Hardening components, hardening substances

Abstract

To provide a curable composition having a high refraction index and reflow resistance, in which a cured product obtained therefrom has little adhesion of foreign substances; and to provide the cured product obtained therefrom.SOLUTION: A curable composition contains (meth)acrylate having a fluorene structure, and an antioxidant having two or more hindered phenolic structures in a molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition and a cured product of the curable composition. [Background technology]

[0002] Surface mounting technology is advancing rapidly, especially in small devices such as mobile phones and laptops. With the spread of lightweight, high-performance electronic devices, electronic components are also rapidly becoming smaller. The camera lens is one of them, and there is a demand for miniaturization, and the refractive index is High thermal conductivity, low Abbe number, high transparency and heat resistance, and low adhesion of foreign matter are required. For example, a camera module for a mobile phone usually contains multiple lenses with different refractive indices. For high refractive index lenses, fluorene polyester resin is mainly used. However, since fluorene-based polyester resin is a thermoplastic resin, it is difficult to apply solder to the resin. It has the disadvantage of being easily melted by heat during flow (poor heat resistance and reflow resistance).

[0003] Resin using (meth)acrylate with fluorene structure to improve reflow resistance A method of introducing a cross-linked structure into the material is known, and it has a high refractive index and excellent transparency. Therefore, it is considered to be useful for various plastic lenses (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-82387 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-98248 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the methods of Patent Documents 1 and 2 have insufficient reflow resistance, and therefore, air leaks from the lens. Chemical components can become foreign matter and contaminate the lens itself and its surrounding parts. In applications where miniaturization is required and greater visibility than ever before is required, the adhesion of such foreign matter can occur. The material is not suitable for use.

[0006] The present invention has been made to improve the above-mentioned problems, and provides a high refractive index, high transparency, and It has reflow resistance and when cured, there is little adhesion of foreign matter to the cured product itself or surrounding components. The present invention aims to provide a curable composition and a cured product thereof. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] (Meth)acrylates having a fluorene structure and having two or more chins in the molecule A curable composition containing an antioxidant having a dibenzofuran structure. [2] The (meth)acrylate having a fluorene structure is a compound represented by the following formula (1): The curable composition according to [1], which is a compound. [ka] In formula (1), R 1 , R 2 , R 3 , R 4 are each independently a hydrogen atom or a methyl group, m represents an integer of 0 to 5; n represents an integer of 0 to 5; [3] Contains (meth)acrylates with a biphenyl or phenoxyphenyl structure The curable composition according to [1] or [2]. [4] Any of [1] to [3] containing a trifunctional or higher polyfunctional (meth)acrylate. The curable composition according to claim 1. [5] The curable composition according to any one of [1] to [4], which contains a polymerization initiator. [6] In simultaneous thermogravimetry and differential thermal analysis, the polymerization initiator is heated at a rate of 10 Mass loss between 160 and 260°C when heated from 30°C to 330°C at °C / min The curable composition according to [5], wherein the ratio is 80% or less. [7] The molecular weight of the antioxidant according to any one of [1] to [6] is 540 or more. Curable composition. [8] The curable composition according to any one of [1] to [7], wherein the antioxidant does not contain a nitrogen atom. composition. [9] The hard coating composition according to any one of [1] to [8], wherein the antioxidant has a melting point of 60°C or higher. chemical composition.

[10] A cured product of the curable composition according to any one of [1] to [9].

[11] A lens made of the cured product according to

[10] . [Effects of the Invention]

[0008] According to the present invention, the composition has reflow resistance, and when cured, the composition does not cause any abnormality to the cured product itself or to surrounding components. A curable composition that forms a cured product with little adhesion of other objects, and has reflow resistance and is capable of bonding itself to surroundings A cured product can be provided that minimizes adhesion of foreign matter to components. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" refers to the total of acrylates or methacrylates. It is a title. The "~" symbol indicates a range of values, and includes the values ​​before and after it as the lower and upper limits. This means:

[0010] <Curable composition> The curable composition of the present invention comprises a (meth)acrylate having a fluorene structure and a molecular It contains an antioxidant having two or more hindered phenol structures within it.

