TW201211078A - Curable composition and cured article thereof - Google Patents

Abstract

Provided are a curable composition, a cured resin obtained by curing this curable composition, and an optical element comprising the cured resin. The curable composition has a low viscosity before curing, and is cured rapidly by heating, to form a cured resin difficult to turn yellow even at high temperature condition under soldering through reflow, and the cured resin has shown a low Abbe number equal to or below 30 while having excellent transparence and heat resistance. The curable composition of this invention contains the following components (A) and (B) at a ratio [(A)/(B), by weight] of 70/30 to 99/1, and further contains a thio compound. component (A): a compound having two (metha)acryloyloxy groups in the molecule, and having a fluorene ring, component (B): a compound having at least one vinyl group or (metha)acryloyloxy group in the molecule, and having no fluorene ring.

Description

201211078 VI. Description of the invention: 'Technical field to which the invention pertains» The present invention relates to a curable composition, a cured product thereof, and an optical member. More specifically, it relates to a curable composition which can form a low viscosity before curing, is rapidly hardened by heating, and has a cured product having excellent optical properties and environmental resistance, and hardens the hardenable composition. An optical member such as a hardened resin and a lens made of the cured resin. [Prior Art] The curable resin composition is used as a plastic material for mechanical component materials, electrical/electronic component materials, automotive component materials, civil construction materials, molding materials, coatings, adhesives, sealing materials, etc., and has been used as a lens in recent years. Materials such as optical members are also attracting attention. As a curable composition which forms a lens having a low Abbe number, a curable composition mainly composed of a (meth) acrylate having an anthracene ring is known (Patent Document 1). However, this hardenable composition has a lens which cannot form a sufficiently low Abbe number, and the heat resistance is not sufficient, and the shape is changed and the light transmittance is remarkably lowered when exposed to high temperatures. Further, the door is known to have a high viscosity and a lack of fluidity. The patent document 2 discloses that a (meth)acrylic acid vinegar having a ring and a naphthalene ring and an anthracene are described. A method in which a ring or a ketone ring is used in combination to enhance fluidity. However, the (meth)acrylic acid vinegar having a naphthalene ring, an anthracene ring or an onion ring is not low in viscosity and needs to be added in a large amount to ensure moderate turbidity 'but it has a color itself, and the addition can sufficiently ensure the fluidity. The amount detracts from its optical properties, and it is difficult to combine both fluidity and optical properties. 323386 4 201211078 Therefore, after the curable composition is applied to a mold, a casting molding method is carried out. It is difficult to obtain a molding method by injection molding because sufficient fluidity cannot be obtained. However, in the injection molding method, the tree material is used!丨 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ If the "burr" strength is weak, there is a broken r& when it is separated from the mold, it is considered to be a problem with the product. Therefore, the method of making the "burr" part large and strong is used, so the resin utilization rate is low. There are uneconomic problems. In the city molding method, such as the heat-resin resin, the pre-curing treatment such as pre-hardening is required for forming the hardening group, and generally the molding method for the resin is excellent. However, as a molding method of a member requiring high-strength, it becomes a complicated molding method. Further, thermoplastic resins such as polyolefin and engineering plastics have yellowing problems due to heating during molding and long-term use of molded articles. The method is known to add an antioxidant (non-specialized D. There are two kinds of the above-mentioned antioxidants, a radical scavenger that captures and deactivates the generated radicals' and the peroxidation to be produced) A peroxide decomposer which decomposes into an inert substance to suppress the generation of a new radical, and a radical scavenger mainly uses a hindered compound or a hindered amine compound, and a peroxide decomposer mainly uses a lanthanoid compound (Patent Document 3) However, the above-mentioned radical scavenger has a function of suppressing radical polymerization, and (4) which is sufficient to exert a yellowing-suppressing effect, and the curable composition itself is not advanced, and the obtained hardened resin is strong. Reduction of 323386 5 201211078 MU phosphorus compound yellowing inhibition effect is small, under high temperature conditions such as welding (for example, 26 〇. 〇 around) difficult ':: flow change' especially as an optical component such as _ The yellowing effect is completely insufficient. Therefore, for example, most of the _ machine Wei = suppression by the reflow method welding step (group step), the additional machine 'group is manufactured by the step of connecting by the connector, the manufacturing step: [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-235196 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2〇3〇3747 3] Japanese Patent Publication No. 2008-524397 [Non-Patent Document] [Non-Patent Document 1] Fei Tian Yue Nan, "Analysis of Causes of Discoloration of Polymer Materials and Countermeasures", Chapter 3, Technical Coloring (2009) ^ [Invention] The object of the present invention is to provide a hardenable composition, which can be formed to have a low viscosity before hardening, and is rapidly hardened by heating, showing a low level. A cured resin which is excellent in transparency and heat resistance and which is hard to be yellowed even under high temperature conditions such as soldering by reflow, and a cured resin obtained by curing the curable composition and made of the cured resin (Optical means for solving the problem) 6 323386 201211078 The inventors of the present invention have intensively reviewed the results of the above-mentioned problems, and found that there are two (f-based) molecules in an extremely high viscosity but excellent in optical properties and heat resistance. a propylene group having an anthracene ring and a hydrazine ring containing a specific amount of at least one vinyl group or a (meth) acryloxy group and having no hydrazine When the compound, while maintaining the optical properties, significantly reduce the viscosity of the flowability can be improved. Further, when a thiol compound is added, a hardening resin which is not easily yellowed can be formed under high temperature conditions such as soldering by a reflow method, and the present invention is completed based on such knowledge. That is, the present invention provides a curable composition containing the following components (4) and (B)' in a ratio of 70/30 to 99/1 in a ratio of [the former/the latter (weight ratio)] and containing a mercaptan Compound. The knives (A). are represented by the following formula (〗), and have two compounds (in the thiol group, and having the ring group R2 〇)

