group.
"(Meth)acrylate" is a general term for acrylate and methacrylate.
"(Meth)acrylic acid" is a general term for acrylic acid and methacrylic acid.
"Light" is a general term for ultraviolet rays, visible light, infrared rays, electron beams, and radiation.
The organic content of metal oxide fine particles A is determined by the thermogravimetric loss when metal oxide fine particles A are heated from 10°C to 500°C at a rate of 25°C/min in a nitrogen atmosphere using a thermogravimetric measuring device. It is.
The median diameter of the metal oxide fine particles in the curable composition is a value determined using a particle size distribution analyzer using a dynamic light scattering method.
The median diameter of the metal oxide fine particles in the cured product is determined by observing a thin section with a transmission electron microscope, and determining the diameter of a sufficient number of metal oxide fine particles (for example, 100 or more, preferably 200 or more) that can be confirmed in the thin section. This is the average value of the measured values.
The glass transition temperature of the homopolymer of (meth)acrylate was determined by differential scanning calorimetry ( This is the midpoint glass transition temperature measured by DSC) method. A homopolymer having a glass transition temperature of 90 to 350°C includes not only those whose glass transition temperature is observed below 350°C, but also those whose glass transition temperature is not observed below 350°C by the DSC method. do.
The transmittance of light at a wavelength of 400 nm of the cured product was determined by the method described in JIS K 7361:1997 (ISO 13468-1:1996) for the cured product of the evaluation sample obtained by the method described in the examples. This is a value measured at 25° C. using the following light.
"Weight average molecular weight" (hereinafter referred to as "Mw") is the polystyrene equivalent molecular weight measured by using gel permeation chromatography using tetrahydrofuran as an eluent and creating a calibration curve using polystyrene of known molecular weight. It is about.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.

[Curable composition]
The curable composition of the present invention essentially contains metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, an antioxidant, and a radical polymerization initiator. The curable composition of the present invention may further contain epoxy (meth)acrylate C. The curable composition of the present invention may further contain urethane (meth)acrylate D. Moreover, the curable composition of the present invention may contain other (meth)acrylates, additives, solvents, etc. as necessary.

Metal oxide fine particles A are metal oxide fine particles that do not have an aromatic ring and have a median diameter of 5 to 20 nm. The Abbe number of the cured product is improved by the metal oxide fine particles A. Furthermore, the metal oxide fine particles A are less susceptible to oxidative deterioration, shape change, and other alterations even in high-temperature, high-humidity environments.

The metal oxide fine particles A may be metal oxide fine particles whose surface is modified with an organic substance. "Metal oxide fine particles A do not have an aromatic ring" means metal oxide fine particles A whose surface is not modified with an organic substance, or even if the surface is modified with an organic substance, the organic substance has an aromatic ring. This means that the metal oxide fine particles A do not have.

Examples of the metal species of the metal oxide fine particles A include Si, Zr, Ti, Al, Ce, Fe, W, Zn, and Y. In terms of compatibility with other components and availability, the metal species of the metal oxide fine particles A are at least one selected from the group consisting of Si, Zr, Ti, Al, Ce, Fe, W, Zn, and Y. One kind is preferable, at least one kind selected from the group consisting of Si, Zr, and Ti is more preferable, and either one or both of Si and Zr is still more preferable.

Examples of metal oxide fine particles A include _SiO2 fine particles, _ZrO2 fine particles, _{TiO2 fine} particles, _Al2O3 fine particles, CeO2 _fine particles, _Fe3O4 fine particles _{, WO3 fine} particles, ZnO fine particles, and _Y2O3 fine particles. can. In terms of compatibility with other _components and availability, metal oxide fine particles A include _SiO2 fine particles, _ZrO2 fine particles, TiO2 _fine particles, _Al2O3 fine particles, _{CeO2 fine particles} , and _Fe3O4 fine particles. , WO ₃ fine particles, ZnO 3 fine particles, and Y ₂ O ₃ fine particles, and more preferably at least one selected from the group consisting of SiO ₂ fine particles, ZrO ₂ fine particles, and TiO ₂ fine particles. More preferably, one or both of SiO ₂ fine particles and ZrO ₂ fine particles are used.

When the metal oxide fine particles A are surface-modified with an organic substance, the surface modification of the organic substance includes coating the fine particle surface with the organic substance through surface treatment, coating the fine particle surface with the organic substance by electrostatic interaction, and intermolecular force such as hydrogen bonding. An example is the adhesion of organic matter.
Examples of organic substances used for surface modification of the metal oxide fine particles A include organosilicon compounds, organophosphorus compounds, and organosulfur compounds.

The organic content of the metal oxide fine particles A is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less. When the organic content of the metal oxide fine particles A is below the upper limit, yellowing due to oxidation of the organic content under high temperature and high humidity is suppressed, and a decrease in transparency of the cured product is suppressed. The lower the organic content of the metal oxide fine particles A, the better, and the lower limit of the organic content is 0% by mass.

The shape of the metal oxide fine particles A may be spherical, chain-like, or other shapes. Among these, the spherical shape is preferable because the metal oxide fine particles A are less likely to aggregate and a decrease in transparency of the cured product can be suppressed.
The metal oxide fine particles A may be solid particles or hollow particles. Among these, solid metal oxide fine particles A are preferable because they have a high refractive index and less loss of transmittance.

The median diameter of the metal oxide fine particles A is 5 to 20 nm, preferably 6 to 15 nm, and more preferably 7 to 10 nm. If the median diameter of the metal oxide fine particles A is equal to or larger than the lower limit of the above range, handling properties are good. Furthermore, since the metal oxide fine particles A are less likely to aggregate, the cured product has higher transparency. If the median diameter of the metal oxide fine particles A is below the upper limit of the above range, light scattering by the metal oxide fine particles A will be small, and the transparency of the curable composition and cured product will be high.

As the metal oxide fine particles A, commercially available products may be used.
Commercially available metal oxide fine particles A include organosilica sol (MEK-ST-40, TOL-ST, IPA-ST, MEK-ST-UP, EG-ST, NPC-ST-30, etc. manufactured by Nissan Chemical Industries, Ltd.). ), surface-modified zirconia particle dispersion (Zircostar ZP-153-A manufactured by Nippon Shokubai, PCPR-50-ETA manufactured by Pixelligent, etc.), titania sol (Optolake 6320z (11RU-7・MK) manufactured by Catalyst and Chemical) etc.) can be exemplified.
The number of metal oxide fine particles A contained in the curable composition may be one, or two or more.

