KR20130000390A - Curable composition and cured material - Google Patents

Abstract

The curable composition which can obtain the hardening resin which is hard to yellow even under high temperature conditions, such as soldering by a reflow system, is provided. The curable composition of the present invention is characterized by comprising a cationically polymerizable compound and at least one organic sulfur compound selected from a thiol compound, a dithiol compound, a sulfide compound and a disulfide compound. As said organic sulfur compound, the compound whose boiling point is 100 degreeC or more is preferable. It is preferable that the said cationically polymerizable compound is at least 1 sort (s) of compound chosen from an epoxy compound, an oxetane compound, and a vinyl ether compound.

Description

Curable composition and hardened | cured material {CURABLE COMPOSITION AND CURED MATERIAL}

This invention relates to a curable composition, its hardened | cured material, and an optical member. In more detail, it is related with the curable composition which can form the hardened | cured material which is hard to be yellowed even at high temperature, the hardened yellowing resin obtained by hardening the said curable composition, and optical members, such as a lens which consists of the said cured resin.

Deterioration of the resin material, yellowing, in particular, deterioration due to oxidation and yellowing are very serious problems. The resin material basically oxidatively deteriorates in the presence of oxygen, which in most cases is caused by energy such as ultraviolet rays or heat. In thermoplastic resins such as polyolefins and engineering plastics, various stabilizers are added in order to prevent deterioration in heating during molding and long-term use of the molded article, but an antioxidant is used as a method of suppressing oxidative deterioration of the resin material. It is widely done. Phenolic antioxidants and the like are typically used, and at the same time, it is necessary to prevent weather resistance, especially ultraviolet ray deterioration, and in consideration of these characteristics, it has been generally performed to select additives or to use a plurality of additives as stabilizers ( Non-Patent Document 1).

On the other hand, in the resin composition which requires the hardening process by ultraviolet irradiation with heating, in the hardening process, it advances radically and ion polymerization (especially cationic polymerization) in parallel, and produces many crosslinking, and is firm and favorable Since the hardened | cured material which has an optical characteristic was obtained, the said stabilizer rather suppressed hardening reaction, and the addition was not preferable. In addition, the resin composition used for optical material uses often impairs optical properties by the addition of a stabilizer, and it is not very preferable in order to derive the original properties obtained from the curable resin composition.

For this reason, trials, such as providing an antioxidant function to a monomer etc., are made | formed. There are two kinds of antioxidants: a radical scavenger that traps and invalidates generated radicals, and a peroxide decomposer that decomposes the generated peroxide into an inert substance and suppresses generation of new radicals. As the former radical trapping agent, a hindered phenol compound and a hindered amine compound are used, and a phosphorus compound is mainly used as the latter peroxide decomposing agent (Patent Document 1).

Since a long-term antioxidant effect is inadequate only with a phenolic antioxidant, using the phenolic antioxidant and phosphorus antioxidant together is increasing the persistence of an antioxidant effect. However, the oxidation prevention under high temperature conditions (for example, about 260 degreeC), such as soldering by a reflow method, is not enough with these antioxidants, and especially yellowing when used as a material for optical members, such as a lens Inhibition was very insufficient. Therefore, for example, most of the camera-equipped mobile phones are manufactured after the soldering process (mounting process) by the reflow method, through the process of connecting the camera module manufactured separately with the connector, and a manufacturing process is complicated. It is supposed to be done.

Japanese Patent Application Publication No. 2008-524397

Tobita Etsuo, "Analysis of Discoloration and Coloring Trouble in Polymer Materials and Their Countermeasures", Chapter 3, Technical Information Society (2009)

An object of the present invention is to provide a curable composition capable of obtaining a cured resin hardly yellowed even under high temperature conditions such as soldering by a reflow method.

