TW201144349A - Curable composition and cured article - Google Patents

Abstract

This invention provides a curable composition having such characteristics as a high transmittance and a high refraction index, the curable composition being useful for obtaining a curable resin of high Abbe's number which has such characteristics that the optical properties and physical properties would hardly change even under high temperature conditions. The curable composition of this invention is characterized in containing (A) an epoxy compound having an aliphatic ring in the molecule, (B) a (meth) acrylic acid ester having an aliphatic ring in the molecule, and (C) a (meth) acrylic acid ester having an epoxy group in the molecule. At least one kind of compound selected from the group consisting of a (meth) acrylic acid ester having an aliphatic ring epoxy group and a (meth) acrylic acid ester having a glicidyl group is used as (C) (meth) acrylic acid ester having an epoxy group in the molecule.

Description

201144349 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a curable composition, a cured product thereof, and an optical member. More specifically, it is excellent in optical properties and physical properties, and at the same time, it is possible to form a curable composition in which the optical properties and physical properties are not cured, a cured resin obtained by curing the curable composition, and An optical member such as a lens made of the cured resin. [Prior Art] In the machine parts, electrical and electronic component materials, automotive component materials, civil construction materials, molding materials, coatings, adhesives, sealing materials, etc., hardenable compositions have been used as plastic materials. It has also attracted attention as a material for optical members such as lenses. In the case of using a hardening composition as a plastic lens material, a plastic lens material containing a (meth)acrylic acid g as a main component is known (Patent Document 1). In this plastic lens material, because of the high viscosity of the (meth)acrylic acid g of the first structure, by adding two epoxy compound-based compounds or monofunctional radical polymerization in the main chain The monomer 'is reduced in viscosity to form a shaped body. However, in such a composition, there is a problem that the refractive index is swayed or lowered. At the same time, there are also problems of hardening shrinkage and high moisture absorption rate. Patent Document 2 proposes a curable composition for solving the hardening composition of the above-mentioned (fluorenyl) acryl vine having an aromatic ring as a main body, and having the problem* and using a (fluorenyl) acrylate vinegar having an aromatic ring. And cationically polymerizable compounds. When the composition is prepared, the improvement in the curing rate of 322757 4 201144349 J, the improvement in workability due to low viscosity, the suppression of hardening and shrinkage of the cured product, and the maintenance of the refractive index can achieve a certain degree of effect. As the plastic lens obtained from the composition, a low Abbe number lens having an Abbe Number of 40 or less can be used. However, the plastic lens obtained by hardening the composition is insufficient in heat resistance, and at a high temperature, the shape is changed or the light transmittance is remarkably lowered. Therefore, for example, a camera-equipped mobile phone or the like is manufactured by a reflow soldering step (m〇unting process), but since the temperature of the step cannot be tolerated (about 26 〇〇c), Therefore, after the soldering step, there must be a step of making a camera module by connecting the connector. At the same time, although there are resin materials having a high Abbe number of Abbe number of 45 or more, there is almost no plastic material which is excellent in heat resistance which can withstand the reflow method. [PRIOR ART DOCUMENT] Patent Document 1: Japanese Patent No. 3130555, Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. Provided is a curable composition which has high light transmittance and refractive index, and which has characteristics which are not easily changed in optical characteristics or physical properties and high Abbe number having an Abbe number of 45 or more even under high temperature conditions. Hardened resin (hereinafter, "hardened resin having a high Abbe number of Abbe number of 45 or more" is simply referred to as "hardened resin of high Abbe number"). Another object of the present invention is to provide a hardened resin having a high Abbe number which has an optical property or a physical property which is not easily changed even under high temperature conditions of 5 322757 201144349 - such as soldering by reflow soldering, and [Offects of the present invention] The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that an epoxy compound having a specific structure and a (meth) acrylate having a specific structure are The hardening composition of the (fluorenyl) acrylate having an epoxy group in the molecule can be cured to have high light transmittance and refractive index, and can be obtained even at a high temperature of, for example, about 26 〇t. The present invention has been completed by a hardened resin having a high Abbe number having a property in which optical characteristics or physical properties are not easily changed. That is, the present invention can provide a curable composition characterized by comprising an epoxy compound (4) having an alicyclic ring in the molecule, (indenyl) acrylic acid having an alicyclic ring in the molecule (B) and having intramolecular Epoxy (indenyl) acrylate (C). In the knives/epoxy group-containing (fluorenyl) acrylate (c), for example, (▼-) propylene having an I-epoxy group and a (meth) acrylate having a glycidyl group can be used. At least one compound. The epoxy compound (A) having an alicyclic ring in the above molecule may be, for example, an epoxy compound selected from the group consisting of an epoxy compound having a lipowei group, an epoxy group directly bonded to a ruthenium by a single bond, and having an alicyclic ring. At least one epoxy compound among the glycidyl ether-based epoxy compounds. The (meth)acrylic acid having an alicyclic ring in the molecule is intended to be (B), and is preferably a polyfunctional (meth)acrylic acid vinegar having an alicyclic ring in the molecule. 6 322757 201144349 ▲ Meanwhile, the present invention can provide a cured resin obtained by curing the above-mentioned curable composition. Further, the present invention can provide an optical member 0 made of the above-mentioned hardening resin. [Effects of the Invention] The curable composition of the present invention is applied to have a high light transmittance and a refractive index by hardening, even at, for example, about 260°. A cured resin having a high Abbe number of optical characteristics (transmittance, refractive index, Abbe number) or a property in which physical properties are not easily changed is also known under high temperature conditions of C. Since the hardened resin does not yellow in the soldering step of the returning method, and the shape does not change, it is particularly useful for use in optical members such as lenses. For example, when a lens made of the cured resin of the present invention is used as a lens of a camera-attached mobile phone, the mounting step of the camera module can be simultaneously performed in a soldering step (mounting step) in a reflow manner. The step of connecting the camera module with the connector after the soldering step is omitted. [Embodiment] The form of the curable composition of the present invention comprises an epoxy compound (A) having an alicyclic ring (aliphatic hydrocarbon %) in the molecule, and an alicyclic ring in the molecule (aliphatic hydrocarbon oxime) (M) acrylate (B) and (fluorenyl) acrylate (C) having an epoxy group in the molecule. In the present invention, an epoxy compound cationically polymerizable compound (cationic curable compound) having an alicyclic ring in the molecule, and a radically polymerizable compound having a monthly (%) (meth) acrylate in the molecule (since) 322757 7 201144349 ; Used in combination with a base-hardening compound), after hardening, a hardened resin having a high Abbe number of high light transmittance and refractive index can be obtained. Meanwhile, when the hardened resin is compared with a cured product obtained only from a cationically polymerizable compound, it has an advantage of high strength, immediate solvent resistance, and hardening with a radical polymerizable compound only. When the materials are compared, the hardening shrinkage rate is low and the hygroscopicity is low. In addition, in the present invention, in addition to these polymerizable compounds, a polymerizable compound of a (meth)acryloxy group having a cationically polymerizable group and a radical polymerizable group in the molecule may be added. Since the polymerizable compound acts as a crosslinking agent for the cationically hardening resin and the radically curable resin, the heat resistance of the cured resin can be remarkably improved, and optical properties (transmittance, refractive index, Abbe number) can be obtained even at high temperatures. Or a hardened resin whose physical properties are not easily changed. [Epoxy compound (A) having an alicyclic ring in the molecule] The epoxy compound (A) having an alicyclic ring in the molecule is not particularly limited as long as it is a compound having an alicyclic ring and an epoxy group in the molecule ( However, 'except for the (meth) acrylate having an epoxy group in the molecule). The epoxy compound (A) having an alicyclic ring in the molecule preferably does not have an aromatic ring. The epoxy compound (A) having an alicyclic ring in the molecule may be used singly or in combination of two or more kinds. The epoxy compound (A) having an alicyclic ring in the molecule is preferably a polyfunctional epoxy compound having two or more epoxy groups in the molecule. The epoxy compound (A) having an alicyclic ring in the molecule includes (i) an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. An alicyclic epoxy compound, (5) an epoxy compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond, (iii) a glycidyl-epoxy compound having an alicyclic ring and a glycidyl alcohol 832757 201144349 oil base. Ring ten == single ring sister ring 'ring _ _, ring Xin ring, ring ring == member, and about the ring K3.0] 壬 burning ring) king" ^, full 虱 ring (two ring , Μ I, β n all 4 rings, all hydrogen phenanthrene rings, total hydrogen: clothing total 虱 fertilizer%, reduced 9 (norbornane) [5 2 丨 gold listening ring, two eggs. 3 _, three ring h) An alicyclic ring (cross-linked carbocyclic ring), etc. Meanwhile, the above-mentioned alicyclic epoxy group may, for example, be an epoxy group ring wire, a 3,4-epoxycycloepoxy group, a tricyclo-like (tetra)-anthracene δ-( Or 9) a group (epoxidized bicycloindole), etc. The alicyclic epoxy compound (i) having the above alicyclic epoxy group can be listed as a compound represented by the following formula (A-1) (2) a compound in which an alicyclic epoxy group is bonded by a single bond or via a linking group).