(Meth)acrylate B is a (meth)acrylate (excluding organopolysiloxane) having an alicyclic condensed ring and having a homopolymer glass transition temperature of 90 to 350°C.
Since (meth)acrylate B has an ethylenically unsaturated group, it can be radically polymerized by light or heat. Since the curable composition of the present invention combines (meth)acrylate B and a radical polymerization initiator and is cured by radical polymerization, it has excellent curability and the resulting cured product has excellent heat resistance.

(Meth)acrylate B preferably does not contain an aromatic ring. Since (meth)acrylate B does not contain an aromatic ring with a low Abbe number and has an alicyclic structure with a high Abbe number, the Abbe number of the cured product is improved.

An alicyclic condensed ring is a condensed alicyclic ring. Alicyclic condensed rings have high bonding strength between carbon atoms, and are unlikely to undergo oxidation or bond breakage under high temperature and high humidity conditions. Therefore, since (meth)acrylate B has an alicyclic condensed ring, the cured product becomes less likely to be colored and its transparency is less likely to decrease.

From the viewpoint of easy availability of (meth)acrylate B, the alicyclic condensed ring includes a norbornyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentanyl group, a tetracyclododecanyl group, a noradamantyl group, A ring derived from at least one group selected from the group consisting of an adamantyl group and an amantyl group is preferred. Among these, isobornyl group or dicyclopentanyl group is preferred.

The number of ethylenically unsaturated groups that (meth)acrylate B has is preferably one or two, from the viewpoint of ease of acquisition and the proportion of alicyclic condensed rings in the molecule, and one is preferable. Particularly preferred.

The glass transition temperature of the homopolymer of (meth)acrylate B is 90 to 350°C, preferably 150 to 350°C, more preferably 200 to 350°C, even more preferably 250 to 350°C. If the glass transition temperature of the homopolymer is equal to or higher than the lower limit of the range, the cured product will be less likely to soften under high temperature and high humidity, and will have excellent various properties. If the glass transition temperature of the homopolymer is below the upper limit of the range, (meth)acrylate B is easily available.

Examples of (meth)acrylate B include dicyclopentanyl acrylate, dicyclopentanyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 2-adamantyl acrylate, and tricyclodecane dimethanol diacrylate. .
The number of (meth)acrylates B contained in the curable composition may be one or two or more.

Epoxy (meth)acrylate C is an epoxy (meth)acrylate that does not have an aromatic ring and has an ethylenically unsaturated group content of 0.1 to 3.0 mmol/g (provided that organopolysiloxane and (meth) ) except for acrylate B).

Epoxy (meth)acrylate C is an epoxy compound to which (meth)acrylic acid is added. Since the epoxy (meth)acrylate C has a hydroxyl group formed by ring opening of an epoxy group, it has particularly good compatibility with the metal oxide fine particles A having a silanol group on the surface. It also has good compatibility with (meth)acrylate B. Therefore, in a curable composition containing epoxy (meth)acrylate C, metal oxide fine particles A, (meth)acrylate B, and epoxy (meth)acrylate C are compatible, and as a result, the transparency of the cured product is reduced. It gets expensive.

Epoxy (meth)acrylate C does not have an aromatic ring. Since the epoxy (meth)acrylate does not have an aromatic ring, a decrease in the Abbe number of the cured product can be suppressed.
The amount of ethylenically unsaturated groups in epoxy (meth)acrylate C is 0.1 to 3.0 mmol/g, preferably 0.3 to 2.7 mmol/g, per 1 g of epoxy (meth)acrylate C. , 0.5 to 2.5 mmol/g is more preferable. If the amount of the ethylenically unsaturated group is at least the lower limit of the range, sufficient curing can be achieved. If the amount of the ethylenically unsaturated group is below the upper limit of the above range, the cured product will be less likely to shrink when the curable composition is cured, and cracks will be less likely to occur in the cured product. Therefore, the cured product can be suitably used as an optical member.

Commercially available products of epoxy (meth)acrylate C include NK Oligo (EA-5311, EA-5511, etc.) manufactured by Shin-Nakamura Chemical Co., Ltd., and Denacol Acrylate (DA-722, DA-314, etc.) manufactured by Nagase ChemteX. ), and epoxy acrylate manufactured by MIWON (Miramer PE230, etc.).

Urethane (meth)acrylate D is a urethane (meth)acrylate that does not have an aromatic ring (excluding organopolysiloxane, (meth)acrylate B, and epoxy (meth)acrylate C).
Since urethane (meth)acrylate D does not have an aromatic ring that lowers the Abbe number, the decrease in the Abbe number of the cured product is suppressed.

Urethane (meth)acrylate D has a urethane bond and two or more (meth)acryloyl groups. Since urethane (meth)acrylate D has urethane bonds exhibiting hydrogen bonding properties, it has particularly good compatibility with metal oxide fine particles A having silanol groups on the surface. It also has good compatibility with (meth)acrylate B and epoxy (meth)acrylate C. Therefore, in the curable composition containing urethane (meth)acrylate D, metal oxide fine particles A, (meth)acrylate B, epoxy (meth)acrylate C, and urethane (meth)acrylate D are compatible, and as a result, The transparency of the cured product increases. Furthermore, it has urethane bonds that exhibit hydrogen bonding properties, which improves the flexibility of the cured product, resulting in higher crack resistance. This effect is particularly noticeable when the thickness of the cured product is 5 mm or more or when the volume of the cured product is 1 cm ³ or more. From the viewpoint of ease of preparation of evaluation samples, the thickness of the cured product is preferably 50 mm or less, and the volume is preferably 50 cm ³ or less.

The amount of ethylenically unsaturated groups in urethane (meth)acrylate D is 0.1 to 3.0 mmol/g, preferably 0.3 to 2.7 mmol/g, per 1 g of urethane (meth)acrylate D. , 0.5 to 2.5 mmol/g is more preferable. If the amount of this substance is at least the lower limit of the above range, sufficient curing can be achieved. If the amount of this substance is below the upper limit of the above range, the cured product will be less likely to shrink when the curable composition is cured, and cracks will be less likely to occur in the cured product. Therefore, the cured product can be suitably used as an optical member.

Commercially available products of urethane (meth)acrylate D include NK Oligo (UA-160TM, U-412A, UA-4200, UA-4400, UA-122P, etc.) manufactured by Shin-Nakamura Chemical Industries, Ltd., and NK Oligo manufactured by Daicel Allnex Corporation. EBECRYL (8402, 8807, 9260, etc.), KRM (8667, 8904, etc.) manufactured by Daicel Allnex, UA-306H, UA-306T, UA-306I, UA-510H manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Examples include UX-3204, UX-4101, and UX-8101.
The number of urethane (meth)acrylates D contained in the curable composition may be one or two or more.