〇r4 〇+r3-0 士2. -0=〇12 is the same or different and represents an aromatic carbocyclic ring. Ri gas; (four) two components (8): intramolecular or different, said. The above paste base, and not the compound of the ring to f-vinyl or (methyl (tetra) as the component (8), preferably the compound represented by the following formula (1) 323386 7 201211078

X: For example, 5 士士

0 II C R6 • C=CH2 (2) n5 (wherein X represents a monovalent or divalent aliphatic hydrocarbon group, an alicyclic fluorenyl group, a monocyclic aromatic hydrocarbon group or a group to which these groups are bonded. R5 Represents an alkylene group, R6 represents a hydrogen atom or a methyl group. η3 represents an integer above 〇, n4 represents 〇 or 1, and η5 represents 1 or 2). The viscosity at 25 ° C is preferably 36 〇〇 mPa · s or less. The thiol compound preferably has a boiling point of at least 10 ° C, and the thiol compound is preferably a linear or branched alkanethiol or a linear or branched alkanedithiol. The curable composition is preferably thermosetting. The present invention also provides a resin obtained by curing the curable composition. The present invention further provides (4) an optical member comprising a cured resin. (Effect of the Invention) The curable composition of the present invention is excellent in fluidity before curing, and it is easy to suppress the generation of bubbles while uniformly applying it to a mold, and the workability is different. Further, since it can be quickly hardened by heating, a metal mold which is easy to be precision can be used as a mold, and the shape of the scale can be reproduced with high precision. Therefore, it is possible to have a precision and a member having a desired shape such as a fine structure by a casting molding method or the like, for example, from a simple mold to a plurality of members. 'The hardened resin obtained by the human being, the Abbe number is 3 〇 or less, and the 323386 8 201211078 'excellent heat resistance' has a yellowing suppression effect which is not easily yellowed even at a high temperature of about 26 ° C. The cured resin of the present invention is particularly suitable for use in optical members such as lenses because of the above characteristics. For example, when a lens made of a hardened resin obtained by hardening a curable composition of the present invention is used as a lens of a camera-equipped mobile phone, the camera can be assembled at the same time in a soldering step (assembly step) by a reflow method. The module, and the connecting step of the camera module by the connector after the soldering step can be omitted. [Embodiment] The curable composition of the present invention contains the following components (4) and (B) as a curable ratio in a ratio of [the former/the latter (weight ratio)] of 7〇/3〇 to "/1; Monomer and contains a thiol compound. [Component (A)] The component (4) of the present month is represented by the above formula (1), and has two (meth)acryloxy groups in the molecule, and has a right station / 'knife U 2 ring B1 〆~η There is a hardening monomer of the ring. In the formula (1), the dissimilar enthalpy: 5 or different 'is an aromatic carbocyclic ring. Rl, R3 are the same or different from the alkyl group, and r2 is the next (10) methyl group. N1, η2 is a phase (four) cardinal or dissimilar ‘a money atom or a ring ζ1, ζ2 may have a substituent to represent G or more. The ring and the 1 to 4 carbon ring such as J-Z1, ring 72, and ring-promoting ring may, for example, be a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring. And (4) carbon rings. Preferably, the aromatic carbocyclic ring is included as a linear chain or a branch of R1, ^# propyl, and a triammine U group, for example, a methylene group, an ethyl group, a methyl group, and a tetramethylene tube. Chain-like extension, Liu Yajiao rhyme 1 to 10 Fanji. The preferred alkylene group comprises a stretching alkyl group (e.g., an alkylene group having 2 to 3 carbon atoms) having a carbon number of 2 to 6 such as a propyl group or a dimethylene group. • 1 2 8 n, n are integers above 〇, preferably 整数 to an integer of 4, and are preferably integers of 1 to 4 from the viewpoint of lower viscosity and excellent fluidity. The anthracene ring and the ring Z1 and the ring Z2 may have a substituent, and examples thereof include an alkyl group such as a mercapto group, an ethyl group, a propyl group, and an isopropyl group (for example, a cl 6 alkyl group, preferably a fluorenyl group); a cycloalkyl group such as a cyclohexyl group (e.g., a c5-8 cycloalkyl group); an aryl group such as a phenyl group or a aryl group (e.g., a C aryl group); an aralkyl group such as a phenyl fluorenyl group (e.g., a C7-16 aralkyl group); a mercapto group such as an ethyl fluorenyl group, a propyl fluorenyl group or a benzoinyl group (e.g., an anthracenyl group); an alkoxy group such as an anthracenyloxy group, an ethoxy group, a propoxy group, or an isopropoxy group (e. An alkoxycarbonyl group such as an oxycarbonyl group or an ethoxycarbonyl group (for example, Cw alkoxycarbonyl group); a cyano group; a carboxyl group; a nitro group; an amine group; a substituted amine group (for example, a di Cm alkylamino group, etc.); a fluorine atom; a halogen atom such as a chlorine atom. In the formula (1) of the present invention, a representative example of a compound having two (meth)acryloyloxy groups in the molecule and having an anthracene ring may, for example, be exemplified below. These may be used alone or in combination of two or more. 10 323386 201211078