(A-1) In the above formula, 'Y1' means a single bond or a linking group. As the linking group, for example, a divalent hydrocarbon group, a carbonyl group (—co—), an ether bond (—〇—), an ester bond (a COO—), a guanamine bond (—c〇NH—), a carbonate bond (— 〇c〇〇), and a plurality of bases in which these groups are combined. The divalent hydrocarbon group may, for example, be a linear or branched alkyl group such as a methylene group, an ethylene group, an isopropylidene group, an exoethyl group, a propyl group, a trimethylene group or a tetramethylene group. (eg Cl_6 extended alkyl) ' 1,2 —cyclopentyl, 1,3 _cyclohexyl, cyclopentylene, 1,2 — extension 322757 9 201144349 cyclohexyl, 1,3 —cyclohexyl, A divalent alicyclic hydrocarbon group such as a cyclohexylene group or a cyclohexylene group (particularly a divalent cycloalkylene group); a group in which a plurality of such groups are bonded. The following are representative compounds included in the compound represented by the formula (A-1).

Meanwhile, in the above formula, η is an integer of 1 to 30. The alicyclic epoxy compound may also be a compound having an alicyclic ring and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups is adjacent to the alicyclic ring. 322757 10 201144349 epoxy (alicyclic epoxy) composed of 2 carbon atoms and oxygen atoms. Shown below are representative compounds (anthracene biepoxide).

Meanwhile, the following compounds may also be used as the alicyclic epoxy compound, such as an alicyclic epoxy compound having three or more alicyclic epoxy groups, or only one alicyclic epoxy group and no other epoxy group. A alicyclic epoxy compound.