The antioxidant includes an antioxidant having a phenol moiety and an antioxidant having a sulfide moiety (excluding the above-mentioned antioxidant having a phenol moiety).
The antioxidant having a phenolic moiety captures radicals that cause coloration generated in the cured product, and suppresses a decrease in transparency of the cured product. An antioxidant having a sulfide moiety can regenerate an antioxidant having a phenol moiety that has scavenged radicals. Therefore, by using an antioxidant having a phenol moiety and an antioxidant having a sulfide moiety in combination, it is possible to suppress a decrease in transparency of a cured product over a long period of time.

Commercially available antioxidants having a phenolic moiety include IRGANOX (trade name) (259, 1010, 1035, 1076, 1098, 1135, etc.) manufactured by BASF Japan, and ADEKA STAB (trade name) (AO-) manufactured by ADEKA. 50, AO-60, etc.). The antioxidants having a phenol moiety may be used alone or in combination of two or more.
Examples of commercially available antioxidants having a sulfide moiety include sulfur-based antioxidant T0205 manufactured by Tokyo Kasei Kogyo Co., Ltd. and ADEKA STAB (trade name) (AO-412S, AO-503, etc.) manufactured by ADEKA. One type of antioxidant having a sulfide moiety may be used alone, or two or more types may be used in combination.

The antioxidant may include an antioxidant other than the antioxidant having a phenol moiety and the antioxidant having a sulfide moiety.
The total proportion of the antioxidant having a phenol site and the antioxidant having a sulfide site among all the antioxidants is preferably 50% by mass or more, and particularly preferably 100% by mass.
The proportion of the antioxidant having a phenol moiety in the total of the antioxidant having a phenol moiety and the antioxidant having a sulfide moiety is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 15 to 90% by mass. 85% by mass is more preferred.
The number of antioxidants contained in the curable composition may be one, or two or more.

The organopolysiloxane contained in the curable composition of the present invention tends to segregate on the surface of the cured product when it is cured. Therefore, a cured product obtained by curing the curable composition of the present invention has excellent adhesion to an inorganic base material or an inorganic compound layer.
The organopolysiloxane is a structural unit represented by the following formula f1 (hereinafter also referred to as "unit f1"), a constitutional unit represented by the following formula f2 (hereinafter also referred to as "unit f2"), and the following formula f3. It has at least one type selected from the group consisting of the structural unit represented by the following formula (hereinafter also referred to as "unit f3") and the structural unit represented by the following formula f4 (hereinafter also referred to as "unit f4"). .

However, in the formulas f1 to f4, R ¹ to R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a cycloalkyl group having 7 to 12 carbon atoms. an aralkyl group, a group having an ethylenically unsaturated group, or a hydrogen atom. -* is a bond.

Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and tert-butyl group. -Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group , 1-ethyl-2-methylpropyl group, and 1-ethyl-1-methylpropyl group.

Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, diphenylmethyl group, and naphthylmethyl group.

Groups having an ethylenically unsaturated group include -Q ¹ -CR=CH ₂ , -Q ¹ -O-CO-CR=CH ₂ (in the above formula, Q ¹ is a single bond or the number of carbon atoms 1 to 6 alkylene groups.R is a hydrogen atom or a methyl group).

The alkylene group having 1 to 6 carbon atoms in Q ¹ includes a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, an isopentylene group, Neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene group, 2-methyl Pentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group , 1,2,2-trimethylpropylene group, 1-ethyl-2-methylpropylene group, and 1-ethyl-1-methylpropylene group.
As Q ¹ , a single bond or an alkylene group having 2 to 4 carbon atoms is preferred from the viewpoint of easy availability of raw materials.

R ¹ to R ⁶ are preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group, from the viewpoint of ease of segregation on the surface.

Among units f1 to f4, units f1, f2, and f3 are preferred, and units f1 and f2 are more preferred, from the standpoint of long-term stability, low viscosity, and ease of handling.
From the viewpoint of curability, the organopolysiloxane preferably has an ethylenically unsaturated group.

The organopolysiloxane may be linear or cyclic.
As the chain-shaped organopolysiloxane, organopolysiloxane F1 represented by the following formula F1 is preferred from the viewpoint of ease of production.

However, in the above formula F1, R ¹¹ and R ²¹ are each independently an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. i and j are each independently from 0 to 2. Q ² and Q ³ are each independently an alkyl group having 1 to 6 carbon atoms when i and j are 0, and a single bond or a single bond when i and j are 1; is an alkylene group, and when i and j are 2, it is a trivalent hydrocarbon group having 1 to 6 carbon atoms. X ¹ and X ² are -CR ⁷ =CH ₂ , -O-CO-CR ⁷ =CH ₂ (however, R ⁷ is a hydrogen atom or a methyl group), or -Si(R ⁸ ) _b ( OR ⁹ ) _3-b (wherein R ⁸ and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms. b is 0 to 3). a is 0 to 300.

Examples of the alkyl group having 1 to 6 carbon atoms for R ¹¹ and R ²¹ are the same as those exemplified as the alkyl group having 1 to 6 carbon atoms for R ¹ to R ⁶ . The plurality of R ¹¹ and R ²¹ may be the same group or different groups. As R ¹¹ and R ²¹ , an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable, from the viewpoint of ease of surface segregation.
a is preferably 0 to 100, more preferably 0 to 50.

Examples of R ⁸ and R ⁹ include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
b is preferably 1 to 2.
As X ¹ and X ² , -CR ⁷ =CH ₂ or -O-CO-CR ⁷ =CH ₂ is preferred, and -O-CO-CR ⁷ =CH ₂ is particularly preferred.
As Q ² and Q ³ , a single bond or an alkylene group having 2 to 4 carbon atoms is preferred from the viewpoint of easy availability of raw materials.

Among organopolysiloxanes F1, organopolysiloxanes F11 represented by the following formula F11 are more preferred.

However, R ¹¹ , R ²¹ , Q ² , Q ³ , R ⁷ , and a in the formula F11 are the same as R ¹¹ , R ²¹ , Q ² , Q ³ , R ⁷ , and a in the formula F1. i and j are each independently from 0 to 2. The plurality of R ¹¹ and R ²¹ may be the same group or different groups. Q ² and Q ³ may be the same group or different groups. A plurality of R ⁷ 's may be the same group or different groups.

As the cyclic organopolysiloxane, organopolysiloxane F2 represented by the following formula F2 is preferable.

However, in the formula F2, R ¹¹ to R ³¹ are the same as R ¹¹ and R ²¹ in the formula F1. Q ⁴ is a single bond or an alkylene group having 1 to 6 carbon atoms. X ³ is the same as X ¹ and X ² in formula F1. c is 0-12. d is 0-12. c+d is 1-24.
c is preferably 0 to 10, more preferably 2 to 8.
d is preferably 0 to 10, more preferably 2 to 8.