Another object of the present invention is to provide a cured resin hardly yellowed under high temperature conditions such as soldering by a reflow method and an optical member made of the cured resin.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, according to the curable composition which mix | blended the specific organic sulfur compound with the cationically polymerizable compound, the cured resin obtained by hardening | curing the said curable composition is a high temperature of about 260 degreeC, for example. Under the conditions, it was found that the degree of yellowing was very small and completed the present invention.

That is, the present invention provides a curable composition comprising a cationically polymerizable compound and at least one organic sulfur compound selected from a thiol compound, a dithiol compound, a sulfide compound, and a disulfide compound.

As an organic sulfur compound, the compound of boiling point 100 degreeC or more is preferable, and the compound of boiling point 150 degreeC or more is especially preferable.

As said cationically polymerizable compound, at least 1 sort (s) of compound chosen from an epoxy compound, an oxetane compound, and a vinyl ether compound is preferable.

The curable composition may further include a radical polymerizable compound. As a radically polymerizable compound, (meth) acrylic acid ester is preferable.

The curable composition may include a compound further having a cationic polymerizable group and a radical polymerizable group in a molecule.

This invention also provides cured resin obtained by hardening | curing said curable composition.

The present invention also provides an optical member made of the cured resin.

According to the curable composition of this invention, hardening resin excellent in the yellowing resistance which is hard to yellow even by high temperature of about 260 degreeC by hardening can be obtained, for example. Such cured resin is hardly yellowed even when used in a soldering process by a reflow method, and therefore, the cured resin can be used particularly for applications of optical members such as lenses. For example, when using the lens which consists of cured resin obtained by hardening | curing the curable composition of this invention as a lens of a mobile telephone with a camera, it is possible to mount a camera module simultaneously in the soldering process (mounting process) by a reflow method. The connection process of the camera module by the connector performed after a soldering process can be abbreviate | omitted.

The curable composition of this invention contains the cationically polymerizable compound as a curable compound, and at least 1 type of organic sulfur compound chosen from thiol, dithiol, sulfide, and disulfide.

Organic Sulfur Compounds

In the present invention, at least one organic sulfur compound selected from a thiol compound, a dithiol compound, a sulfide compound, and a disulfide compound is blended in the curable composition. By mix | blending such an organic sulfur compound, yellowing under the high temperature of cured resin obtained by hardening | curing a hardening composition can be suppressed.

When a cured product of the curable composition containing a cationically polymerizable compound, particularly a cured product of an epoxy compound or an oxetane compound, is placed at a high temperature, radicals are generated in the polymer molecules of the cured resin by the peroxide generated at a high temperature, and the radicals are polymer molecules. It is considered that a conjugated unsaturated bond is formed by taking out a hydrogen atom, and yellowing occurs due to the conjugated unsaturated bond. When an organic sulfur compound such as thiol is blended in the curable composition, the radicals generated by the high radical chain transfer action are captured, and the formed conjugated unsaturated bonds and the antithiol reaction are caused to dissipate the unsaturated bonds. It is guessed that yellowing of resin can be suppressed effectively. For example, when a thiol compound is used, the thiol compound is changed to disulfide by radical chain transfer, and the disulfide traps peroxide or singlet oxygen, while the diol compound itself reacts with a conjugated unsaturated bond and an enantiol reaction. It is thought to destroy the unsaturated bonds that cause yellowing.

As an organic sulfur compound, what is difficult to volatilize and foam by heating in the reflow process which is a short time high temperature heating process, is contained in hardened | cured material without generating volatilization and foaming, when a monomer composition is bridge | crosslinked and hardened | cured. It is good, for example, boiling point 100 degreeC or more, More preferably, boiling point 150 degreeC or more, Most preferably, it is boiling point 180 degreeC or more. Moreover, it is preferable that the compatibility with a curable compound is high, and a uniform curable composition is obtained from the point of the optical characteristic etc. of the cured resin obtained. In addition, in this specification, when it only calls a boiling point, it means the boiling point in normal pressure.