Co-f O-CCH^CO ^ o-ch2-C^° CO -f 0 C0 Too 0 _ CHg-

CH — i2—co o ~^ch2)j co o—ch2~C^x^0 I —co-f O-fCH^CO -^0-CH2-C^0 C0~f 〇-(CH2>jC0 〇—ch2-C^〇〇ν

-co-f 0-(CH2)^C0 卞 0—CH2-[3^C

OH Meanwhile, in the above formula, a, b, c, d, e, and f are integers of 0 to 30. The epoxy compound (ii) in which the epoxy group is directly bonded to the alicyclic ring by a single bond is, for example, a compound represented by the following formula (A-2). 11 322757 201144349 $

(ΛΑ) In the above formula, 'R1 is an alcohol from the q-valent alcohol [Rl—(the base after 0H, p is an integer that removes q 10 from the integer H to 3〇. Among the bases in q brackets, p is They are the same hydrazine or the same as the valence (0H)q, which can be exemplified by a mixture of alcohols and ethanol. q Monohydric alcohols such as isopropanol and butanol; ethylene glycol, ... C-propane H4 —τ diol, neopentyl glycol, — 丝 一 一 — ^ 一醉, 二一一一一:, diethylene glycol, dipropylene glycol, polypropylene glycol and other binary glycerin, diglycerin, erythritol, Tri- (tetra)-based ethidium, triterpenoid, tetraol, dipentaerythritol, sorbitol and other triols. Pre-alcohol: can be used to (4) polyols, poly-polyhydric alcohols, polycarbonate-based polyols, Poly(tetra): alcohol, etc. The aforementioned alcohol 'is preferably an aliphatic alcohol having a carbon number of U10 (especially an aliphatic polyol such as β-dimethylolpropane). 疋 as for a glycidyl type having an alicyclic ring and a glycidyl squara group The epoxy compound (iii) may, for example, be an alicyclic alcohol (especially an alicyclic polybasic (f)). This compound may also be an epoxidized group of an aromatic ring and an epoxy group. (For example, an aromatic ring-nuclear hydrogenated compound derived from the condensation reaction of a substance A, a double F, a double s, a double bis, and a double condensed reaction with a table _) The glycidyl ether type epoxy compound (111) having an alicyclic ring and a glycidyl ether group can be exemplified by the following compounds. 322757 12 201144349

I

The ratio of the oxygen compound (A) having an alicyclic ring in the molecule of the curable composition of the present invention may vary depending on the use of the cured resin, etc., but may be integral to the curable composition (or hardenability). The total amount of the compound is, for example, about 10 to 70% by weight, preferably 20 to 60% by weight, and preferably about 30 to 50% by weight. When the amount of the epoxy compound (A) having an alicyclic ring in the molecule is too small, the hardening shrinkage is increased in addition to the problem of moldability, and problems such as an increase in hygroscopicity and a decrease in moisture resistance are likely to occur. At the same time, when the amount of the epoxy compound (A) having an alicyclic ring in the molecule is too large, the amount of change in the wire property at the S temperature such as the reflowing condition to be described later is increased, and the problem of heat resistance is likely to occur. [(Methyl)acrylic acid vinegar (8) having an alicyclic ring in the molecule] As for the (meth)acrylic acid vinegar (b) having an alicyclic ring in the molecule, as long as it has an alicyclic ring and (?) (tetra) in the molecule The compound of the oxy group, that is, the (meth)acrylic acid having an alicyclic ring in the molecule (excluding the (meth)acrylic acid having an epoxy group in the molecule) is preferably 322757 13 201144349 does not have Aromatic ring. The (fluorenyl) acrylate (B) having an alicyclic ring in the molecule may be used singly or in combination of two or more. The (fluorenyl) acrylate (B)' having an alicyclic ring in the molecule is preferably a polyfunctional (fluorenyl) acrylic acid having two or more (fluorenyl) acryloxy groups in the molecule. Meanwhile, the (meth) glycerol (B) having an alicyclic ring in the molecule is preferably an acrylate having an alicyclic ring in the molecule. When the radical polymerization rate of a monomer having an acryloxy group and a monomer having a methacryloxy group is compared, the former is relatively slow. On the other hand, in general, when the reaction rate of radical polymerization is compared with the reaction rate of cationic polymerization, the reaction of radical polymerization is relatively fast. As in the present invention, in the system in which the radical polymerization and the cationic polymerization are carried out, it is preferable to carry out the radical polymerization and the cationic polymerization as much as possible in terms of physical properties of the cured resin and the like. When the radical polymerization is carried out in advance, the curing shrinkage ratio of the formed hardened resin is increased, and even after the radical polymerization is completed, a large amount of unreacted radical polymerizable group remains, and the heating after hardening is performed. The reaction or decomposition of the cationically polymerizable group is caused during the treatment, and the physical properties of the hardened resin may be impaired. Therefore, the (())-acrylic acid S having an alicyclic ring in the molecule is preferably acrylic acid g having an alicyclic ring in the molecule. As for the above alicyclic ring, a single ring alicyclic ring (3 to 15 members, and a ring of about $6 to 6 members) such as a ring-ring ring, a ring-burned ring, a ring-burning ring, and a ring-shaped ring is exemplified. Burning ring is preferred); decahydronaphthalene ring (all hydrogen ring), total nitrogen ring (bicyclo[4.3.0] ring) 'hydrogen ring, all gas ring, all nitrogen ring, All hydrogen dangerous ring, all hydrogen 16 ring, reduced danning ring (bicyclo[2 upper 1] heptane ring), iso-araconne ring, adamantane ring, bicyclo[3 3.0]octane ring, tricyclic [521 〇2,6] 322757 14 201144349 , decane ring, tricyclo[6.2.1.〇2'7] undecane ring and other polycyclic rings (about 2 to 4 rings) • alicyclic (crosslinked carbocyclic ring), etc. . In the (B) group having an alicyclic thiol group, the alicyclic group may be directly bonded to the (fluorenyl) acryloxy group or may be bonded via a linking group. The linking group may, for example, be a divalent hydrocarbon group, a carbonyl group (—co—), a stern bond (—〇—), an ester bond (—coo — ), a guanamine bond (—c〇NH—), a carbonate bond (an OCOO— And a plurality of bases in which these groups are combined. The divalent hydrocarbon group may, for example, be a linear or branched chain extension group such as an anthracenylene group, an ethylene group, an isopropylidene group, an ethylidene group, a propylidene group or a tetradecylene group. (e.g., an alkyl group and preferably an alkyl group of Ci_6); anthracene, 2-cyclopentyl group, 1,3-cyclopentyl group, cyclopentylene group, anthracene, 2-cyclohexylene group, anthracene. — a bivalent alicyclic nicotinyl group (especially a divalent cycloalkylene group) such as a cyclohexyl group, an I, 4-cyclohexylene group or a cyclohexylene group; a group in which a plurality of such groups are bonded. The (meth) acrylate (B) having an alicyclic ring in the molecule may, for example, be a compound represented by the following formula (B-1).