Specific examples of organopolysiloxane F2 include a compound represented by the following formula F21, a compound represented by the following formula F22, and a compound represented by the following formula F23. However, R ¹¹ to R ³¹ , Q ⁴ , and X ³ in the following formulas F21 to F23 are the same as R ¹¹ and R ²¹ in formula F1, and Q ⁴ and X ³ in formula F2.

The Mw of the organopolysiloxane is preferably 100 to 100,000, more preferably 120 to 75,000, and even more preferably 150 to 50,000. If the Mw of the organopolysiloxane is greater than or equal to the lower limit of the above range, surface segregation is possible. If the Mw of the organopolysiloxane is less than or equal to the upper limit of the above range, it can be uniformly dissolved with other components.

Note that the organopolysiloxane may have an epoxy group.
The number of organopolysiloxanes contained in the curable composition may be one or two or more.

Examples of the radical polymerization initiator include photo radical polymerization initiators and thermal radical polymerization initiators. A photoradical polymerization initiator is preferred from the viewpoint of easy production of a cured product.
Examples of the photoradical polymerization initiator include alkylphenone type, acylphosphine oxide type, titanocene type, oxime ester type, oxyphenylacetate type, benzoin type, benzophenone type, thioxanthone type, benzyl-(o-ethoxycarbonyl)-α- Examples include monooxime, glyoxyester, 3-ketocoumarin, 2-ethyl anthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, and tert-butyl peroxypivalate. From the viewpoint of sensitivity and compatibility, alkylphenone type, acylphosphine oxide type, benzoin type or benzophenone type is preferable.

Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, and dicumyl peroxide. From the viewpoint of decomposition temperature, 2,2'-azobisisobutyronitrile and benzoyl peroxide are preferred.
The number of radical polymerization initiators contained in the curable composition may be one, or two or more.

The curable composition of the present invention includes a surfactant, a thixotropic agent, an antifoaming agent, a light stabilizer, an antigelation agent, a photosensitizer, a resin, a resin oligomer, a carbon compound, a metal fine particle, and a metal oxide particle. (However, metal oxide fine particles A are excluded), silane coupling agents, other organic compounds, and other additives may be included.

The curable composition of the present invention may also contain a solvent. However, it is preferable to remove the solvent before curing the curable composition.
As the solvent, any solvent that can dissolve (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, urethane (meth)acrylate D, antioxidant, and radical polymerization initiator can be used. Among these, solvents having one or more of an ester structure, a ketone structure, a hydroxyl group, an aromatic hydrocarbon group, and an ether structure are preferred. As the solvent, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-propanol, and toluene are preferred, and methyl ethyl ketone, 2-propanol, and toluene are particularly preferred.
When a solvent is used in the present invention, the content of the solvent in the curable composition may be appropriately adjusted depending on the desired viscosity, coatability, desired film thickness, etc.

The proportion of metal oxide fine particles A in the curable composition is based on the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. It is preferably 3 to 55% by weight, more preferably 5 to 51% by weight, even more preferably 15 to 50% by weight, particularly preferably 15 to 40% by weight, and most preferably 15 to 25% by weight. If the proportion of metal oxide fine particles A is at least the lower limit of the above range, the Abbe number of the cured product will be high. If the proportion of metal oxide fine particles A is below the upper limit of the above range, the compatibility with other components will be good, the metal oxide fine particles A will be easily dispersed uniformly in the curable composition, and the transparency of the cured product will be improved. Excellent in In addition, the cured product is less likely to become brittle and cracks are less likely to occur in the cured product.

The proportion of (meth)acrylate B in the curable composition is based on the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. It is preferably 3 to 70% by weight, more preferably 5 to 66% by weight, even more preferably 20 to 65% by weight, particularly preferably 40 to 55% by weight, and most preferably 45 to 50% by weight. When the proportion of (meth)acrylate B is at least the lower limit of the above range, the curable composition has good curability. If the proportion of (meth)acrylate B is below the upper limit of the above range, the Abbe number of the cured product will be high.

The proportion of organopolysiloxane in the curable composition is 3 to 3 of the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. It is preferably 60% by weight, more preferably 5-55% by weight, even more preferably 10-50% by weight, particularly preferably 15-45% by weight, and most preferably 20-40% by weight. If the proportion of organopolysiloxane is at least the lower limit of the above range, it will have excellent adhesion to the inorganic base material and the inorganic compound layer. If the proportion of organopolysiloxane is below the upper limit of the above range, the properties of other components will not be impaired.

Epoxy (meth)acrylate C is included as necessary in the curable composition of the present invention. The proportion of epoxy (meth)acrylate C in the curable composition is based on the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. , preferably 0 to 80% by weight, more preferably 10 to 65% by weight, even more preferably 20 to 50% by weight, particularly preferably 22 to 46% by weight, and most preferably 24 to 42% by weight. When the proportion of epoxy (meth)acrylate C is at least the lower limit of the above range, it has good compatibility with other components, and the cured product has excellent transparency. If the proportion of epoxy (meth)acrylate C is below the upper limit of the above range, the Abbe number of the cured product will be high.

Urethane (meth)acrylate D is included in the curable composition of the present invention as necessary. The proportion of urethane (meth)acrylate D in the curable composition is based on the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. , preferably 0 to 40% by weight, more preferably 3 to 36% by weight, and even more preferably 5 to 32% by weight. If the proportion of urethane (meth)acrylate D is equal to or higher than the lower limit of the above range, the flexibility of the cured product can be improved, resulting in high crack resistance. If the proportion of urethane (meth)acrylate D is below the upper limit of the above range, the Abbe number of the cured product will be high.

The proportion of the antioxidant in the curable composition is based on 100 parts by mass of the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and even more preferably 1 to 6 parts by weight. If the proportion of the antioxidant is at least the lower limit of the above range, it is possible to suppress the decrease in transparency of the cured product over a long period of time. If the proportion of the antioxidant is below the upper limit of the above range, deterioration in the curability of the cured product can be prevented.

The proportion of the radical polymerization initiator in the curable composition is 100 parts by mass of the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. On the other hand, it is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, and even more preferably 0.5 to 5 parts by weight. If the ratio of the radical polymerization initiator is at least the lower limit of the above range, a cured product can be easily formed. If the ratio of the radical polymerization initiator is below the upper limit of the above range, uniform mixing is possible, so the amount of the radical polymerization initiator remaining in the cured product is reduced, and deterioration of the physical properties of the cured product is suppressed.