As a thiol compound, 1-hexane thiol (boiling point 150 degreeC), 1-heptane thiol (boiling point 177 degreeC), 1-octane thiol (boiling point 200 degreeC), tert-octane thiol (boiling point 156 degreeC), 1 Nonanothiol, 1-decanethiol (boiling point 241 ° C), 1-undecanethiol (boiling point 104 ° C / 3mmHg), 1-dodecanethiol (boiling point 143 ° C / 16mmHg), 1-tetradecanethiol (boiling point 310 ° C) ), 1-hexadecane thiol, 1-octadecane thiol, and the like, and linear or branched alkane thiols having about 6 to 30 carbon atoms (preferably about 6 to 20 carbon atoms).

As a dithiol compound, 1, 4- butanedithiol (boiling point 195 degreeC), 2,3-butanedithiol (boiling point 87 degreeC / 50mmHg), 1,5-pentanedithiol (108 degreeC / 15mmHg), for example ) 1,6-hexanedithiol (boiling point 237 ° C), 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol (boiling point 297 ° C) , 1,12-dodecanedithiol, 1,14-tetradecanedithiol, 1,16-hexadecanedithiol, 1,18-octadecanedithiol, and the like having about 4 to 30 carbon atoms (preferably 4 to 20 carbon atoms) Degree) linear or branched alkanedithiol, etc. are mentioned.

Examples of the sulfide compound include dihexyl sulfide (boiling point of 260 ° C.), diheptyl sulfide (boiling point of 298 ° C.), dioctyl sulfide (boiling point of 309 ° C.), didecyl sulfide (boiling point of 217 ° C./8 mmHg), dododecyl sulfide, and di Linear or branched dialkyl sulfides (alkyl sulfides) having about 6 to 40 carbon atoms (preferably about 10 to 40 carbon atoms) such as tetradecyl sulfide, dihexadecyl sulfide, and dioctadecyl sulfide; Aromatic sulfides having about 12 to 30 carbon atoms such as diphenyl sulfide (boiling point 296 ° C.), phenyl-p-tril sulfide (boiling point 312 ° C.), and 4,4-thiobisbenzenethiol (boiling point 148 ° C./12 mmHg); Thiodicarboxylic acids, such as 3,3'- thiodipropionic acid (boiling point 409 degreeC) and 4,4'- thiodibutanoic acid, etc. are mentioned. Among these, dialkyl sulfide is preferable.

As a disulfide compound, for example, dipropyl disulfide (boiling point of 193 ° C), diisopropyl disulfide (boiling point of 177 ° C), dibutyl disulfide (boiling point of 226 ° C), diisobutyl disulfide (109 ° C / 13 mmHg), di-tert-butyl disulfide (boiling point of 142 ° C./17 mmHg), dihexyl disulfide (boiling point of 229 ° C.), diheptyl disulfide, dioctyl disulfide, didecyl disulfide (boiling point of 208 ° C./2 mmHg), Linear or branched dialkyl disulfides having about 4 to 40 carbon atoms (preferably about 6 to 40 carbon atoms) such as didodecyl disulfide, ditetradecyl disulfide, dihexadecyl disulfide, dioctadecyl disulfide, and the like. Etc. can be mentioned.

Among these organic sulfur compounds, a thiol compound, a dithiol compound, and a disulfide compound are preferable from the viewpoint of a yellowing inhibitory effect, and a thiol compound and a disulfide compound are particularly preferable.

The usage-amount of the said organic sulfur compound can be used in the range which does not impair the curability of a curable compound, Although it changes also with the kind of organic sulfur compound, For example, with respect to the total amount (or total amount of curable composition) of a curable compound. 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably about 0.2 to 3% by weight. When there is too much quantity of an organic sulfur compound, the curability of a curable compound may be impaired. When the amount of the organic sulfur compound is too small, the yellowing inhibitory effect of the cured resin is reduced.