[0011] (Meth)acrylates having a fluorene structure are materials for increasing the refractive index. It has a (meth)acrylate moiety to provide reflow resistance, and is hardened by a radical reaction. As the (meth)acrylate having a fluorene structure, there are known Among these, those with high refractive index and glass transition temperature after curing can be used. The compound of the following formula (1) is preferred because it has a lower viscosity than the compound of the present invention. [ka]

[0012] In formula (1), R 1 , R 2 , R 3 , R 4 are each independently a hydrogen atom or a methyl group, m represents an integer of 0 to 5, and n represents an integer of 0 to 5. Among them, the refractive index of the cured product is high. Because of this and the increased reactivity, 1 and R 4 is preferably a hydrogen atom. From the viewpoint of formability, m and n are each preferably 1 or 2, and more preferably 1. In addition, R 2 and R 3 From the viewpoint of formability, it is better that hydrogen atoms are also present. This is the preferred form.

[0013] In addition, the curable composition may contain a (meth)acrylate having a fluorene structure from the viewpoint of increasing the refractive index. From the viewpoint of improving the solubility in the curable composition of acrylate and moldability, biphenyl or phenanthroline is used. It is also a preferred embodiment to contain a (meth)acrylate having an alkoxyphenyl structure.

[0014] As the (meth)acrylate having a biphenyl or phenoxyphenyl structure, there are conventionally A (meth)acrylate having a biphenyl structure can be used. Examples of the acrylates include ortho-phenylphenoxyethyl (meth)acrylate, meta-phenylphenoxyethyl (meth)acrylate, Phenylphenoxyethyl (meth)acrylate, para-phenylphenoxyethyl (meth)acrylate ) acrylate, ortho-phenylphenoxypropyl (meth)acrylate, meta-f Phenylphenoxypropyl (meth)acrylate, para-phenylphenoxypropyl ( meth)acrylate, ortho-phenylphenoxybutyl (meth)acrylate, meth- Phenylphenoxybutyl (meth)acrylate, para-phenylphenoxybutyl (meth)acrylate phenylphenoxyalkyl (meth)acrylates such as ortho-phenoxy Phenoxyethoxyethyl (meth)acrylate, meta-phenylphenoxyethoxy Diethyl (meth)acrylate, para-phenylphenoxyethoxyethyl (meth)acrylate acrylates, phenylphenoxyalkoxyalkyl (meth)acrylates, ortho- Phenylmethyl (meth)acrylate, meta-biphenylmethyl (meth)acrylate, Para-biphenylmethyl (meth)acrylate, ortho-biphenylethyl (meth)acrylate acrylate, meta-biphenylethyl (meth)acrylate, para-biphenylethyl (meth)acrylate ortho-biphenylpropyl (meth)acrylate, meta-biphenyl para-biphenylpropyl (meth)acrylate, para-biphenylpropyl (meth)acrylate, butyl-biphenyl butyl (meth)acrylate, meta-biphenyl butyl (meth)acrylate Biphenyl alkyl (meth)acrylate, para-biphenyl butyl (meth)acrylate, etc. Among these, phenylphenoxyalkyl(meth)acrylates and the like can be mentioned. acrylate, phenylphenoxyalkoxyalkyl (meth)acrylate and biphenyl Alkyl (meth)acrylate is preferred from the viewpoint of high refractive index, and solubility and moldability are also taken into consideration. and phenylphenoxyalkyl (meth)acrylate and phenylphenoxyalkoxy Phenylphenoxyethyl (meth)acrylate is more preferred, and phenylphenoxyethyl (meth)acrylate is more preferred. The ortho position is more preferred. Among the positional isomers, the ortho position is more preferred. Considering these, acrylates are preferred to methacrylates. They may be used alone or in combination of two or more.