0 II CHg^C —C—0—γ

R3

In the above formula, 'ring Z1 represents alicyclic ring γ2, 丫3 is the same or different and represents a single (tetra) linking group. As for the alicyclic ring in the ring ζι, an alicyclic ring is exemplified. Therefore, it is preferable to be a multi-ring alicyclic ring (cross-linked carbon ring) such as a three-negative. Examples of the linking group in Y2 and Y3 include the above-exemplified linking groups. The linking group in the middle, particularly preferably a divalent hydrocarbon group (especially a stretching base), a core or two or more divalent hydrocarbon groups (especially an extruded wire) combined with an oxygen atom (one 〇-) of 322757 15 201144349 or more Base. Representative examples of the compound represented by the formula (Β-1) include 1,4-cyclohexanediol di(meth)acrylate and 1,4-cyclohexanedimethanol di(decyl)acrylate. , bicyclo [2.2.1] heptane dimethanol di(methyl) acrylate, 1,3 - adamantane bis(indenyl) acrylate, 1,3 _ hexaerythritol di(methyl) Acrylate, tricyclo[5.2.1.〇2·6]decanedioxanyl (indenyl) acrylate, and the like. (Meth)acrylic acid vinegar (Β) having an alicyclic ring in the molecule, and cyclohexyl (meth) acrylate, cyclohexane methanol (meth) acrylate, 1 - adamantyl (meth) acrylate may also be used. Ester, i-adamantane sterol (mercapto) acrylate, iso-spinyl (meth) acrylate, tricyclo [5.2.1.02,6] decane methanol (mercapto) acrylate [= dicyclopentyl Monofunctional (meth)propionic acid vinegar such as (meth) acrylate] or dicyclopentyloxyethyl (meth) acrylate. The proportion of the (meth) acrylate (B) having an alicyclic ring in the curable composition of the present invention varies depending on the use of the cured resin, etc., but is integral with the curable composition (or a curable compound). The total amount) is, for example, 10 to 70% by weight, and preferably 2 to 6 % by weight, and more preferably 30 to 50% by weight. When the amount of the methacrylate in the molecule is too small, the amount of change in the optical characteristics at a high temperature, such as the reflowing conditions described later, is increased, and the problem of heat recovery is likely to occur. At the same time, if the amount of the (meth) acrylate (8) having an alicyclic ring in the molecule is too large, the hardening shrinkage is increased to cause a problem of formability, and at the same time, the hygroscopic property is also increased to easily produce (9) wetness. Reduce the problem. 322757 16 201144349 , [(meth) acrylate (c) having an epoxy group in the molecule], as for the (meth) acrylate (c) having an epoxy group in the molecule, as long as it has intramolecular The (meth) acrylate (C) having an epoxy group in the molecule may be used singly or in combination of two or more kinds. The (meth) acrylate (c) having an epoxy group in the molecule is the same as that of the (meth) acrylate (B) having an alicyclic ring in the above molecule (the radical polymerization and the cationic polymerization are equalized as much as possible) Ring in the molecule The acrylate of the group is more preferable. The (meth) acrylate (C) having an epoxy group in the molecule may, for example, be (meth)acrylic acid vinegar having an alicyclic epoxy group, (ii) having a scale. As for the alicyclic epoxy group, the ring is composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and the alicyclic ring is exemplified. Out: ring ring of ring, ring of ring, ring of ring = 12 ring of ring, etc. (3 to the member, and the Wei ring of the big member is preferred); decahydronaphthalene ring (perhydronaphthalene) Ring), all ^=[4.3..]壬烧环), whole gas onion ring, all hydrogen ring, full gas ring (two rings [called Geng burning clothes) different New%, diamond ring, two rings [33 〇] Xin [" 丄〇, 6] 癸 ring, three ring 〇 2, 7] eleven two clothes 2 to 4 ring) alicyclic (crosslinked carbon ring), etc. alicyclic ring = approximately as: ring Oxycyclopentyl, 3,4-cyclohexylcyclohexyl, ^collistin = 3,4-epoxytricyclo[5 21〇2,6 (a) 瑷 Lu Bei or 9) Based on the formula (a), the sputum 疋 疋 疋 土 土 土 土 土 , , , , , , , , , , , , , , , 322 322 322 322 322 322 322 322 322 322 44349 An alicyclic epoxy group such as an 8-(or 9) group is preferably an oxime group which is an epoxy group composed of two adjacent carbon atoms and an oxygen atom of the crosslinked carbocyclic ring.

(a) - (meth) hexahydrate which has an alicyclic epoxy group, and the compound represented by the following formula (C-1). The (meth)acrylic acid having a glycidyl group (ii) can be exemplified by the compound represented by the following formula (c-2).