Cationic Polymerizable Compound (Cationically Curable Compound) (A)

The curable composition of this invention contains the cationically polymerizable compound (A). When the composition containing the cationically polymerizable compound is cured, a cured resin of low curing shrinkage and low hygroscopicity is generally obtained. The cationic polymerizable compound (A) is not particularly limited as long as it is a compound capable of cationic polymerization, but epoxy compounds, oxetane compounds, vinyl ether compounds and the like are preferable from the viewpoints of curability, physical properties of the cured resin, optical properties, and the like. A cationically polymerizable compound (A) can be used individually or in combination of 2 or more types. As the cationically polymerizable compound (A), it is particularly preferable to use at least an epoxy compound and / or an oxetane compound, in particular at least an epoxy compound.

[Epoxy Compound]

The epoxy compound includes an epoxy compound (A1) having an aromatic ring and an epoxy group in a molecule, an epoxy compound having an alicyclic (aliphatic carbocyclic ring) and an epoxy group (but no aromatic ring) (A2) in the molecule, and an aromatic ring and an alicyclic ring in a molecule. There is an epoxy compound (A3) having no. The epoxy compound may be a monofunctional epoxy compound having only one epoxy group in a molecule, or may be a polyfunctional epoxy compound having two or more epoxy groups in a molecule. As an epoxy compound, it is preferable to use at least a polyfunctional epoxy compound. An epoxy compound can be used individually or in combination of 2 or more types.

In the epoxy compound (A1) which has an aromatic ring and an epoxy group in a molecule | numerator, as an aromatic ring, a benzene ring, a biphenyl ring, a naphthalene ring, a fluorene ring, anthracene ring, a stilbene ring, a dibenzodiophene ring, a carba A sol ring or the like. It is preferable that an aromatic ring contains an aromatic carbocyclic ring at least.

As a typical example of the epoxy compound (A1) which has an aromatic ring and an epoxy group in a molecule | numerator, it is obtained by condensation reaction of bisphenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and epihalohydrin, for example. Epibis-type glycidyl ether type epoxy resins; High molecular weight epibis type glycidyl ether type epoxy resins obtained by further reacting these epibis type glycidyl ether type epoxy resins with bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol; Obtained by condensation reaction of phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and bisphenol S with aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde and the like A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensation reaction of polyhydric phenols with epihalohydrin; Epoxy compound in which two phenol skeletons are bonded to 9 positions of the fluorene ring, and a glycidyl group is bonded to the hydroxyl groups of the two phenol skeletons directly or through an alkyleneoxy group, respectively [bisarylfluorene skeleton Epoxy compound which has a], etc. are mentioned.

As a preferable example of the epoxy compound (A1) which has an aromatic ring and an epoxy group in a molecule | numerator, the compound represented by following formula (A1-1), (A1-2), (A1-3) is mentioned.

In the above formula, R ¹ , R ² are the same or different, and represent an alkylene group, ring Z ¹ , ring Z ² are the same or different, represent an aromatic carbocyclic ring, k1, k2 are the same or different, and 0 or 1 The above integer is shown, m1 and m2 are the same or different, and represent an integer of 0 or 1 or more. However, m1 + m2 is 1 or more. In Formula (A1-3), the fluorene ring, ring Z ¹ and ring Z ² may have a substituent.

As an alkylene group in R <^1> , R <^2> , C1-C10 linear or branched alkylene groups, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group, are mentioned, for example. . Preferred alkylene groups include alkylene groups having 2 to 6 carbon atoms (particularly alkylene groups having 2 to 3 carbon atoms) such as ethylene, propylene and trimethylene groups.