The ratio of the sum of the components (A) in the curable composition is from 5 to 99% by weight, preferably from 55 to 80% by weight, based on the total amount of the curable monomer. When the ratio of the sum of the components (A) in the curable composition is within the above range, the fluidity of the curable composition is remarkably lowered, and the workability tends to be lowered. Further, the obtained cured resin is liable to cause streaks. On the other hand, when the ratio of the total of the components (A) in the curable composition is less than the above range, the heat resistance tends to be lowered.

[Component (B) J) The component (B) of the present invention is a compound having a reinforcing curable composition by blending it with the curable composition of the present invention containing the above component (A) having a viscosity of 5% by weight or more. A flowable hardening monomer characterized by having at least one vinyl group or (meth) acryloxy group in the molecule and having no compound. The component (Β) of the present invention is preferably a compound represented by the above formula (2). In the formula (7), an X-based i-valent or divalent aliphatic hydrocarbon group or an alicyclic hydrocarbon 323386 11 201211078 • a monocyclic aromatic hydrocarbon group or a group in which these groups are bonded represents a (tetra) group, a ... atom or a methyl group . n, an integer greater than 0, n4 represents 〇 or l'n is not 1 or 2. Examples of the monovalent aliphatic nicotyl group of X include a methyl group, a acetaminophen, a diyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a butyl group, a pentylene hexyl group, and an anthracene. A base having a carbon number of i to 20 (preferably i to (7), more preferably 1 to 3); a vinyl group, a propyl group, a ^= to 2 〇 (preferably 2 to 10) More preferably, it is a 2 to 3) can; an alkynyl group having a carbon number of 2 to 2 Å (preferably 2 to 1 Torr to 3) such as an acetyl group or a propynyl group. The alicyclic hydrocarbon group may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclohexyl group or a cyclooctyl group, and may have 3 to 2G members (preferably 3 to 15 or the like == to 8 members). a cyclopentenyl group, a cyclohexenyl group having a specific number of 3 to 2 members (preferably 3 to 15 members, more preferably 5 to 8 members), and a cycloalkenyl group; Team 竑 | a .,w Μ 1 base descending Kanji, Jinxiaji, double ring [3.3.0] octyl, tricyclic [5.2丄〇2,6] 癸 base, three ring [621〇2,7] 十One base, 』 [4.4.〇W, n>] 12-burning base and other bridged ring type smoke bases. (4) = Divalent monovalent monocyclic aromatic hydrocarbon group, for example, an aromatic nicotinic group other than a phenyl group or a 4-hydrazone-specific fused-ring aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the monocyclic aromatic hydrazine=example h may be exemplified by the removal of (10) gas from the above-mentioned i-valent aliphatic smoky group, the fat-soluble industrial base and the early cyclic aromatic hydrocarbon group. The base of the atom. The aromatic (4) group of the ketone group of the alicyclic group and the monocyclic group, the group of the mouth and the group may be exemplified by two or more of the above-mentioned i-valent or divalent 323386 12 201211078 aliphatic hydrocarbon group and fat. The cyclic hydrocarbon group and the monocyclic aromatic group are bonded to each other via a single bond or via a linking group. μ As the above-mentioned linking group, for example, a carbonyl group (_c〇_), a hydrazone bond (_〇_), a vinegar bond (-COO-), a guanamine bond (-CONH-), or a carbonate bond (_OC〇〇~人) can be exemplified. a plurality of such bases. %σ The above-mentioned monovalent or divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, monocyclic aromatic cigarette group, and hydrocarbon group to which the group is bonded may have various substituents such as a halogen atom, a pendant oxy group, a hydroxy group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, a decyloxy group, etc.), a carboxyl group, a substituted oxycarbonyl group (alkoxy group, azure group, Fangxian County, etc.), take the dump = = thiol, cyano, nitro, fluorenyl, substituted or unsubstituted amine, sulfonic acid, hetero-J., etc. The base may be protected by a protecting group conventionally used in the field of organic synthesis 4, and the ring of the lysine hydrocarbon group and the hydrocarbon group may have a heterocyclic condensation of a non-aromatic property. The alkyl group of the formula (2) represents an alkyl group, for example, a sub a methyl group, a stretching propyl group, a triphenyl group, a tetramethylene group, a hexamethyl group, etc.: a straight or branched alkyl group of 1 〇. Preferably, the alkyl group contains an exudate group and a stretching group. Base, three a linear or branched bond having a carbon number of 2 to 6 such as a methyl group (especially a linear or branched exfoliating group having 2 to 3 carbon atoms) ^ n3 represents an integer of 0 or more, preferably An integer of 10, an integer J of 4 is represented by i or 2. When the ratio is jade and when 5 is 2, the ratio of the cross-linking point of the resin composition as a whole becomes less and the hardening 1 decreases. 'The softness of the obtained hardened resin is increased, and the surface of the hard fat-based fat can be suppressed from being generated, and the superiority of the hardened resin can be suppressed. Further, the 323386 13 201211078 of the present invention means an optically uneven state of the surface of the cured resin. It means that the surface of the resin is observed to have wrinkles/undulations/concavities and the like. The viscosity of the component (B) of the present invention at 25 ° C is about 300 mPa · s or less, and preferably from 1 〇〇 to 200 mPa · s. When the viscosity at 25 ° C is higher than the above range, it is difficult to increase the fluidity of the curable composition by a small amount of addition, and it is difficult to maintain the curable composition optical. The characteristics tend to impart fluidity that facilitates work. At the same time, as a representative example of the component (B), a representative example is exemplified. The following compounds. 14 323386 201211078 CH2=C C=CH2 XT (2a)