[0015] Examples of (meth)acrylates having a phenoxyphenyl structure include ortho-phenoxyphenyl. Phenoxyphenylmethyl (meth)acrylate, meta-phenoxyphenylmethyl (meth)acrylate Acrylate, para-phenoxyphenylmethyl (meth)acrylate, ortho-phenoxyphenylmethyl (meth)acrylate Phenoxyphenylethyl (meth)acrylate, meta-phenoxyphenylethyl (meth)acrylate Acrylate, para-phenoxyphenylethyl (meth)acrylate, ortho-phenoxy Diphenylpropyl (meth)acrylate, meta-phenoxyphenylpropyl (meth)acrylate Acrylate, para-phenoxyphenylpropyl (meth)acrylate, ortho-phenoxyphenyl Phenoxyphenylbutyl (meth)acrylate, meta-phenoxyphenylbutyl (meth) Acrylate, para-phenoxyphenyl butyl (meth)acrylate, ortho-phenoxyphenyl Phenoxyphenylpentyl (meth)acrylate, meta-phenoxyphenylpentyl (meth)acrylate ) acrylate, para-phenoxyphenylpentyl (meth)acrylate, ortho- Phenoxyphenylhexyl (meth)acrylate, meta-phenoxyphenylhexyl ( phenoxyphenyl hexyl (meth)acrylate, para-phenoxyphenyl hexyl (meth)acrylate, etc. Phenoxyphenyl alkyl (meth)acrylate, ortho-phenoxyphenyloxymethy (meth)acrylate, meta-phenoxyphenyloxymethyl (meth)acrylate , para-phenoxyphenyloxymethyl (meth)acrylate, ortho-phenoxyphenyl Phenoxyethyl (meth)acrylate, meta-phenoxyphenyloxyethyl (meth)acrylate p-phenoxyphenyloxyethyl (meth)acrylate, ol Meta-phenoxyphenyloxypropyl (meth)acrylate, meta-phenoxyphenyl Para-phenoxyphenyloxypropyl (meth)acrylate, para-phenoxyphenyloxypropyl (meth)acrylate meth)acrylate, ortho-phenoxyphenyloxybutyl (meth)acrylate, meth Ter-phenoxyphenyloxybutyl (meth)acrylate, para-phenoxyphenyl Phenoxyphenyloxyalkyl (meth)acrylates such as oxybutyl (meth)acrylate acrylate, ortho-phenoxyphenyl methoxyethyl (meth)acrylate, meta- Phenoxyphenyl methoxyethyl (meth)acrylate, para-phenoxyphenyl meth ethoxyethyl (meth)acrylate, ortho-phenoxyphenylethoxyethyl (meth)acrylate Acrylate, meta-phenoxyphenylethoxyethyl (meth)acrylate, para- Phenoxyphenylalkoxy such as phenoxyphenylethoxyethyl (meth)acrylate Among these, phenoxyphenyl Alkyl (meth)acrylates are preferred from the viewpoint of solubility and moldability, and phenoxyethanol is particularly preferred. Phenoxyphenylmethyl (meth)acrylate and phenoxyphenylethyl (meth)acrylate From the viewpoint of a high refractive index, phenoxyphenylmethyl (meth)acrylate is more preferable. Among the positional isomers, the meta position is more preferable. Furthermore, in consideration of reactivity, Acrylates are preferred over methacrylates. These compounds may be used alone. However, two or more types may be used in combination. In consideration of moldability and yellowing at high temperatures, phenoxyethanol is preferred. A (meth)acrylate having a diphenyl structure is more preferred.

[0016] The curable composition may contain other active energy ray-curable compounds other than those mentioned above. For example, (meth)acrylate containing an aromatic ring is used because of its high refractive index. Benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxy By including these compounds, moldability can be improved. In addition, it is possible to obtain a suitable viscosity. Phenyl methacrylate and phenyl methacrylate are more preferred.

[0017] Furthermore, from the viewpoint of moldability, a fluorene structure, a biphenyl structure, or a phenoxyphenyl structure may be used. Monofunctional (meth)acrylates, bifunctional (meth)acrylates, excluding (meth)acrylates having a methyl group structure ) acrylate, a mixture of one or more trifunctional or higher multifunctional (meth)acrylates, Any commercially available hardening resin material or any other material that does not impair the object of this embodiment may be used. Other components may be added as long as they are not added to the cured product. In order to take into consideration the strength as a component and to make the cured product less likely to deform even at high temperatures, glass rolling is used. A high transition point is desirable, but to achieve this, multifunctional (meth)acrylates with three or more functional groups are used. It is preferable that the compound contains methyl methyl acrylate.

[0018] Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, Acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Uryl (meth)acrylate, Stearyl (meth)acrylate, Morpholyl (meth)acrylate Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth) Acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate (meth)acrylate, tricyclodecane (meth)acrylate, polyethylene glycol Cyclohexyl (meth)acrylate, tetrahydrofurfuryl dicyclopentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl Allyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate acrylate, 2-ethoxyethyl (meth)acrylate, adamantyl (meth)acrylate, (Meth)acrylic acid and the like.