(C-1) 1 II „ —C—0—γ4 Μ-ϋ—0 —γ

(02) In the above formula, R3 represents a halogen atom or a methyl group, γ4 represents a single bond, an alkylene group having 1 to 10 carbon atoms, or 1 to 2 alkylene groups having 1 to 1 carbon number and 1 to 2 More than one oxygen atom (monoterpene-) is bonded to the group, and ring Ζ2 represents an alicyclic epoxy group. As for the carbon number in γ4! The alkylene group may be a linear or branched alkyl group such as an anthracenylene group, an exoethyl group, a propyl group, a triadenylene group, a tetradecylene group or a hexamethylene group. As for Y4', it is particularly preferred to be a single bond, an alkylene group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms (oxygen atom at the right end), and a plurality of alkylene groups having 1 to 6 carbon atoms (for example). , about 2 to 2 )) a polyalkylene group (the terminal oxygen atom is at the right end). 322757 18 201144349, a more specific example of the compound represented by the formula (c-i), and the following compounds can be mentioned.

In the above formula, R3 and Y4 are the same as described above. More specific examples of the (meth) acrylate having a glycidyl group include glycidyl (mercapto) acrylate and the like. The ratio of the (fluorenyl) acrylate (C) having an epoxy group in the molecule in the curable composition of the present invention is, for example, 1 to 1 with respect to the entire curable composition (or the total amount of the curable compound). 5 % by weight, preferably 5 to 40% by weight, and preferably about 1 to 3 % by weight. When the amount of the (meth) acrylate (c) having an epoxy group in the molecule is within the above range, it is possible to maintain the advantages of the respective hardening resins of the cationic hardening resin and the radical hardening resin by the above (C The crosslinking agent of the component acts to improve the heat resistance of the hardening resin. [Other components] The curable composition of the present invention may contain other curable compounds (cations other than the above components (A), (B), and (C) without impairing the optical properties and physical properties of the cured resin. A polymerizable compound, a radically polymerizable compound, or the like). Meanwhile, the curable composition of the present invention may contain a cationic polymerization initiator, a hardener, a hardening accelerator, a radical polymerization initiator, and photosensitization according to the type of the curable compound used in 322757 19 201144349, and the like. Agents, various additives. The ratio of the total amount of the components (A), (B), and (C) to the total amount of the curable compound in the curable composition of the present invention is, for example, 60% by weight or more, preferably 80% by weight or more. More preferably, it is 90% by weight or more. Meanwhile, the ratio of the total amount of the components (A), (B), and (C) to the total amount of the curable composition of the present invention is, for example, 60% by weight or more, preferably 80% by weight or more. More preferably, it is 90% by weight or more. The cationic polymerization initiator is an initiator (hardening catalyst; oxygen generator) which is a substance which initiates cationic polymerization by heating or light. The cationic polymerization initiator is preferably a thermal cationic polymerization initiator. The compounding amount of the cationic polymerization initiator is, for example, from 0 to 15% by weight, preferably from 0.01 to 10% by weight, based on the whole of the hardening composition. By blending in this range, a cured product having good heat, transparency, weather resistance, and the like can be obtained. Examples of the above cationic polymerization initiator include an aryldiazonium salt [for example, PP-33, manufactured by Asahi Kasei Kogyo Co., Ltd.], an aryldiiodide salt, an aryldithizone salt [for example, FC- 509, 3M company, UVE1014 [GE], CP-66, CP-77 [made by Asahi Kasei Kogyo Co., Ltd.], SI-60L, SI-80L, SI-100L, SI-110L [Sanshin Chemical Industry Co., Ltd.], an aromatic hydrocarbon (arene) ion-missing salt [for example, CG-24-61, manufactured by Ciba Geigy Co., Ltd.]. Further, a series of a metal such as aluminum or titanium, a chelate compound of acetamidine acetate or a diketone, and a sterol or a phenol may be used. Chelating compounds have 20 322757 201144349 Ming San Yi 醯 醯 醯 、 铭 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Examples of the triterpene alcohol or bisphenol s. An acid anhydride can be used as the hardener. As the acid anhydride, an acid anhydride used for curing a general epoxy compound can be used, but it is preferably an acid anhydride which is liquid at normal temperature, and specific examples thereof include methyltetrahydrophthalic anhydride, mercaptohexahydrophthalic anhydride, and twelve. Dilute succinic anhydride, methyl terminal mercaptotetrahydrouric anhydride, and the like. Meanwhile, in the range which does not adversely affect the impregnation property of the hardenable composition of the present invention, an acid anhydride which is solid at normal temperature, for example, a citric acid needle, a tetrahydrophthalic anhydride, a hexahydrophthalic anhydride, or a methylcyclohexene can be used. Dicarboxylic anhydride and the like. When an acid anhydride which is solid at normal temperature is used, it is preferably dissolved in a liquid acid anhydride at normal temperature, and used as a liquid mixture at normal temperature. The amount of the curing agent to be added may vary depending on the type and amount of the cationically curable compound in the curable composition, but is, for example, from 〇 to 60% by weight and from about 5 to 40 with respect to the entire curable composition. The weight % is preferred. When an acid anhydride is used as the hardener, the hardening accelerator is a compound having a function of promoting the hardening reaction. The hardening accelerator is not particularly limited, and may be a hardening accelerator generally used, and for example, a diazabicycloundecene hardening accelerator (1,8-diazabicyclo[5.4.0] Tertiary (DBU) or its salt), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, tertiary amine, 2-ethyl-4-methyl Imidazoles such as imidazole, anthracene, ethyl 2-ethyl- 4-methylimidazole, organic phosphine compounds such as triphenylphosphine, tertiary amine salts, quaternary ammonium salts, phosphonium salts, tin octoate, octyl金属 and other metal salts. Among these compounds, a diazabicyclo-l-zinc hardening accelerator is preferred. The compounding amount of the hardening accelerator 322757 21 201144349 is, for example, 〇 to 5% by weight, preferably about 5% to 3% by weight, based on the entire curable composition. If