Elastically recalled aromatic ring in Z ^1, Z ² ring, there may be mentioned an aromatic carbocyclic ring of 1-4 degree, such as benzene ring, naphthalene ring, anthracene ring. Preferred aromatic carbocyclic rings include benzene rings, naphthalene rings and the like.

k1 and k2 are each 0 or an integer of 1 or more, but preferably 0 or an integer of 1 to 10, more preferably 0 or an integer of 1 to 4. m1 and m2 are each 0 or an integer of 1 or more, but are preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

In the formula (A1-3), examples of the substituent which the fluorene ring, ring Z ¹ , and ring Z ² may have include alkyl groups such as methyl, ethyl, propyl, and isopropyl groups (eg, C _{1). -6} alkyl group, preferably methyl group); Cycloalkyl groups such as cyclopentyl and cyclohexyl groups (eg, C _5-8 cycloalkyl groups); An aryl group (e.g., C _{6 -15} aryl group) such as phenyl, naphthyl; Aralkyl such as a benzyl group kilgi (e.g., C _{7 -16} aralkyl kilgi); An acyl group such as acetyl, propionyl, benzoyl group (e.g., C _{1 -10} acyl group); An alkoxy group such as methoxy, ethoxy, propyloxy, iso-propyl oxy group (e.g., C _{1 -6} alkoxy group); Alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl group (e.g., C _{1 -4} alkoxy-carbonyl group); Cyano group; Carboxyl groups; A nitro group; An amino group; Substituted amino group (e.g., di-C _{1 -4} alkyl group and the like); Halogen atoms such as a fluorine atom and a chlorine atom, and the like.

As the epoxy compound having an alicyclic ring and an epoxy group in the molecule (without an aromatic ring) (A2), an alicyclic epoxy compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring ; An epoxy compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond; The glycidyl ether type epoxy compound which has alicyclic and glycidyl ether group, etc. are mentioned. As an alicyclic ring, Monocyclic alicyclic rings, such as a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, and a cyclododecane ring (3- to 15-membered, preferably about 5 to 6-membered cycloalkane ring); Decalin ring (perhydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenylene ring , Norbornane ring (bicyclo [2.2.1] heptane ring), isobonane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [6.2 .1.0 ^2,7 ] polycyclic (about 2-4 ring) alicyclic (crosslinked carbocyclic rings), such as an undecane ring, etc. are mentioned. As the alicyclic epoxy group, for example, an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (or 9) yl group (epoxy Dicyclopentadienyl group) etc. are mentioned.

As an alicyclic epoxy compound which has the said alicyclic epoxy group, the compound represented by following formula (A2-1) (compound which two alicyclic epoxy groups couple | bonded with a single bond or through a coupling group) is mentioned.

In the above formula, Y 1 represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (-CO-), an ether bond (-O-), an ester bond (-COO-), an amide bond (-CONH-), and a carbonate bond (-OCOO- ) And groups in which a plurality thereof are bonded to each other. Divalent hydrocarbon group, methylene, ethylidene, isopropylidene, ethylene, straight-chain or branched-chain alkylene group such as propylene, trimethylene, tetramethylene group (e.g., C _{1 -6} alkyl group); 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylidene group, etc. Divalent alicyclic hydrocarbon group (especially bivalent cycloalkylene group); Examples in which a plurality of these are combined are exemplified.

Representative compounds contained in the compound represented by formula (A2-1) are shown below.

In addition, in said formula, n is an integer of 1-30.

As an alicyclic epoxy compound, In addition, the compound which is an epoxy group (alicyclic epoxy group) which has alicyclic and two or more epoxy groups in a molecule, and only one of two or more epoxy groups consists of two adjacent carbon atoms and oxygen atoms which comprise an alicyclic ring is mentioned. Can be mentioned. This representative compound (limonene diepoxide) is shown below.

Moreover, as an alicyclic epoxy compound, the alicyclic epoxy compound which has three or more alicyclic epoxy groups as follows, or the alicyclic epoxy compound which has only one alicyclic epoxy group and does not have an epoxy group can also be used.

In addition, in said formula, a, b, c, d, e, f are integers of 0-30.

As an epoxy compound which the epoxy group couple | bonded with the said alicyclic directly by a single bond, the compound represented by a following formula (A2-2) is mentioned, for example.