[0019] The difunctional polyfunctional (meth)acrylate is not particularly limited, but examples thereof include For example, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi All di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate Alkanediol di(meth)acrylates, bisphenol A ethylene oxide modified Di(meth)acrylate, bisphenol F, ethylene oxide modified di(meth)acrylate bisphenol-modified di(meth)acrylates, polyethylene glycol di(meth)acrylates, etc. acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate di(meth)acrylate, epoxy di(meth)acrylate, etc.

[0020] The trifunctional or higher polyfunctional (meth)acrylate is not particularly limited, but may be: For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetraacetate Pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethicone Trimethylolpropane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate , ethylene oxide modified pentaerythritol tetra(meth)acrylate, ethylene Ethylene oxide such as oxide-modified pentaerythritol tri(meth)acrylate Modified (meth)acrylate, ethylene oxide isocyanurate modified tri(meth)acrylate isocyanurate, ε-caprolactone-modified tris(acryloxyethyl) isocyanurate, etc. Cyanuric acid modified tri(meth)acrylate, pentaerythritol triacrylate hexyl Methylene diisocyanate urethane prepolymer, pentaerythritol triacrylate Toluene diisocyanate urethane prepolymer, dipentaerythritol pentaerythritol Urethane (meth) such as acrylate hexamethylene diisocyanate urethane prepolymer Among these, those that can increase the glass transition temperature of the cured product are In terms of curability, strength, and reflow resistance, trimethylolpropane tri(meth)acrylate Dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate pentaerythritol tri(meth)acrylate and pentaerythritol tri(meth)acrylate are more preferred. stomach.

[0021] The curable composition may contain an active energy ray-curable compound other than (meth)acrylate. For example, styrene, vinyl halide, vinyl acetate, etc. Vinyl compounds, vinylidene halides, 1,3-butadiene, isoprene, chloroprene Furthermore, sulfur compounds are used to prevent discoloration during high-temperature processes. It is preferable that the cured product does not contain any yellow or nitrogen elements, and in particular, sulfur elements. From the viewpoint of uniformity of the components, it is preferable that the composition does not contain siloxane compounds or inorganic components. If the thickness is not uniform, visibility will be reduced and the surface will become brittle.

[0022] The curable composition further contains an antioxidant having two or more hindered phenol structures in the molecule. This compound is used to prevent yellowing during high-temperature processes such as reflow. It has excellent anti-yellowing properties and suppresses the generation of foreign matter at high temperatures. This becomes possible.

[0023] Examples of antioxidants having two or more hindered phenol structures in the molecule include: 6,6'-di-t-butyl-4,4'-butylidenedi-meta-cresol, 3,9-bis {2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyl nyl]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5] Undecane, ethylenebis(oxyethylene)bis-(3-(5-t-butyl-4-hydroxybenzoate) propionate), hexamethylenebis(3-(3,5-di-t -butyl-4-hydroxyphenyl)propionate), thiodiethylenebis[3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate], N-N'-Hexa Benzene-1,6-diylbis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzol) 4,4(1H,3H,5H)-diazin-1,3,5-triazine-2,4,6(1H,3H,5H)-trione ',4''-(1-methylpropanyl-3-ylidine)tris(6-t-butyl-meth- cresol), 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenyl Methyl)-2,4,6-trimethylbenzene, 3,3',3'',5,5',5' '-Hexa-t-butyl-α,α',α''-(mesitylene-2,4,6-triyl) ri-para-cresol, tetrakis-[methylene-3-(3',5'-di-t-butyl- Among these, yellow is the most popular. To prevent deterioration and suppress the generation of foreign matter at high temperatures, three or more hindered phenols are used in the molecule. Compounds having a structure are preferred, and more preferably four or more. kis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate Rhopionate]methane is most preferred.

[0024] In addition, from the viewpoint of preventing the generation of foreign matter, the molecular weight is preferably 540 or more, more preferably 600 It is preferably in the range of 700 or more, more preferably 700 or more, and most preferably 800 or more. Regarding this point, we have considered the prevention of foreign matter generation due to the evaporation and decomposition of compounds and the difficulty of seeing foreign matter. It is desirable to take this into consideration, and the lower limit is preferably 60°C or higher, more preferably 80°C or higher. , more preferably 100°C or higher, and the upper limit is preferably 250°C or lower. The temperature is more preferably 200°C or lower, and even more preferably 150°C or lower. From the viewpoint of preventing yellowing of the product, it is preferable that the oxide does not contain nitrogen atoms or sulfur atoms. The inhibitors may be used alone or in combination of two or more.