the amount of the formulation is too small, there may be a case where the hardening promoting effect is insufficient, and if the amount is too large, the hue of the hardened material may be deteriorated. As the radical polymerizable initiator (free radical generator), a known conventional initiator as a photoradical or thermal radical polymerization initiator can be used. As representative examples of the photoradical polymerization-based initiator, benzoin, benzoin ethers such as benzoin, benzoin ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dioxyl group 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, dichloroacetophenone, 2-mercapto-purine-^-(fluorenylthio)phenyl] —2-—Folinin—propane—! - ketone, 2-benzylidene-2-dimethylammonium_ι_(4_morphinylphenyl)-butane-1-ketone and other acetophenones; 2-mercaptopurine, 2_ Ethyl hydrazine, 2-t-butyl hydrazine, 1-chloroindole, 2-pentyl hydrazine and the like; 2,4-dimethyl thioxanthone, 2,4-diethyl thiophene Thioxanone such as ketone, 2-chlorothioxanthone, 2,4-isopropylthioxanthone, ketal such as acetophenone didecyl ketal and benzoyl dimethyl ketal; diphenyl Benzophenones such as ketones; xanthone; I?-bis(9-acridinyl)heptane. Examples of the thermal radical polymerizable initiator include, for example, disturbate peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, peracetones, and ketones. An organic peroxide in the form of an oxide or an alkyl hydroperoxide. Specific examples of such thermal polymerization initiators include benzoyl peroxide, butyl perbenzoate, and azobisisobutyronitrile. In a commercial product of a radical polymerization initiator, for example, photoradical polymerization is 22 322757 201144349. For example, Irgacure (registered trademark) 184 (1 - cyclyl phenyl hydrazine), Irgacure, available from Ciba Corporation (registered trademark) 5〇〇( 1 —ylcyclohexylphenyl-, dibenzophenone) and other photopolymerization initiators of Irgacure (registered trademark) type; Darocur (registered trademark) 1173, 1116, 1398, 1174 And 1〇2〇 (available from Merck) and so on. The amount of the radical polymerization initiator to be added may vary depending on the kind and amount of the radical polymerizable compound in the curable composition, but is, for example, about 0.1 to 20% by weight based on the total amount of the curable composition. The photosensitizer is preferably used in combination with a photopolymerization initiator. As the photosensitizer, a conventionally known photo sensitizer can be used. For example, ethyl N,N-didecylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-didecylaminobenzoic acid, triethylamine, A tertiary amine such as triethanolamine. It is possible to use such a sensitizer or a combination of two or more kinds thereof. The content of the photosensitizer is not particularly limited, but is, for example, about 0.1 to 5% by weight based on the entire curable composition. As the additive which can be added to the curable composition of the present invention, for example, an organic cerium oxide compound, metal oxide particles, rubber particles, an anthraquinone or a fluorine-based antifoaming agent, a decane coupling agent, and a filler can be mentioned. , plasticizer, flow = 4 丨, antistatic agent, mold release agent, flame retardant, colorant, antioxidant, ultraviolet absorber, ion adsorbent, pigment, etc. The blending amount of these various additives is, for example, 5% by weight or less based on the entire curable composition. The curable composition of the present invention may contain a solvent. However, when the amount is too large, bubbles may be formed in the cured resin. Therefore, the curable composition is preferably 10% by weight or less, and particularly preferably 1% by weight or less based on the total amount of the curable composition. 23 322757 201144349 1 The curable composition of the present invention is prepared by blending, for example, the above (A), (B) and 5 (C) components, and a cationic polymerization initiator, a hardener, a hardening accelerator, and a radical. After the polymerization initiator, the photosensitizer, various additives, and the like, the mixture is stirred and mixed under vacuum to remove the bubbles, and then prepared. The temperature at the time of stirring and mixing is, for example, about 10 to 60 ° C. In stirring and mixing, well-known equipment such as a self-rotating mixer, a single-shaft or multi-axis extruder, a planetary mixer, a kneader, a dissolver, or the like can be used. By using the curable composition of the present invention, a cured resin having excellent optical properties and physical properties can be obtained. The light transmittance (400 nm) of the obtained cured resin is, for example, 80% or more (more preferably 85% or more), and the internal transmittance (400 nm) is, for example, 85% or more (and preferably 90% or more), and refractive index ( 589 nm) is, for example, 1.45 or more (and preferably 1.50 or more), and an Abbe number of 45 or more (and preferably 50 or more), and can be used as a cured resin having excellent optical properties of high transparency and resolution. Meanwhile, the water absorption rate is, for example, 2% by weight or less (and preferably 1% by weight or less), and the glass transition temperature is, for example, 100° C. or higher (and preferably 12 (TC or more), and the linear expansion coefficient is, for example, 120 ppm/K or less). (it is preferably 100 ppm/K or less), and the curing shrinkage ratio is, for example, 10% or less (and preferably 8% or less), and is excellent in curing properties from the viewpoint of moldability and moisture resistance. Even if the hardening resin is placed under a high temperature condition (for example, about 260 ° C), the light transmittance, the refractive index, and the Abbe number are hardly changed, and the shape does not change. The cationic hardening composition of the present invention is hardened even if it is hardened. The high temperature 24 322757 201144349 can also be obtained with hardened resins whose optical properties or physical properties are not easily changed, so it is especially suitable for optical applications (optical materials), optical devices, display applications, electrical and electronic components, etc. The rate varies depending on the wavelength of the light, and a phenomenon of aberration (permeation or blurring) occurs on the image. Chromatic aberration is used to reduce the influence of the chromatic aberration. It is a combination of a high Abbe number lens resin and a low Abbe number lens resin to form a structure that corrects chromatic aberration. The glass of the lens used in the camera can be divided into two types of glass according to the Abbe number, generally The glass having a shell number of 50 or