In the above formula, R ³ is a group obtained by removing q OH from q-valent alcohol [R ^3- (OH) _q ], p is an integer of 1 to 30, and q is an integer of 1 to 10. In groups in q parentheses, p may be the same or different, respectively. Examples of the q-valent alcohol [R ^3- (OH) _q ] include monohydric alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, and 1-butanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Dihydric alcohols such as polypropylene glycol; And trihydric or higher alcohols such as glycerin, diglycerin, erythritol, trimethylol ethane, trimethylol propane, pentaerythritol, dipentaerythritol, and sorbitol. The alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol or the like. As said alcohol, a C1-C10 aliphatic alcohol (especially aliphatic polyhydric alcohols, such as trimethylol propane) is preferable.

The glycidyl ether of an alicyclic alcohol (especially an alicyclic polyhydric alcohol) is mentioned as a glycidyl ether type epoxy compound which has an alicyclic and glycidyl ether group. This compound may be a compound in which the aromatic ring of the epoxy compound (A1) having an aromatic ring and an epoxy group in the molecule is nuclear hydrogenated. The following compounds are illustrated as a glycidyl ether type epoxy compound which has an alicyclic and glycidyl ether group.

As an epoxy compound (A3) which does not have an aromatic ring and an alicyclic ring in the said molecule | numerator, For example, Glycidyl ether of the said q value alcohol [R <^3> (OH) _q ]; Glycidyl esters of monovalent or polyvalent carboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid and itaconic acid; Epoxidized fats and oils which have a double bond, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; And epoxides of polyolefins (including polyalkadienes) such as epoxidized polybutadiene.

Oxetane Compound

As an oxetane compound, any of a monofunctional oxetane compound and a polyfunctional oxetane compound may be sufficient, and a well-known oxetane compound can be used. An oxetane compound can be used individually or in combination of 2 or more types.

As an oxetane compound, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl), for example Oxetane, di [1-ethyl- (3-oxetanyl)] methyl ether, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, 1,4-bis { [(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, oxetanyl-silses Quioxane, a phenol novolak oxetane, etc. are mentioned.

[Vinyl ether compound]

As a vinyl ether compound, any of a monofunctional vinyl ether compound and a polyfunctional vinyl ether compound may be sufficient, and a well-known vinyl ether compound can be used. A vinyl ether compound can be used individually or in combination of 2 or more types.

As a vinyl ether compound, For example, Aryl vinyl ether, such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; Cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; Vinyl ethers having hydroxyl groups such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 2-hydroxybutyl vinyl ether; Hydroquinone divinyl ether, 1, 4- butanediol divinyl ether, cyclohexanedivinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. Polyfunctional vinyl ether etc. are mentioned.

As a cationically polymerizable compound (A), in addition to the above, the compound which has a heterogeneous cationically polymerizable group in a molecule | numerator can also be used. For example, as a compound which has an epoxy group (for example, an alicyclic epoxy group) and a vinyl ether group in a molecule | numerator, the compound of Unexamined-Japanese-Patent No. 2009-242242 can be used. Moreover, as a compound which has an oxetane group and a vinyl ether group in a molecule | numerator, the compound of Unexamined-Japanese-Patent No. 2008-266308 can be used.

Although the ratio of the cationically polymerizable compound (A) in the curable composition of this invention differs also according to the use of curable resin, etc., it is 5-100 weight% with respect to the whole curable composition (or the total amount of curable compound), for example. Preferably it is 10 to 90 weight%, More preferably, it is about 15 to 80 weight%.

[Other Curable Compounds]

The curable composition of this invention can contain a radically polymerizable compound (radical curable compound) (B) with the said cationically polymerizable compound (A). A radically polymerizable compound (B) can be used individually or in combination of 2 or more types. It may also contain a cation and radical polymerizable compound (C) having a cation polymerizable group and a radical polymerizable group in the molecule. A cation and a radically polymerizable compound (C) can be used individually or in combination of 2 or more types.