[0025] The curable composition preferably further contains a polymerization initiator. This accelerates the curing reaction of the curable composition, resulting in a strong cured product. As the initiator, a conventionally known material can be used. compounds with active groups that generate cations, etc.) and photopolymerization initiators (irradiated with active energy rays) (compounds with active groups that generate radicals upon irradiation) A photopolymerization initiator is preferred from the viewpoint that it can be easily used.

[0026] Thermal polymerization initiators include 2,2'-azobisbutyronitrile and 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) azo compounds such as benzoyl peroxide and di-t-butyl peroxide , lauroyl peroxide, t-butyl peroxy 2-ethylhexanoate, t- Hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy Peroxides such as 2-ethylhexanoate and t-hexyl hydroperoxide Thermal radical polymerization initiators such as benzenesulfonate esters and alkylsulfonium salts thermal cationic polymerization initiators, inorganic compounds such as hydrogen peroxide, sodium persulfate, and ammonium persulfate Peroxides, etc. Among these, thermal radical polymerization initiators are preferred.

[0027] Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, a photocatalytic polymerization initiator, and a photopolymerization initiator. Among these, photo-radical polymerization initiators are preferred. The dicarboxylic polymerization initiator is 2-hydroxy-2-methyl-1-phenylpropane-1- ion, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl) benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-[4-(methylthio) (O)phenyl]-2-morpholino-1-propanone, oligo{2-hydroxy-2-methyl Benzyl dimethyl ether}, 1-[4-(1-methylvinyl)phenyl]propanone Alkyl alcohol, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, etc. Benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone Methylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone Benzophenone-type compounds such as anthraquinone; t-butylanthraquinone, 2-ethylanthraquinone anthraquinone-type compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholine); (trimethylphenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone Thioxanthone-type compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl Phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine Acylphosphine oxide compounds such as phenylglyoxylic acid phenyl glyoxylate type compounds such as methyl ester of phenyl glyoxylate. Among these, alkylphenone compounds are preferred because they can prevent the cured product from becoming discolored. Furthermore, from the viewpoint of preventing foreign matter, it is more preferable that the molecular weight of the radical generated is 95 or less. More preferably, the hydroxyl group is 70 or less. Phenylpropan-1-one and 2-hydroxy-1-{4-[4-(2-hydroxy-2 {-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one is the most preferred. These polymerization initiators may be used alone or in combination of two or more. good.

[0028] In particular, from the viewpoint of reducing foreign matter and providing a cured product with good visibility, In high-temperature processes such as reflow treatment, the amount of unreacted polymerization initiator that volatilizes is small. As an indicator of this, the temperature rises in an air atmosphere when thermogravimetry and differential thermal simultaneous measurements are performed. When heated from 30 to 330°C at a heating rate of 10°C / min, the temperature decreased between 160 and 260°C. The minority mass is preferably 80% or less, more preferably 50% or less, and even more preferably is 30% or less, particularly preferably 10% or less, and most preferably 5% or less.

[0029] The curable composition may contain compounds other than those mentioned above as long as they do not impair the effects of the present invention. The other components may include, for example, curing aids, various resins, rubbers, Particles, antistatic agents, plasticizers, ultraviolet absorbers, infrared absorbers, light stabilizers, leveling agents, extinguishing agents These include various additives such as foaming agents, thixotropic agents, polymerization inhibitors, release agents, fillers, fluorescent materials, pigments, and dyes. can be done.

[0030] The total mass of all structural units constituting the curable composition is The proportion of acrylate is preferably 15 to 95% by mass, more preferably 25 to 85% by mass. %, and more preferably in the range of 40 to 75 mass %. It can be made higher.

[0031] The ratio of the antioxidant to the total mass of all the constituent units constituting the curable composition is preferably is 0.01 to 10 mass%, more preferably 0.03 to 5 mass%, and even more preferably 0.1 By setting the content within the above range, yellowing due to high-temperature processes such as reflow can be prevented. The anti-degeneration effect is enhanced.