less is called flint glass, and the glass of 50 or more is called crown glass. The hardened resin obtained from the curable composition of the present invention can be applied as a high Abbe number. The cured resin of the present invention can be obtained by curing the curable composition. The method of curing can be combined with the type of the curable compound in the curable composition, and the like. For example, the curable composition is placed in a mold suitable for the shape of the cured product, and is irradiated with an active energy ray (for example, ultraviolet ray) to be hardened, and then heated to obtain a cured product of the object. It is also possible to obtain a cured product of the object by heating only. Moreover, when ultraviolet rays are used as the active energy ray, the irradiation amount is, for example, about 1, 〇〇〇 to 4,000 mJ/cm 2 . Meanwhile, the heating temperature may vary depending on the kind of the hardening compound, but is, for example, 8 Torr to 2 Torr C, and is preferably about 110 to 160. (: It is preferable. Further, the cured product may be taken out from the mold. Postcure (baking). As described above, since the cured product of the present invention does not change its optical characteristics or physical properties even at a temperature of about 322757 25 201144349, which is about 26 〇t>c, it can be changed. Applicable as an optical member. As the optical member, for example, a photographic lens, a spectacle lens, a filter, and a diffraction of a camera (a camera for a car, a digital camera, a camera for a PC, a camera for a mobile phone, a monitor camera, etc.) can be cited. Grating, prism, light guide, beam collecting lens, light diffusing lens, mask glass for display, photoreceptor, optical switch, led, light emitting element, optical waveguide, optical splitter, optical fiber adhesive, display element The substrate, the color filter substrate, the touch panel substrate, the display protective film, the display backlight, the light guide plate, the anti-reflection film, and the like. [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of the Examples. (Example 1) an epoxy-[2,2-bis(hydroxymethyl)-1-butanol monoepoxy-4-(2-oxiranyl)cyclohexane adduct (including In the compound represented by the above formula (A-2); manufactured by Daicel Chemical Industry Co., Ltd., trade name "=PE3150")] 30 parts by weight, (meth)acrylic acid vinegar [tricyclic [5.2.1.02,6]癸Alkyl decyl alcohol diacrylate (included in the compound of the above formula; manufactured by Daicel Cytec Co., Ltd., trade name r IRR2 j 4K)] 5 parts by weight, (meth) acrylate having an epoxy group [Epoxidized dicyclopentenyl acrylate (=3,4-epoxytricyclo[5.21 〇2,6]decane-8-acrylic acid and 3,4-epoxytricyclic [mp6] anthracyl malonate (containing 20 parts by weight of the above formula (a compound represented by CD; manufactured by Daicd Chemical Industry Co., Ltd., trade name "E-DCPA"), and oxygen generation 322757 26 201144349, an agent ( Aryl sulfide salt-based oxygen generator; San-apro DuPont, trade name "cpi, -100P") 1 part by weight, a radical generator (acetophenone radical generator; manufactured by Ciba Geigy Co., Ltd., trade name " Irgacurel 84") The ratio of the parts by weight of i is mixed, and after mixing and mixing with a self-rotating public-type agitator, a uniform and transparent curable composition (optical material composition liquid) is obtained. Next, the obtained optical material composition liquid is poured to In the glass mold, the mold is preliminarily coated with a release agent and then vapor-deposited to a thickness of 〇5 mm. Next, the optical material composition after casting is irradiated with ultraviolet rays (irradiation amount: 2,600 mJ/cm 2 ) to prepare a cured resin. In the atmosphere, the cured product was heated at 160 C for 1 hour to obtain a uniform and transparent plate-shaped cured resin having a thickness of 0.5 mm. This hardened resin can be easily detached from the glass mold. The obtained hardened resin provides the evaluation described later. (Example 2) The same operation as in Example 1 was carried out except that glycidyl methacrylate was used as the (fluorenyl) acrylate having an epoxy group, and hardening was obtained. Resin. (Comparative Example 1) In addition to the curable compound, 1,2-epoxy 4-(2-oxirane) of the epoxy compound [2,2-bis(hydroxymethyl)-1-butanol was used. Base) cyclohexane plus The product (included in the compound represented by the above formula (A-2); manufactured by Daicel Chemical Industry Co., Ltd., trade name "EHPE3150")] 30 parts by weight, (meth) acrylate [tricyclic [5.2.1.02, 6] Decane dimethanol diacrylate (comprised in the compound represented by the above formula (B-1); DaicelCytec Dufa, trade name "IRR214K")] 70 parts by weight, and not formulated with epoxy 27 322757 201144349, A hardening resin was obtained in the same manner as in Example 1 except for the fluorenyl) acrylate. The properties of the cured resin obtained in the examples and the comparative examples and the heat resistance test (evaluation of yellowing resistance under reflow conditions) were carried out under the following methods and conditions. The results are shown in Table 1. Table 1 Example 1 Example 2 Comparative Example 1 Resin surface with or without traces No internal transmittance (400 nm) (%) 98.3 98.6 97.6 and ten heat 5 type test IJ hardened resin refractive index (589 nm) 1.5245 1.5212 1.5292 Abbe number 53.9 54.0 51.4 Water absorption (%) 1.1 1.4 1.1 Glass transition temperature (°C) 122 123 105 Linear expansion coefficient (ppm/K) 97 104 97 Elasticity (GPa) 2.9 2.8 3.1 Hardened resin after the heat test Internal transmittance (400 nm) (%) 87.0 91.9 82.8 Yellowing rate (%) 11.5 6.8 15.1 (1) Shape of resin surface The surface of the cured resin was visually inspected for streace. Meanwhile, the streaks indicate optically inhomogeneous states, and refer to wrinkles and undulations observed on the surface of the cured resin. 28 322757 201144349 (2) Internal transmittance The internal transmittance of the hardened resin can be calculated by the following formula. Internal transmittance (400 nm) = transmittance in 400 nm / (1 - r) 2 r = { (η - 1) / (n + i) } 2 n is a refractive index in 400 nm. The light transmittance in 400 nin is measured by using a spectrophotometer (trade name "U-3900", manufactured by High Technology Co., Ltd.). The refractive index is measured by using the method of the following (3) to measure the refractive index at 4 〇〇 nm. value. (3) Refractive index The refractive index of the cured resin is a refractive index of 589 nm at 25 C measured by a refractometer (manufactured by Metricon Co., Ltd., "Model 2010") in accordance with the method of JIS K7142. (4) Linear expansion coefficient