Or Ο H II I CH2-0 —C-C=CH2 (2b) o CH2CH2O jc·

CH2=C— C — O— C9H18 —〇 —c (2f) H I C=CH2Γ1 ^4,8

H (2d) o -C=CH2

. UC=CH2 o (CH3 Η 11 I CH2=CC — 〇+CH2CH-0 (2g) (2h) c I -( S2 H -C=CH25 —7,12 OH If IO—CH2 CH2 - 0 — C - C=CH2 (2i) Η 0 I II CH2—CC —0-CH2

Ο H II I CH2-O — CC=CH2 (2j) Η O CH3 CH2—C—C —〇4*CH2CH2Οί u Λ—C~^ c OCH2CH2 + O — c Js3 ί ^ Js4 CH3 (2k) s3 +s4 'HI :-C=CH2=4 15 323386 201211078 υϋ- ο ο O-CH2CH2O — C -C=CH2 CH3 0-4-CH2 CH2〇+- C -C =CH2 I S5 I CH3 CHS (2m) 5^ =9 (21) II -CC=CH2 I CH3 (2n) CH20-C —C=CH2 I CH3 (20) ^ CH2 — O a C —C—CH2 CH3 O CH3 o II I II CH2=C-C_OCH2— C - CH20-C-C=CH2 III CH3 CH3 CH3 (2p) (2q) o CH3 CH2=(j:- C — 0 CH2CH2 OJ^- C -C=CH2 S CH3 (2r)

o CH3 s7 -^8 ==10 CH3

CH2=C- C — 0 4 CH2 CH2 O CH2CHO- JS9 L CH3 510 CH2CH20- o II -O —C-C=CH2 Sn I CH3 (2t) s9 +sii _ 6,s1〇M2 0 o

II II CH2=C—C—O—C4H8—O—C—C=CH2 CH3 CH3 (2u)