Since the hardened | cured material obtained from the dual curable composition which combined the cationically polymerizable compound (A) and the radically polymerizable compound (B) compared with the hardened | cured material only of a cationically polymerizable compound (A), since a molecular chain forms a network structure, The strength of the cured product is high, and the solvent resistance is also improved. Moreover, compared with the hardened | cured material only of a radically polymerizable compound (B), there exists an advantage that generally hardening shrinkage is small and hygroscopicity is also low. Moreover, in the ternary curable composition which added the cation and radically polymerizable compound (C) which have a cationically polymerizable group and a radically polymerizable group in a molecule | numerator to a cationically polymerizable compound (A) and a radically polymerizable compound (B), The compound which has a cationically polymerizable group and a radically polymerizable group in a molecule | numerator acts as a crosslinking agent of a cation curable resin and a radical curable resin, and can improve physical properties, such as heat resistance, and an optical characteristic significantly.

[Radical polymerizable compound (radical curable compound) (B)]

The radically polymerizable compound (B) is not particularly limited as long as it is a compound capable of radical polymerization, for example, a compound having a (meth) acryloyl group [(meth) acrylic acid ester, (meth) acrylic acid amide, etc.], a styrene compound Although olefins etc. can be used, The compound which has a (meth) acryloyl group, especially (meth) acrylic acid ester is preferable from a viewpoint of polymeric property, the physical property of cured resin, etc. By using a radically polymerizable compound, the heat resistance of cured resin can be improved.

Moreover, it is more preferable that it is acrylic acid ester also in (meth) acrylic acid ester. When comparing the radical polymerization rate of the monomer which has an acryloyloxy group, and the monomer which has a methacryloyloxy group, the former is slow. On the other hand, generally, when comparing the reaction rate of radical polymerization with the reaction rate of cationic polymerization, radical polymerization is faster. In the system in which radical polymerization and cationic polymerization proceed in parallel as in the present invention, it is preferable to proceed radical polymerization and cationic polymerization as uniformly as possible in view of physical properties of the cured resin. When the radical polymerization proceeds first, the cure shrinkage of the resulting cured resin increases, and since many unreacted cationically polymerizable groups remain even after completion of the radical polymerization, reaction or decomposition of the cationically polymerizable group occurs in the heat treatment after curing. Physical properties of the cured resin may be impaired. For this reason, acrylic acid ester is more preferable among (meth) acrylic acid ester.

In the (meth) acrylic acid ester, the (meth) acrylic acid ester (B1) which has an aromatic ring and a (meth) acryloyloxy group in a molecule | numerator, (meth) acrylic acid ester which has an alicyclic and a (meth) acryloyloxy group in a molecule | numerator (however, (Meth) acrylic acid ester (B3) which does not have an aromatic ring and an alicyclic ring in a molecule | numerator (B2) and a molecule | numerator. The (meth) acrylic acid ester may be a monofunctional (meth) acrylate having only one (meth) acryloyloxy group, or may be a polyfunctional (meth) acrylate having two or more (meth) acryloyloxy groups. As (meth) acrylic acid ester, it is preferable to use at least polyfunctional (meth) acrylate. These (meth) acrylic acid ester can be used individually or in combination of 2 or more types.

In the (meth) acrylic acid ester (B1) which has an aromatic ring and a (meth) acryloyloxy group in a molecule | numerator, as an aromatic ring, a benzene ring, a biphenyl ring, a naphthalene ring, a fluorene ring, anthracene ring, steel Ben ring, dibenzothiophene ring, carbazole ring, etc. are mentioned. It is preferable that an aromatic ring contains an aromatic carbocyclic ring at least. Moreover, as (meth) acrylic acid ester (B1) which has an aromatic ring and a (meth) acryloyloxy group in a molecule | numerator, the compound which has a conjugated structure comprised from seven or more carbon atoms is preferable. According to such a compound, hardening resin which has a high refractive index by hardening can be obtained.