[0032] biphenyl or phenoxyethanol relative to the total mass of all structural units constituting the curable composition The proportion of the (meth)acrylate having a phenyl structure is preferably 80% by mass or less, more preferably The range is preferably 50% by mass or less, and more preferably 40% by mass or less. The range is preferably 5% by mass or more, and more preferably 8% by mass or more. By doing so, the refractive index can be increased, and the (meth)acrylate having a fluorene structure It also has better compatibility with

[0033] The amount of trifunctional or higher polyfunctional (meth)acrylates relative to the total mass of all structural units constituting the curable composition is Acrylate (having a fluorene structure, a biphenyl structure or a phenoxyphenyl structure) The proportion of (meth)acrylates (excluding) is preferably 50% by mass or less, more preferably 40% by mass or less. The range is preferably 5% by mass or less, more preferably 35% by mass or less. The range is preferably 8% by mass or more, and more preferably 8% by mass or more. While maintaining the same properties, it also increases the glass transition temperature, improves moldability, and improves the strength of the cured product. It is possible to do this.

[0034] The ratio of the polymerization initiator to the total mass of all the structural units constituting the curable composition is preferably is 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less The lower limit is preferably 0.2 mass % or more, more preferably 0.3 mass % or more. By setting the content within the above range, the curability of the polymerizable composition is improved, and the strength and transparency are high. It also has high adhesion and produces a cured product with little foreign matter.

[0035] <Cured product> The cured product is obtained by curing the above-mentioned curable composition. The cured product can be obtained by the following method: For example, the curable composition is formed into a predetermined shape, and then cured to form a hardened product having the predetermined shape. In this way, a cured product having a predetermined shape can be obtained. Examples of such methods include a coating method in which a curable composition is applied to a film substrate, a potting method, and the like. molding method, casting molding method, printing molding method, liquid resin injection molding method In addition, the curable composition can be cured by the LIM method, transfer molding method, etc. The polymerization method may be photopolymerization, thermal polymerization, or the like, depending on the type of polymerization initiator contained in the curable composition. Either polymerization or redox polymerization can be used.

[0036] When a curable composition is cured by photopolymerization to obtain a cured product, the wavelength of light irradiated onto the curable composition Although there are no particular limitations on the type of irradiation, it is preferable to irradiate with ultraviolet light having a wavelength of 200 to 400 nm. Specific examples of ultraviolet light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. Examples include lamps, high-power metal halide lamps, and UV-LED lamps. For example, when ultraviolet light is used, the cumulative light intensity is 100 mJ / cm 2 More than 10000m J / cm 2 It is preferable to irradiate at a dose of 500 mJ / cm or less. 2 More than 8000m J / cm 2 The more preferable illuminance is 5 mW / cm or less. 2 More than 1000mW / cm 2 Less than 10 mW / cm is preferable. 2 More than 500mW / cm 2 The following is more preferable: , 20mW / cm 2 More than 300mW / cm 2 The following is even more preferred:

[0037] After the curable composition has been photopolymerized, it is preferable to further carry out after-curing. This makes it possible to reduce the amount of unreacted (meth)acryloyl groups remaining in the cured product. This allows for increased strength of the cured product. Preferably, the temperature is 160°C for 0.1 to 24 hours, and more preferably, the temperature is 80 to 130°C for 0.2 to 10 hours. It's nice.

[0038] When the curable composition is cured by thermal polymerization to obtain a cured product, the curing conditions are not particularly limited. The curing temperature is preferably 40 to 200°C, since this makes it easier to obtain a cured product with reduced coloration. , 60 to 150°C is more preferable. In LIM and transfer molding, a curable composition is placed in a preheated mold. The curing time (heating time) when injecting and molding varies depending on the curing temperature. For example, When the curing temperature is 100°C, the time is preferably 1 to 180 seconds, more preferably 1 to 120 seconds, and On the other hand, in the case of the casting molding method, the hardening composition is placed in a mold at room temperature. The curing time when the composition is heated after injection varies depending on the curing temperature. For example, When the temperature is 70°C, the heating time is preferably 5 minutes to 5 hours, and more preferably 10 minutes to 3 hours. After the curable composition is thermally polymerized, it is preferable to further carry out after-curing. The post-cure conditions are preferably 50 to 150°C for 0.1 to 10 hours, and 70 to 1 More preferably, the temperature is 30°C for 0.2 to 5 hours.

[0039] When a curable composition is cured by redox polymerization to obtain a cured product, the curable composition is By using an initiator, it can be cured at room temperature of 5℃ to 40℃. The amount of remaining unreacted (meth)acryloyl groups can be reduced, and the strength of the cured product can be improved. The curing temperature is preferably 15 to 40°C since it can be increased as much as possible. The curable composition is less likely to gel and can be handled stably. Therefore, a reducing agent is added to the curable composition in advance. Preferably, the curing is carried out by dissolving the compound in a substance and then adding peroxide to the solution.