The total amount of other components such as additives is based on 100 parts by mass of the total mass of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D. The amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

In addition, when the curable composition of the present invention contains epoxy (meth)acrylate C and does not contain urethane (meth)acrylate D, the standard for calculating the proportion of each component is that the proportion of urethane (meth)acrylate D is 0. Because it is mass %, it is substantially the sum of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, and epoxy (meth)acrylate C.
When the curable composition of the present invention contains urethane (meth)acrylate D and does not contain epoxy (meth)acrylate C, the standard for calculating the proportion of each component is that the proportion of epoxy (meth)acrylate C is 0% by mass. Therefore, it is substantially the sum of metal oxide fine particles A, (meth)acrylate B, organopolysiloxane, and urethane (meth)acrylate D.
When the curable composition of the present invention does not contain both epoxy (meth)acrylate C and urethane (meth)acrylate D, the criteria for calculating the proportions of each component are substantially metal oxide fine particles A, (meth) ) is the sum of acrylate B and organopolysiloxane.

[Cured product]
The cured product of the present invention is a cured product of the curable composition of the present invention, and includes a matrix resin having an alicyclic condensed ring and metal oxide fine particles dispersed in the matrix resin.
The matrix resin contains components other than the metal oxide fine particles A, such as (meth)acrylate B, epoxy (meth)acrylate C, urethane (meth)acrylate D, and organopolysiloxane in the curable composition of the present invention. It is hardened.

The proportion of metal oxide fine particles in the cured product is preferably 3 to 55% by mass, more preferably 5 to 51% by mass, and even more preferably 15 to 50% by mass of the total of the matrix resin and metal oxide fine particles. If the proportion of the metal oxide fine particles is at least the lower limit of the above range, the cured product is unlikely to suffer from oxidative deterioration, shape change, or other alterations even in a high-temperature, high-humidity environment. If the proportion of metal oxide fine particles is below the upper limit of the above range, the cured product will have excellent transparency. In addition, the cured product is less likely to become brittle and cracks are less likely to occur in the cured product.
The proportion of the matrix resin in the cured product is preferably 45 to 97% by mass, more preferably 49 to 95% by mass, and even more preferably 50 to 85% by mass of the total of the matrix resin and metal oxide fine particles.

The thickness of the cured product is not particularly limited, and can be, for example, 0.05 to 10.0 mm.
As a method for forming a cured product, the curable composition is brought into contact with a mold having an inverted pattern of a fine pattern on its surface, and the curable composition is cured to form a cured product having a fine pattern on its surface. The method (imprint method) can be exemplified. Alternatively, a method (cast molding method) may be used in which a curable composition is injected into a cavity of a mold and the curable composition is cured to form a cured product.
The curing method may be photocuring or thermosetting, and may be appropriately selected depending on the polymerization initiator. As the curing method, photocuring is preferred from the viewpoint of ease of manufacturing a cured product.

The transmittance of light at a wavelength of 400 nm per 1 mm thickness of the cured product obtained by curing the curable composition of the present invention is preferably 30% or more, more preferably 50% or more, even more preferably 88% or more, and 90% or more. More preferred. If the transmittance is greater than or equal to the lower limit, the cured product will have even better transparency.

The transmittance of light with a wavelength of 400 nm per 1 mm of the thickness of the cured product is determined from the following formula 1.
T=T ₁ × (1-r) ² ...Formula 1
However, T is the transmittance of light with a wavelength of 400 nm per 1 mm of the thickness of the cured product. r={(n-1)/(n+1)} ² . T ₁ is the internal transmittance of light with a wavelength of 400 nm per 1 mm of the thickness of the cured product, and is determined from the following equation 2. n is the refractive index of the cured product at 25° C. with respect to light with a wavelength of 400 nm.
T ₁ = (T _Y /100) ^1/Y ×100 ... Formula 2
However, T _Y is the internal transmittance of light with a wavelength of 400 nm per thickness Y mm of the cured product, and is determined from the following formula 3.
T _Y = (transmittance of light with a wavelength of 400 nm per thickness Ymm of cured product)/(1-r) ² ...Formula 3

The internal transmittance of light at a wavelength of 400 nm per 1 mm of thickness of the cured product, calculated from Formulas 2 and 3, is preferably 50% or more, more preferably 90% or more, even more preferably 95% or more, and 97% or more. More preferred. If the internal transmittance is at least the lower limit of the range, the cured product will have particularly excellent transparency. The higher the internal transmittance, the better, and the upper limit is 100%.

The internal transmittance of light with a wavelength of 400 nm per 1 mm of thickness of the cured product after being maintained for 1000 hours in an atmosphere with a temperature of 85 ° C. and a relative humidity of 85% is preferably 50% or more, more preferably 90% or more, and 95%. More preferably, it is 96% or more. When the internal transmittance is equal to or higher than the lower limit of the range, deterioration in transparency of the cured product can be suppressed over a long period of time.

The retention rate of the internal transmittance of light with a wavelength of 400 nm before and after the heat and humidity test is calculated per 1 mm of the thickness of the cured product using the following formula 4.
Retention rate of internal transmittance (%) = (Internal transmittance of light with a wavelength of 400 nm per 1 mm of thickness of the cured product after heat resistance test / Internal transmittance of light with a wavelength of 400 nm per 1 mm of thickness of cured product before heat resistance test Transmittance)×100...Formula 4

The internal transmittance retention rate before and after the heat-and-moisture test, calculated from Equation 4, is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more. If the retention rate of the internal transmittance is equal to or higher than the lower limit of the range, deterioration in transparency of the cured product can be suppressed over a long period of time.

As explained above, the curable composition of the present invention contains metal oxide fine particles A, (meth)acrylate B, a specific antioxidant, organopolysiloxane, and a radical polymerization initiator as essential components. Since it contains (meth)acrylate B and a radical polymerization initiator and is cured by radical polymerization, the curable composition of the present invention has excellent curability and the cured product has excellent heat resistance. Further, since it contains organopolysiloxane, the cured product obtained by curing the curable composition of the present invention has excellent adhesion to an inorganic substrate or an inorganic compound layer. Therefore, even if exposed to a high temperature and high humidity environment for a long period of time, peeling is unlikely to occur between the cured product and the inorganic base material or between the cured product and the inorganic compound layer.
Further, in the curable composition of the present invention, metal oxide fine particles A, (meth)acrylate B, a specific antioxidant, and epoxy (meth)acrylate C and urethane (meth)acrylate D are used as necessary. Therefore, the cured product formed has excellent transparency.

[Laminated body]
The laminate of the present invention includes a cured product obtained by curing the curable composition of the present invention, and an inorganic compound layer provided on the cured product. The laminate of the present invention may include, for example, an inorganic base material, a cured product obtained by curing the curable composition of the present invention provided on the surface of the inorganic base material, and a cured product obtained by curing the curable composition of the present invention provided on the surface of the inorganic base material, and a An example is a laminate having an inorganic compound layer provided on the surface.