CH3 The component (B) of the present invention is excellent in economical efficiency and can maintain excellent optical properties (especially low Abbe number, translucent 16 323386 201211078 . From the viewpoint of improving the fluidity, it is preferred that the compound of the formula (2) is a monovalent or divalent monocyclic aromatic hydrocarbon group, and particularly preferably, from the viewpoint of suppressing generation of streaks, The compound of the formula (2), which is a monovalent aromatic hydrocarbon group in the formula (2) and wherein n5 is 1, is represented by the above formulas (10)), (2c), (2d) and (2P). These may be used singly or in combination of two or more. The ratio of the sum of the components (7)) in the curable composition is 丨 to 3% by weight, preferably 5 to 25% by weight, based on the use of the curing resin, etc., preferably 5 to 25% by weight. 2% by weight. Further, the compounding ratio of the component (A) to the component (B) in the curable composition is from 70/30 to 99/1', preferably from 75/25 to 95/5, preferably from 75/25 to 95/5. Department 80/20 to 95/5. When the ratio of the sum of the components (B) in the curable composition is more than the above range, it is difficult to maintain excellent optical characteristics and the heat resistance tends to be lowered. On the other hand, when the ratio of the sum of the components (B) in the curable composition is less than the above range, the fluidity of the curable composition is remarkably lowered, and the workability tends to be lowered. Further, the obtained cured resin is liable to cause streaks. [Thizzol compound] The present invention is characterized in that a thiol compound is formulated in a curable composition. The thiol compound contains a monothiol compound and a dithiol compound. The hardening resin having a radically polymerizable compound having a square ring is subjected to a high temperature to generate a radical by the generated peroxide to form a polymer chain of the cured resin. It is considered that the radical extracts a hydrogen atom of the polymer chain to form a conjugated unsaturated bond, and yellowing occurs by formation of the conjugated unsaturated bond. It is presumed that the curable composition of the present invention contains a radically polymerizable compound having an aromatic ring and a thiol, and the thiol compound captures the peroxide produced at a high temperature of 17 323386 201211078 simultaneously with the formation of a polymer chain. The yoke unsaturated bond undergoes a dilute mercaptan reaction (ene_thi〇i reacti〇n), which has the effect of eliminating the common unsaturated* bond, and can effectively inhibit the yellowing of the resin at high temperatures. Further, the radical-type electron-attracting radical generated by the thiol compound, the radical species associated with the radical hardening polymerization, is also an electron-attracting radical. In general, the chain transfer energy between the electrons and the free radicals is not high, and it is presumed to be different from the case where a phenolic antioxidant is used as a yellowing inhibitor to prevent the radical curing polymerization. Thereby, the curable composition of the present invention is cured at a high curing rate, and has excellent yellowing resistance, and can form a hardening resin which suppresses the degree of yellowing to a minimum even when exposed to, for example, a high temperature of about 26 rc. It is preferable that the curable composition is not volatilized or foamed when it is cross-linked or hardened, and is not easily volatilized or exposed even in a state of being contained in the hardened resin even under exposure to high temperature conditions (for example, heating in a reflow step). For the bubble, for example, a boiling point of 100 〇C or more, wherein the boiling point is 15 (TC or higher is preferred, and the boiling point is preferably 180 ° C or higher. Further, in the present specification, only the boiling point means the boiling point under normal pressure. 'From the point of view that the reactivity with the above component (A) is stable and the storage stability is excellent, 'as the thiol compound of the present invention, it is preferred to use a neutral thiol as compared with an acidic or basic thiol compound. Further, 'from the viewpoint of imparting excellent optical properties to the obtained cured resin, 'the preferred one is compatible with the above-mentioned component (A) and component (B), and a uniform hardenability composition can be obtained. Object The thiol compound may, for example, be 1-hexyl mercaptan (boiling point 15 〇. 〇, 1 - heptyl mercaptan (boiling point 177. 〇, 1-octyl thiol (boiling point 200. 