[0040] The refractive index of the cured product is measured at 25°C using sodium D line (589 nm). , preferably 1.590 or more, more preferably 1.595 or more, It is more preferable that the ratio is 0.596 or more. There is no particular upper limit, but it is preferably 1. By keeping the above range, various designs are possible and the range of applications is wide. do.

[0041] The glass transition point of the cured product was determined by measuring the dynamic viscoelasticity and loss of the cured product using a dynamic viscoelasticity measuring device. The loss tangent is measured, and the temperature at which the loss tangent (tanδ) shows the maximum value is preferably 100°C or higher. Preferably, the temperature is 110°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. It is preferable that the temperature is 130°C or higher. There is no upper limit, but it is preferably 250°C or lower. By setting the content within the above range, the shape of the cured product is stable and less likely to deform even at high temperatures. This improves the reliability of the material and broadens the range of applications it can be used in. can.

[0042] <Lens> The lens is made of a cured product obtained by curing the above-mentioned curable composition. For example, electronic devices such as mobile phones, laptops, tablets, digital cameras, and automobiles The lens can be used for cameras and the like that are attached to buildings, etc. The lens can be made of the cured product of the present invention alone or The molded article may be made of a transparent substrate such as a flat glass or a glass wafer. The lens may be a hybrid lens comprising the above-mentioned cured product molded on a transparent substrate. [Example]

[0043] The present invention will be described in more detail below with reference to examples, but the present invention will not be limited to the gist of the present invention. However, the present invention is not limited to the following examples. The measurement and evaluation methods used in the present invention are as follows.

[0044] (1) In simultaneous thermogravimetry and differential thermal analysis, the temperature was increased to 30°C at a rate of 10°C / min in an air atmosphere. Mass loss between 160 and 260°C when heated to 330°C The polymerization initiator was analyzed using a thermal analyzer (Rigaku Thermo Plus EVO TG 8120), the heating rate was 10°C / min, the starting temperature was 30°C, and the set temperature was 330°C. Measurements were carried out under the condition of an air flow rate of 50 mL / min. The temperature was between 160 and 260°C. The mass percentage decrease was calculated.

[0045] (2) Melting point In simultaneous thermogravimetry and differential thermal measurements, the temperature was raised from 30°C at a rate of 10°C / min in an air atmosphere. When heated to 330℃, the temperature (℃) is plotted on the horizontal axis and the differential thermal analysis value (μV) on the vertical axis. The temperature at the minimum value was read.

[0046] (3) Refractive index The curable composition was cured to prepare a cured product having a thickness of 1 mm. The fluorine D line (589 nm, 25°C) was measured using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., "DR The measurement was carried out using methylene iodide (Corporation (manufactured by Atago) was used.

[0047] (4) Glass transition temperature The curable composition was cured to prepare a cured product having a thickness of 1 mm. The temperature at which the loss tangent (tanδ) reaches its maximum value is called the glass transition point of the cured product. The measurements were carried out using a dynamic viscoelasticity measuring device (TA Instruments Japan Co., Ltd.). The measurement conditions were tension mode and measurement frequency 10 Hz. did.

[0048] (5) Evaluation of foreign matter The curable composition was cured to prepare a cured product (lens) having a thickness of 1 mm. The side is covered with a silicone rubber sheet (Azwan Corporation silicone rubber sheet 300mm x 30 The sample was sandwiched between two pieces of glass (0mm x 1t) and fixed on both sides with glass plates. The composition is glass plate / silicone rubber sheet / hardened product / silicone rubber sheet / glass plate. A heating test was carried out at 240°C for 10 minutes, and the cured product (lens) and foreign matter adhering to the glass plate were visually inspected. When no foreign matter was observed, it was rated as A (good condition), and when foreign matter was observed, it was rated as B. It was evaluated as follows.