Examples of the inorganic base material include base materials made of inorganic materials such as glass, quartz glass, and metal. The inorganic base material may be a flat base material or a curved base material.
The thickness of the inorganic base material is not particularly limited, and can be, for example, 0.025 to 5.0 mm.

The glass transition temperature of the cured product is preferably 90 to 350°C, more preferably 100 to 350°C, even more preferably 150 to 350°C, particularly preferably 200 to 350°C. If the glass transition temperature of the cured product is equal to or higher than the lower limit, the cured product will not easily soften under high temperature and high humidity. If the glass transition temperature of the cured product is below the upper limit, it is easy to obtain the curable composition of the present invention.

The refractive index of the cured product for light with a wavelength of 589 nm is preferably 1.45 or more, more preferably 1.48 to 1.53. If the refractive index is within the above range, Fresnel reflection is unlikely to occur even when combined with other members such as a glass substrate, and loss of transmittance is small.

The Abbe number of the cured product determined from the following formula 5 is preferably 54 or more, more preferably 56 or more, and even more preferably 58 or more. If the Abbe number is equal to or greater than the lower limit of the range, chromatic aberration is unlikely to occur. The Abbe number is better as it is higher, and the upper limit is not particularly limited, but it is about 70 considering that it is an organic substance.
ν _D = (n _D -1)/(n _F -n _C ) ...Formula 5
However, _νD is Abbe's number. _nD is the refractive index for light with a wavelength of 589 nm. _nF is the refractive index for light with a wavelength of 486 nm. n _C is the refractive index for light with a wavelength of 656 nm.

The thickness of the cured product in the laminate is not particularly limited, and can be, for example, 0.05 to 10.0 mm.
As a method for forming a cured product, the curable composition is brought into contact with a mold having an inverted pattern of a fine pattern on its surface, and the curable composition is cured to form a cured product having a fine pattern on its surface. The method (imprint method) can be exemplified. Alternatively, a method (cast molding method) may be used in which a curable composition is injected into a cavity of a mold and the curable composition is cured to form a cured product.
The curing method may be photocuring or thermosetting, and may be appropriately selected depending on the polymerization initiator. As the curing method, photocuring is preferred from the viewpoint of ease of manufacturing a cured product.

Examples of the inorganic compound forming the inorganic compound layer include metal compounds. Examples of the metal species of the metal compound include Si, Zn, Zr, Ti, Ta, Nb, In, Sn, Y, W, Al, Cr, and Ga. From the viewpoint of optical property control, the metal species of the metal compound is at least one selected from the group consisting of Si, Zn, Zr, Ti, Ta, Nb, In, Sn, Y, W, Al, Cr, and Ga. Preferably, Si, Ti, Ta or Nb is more preferable.

Inorganic compounds forming the inorganic compound layer include _SiO2 , SiC, ZnO, _ZrO2 , _TiO2 , _Ta2O5 , _{Nb2O5 , In2O3} , _{SnO2 , Y2O3 , WO3 , Examples} include _Al2O3 , TiC, TiN, _{Cr2O3 , and Ga2O3 .} From the viewpoint of optical property control, inorganic compounds include SiO ₂ , SiC, ZnO, ZrO ₂ , TiO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , In ₂ O ₃ , SnO ₂ , Y ₂ O ₃ , WO ₃ , Al ₂ O ₃ , TiC, TiN, Cr ₂ O ₃ and Ga ₂ O ₃ is preferred, and SiO ₂ , TiO ₂ , Ta ₂ O ₅ or Nb ₂ O ₅ is more preferred.

An example of the inorganic compound layer is a vapor-deposited layer of a metal compound.
The thickness of the inorganic compound layer is not particularly limited, and can be, for example, 10 to 5000 nm.
Examples of methods for forming the inorganic compound layer include vacuum evaporation and sputtering.

The laminate of the present invention described above has excellent heat resistance because it has a cured product obtained by curing the curable composition of the present invention, and has excellent adhesion between the cured product and the inorganic base material and the inorganic compound layer, so it can be used at high temperatures. Does not easily peel off even if exposed to high humidity environments for long periods of time.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the following description. Examples 1 to 5 are examples, and Examples 6 and 7 are comparative examples.
[Evaluation method]
(Median diameter of metal oxide fine particles)
It was determined using a dynamic light scattering particle size distribution analyzer (manufactured by Otsuka Electronics Co., Ltd., FPAR1000).

(Preparation of evaluation sample I)
A (meth)acrylate or a curable composition was applied to the surface of a quartz glass substrate that had been subjected to mold release treatment. A slide glass substrate that had been subjected to mold release treatment and a quartz glass substrate were faced to each other with a spacer having a thickness of 100 μm interposed therebetween, and a curable composition was sandwiched between them. In this state, the curable composition was irradiated with ultraviolet light from a high-pressure mercury lamp at an exposure amount of 3000 mJ/cm ² . The released quartz glass substrate was peeled off, the surface of the cured product was washed with ethanol, dried, and then heat treated at 180° C. for 15 minutes. By peeling off the slide glass substrate, an evaluation sample I (cured product) with a thickness of 100 μm was obtained.

(Glass-transition temperature)
Using a differential scanning calorimeter (manufactured by TA Instruments, DSC-Q20), the temperature of evaluation sample I was raised from 10°C to 350°C at a rate of 20°C/min in a nitrogen atmosphere, and the glass transition temperature was determined. . For those whose glass transition temperature was not observed at 350°C, the glass transition temperature was set to 350°C or higher.

(Amount of ethylenically unsaturated group)
^{The 1} H-NMR spectrum of the epoxy acrylate or curable composition was measured using an FT-NMR device (manufactured by JEOL Ltd., JNM-AL300) (300 MHz, solvent: CDCl ₃ , standard: tetramethylsilane). Using 1,4-bis(trifluorobenzene) as an internal standard, the amount of ethylenically unsaturated groups was calculated at around 6 ppm.

(Refractive index of curable composition)
Measurement was performed using an Abbe refractometer (Multi-wavelength Abbe refractometer DR-M2, manufactured by Atago Corporation) at a temperature of 25° C. and a wavelength of 589 nm.

(Abbe number of curable composition)
Using an Abbe refractometer (same as above), the refractive index at each wavelength of 589 nm, 486 nm, and 656 nm was measured at a temperature of 25° C., and calculated from Equation 5 above.