〇, tertiary octane 18 323386 201211078 alcohol) (boiling point 156 ° C), 1-decyl mercaptan, 1-decyl mercaptan (boiling point 241 ° C), 1-undecyl mercaptan (boiling point 104 ° C / 3 mmHg), l-dodecane mercaptan (boiling point) 143 ° C / 16 mmHg), 1-tetradecyl mercaptan (boiling point 310 ° C), 1-hexadecanethiol, 1-octadecyl mercaptan and other carbon number of about 6 to 30 (preferably carbon number 6 A linear or branched alkanethiol to 20 or so. The dithiol compound may, for example, be 1,4-butanedithiol (boiling point: 195 ° C) or 2,3-butanedithiol. (boiling point 87 ° C / 50 mmHg), 1,5-pentanedithiol (108 ° C / 15 mmHg), 1,6-hexanedithiol (boiling point 237 ° C), 1,7-heptanedithiol, 1 , 8-octanedithiol, 1,9-nonanedithiol, 1,10-fluorene dithiol (boiling point 297 ° C), 1,12-dodecanedithiol, 1,14-tetradecane a linear or branched chain having a carbon number of 4 to 30 (preferably, a carbon number of 4 to 20) such as dithiol, 1,16-hexadecanedithiol or 1,18-octadecanedhithiol. Alkanedithiol, etc. Among the compounds, from the viewpoint of exhibiting a more excellent yellowing inhibitory effect, a linear alkanethiol having 10 to 15 carbon atoms such as mercapto mercaptan, dodecanethiol or decanedithiol or Alkanedithiol, etc., particularly preferably thiol and decyl mercaptan. The amount of the thiol compound used can be suitably adjusted within the range of the curability of the non-hardenable composition, although it varies depending on the type of the thiol compound. With respect to the total amount of the hardenable monomer, for example, it is 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. When the amount of the thiol compound used is too large, the curability of the curable composition is lowered or streaking tends to occur. On the other hand, when the amount of the thiol compound used is too small, the yellowing resistance of the cured resin tends to decrease. [Other Ingredients] 19 323386 201211078 The curable composition of the present invention may be added with a thermal radical polymerization initiator or other various additives depending on the use of the cured resin. Examples of the thermal radical polymerization initiators include hydrogen peroxides, dialkyl peroxides, peroxyesters, dioxonium peroxides, peroxydicarbonates, peroxyketals, and the like. Organic peroxides such as ketone peroxides. Specific examples of the 4 thermal radical polymerization initiator include, for example, 1,1 bis(peroxytributyl)cyclohexane, peroxydiphenyl fluorenyl, and benzoic acid tributyl phthalate. Ester and the like. Among the thermal radical polymerization initiators, a compound which generates a gas component accompanying the generation of a radical such as an azo radical polymerization initiator may cause a poor residual resin of the cured resin. As the thermal radical polymerization initiator, for example, the trade name "PERHEXA C" [1,1_bis(peroxytributyl)cyclohexane, Nippon oil (stock)], and the trade name "PEROYLL" can be used. Commercial products such as dilauroyl peroxide and Nippon oil (stock). The amount of the thermal radical polymerization initiator to be added is, for example, about 0.1 to 10% by weight, preferably about 至 to 5% by weight, based on the entire curable composition. In addition, as an additive, for example, a curable monomer other than the above components (A) and (B), a compound 〇rgan〇sil〇xane compound, metal oxide particles, rubber particles, and poly ♦ Oxygen or (4), antifoaming agent, ceramide coupling agent, filler, plasticizer, leveling agent, antistatic agent, release agent, flame retardant, coloring agent, antioxidant, line absorbent, Ion sorbents, pigments, etc. The amount of the respective additives to be added is, for example, 5% by weight or less based on the entire curable composition. The curable composition of the present invention may contain 323386 20 201211078 solvent, but excessively, bubbles may be generated in the cured resin. The total amount of the curable composition is preferably 10% by weight or less, and particularly preferably 1% by weight or less. The curable composition of the present invention is prepared, for example, by mixing a predetermined amount of the component (A), the component (B), and a thiol compound with a thermal radical polymerization initiator, various additives, and the like as needed, and vacuuming as needed. The lower side is prepared by stirring/mixing while removing the bubbles. The temperature at the time of stirring/mixing is, for example, about 10 to 60 °C. For the stirring/mixing, a known device such as a self-rotating conversion mixer, a single-shaft or multi-axis extruder, a planetary mixer, a kneader, a dissolver or the like can be used. The curable composition of the present invention has a viscosity at 25 ° C of 3,600 mPa·s or less, preferably 2,000 mPa·s or less, more preferably i5 〇〇mpa·s or less, and particularly preferably less than 100 mPa·s. When the viscosity is more than the above range, the fluidity is lowered, and the applicability and the filling property are lowered, and the injection pressure is lowered, and the moldability to the mold is lowered. Therefore, the adjustment of the operating temperature, the defoaming treatment, the curing conditions (hardening temperature, curing time, temperature rising rate, cooling rate, etc.) are adjusted, and the workability of the molding work of the curable composition is lowered. The curable composition prepared by the above method is molded by a conventional molding method such as a casting method or an injection molding method, and then a radical polymerization reaction is promoted by heating to obtain a cured resin. As heating conditions, the heating temperature is from 8 Torr to 2 Torr (about rc (preferably from about π 〇 to about 16 〇 C). The heating time is about 1 to 5 minutes (preferably about 1 to 3 minutes). The curable composition has rapid curability, and the hardened resin can be formed very rapidly by heating under the above-described heating conditions of 323386 21 201211078. The hardening rate of the cured resin of the present invention is measured by the DSC method, for example, l5 〇 C, 7 minutes or more in 5 minutes. (preferably 80% or more) is preferable, and it is preferably 7% or more (preferably 80% or more) in 2 minutes for i4〇〇c. Further, after the hardened resin is taken out from the