[0049] (Production of curable composition) The materials shown in Table 1 were mixed in the mass ratios shown in Table 1. The materials in Table 1 are as follows: do. (Meth)acrylate having a fluorene structure: A In the above formula (1), R 1 , R 2 , R 3 , R 4 is a hydrogen atom, and m and n are 1. thing. (Meth)acrylate having a biphenyl structure: B-1 ortho-phenylphenoxyethyl acrylate (Meth)acrylate with a phenoxyphenyl structure: B-2 Meta-phenoxyphenyl methyl acrylate Trifunctional or higher multifunctional (meth)acrylates: Trimethylolpropane trimethacrylate (C-1) Dipentaerythritol hexaacrylate (C-2) 15-functional urethane acrylate (U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd.) (C- 3) Benzyl methacrylate: D Photoinitiator: 2-Hydroxy-2-methyl-1-phenylpropan-1-one (E-1) (Thermogravimetry and differential thermal simultaneous measurement was performed in an air atmosphere at a temperature rise rate of 10°C / min from 30°C to Mass loss between 160 and 260°C when heated to 330°C: 0.2%) 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzoyl] {Dimethyl}phenyl}-2-methylpropan-1-one (E-2) (Thermogravimetry and differential thermal simultaneous measurement was performed in an air atmosphere at a temperature rise rate of 10°C / min from 30°C to Mass loss between 160 and 260°C when heated to 330°C: 4.7%) Antioxidant with four hindered phenol structures in the molecule: F Tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl] (Nyl)propionate]methane (Melting point 116°C, Molecular weight 1178) Antioxidants with one hindered phenol structure in the molecule: G Octadecyl-3-(3',5'-di-t-butyl-4-hydroxyphenyl)propyl Onate (melting point 51°C, molecular weight 531) Curing agent: H Di-n-hexyl sulfide

[0050] [Table 1]

[0051] [Example 1] The curable composition shown in Table 1 was applied to a silicone rubber sheet having a thickness of 1 mm and an inner diameter of 30 mm. The mixture was poured into a mold made of glass plates, and then sealed by stacking glass plates on top. On the glass surface, the illuminance is 60mW and the cumulative light amount is 2000mJ / cm 2 UV radiation from high pressure mercury The cured product (lens) was then irradiated with ray and 30 mm in diameter and 1 mm in thickness. The cured product was peeled off from the plate and then heat treated at 160°C for 1 hour. The cured product thus obtained was measured or evaluated for the items shown in Table 2 using the methods described above. As shown in Table 2, the refractive index and glass transition point were high, and no foreign matter was generated, resulting in a favorable result.

[0052] [Examples 2 to 10] The same procedure as in Example 1 was repeated except that the composition of the curable composition was changed as shown in Table 1. The properties of the cured product are shown in Table 2 below.

[0053] [Comparative Examples 1 and 2] The same procedure as in Example 1 was repeated except that the composition of the curable composition was changed as shown in Table 1. The properties of the obtained cured product are shown in Table 2 below. This was what was occurring.

[0054] [Table 2]

Claims

1. The composition contains a (meth)acrylate having a fluorene structure, a (meth)acrylate having a phenoxyphenyl structure, a trifunctional or higher polyfunctional (meth)acrylate (excluding (meth)acrylates having a fluorene structure, a biphenyl structure, or a phenoxyphenyl structure), and an antioxidant having two or more hindered phenol structures in the molecule; The (meth)acrylate having a fluorene structure is a compound represented by the following formula (1): A curable composition, wherein the proportion of the (meth)acrylate having a fluorene structure is 25 to 85 mass%, the proportion of the (meth)acrylate having a phenoxyphenyl structure is 5 to 80 mass%, and the proportion of the trifunctional or higher polyfunctional (meth)acrylate is 5 to 50 mass%, relative to the total mass of all structural units constituting the curable composition. 【Chemistry 1】 In formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a methyl group, m represents an integer of 0 to 5, and n represents an integer of 0 to 5.

2. The curable composition according to claim 1 , which contains a (meth)acrylate having a biphenyl structure.

3. The curable composition according to claim 1 or 2, which contains a polymerization initiator.

4. The curable composition according to claim 3, wherein the polymerization initiator exhibits a mass loss of 80% or less between 160 and 260°C when heated from 30°C to 330°C at a heating rate of 10°C / min in an air atmosphere in simultaneous thermogravimetry and differential thermal analysis.

5. The curable composition according to any one of claims 1 to 4, wherein the antioxidant has a molecular weight of 540 or more.

6. The curable composition according to any one of claims 1 to 5, wherein the antioxidant does not contain a nitrogen atom.

7. The curable composition according to any one of claims 1 to 6, wherein the antioxidant has a melting point of 60°C or higher.

8. A cured product of the curable composition according to any one of claims 1 to 7.

9. A lens comprising the cured product according to claim 8.

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