(curability)
The curable composition was subjected to UV irradiation using a viscoelasticity measuring device (trade name "MCR301", manufactured by Anton Paar Japan Co., Ltd.) and an ultraviolet irradiation device (trade name "LC8", manufactured by Hamamatsu Photonics Co., Ltd.). The reaction rate (curing property) was evaluated by measuring the viscoelastic behavior at the time of the reaction. Specifically, the point at which the storage elastic modulus reaches 1 x 10 ⁴ Pa is used as a guideline for the gelation point, and the time after UV irradiation (the time from the start of UV irradiation until the storage elastic modulus reaches 1 x 10 ⁴ Pa) (seconds)) was measured. The analysis conditions of the viscoelasticity measuring device are as follows.
Measurement mode: Vibration mode Measurement plate shape: Parallel (12mmφ)
Measurement temperature: 25℃
Measurement frequency: 1Hz
Measured strain: 0.1%

(Preparation of evaluation samples II and III)
A curable composition was applied to the surface of a quartz glass substrate that had been subjected to mold release treatment. A slide glass substrate that had not been subjected to mold release treatment and a quartz glass substrate that had been subjected to mold release treatment were faced to each other with a spacer having a thickness of 1 mm interposed therebetween, and the curable composition was sandwiched between them. In this state, the curable composition was irradiated with ultraviolet light from a high-pressure mercury lamp at an exposure amount of 3000 mJ/cm ² . Evaluation in which a 1 mm thick cured product was formed on the surface of the slide glass substrate by peeling off the release-treated quartz glass substrate, washing the surface of the cured product with ethanol, drying it, and heat-treating it at 180°C for 15 minutes. Sample II was obtained.
Evaluation sample III was produced in the same manner as evaluation sample II, except that a primer-treated slide glass substrate was used instead of a slide glass substrate that was not subjected to release treatment.

(Preparation of evaluation sample IV)
On the cured product of evaluation sample II or III, metal oxides (SiO ₂ , TiO ₂ , Nb _{2 O 5} , Ta ₂ O ₅ , ZrO ₂ ) were deposited by sputtering to form an inorganic compound layer with a thickness of 200 nm.

(Refractive index of cured product)
Using a refractive index measuring device (prism coupler: 2010/M, manufactured by Metricon, USA), the refractive index of the cured product of evaluation sample I with a thickness of 100 μm was measured for light with wavelengths of 473 nm, 594 nm, and 658 nm at a temperature of 25 ° C. Then, the refractive index for light with a wavelength of 589 nm was calculated using Metricon Fit attached to the device.

(Abbe number of cured product)
The refractive index of the cured product for evaluation at each wavelength was calculated using the Metricon Fit attached to the refractive index measuring device, and the Abbe number was calculated from the above equation 5.

(Moisture heat resistance test)
Evaluation samples II, III, and IV were held in an atmosphere with a temperature of 85° C. and a relative humidity of 85% for 1000 hours.

(Measurement of transmittance)
Evaluation before and after the heat and humidity test The transmittance of the cured products of samples II and III to light with a wavelength of 400 nm was measured using an ultraviolet/visible/near-infrared spectrophotometer (manufactured by Shimadzu Corporation, Solid Spec-3700). .

(Adhesion between cured product and inorganic compound layer)
An adhesive tape specified by JIS Z1522 was attached to the inorganic compound layer of evaluation sample IV after the heat-and-moisture test and then peeled off. Next, the appearance of the inorganic compound layer side was visually observed, peeling of the inorganic compound layer was confirmed, and the adhesion to the inorganic compound layer was evaluated based on the following criteria.
○: No peeling occurred.
Δ: Partial peeling occurred.
×: Completely peeled off.

[material]
The raw materials used in this example are shown below.
(Metal oxide fine particle A dispersion)
Metal oxide fine particle A-1 dispersion liquid: Organosilica sol (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-40, dispersion medium: methyl ethyl ketone, SiO ₂ concentration: 40% by mass, particle shape: spherical, particle diameter (median diameter): 10 nm, organic content of fine particles: 3% by mass).
Metal oxide fine particle A-2 dispersion liquid: Organosilica sol (manufactured by Nissan Chemical Industries, Ltd., TOL-ST, dispersion medium: toluene, SiO ₂ concentration: 40% by mass, particle shape: spherical, particle diameter (median diameter): 10 nm, Organic content of fine particles: 5% by mass).
Metal oxide fine particle A-3 dispersion liquid: Surface-modified zirconia particle dispersion liquid (manufactured by Pixelligent, (product name) PCPR-50-ETA, dispersion medium: ethyl acetate, ZrO ₂ concentration: 50% by mass, particle diameter (median diameter) ): 10 nm, organic content of fine particles: 17% by mass).
Metal oxide fine particle A-4 dispersion liquid: titania sol (manufactured by Catalyst and Chemical, (product name) Optolake 6320z (11RU-7/MK), dispersion medium: propylene glycol monomethyl ether acetate, TiO ₂ concentration: 20% by mass, particles Diameter (median diameter): 13 nm, organic content of fine particles: 8% by mass).

((meth)acrylate B)
Acrylate B-1: dicyclopentanyl acrylate (compound represented by the following formula B-1, manufactured by Tokyo Kasei Kogyo Co., Ltd., glass transition temperature of homopolymer: 120°C).
Acrylate B-2: Isobornyl acrylate (compound represented by the following formula B-2, manufactured by Tokyo Kasei Kogyo Co., Ltd., glass transition temperature of homopolymer: 90°C).
Methacrylate B-3: 1-adamantyl methacrylate (compound represented by the following formula B-3, manufactured by Osaka Organic Chemical Industry Co., Ltd., ADMA, glass transition temperature of homopolymer: 250° C.).

(Epoxy (meth)acrylate C)
Epoxy acrylate C-1: Epoxy acrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK Oligo EA-5311, a compound obtained by adding acrylic acid to a reaction product of trimethylolpropane and epichlorohydrin, amount of ethylenically unsaturated group) :2.8 mmol/g).
Epoxy acrylate C-2: Epoxy acrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK Oligo EA-5511, a compound obtained by adding acrylic acid to glycidyl ether, amount of ethylenically unsaturated group: 1.5 mmol/g).

(Urethane (meth)acrylate D)
Urethane acrylate D-1: Urethane acrylate (manufactured by Shin Nakamura Chemical Co., Ltd., UA-4200, mass average molecular weight: 1300, amount of ethylenically unsaturated group: 1.5 mmol/g).

(Antioxidant)
Antioxidant E-1: Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane (compound represented by the following formula E-1. Manufactured by BASF Japan, IRGANOX (Product name) 1010).
Antioxidant E-2: 2,2'-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (compound represented by the following formula E-2. BASF Japan Co., Ltd.) manufactured by IRGANOX (trade name) 1035).
Antioxidant E-3: Didodecyl 3,3'-thiodipropionate (compound represented by the following formula E-3, manufactured by Tokyo Kasei Kogyo Co., Ltd.).
Antioxidant E-4: 2,2'-methylenebis(4,6-di-t-butylphenyl)octyl phosphite (compound represented by the following formula E-4. Manufactured by ADEKA, (trade name) HP- 10).