mold, After the hardening composition of the present invention is excellent in fluidity, the casting method is particularly suitable. Therefore, it is economical to use the curable composition more efficiently than the injection molding method. Further, the curable resin having the target shape is produced. Further, since the curable composition of the present invention is thermosetting, a metal mold can be used for molding. Therefore, the metal mold can be easily produced compared to a glass mold or the like. More tiny / fine Therefore, according to the curable composition of the present invention, a hardened resin having a minute/precision shape can be easily formed. The cured resin of the present invention obtained by the above method is excellent in transparency, for example, a hardened resin having a thickness of 0.5 mm. The internal transmittance (%) at 40 〇 nm is 90% or more, preferably 95% or more, and particularly preferably 98% or more. Further, the cured resin of the present invention is excellent in yellowing resistance, for example, thickness 〇. The yellowing rate of the hardening resin of 5 mm is 2% or less after the heat resistance test, preferably 1.5% or less, and particularly preferably 1.0% or less. Further, the yellowing rate of the present invention is before and after the heat resistance test described below. The internal permeability reduction degree of 4 〇〇 nm is obtained by the following formula. Heat resistance test: A hardened resin having a thickness of 0.5 mm is described in accordance with JEDEC specifications using a tabletop reflow furnace manufactured by Shinapex Co. Ltd. 323386 22 201211078 Reflow temperature profile is the criterion for repeated three times of heat resistance test yellowing rate (%) = {(internal transmittance before heat resistance test) _ (internal transmittance after heat resistance test)} / (Internal penetration before heat resistance test) Further, the cured resin of the present invention is excellent in heat resistance, and for example, the glass transition temperature is 100 ° C or higher, preferably 110 to 17 Å. The cured resin of the present invention has an Abbe number of 30 or less, preferably a system. 28 or less, the special system is 27 or less. The refractive index of the lens varies depending on the wavelength of the light, and a phenomenon (chromaticity) occurs in which the imaging is deviated (bleeding or blurring). In order to reduce the influence of the chromatic aberration, the general lens is caused by A combination of a high Abbe number lens resin and a low Abbe number lens resin to form a corrected chromatic aberration structure. The glass used for the lens of the camera is classified into two types according to the Abbe number, and the Abbe number is generally used. 50 or less is called flint glass, and 5 or more is called crown glass. The hardening resin of the present invention can be suitably used as a resin for lenses having a low Abbe number. As described above, the curable resin of the present invention is excellent in transparency and heat resistance. For example, it can be suitably used as an optical member at 26 (a high temperature at a high temperature of about TC). The optical member may, for example, be a camera (on-vehicle camera, Digital camera, PC camera, mobile phone camera, surveillance camera, etc.) Photographic lens, spectacle lens, color filter, diffraction grating, 稜鏡, light guide bow ' 'beam concentrating lens, light diffusing lens, display device Cover glass, light sensor, photoswitch, LED, light-emitting element, optical waveguide, optic splitter, optical fiber adhesive, substrate for display element, substrate for color filter, touch panel A substrate, a display protective film, a display backlight, a light guide plate, an anti-reflection film, etc. 323386 23 201211078 (Embodiment) Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited Examples 1 to 8 and Comparative Examples 1 and 2 The components described in the following Table 1 were formulated according to the blending composition (values are parts by weight), and stirred by a self-rotating mixer. /mixing to obtain a uniform and transparent hardenable composition. [Table 1] 24 323386 201211078 l<Comparative Example 2 § 〇Comparative Example 1 § 〇τ-~ CM Example 8 § τ - csl Example 7 S τ - CM Example 6 in 00 τ - csj Example 5 § m LO τ - CM Example 4 § ο Csl Example 3 g ο τ - LO Example 2 § ο τ - CM Example § ο τ - Ύ - EA-F5503 EA-0200 DVB IRR214K A-LEN-10 PER HEXA C80 癸 thiol hydrazine dithiol Irg1010 /-, < (Component (Β) radical polymerization initiator thiol compound 25 323386 201211078 Description About the short list in Table 1 * [Component (A)] 'EA-F5503: a benzoyl acrylate dilution of the compound represented by the following formula (la) (content of the compound represented by the following formula (la): 73% by weight), "OGSOLEA-F5503", manufactured by Osaka Gas Chemicals Co., Ltd. EA-0200: 95% by weight of a compound represented by the following formula (lb), trade name "OGSOL EA-0200", Osaka Gas Chemicals Co., Ltd. [Component (B)] DVE: 2B as shown in the following formula (2a) Alkene benzene IRR214K: a compound represented by the following formula (2j), trade name "IRR214K", A-LEN-10 manufactured by DAICEL-CYTEC Co., LTD.: a compound represented by the following formula (2c), trade name " A-LEN-10", manufactured by Shin-Nakamura Chemical Co., Ltd. [thermal radical polymerization initiator] PERHEXAC80: trade name "PERHEXA-C80", 1,1-di(peroxytributyl)cyclohexane, Japanese oil (share) system [other]