The linear expansion coefficient of the hardened resin is the use of TMA measuring equipment (SII

The product name "tmA/SS100" manufactured by Nanotechnology Co., Ltd., at a temperature increase rate of 5 ° C / min, and a measurement temperature range of 30 ° C to 25 (TC, after measuring the coefficient of thermal expansion, 'the linear slope of the low temperature portion indicates the coefficient of linear expansion. (5) The water absorption rate of the water-absorbent-hardening resin is measured by the method according to JIS K7209. (6) The elastic modulus of the elastic modulus-hardening resin is a solid viscoelasticity measuring device (trade name: rRSAni, manufactured by TA Instrument Co., Ltd.). The temperature is 25 ° C / min, the temperature range is measured - 艽 艽 to 270 ° C, and the dynamic viscoelastic properties are measured, and the elastic modulus at 25 ° C is read. 29 322757 201144349 , (7) Glass transition temperature; Hardened resin The glass transition temperature is measured by a differential scanning calorimeter (manufactured by TA Instrument Co., Ltd., trade name "Q2000"), and heated at a temperature increase rate of 20 ° C / min from 50 ° C to 250 ° C, and After cooling at 250 ° C to 50 ° C at a cooling rate of 20 ° C / min, the measurement was carried out at a temperature increase rate of 20 ° C / min in the measurement temperature range of 50 ° C to 250 ° C. (8) The Abbe number of the Abbe number hardening resin is Calculated by the following formula: Abbe number = (nd - 1 ) / ( nF + nc ) where nd is the refractive index in 589.2 nm, nF is the refractive index in 486.1 nm, and nc is in the 656.3 nm At the same time, the refractive index is the value of the refractive index at each wavelength measured by the method of the above (3). (9) Heat resistance test (evaluation of yellowing resistance under reflow conditions) Under atmospheric conditions, The hardened resin was continuously subjected to a heat resistance test for 3 minutes in an oven heated to 270 ° C in advance, and then the transmittance in 400 nm of the cured resin which was supplied for thermal test and the refractive index in 400 nm were measured. The internal transmittance was calculated. The reduction rate of the internal transmittance calculated by the following formula was used as the yellowing rate, and the yellowing resistance under the reflow condition was evaluated.

Reduction rate of internal transmittance (%) = (internal transmittance before heat resistance test - internal transmittance after heat resistance test) / (internal transmittance before heat resistance test) xlOO 30 322757 201144349 Using an epoxy compound having an alicyclic ring, The curable composition of Examples 1 and 2 having an alicyclic (fluorenyl) acrylate and a (fluorenyl) acrylate compound having an epoxy group, and without using an epoxy group-containing (fluorenyl) propylene When the curable composition of Comparative Example 1 of the acid-based compound was compared, the former obtained a cured resin having an extremely high glass transition temperature, and a cured resin having a high heat transmittance such as a high light transmittance after the heat resistance test was obtained. Therefore, a hardened resin which is made of a hardening composition using an epoxy compound having an alicyclic ring, a (fluorenyl) acrylate having an alicyclic ring, and a (meth) acrylate compound having an epoxy group is formed by a heat-resistant surface. Moreover, it has a south transparency. Therefore, it can be applied to various applications such as optical applications such as lens units and optical component applications. [Simple description of the diagram] None. [Main component symbol description] None 0 31 322757

Claims (1)

201144349 VII. Patent application scope: 1. A curable composition characterized by comprising an epoxy compound (A) having an alicyclic ring in the molecule, and a (fluorenyl) acrylate (B) having an alicyclic ring and a molecule. (Mercapto) acrylate (C) having an epoxy group. 2. The curable composition according to claim 1, wherein the (meth) acrylate (C) having an epoxy group in the molecule is selected from (meth)acrylic acid having an alicyclic epoxy group. At least one compound of an ester and a (meth) acrylate having a glycidyl group. 3. The curable composition according to claim 1 or 2, wherein the epoxy compound (A) having an alicyclic ring in the molecule is an epoxy compound selected from the group consisting of an epoxy group having an alicyclic epoxy group, and an epoxy group. An epoxy compound which directly bonds an alicyclic ring with a single bond, and at least one epoxy compound which has an epoxy compound having an alicyclic ring and a glycidyl ether group. 4. The curable composition according to any one of claims 1 to 3, wherein the (meth) acrylate (B) having an alicyclic ring in the molecule is a polyfunctional one having an alicyclic ring in the molecule. (fluorenyl) acrylate. A hardening resin obtained by curing the curable composition according to any one of claims 1 to 4. An optical member which is obtained by the hardening resin described in claim 5 of the patent application. 322757 201144349 . IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: No. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (A-1) 3 322757