(organopolysiloxane)
Organopolysiloxane F-1: Organopolysiloxane (compound represented by the following formula F-1, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164AS).
Organopolysiloxane F-2: Cyclic siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., (trade name) X-40-2670).
Organopolysiloxane F-3: A mixture of polyether-modified polydimethylsiloxane and polyether (manufactured by BYK-Chemie Japan, (trade name) BYK-307).

(epoxy compound)
Epoxy compound I-1: (3,4,3',4'-diepoxy)bicyclohexyl, a compound synthesized by the method described in [0138] Preparation Example 1 of JP-A-2018-008518.
Epoxy compound I-2: non-ester hydrogenated bisphenol diglycidyl compound (manufactured by Mitsubishi Chemical Corporation, YX8000).

(radical polymerization initiator)
Radical polymerization initiator G-1: 2-hydroxy-2-methylpropiophenone (manufactured by BASF Japan, Irgacure (trade name) 1173).
Radical polymerization initiator G-2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Japan, Irgacure (trade name) TPO).

(Cationic polymerization initiator)
Cationic polymerization initiator H-1: 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate (manufactured by San-Apro, (trade name) CPI-101A).

[Examples 1 to 7]
Metal oxide fine particle dispersion A, (meth)acrylate B, organopolysiloxane, epoxy (meth)acrylate C, and urethane (meth)acrylate D were mixed in a solvent such that the solid content ratio was as shown in Table 1. Methyl ethyl ketone, toluene, ethyl acetate, or propylene glycol monomethyl ether acetate was used alone or in combination to form a homogeneous mixture, and the solvent was distilled off under reduced pressure at 40°C. Next, an antioxidant and a radical polymerization initiator were added to the obtained mixture in the amounts shown in Table 1 to obtain a curable composition.
The evaluation results for each example are shown in Tables 2 and 3.

As shown in Tables 2 and 3, the curable compositions of Examples 1 to 5 containing metal oxide fine particles A, (meth)acrylate B, antioxidant, organopolysiloxane, and radical polymerization initiator had curable It was excellent. Furthermore, the adhesiveness between the cured product and the inorganic compound layer after the heat-and-moisture test was excellent, and the change in transmittance of the cured product before and after the heat-and-moisture test was small.
On the other hand, in the curable composition of Example 6 which did not contain organopolysiloxane, the adhesiveness between the cured product and the inorganic compound layer was poor. The curable composition of Example 7 which did not contain (meth)acrylate B had poor curability and poor moist heat resistance of the cured product.

Claims (9)

Metal oxide fine particles A that do not have an aromatic ring and have a median diameter of 5 to 20 nm;
(meth)acrylate B having an alicyclic condensed ring and having a homopolymer glass transition temperature of 90 to 350°C, excluding organopolysiloxane;
antioxidant and
organopolysiloxane,
A radical polymerization initiator;
Further containing an epoxy (meth)acrylate C other than the organopolysiloxane and the (meth)acrylate B, which does not have an aromatic ring and has an ethylenically unsaturated group content of 0.1 to 3.0 mmol/g. fruit ,
The organopolysiloxane may further contain urethane (meth)acrylate D that does not have an aromatic ring, excluding the (meth)acrylate B and the epoxy (meth)acrylate C,
The antioxidant includes an antioxidant having a phenol moiety and an antioxidant having a sulfide moiety, excluding the antioxidant having a phenol moiety,
The organopolysiloxane is organopolysiloxane F11 represented by the following formula F11,
Of the total mass of the metal oxide fine particles A, the (meth)acrylate B, the organopolysiloxane, the epoxy (meth)acrylate C, and the urethane (meth)acrylate D, the proportion of the metal oxide fine particles A is 3 to 55% by mass, the proportion of the (meth)acrylate B is 3 to 70% by mass, the proportion of the organopolysiloxane is 3 to 60% by mass, and the proportion of the epoxy (meth)acrylate C is 10 to 80% by mass,
A curable composition, wherein the cured product obtained by curing the curable composition has a transmittance of 30% or more for light at a wavelength of 400 nm per 1 mm of thickness .

(However, R ¹¹ and R ²¹ in the above formula F11 are each independently an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. i and j are each independently 0 to 2.Q ² and Q3 ^each independently represent an alkyl group having 1 to 6 carbon atoms when i and j are 0, and a single bond or an alkyl group having 1 to 6 carbon atoms when i and j are 1. It is an alkylene group, and when i and j are 2, it is a trivalent hydrocarbon group having 1 to 6 carbon atoms. Plural R ¹¹ and R ²¹ may be the same group or different groups. Q ² and Q ³ may be the same group or different groups. Plural R ⁷ may be the same group or different groups. a is from 0 to 300.) Of the total mass of the metal oxide fine particles A, the (meth)acrylate B, the organopolysiloxane, the epoxy (meth)acrylate C, and the urethane (meth)acrylate D , The proportion is 0 to 40% by mass,
of the antioxidant based on 100 parts by mass of the metal oxide fine particles A, the (meth)acrylate B, the organopolysiloxane, the epoxy (meth)acrylate C, and the urethane (meth)acrylate D. The curable composition according to claim 1, wherein the proportion is 0.1 to 10 parts by weight, and the proportion of the radical polymerization initiator is 0.1 to 10 parts by weight. The curable material according to claim 1 or 2, wherein the metal species of the metal oxide fine particles A is at least one selected from the group consisting of Si, Zr, Ti, Al, Ce, Fe, W, Zn, and Y. Composition. The curable composition according to any one of claims 1 to 3, wherein the metal oxide fine particles A are at least one selected from the group consisting of SiO ₂ fine particles, ZrO ₂ fine particles, and TiO ₂ fine particles. The curable composition according to any one of claims 1 to 3, wherein the metal oxide fine particles A are either or both of SiO ₂ fine particles and ZrO ₂ fine particles. A cured product obtained by curing the curable composition according to any one of claims 1 to 5 . A laminate comprising a cured product obtained by curing the curable composition according to any one of claims 1 to 5 , and an inorganic compound layer provided on the cured product. The inorganic compound forming the inorganic compound layer contains at least one metal species selected from the group consisting of Si, Zn, Zr, Ti, Ta, Nb, In, Sn, Y, W, Al, Cr, and Ga. , The laminate according to claim 7 . The inorganic compound forming the inorganic compound layer is _SiO2 , SiC, ZnO, _ZrO2 , _TiO2 , _Ta2O5 , _{Nb2O5 , In2O3} , _{SnO2 , Y2O3 , WO3 ,} The laminate according to claim ₇ , which is at least one selected from the group consisting of _Al2O3 , TiC, TiN, _{Cr2O3 , and Ga2O3} .