IrglOlO: trade name "Irganox 1010", manufactured by Ciba Specialty Chemicals Corporation 26 323386 201211078

(2a)

The curable compositions obtained in the examples and comparative examples were evaluated in the following manner. [Viscosity] The viscosity of the curable composition was measured by a rheometer (trade name "PHYSIC A UDS200", manufactured by Paar Physica Co., Ltd.) at 25 ° C at a viscosity (mPa · s) at a rotation speed of D = 20 / sec. [Coating property] 27 323386 201211078 The curable composition obtained in the examples and the comparative examples was poured into a 10 mL syringe, and defoamed under reduced pressure using a self-rotating public-transition mixer. Then, using a high-precision liquid coating apparatus (trade name "Dispenser ultra 2400", manufactured by EFD), the coating was applied to a slit having a width of 1.0 mm for five times, and evaluated according to the following criteria. Evaluation criteria No bubbles were observed for all 5 times: ◎ 5 times, 1 to 2 bubbles were observed: 〇 5 times, 3 to 4 bubbles were observed: △

Bubbles were observed in all of the following five times: X Next, the curable composition obtained in the examples and the comparative examples was injection molded into a mold having a thickness of 0.5 mm which was previously coated with a release agent, and was used in an atmosphere. After heating in a 200 ° C preheated oven for 3 minutes, it was heated in an oven preheated at 140 ° C for 2 minutes to release. Then, it was baked at 160 ° C for 30 minutes to obtain a cured resin (5 each). [Resin surface shape] The surface of the curable composition obtained as described above was visually observed and evaluated in accordance with the following criteria. None of the five evaluation criteria showed streaks: ◎ Of the 5, 1 to 2 of the stripes were observed: 〇5 of the 5, 3 to 4 of the observed stripes: △ 5 all observed stripes: X [ Internal penetration rate] 28 323386 201211078 For the hardened resin, the internal transmittance is calculated by the following formula: β Internal transmittance (400 nm) = light transmittance at 400 nm / (1-r) 2 r = {(nl) / (n+l)}2 Using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, trade name "U-3900"), the light transmittance at 40 〇 nm is measured at a refractive index of 400 nm, and the following method is used. The value of the refractive index at 4 〇〇 nrn was measured. [Refractive Index] The refractive index of the cured resin is measured by a method based on JIS K7142, and a refractive index of 589 nm at 25 ° C is measured using a refractive index of 0 ("Model 2010", manufactured by Metricon Corporation). [Abbe number] The Abbe number of the cured resin was calculated by the following formula. Abbe number = (nd_l) / (nf > nc) where nd represents a refractive index at 589.2 nm, nf represents a refractive index at 486 lnm, and ne represents a refractive index at 656 3 nm. Further, the refractive index is the value of the refractive index at each wavelength measured by the above method. [Slope conversion temperature] The glass transition temperature of the hardened resin is measured by a differential scanning calorimeter (manufactured by TA Instruments Corporation). - Afterwards (from -50C to 20 ° C / min to 25 ° C, then from 25 () ^ -2 (TC / min to 5 〇 〇 〇 〇 , , , , , , , , , , , , , The measurement is carried out at a temperature range of -5 to 250. [Linear expansion coefficient] The linear expansion coefficient of the cured resin is measured by a TMA measuring device (trade name: 323386 29 201211078 "TMA/SS100", manufactured by SIINano Technologylnc.) at a heating rate. • 5 ° C / min, the linear expansion rate is measured in the measurement temperature range of 30 ° C to 250 ° C, and the slope of the straight line on the low temperature side is expressed as the coefficient of linear expansion. In addition, the description in Table 2 is below the glass transition temperature. Linear expansion coefficient (ppm/art)/linear expansion coefficient (ppin/°c) above the glass transition temperature. [Heat resistance test] Using a tabletop reflow oven manufactured by Shinapex Co. Ltd., hardening resin 'based on TEDEC The reflow temperature setting groove described in the specification is the criterion for continuous 3 (4) thermal test, and the internal transmittance before and after the test of the light transmittance (10) and the yield of the heat resistance (4) are measured by the above method. Heat resistance. 述 式 求 page rate (%), evaluation Yellowing rate (%) = {(stable permeability after test before heat resistance test)} / (Materials in the following table will be used to sort out the above evaluation results to indicate the penetration rate) xioo [Table 2] 323386 30 201211078 Comparative Example 2 580 ◎ 〇96.8 1.6138 26Ό 1 1 94.2 Comparative Example 1 363 ◎ XIII 1 1 1 1 Example 8 3520 < 〇99.2 1.5975 27.9 1 1 1 1 Example 7 1660 〇〇99.6 I- ! 1.5992 I- i 27.7 CO 97/169 99.2 inch 〇 Example 6 1034 ◎ ◎ 99.2 1.6118 26.0 卜τ—τ—103/192 98.4 00 〇 Example 5 1010 ◎ 〇99.2 1.6096 I i 26.7 Floating r-96/170 98.6 CO d Implementation Example 4 406 ◎ 〇 98.5 1.6121 26.3 1 1 1 98.2 CO d Example 3 350 ◎ < 90.3 II 1 1 1 1 | Example 2 359 ◎ 〇 99.5 1.6111 26.4 CO r —· 104/163 99.3 CSJ d Example 1 CO CD CO ◎ 〇98.3 1.6114 26.3 1 I 97.2 τ—· Viscosity (mPa-s) Shape of coated resin surface Internal transmittance (〇/〇) Refractive index Abbe number Glass transition temperature (°c) E w Internal penetration rate of firefly (〇/〇) Yellowing rate (%) Hardening resistance of hardened resin before heat test The hardening resin after the heat test 31 323386 201211078 (Industrial Applicability) According to the curable composition of the present invention, since the fluidity before curing is excellent, the generation of bubbles can be suppressed while being uniformly applied to the mold. Further, since it can be quickly hardened by heating, a metal mold which is easy to perform precision can be used as a mold, and the shape of the mold can be reproduced with high precision. Therefore, it is possible to accurately and efficiently manufacture a member having an intended shape such as a fine structure by a casting molding method or the like. In addition, the cured resin obtained by the above has an Abbe number of 30 or less, and is excellent in transparency and heat resistance, and has a yellowing suppression effect which is not easily yellowed even at a high temperature of about 260 ° C. Therefore, it is particularly suitable for a lens or the like. The use of optical components. [Simple description of the diagram] None. [Main component symbol description] No 0 32 323386

Claims (1)

201211078 VII. Patent application scope: 1. A curable composition containing the following components (A) and (B) in a ratio of 70/30 to 99/1 in the ratio of the former/the latter (weight ratio). And a thiol compound; Component (A): a compound represented by the following formula (1) having two (fluorenyl) acryloxy groups in the molecule and having an anthracene ring R 2 Ο I II CH2=CC-OR ^O OR4 0-[-R3-0-]-CC = CH2 (wherein, rings Z1 and Z2 are the same or different, indicating an aromatic carbocyclic ring; R1 and R3 are the same or different, indicating an alkylene group, R2 R4 is the same or different and represents a hydrogen atom or a methyl group; η1, η2 are the same or different, representing an integer of 0 or more; Component (Β): having at least one vinyl group or (meth) propylene oxide in the molecule a compound that does not have an anthracene ring. 2. The sclerosing composition according to claim 1, wherein the component (Β) is a compound represented by the following formula (2): Χ- —— 0 Wherein X represents a monovalent or divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a monocyclic aromatic hydrocarbon group or a group to which the groups are bonded; R5 represents an alkylene group, and R6 represents a hydrogen atom or a fluorenyl group; Η3 represents an integer of 0 or more, η4 1 323386 201211078 represents 0 or 1, and η5 represents 1 or 2). 3. If the sclerosing composition described in the first or second paragraph of the patent application 'the viscosity of '25 C' is 3600 mPa.s or less ό 4. If any of the first to third items of the patent application scope The curable composition according to the item, wherein the thiol compound has a boiling point of 1 Å or more. 5. The sclerosing composition according to any one of claims 1 to 4, wherein the thiol compound is a linear or branched alkanethiol or a linear or branched chain. Alkanedithiol. 6. The curable composition according to any one of claims 1 to 5, wherein the one is thermosetting. A hardening resin obtained by curing the curable composition according to any one of claims 1 to 6. 8. An optical member comprising the hardened resin described in claim 7 of the patent application. 323386 2 201211078 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: 3 323386