In said (B1), an aromatic ring and a (meth) acryloyloxy group may be couple | bonded directly, and may couple | bond with the coupling group. As a coupling group, the thing similar to the coupling group in Y <^1> in said Formula (A2-1) is mentioned.

As a typical example of said (B1), For example, (meth) acrylic acid ester of bisphenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol; (Meth) acrylic acid ester of the adduct of ethylene oxide and / or propylene oxide of the said bisphenol; (Meth) acrylic acid in which two phenol skeletons are bonded to the 9 position of the fluorene ring, and a (meth) acryloyloxy group is bonded to the hydroxyl group of the two phenol skeletons directly or through an alkyleneoxy group, respectively. Ester [(meth) acrylic acid ester having bisaryl fluorene skeleton]; (Meth) acrylic acid ester etc. which the (meth) acryloyloxy group couple | bonded with two hydroxyl groups of biphenol directly or through an alkyleneoxy group, respectively, are mentioned.

As a preferable example of the (meth) acrylic acid ester (B1) which has an aromatic ring and a (meth) acryloyloxy group in a molecule | numerator, the compound represented by following formula (B1-1) and (B1-2) is mentioned.

In the above formula, R ⁴ , R ⁵ are the same or different, represent a hydrogen atom or a methyl group, R ⁶ , R ⁷ are the same or different, represent an alkylene group, ring Z ³ , ring Z ⁴ are the same or different, An aromatic carbocyclic ring is represented, r1 and r2 are the same or different, and represent an integer of 0 or 1 or more, s1, s2 are the same or different, and represent an integer of 0 or 1 or more. However, s1 + s2 is 1 or more. In Formula (B1-1), the fluorene ring, ring Z ³ , and ring Z ⁴ may have a substituent.

As an alkylene group in R <^6> , R <^7> , C1-C10 linear or branched alkylene groups, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group, are mentioned, for example. . Preferred alkylene groups include alkylene groups having 2 to 6 carbon atoms (particularly alkylene groups having 2 to 3 carbon atoms) such as ethylene, propylene and trimethylene groups.

Elastically recalled aromatic ring at Z ^3, Z ^4, ring, there may be mentioned an aromatic carbocyclic ring of 1-4 degree, such as benzene ring, naphthalene ring, anthracene ring. Preferred aromatic carbocyclic rings include benzene rings, naphthalene rings and the like.

r1 and r2 are each 0 or an integer of 1 or more, but are preferably 0 or an integer of 1 to 10, more preferably 0 or an integer of 1 to 4. s1 and s2 are each 0 or an integer of 1 or more, but are preferably 1 to 4, more preferably 1 or 2, particularly preferably 1.

Formula (B1-1) in, fluorene ring, ring Z ^3, Z ⁴ is a ring which may have substituents, for example, for alkyl group (such as methyl, ethyl, propyl, isopropyl, C _{1 -6} alkyl group, preferably methyl group); Cycloalkyl groups such as cyclopentyl and cyclohexyl groups (eg, C _5-8 cycloalkyl groups); An aryl group (e.g., C _{6 -15} aryl group) such as phenyl, naphthyl; Aralkyl such as a benzyl group kilgi (e.g., C _{7 -16} aralkyl kilgi); An acyl group such as acetyl, propionyl, benzoyl group (e.g., C _{1 -10} acyl group); An alkoxy group such as methoxy, ethoxy, propyloxy, iso-propyl oxy group (e.g., C _{1 -6} alkoxy group); Alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl group (e.g., C _{1 -4} alkoxy-carbonyl group); Cyano group; Carboxyl groups; A nitro group; An amino group; Substituted amino group (e.g., di-C _{1 -4} alkyl group and the like); Halogen atoms such as a fluorine atom and a chlorine atom, and the like.

As said (B1), you may use monofunctional (meth) acrylates, such as phenyl (meth) acrylate and benzyl (meth) acrylate, in addition to the above.

In (meth) acrylic acid ester which has an alicyclic and a (meth) acryloyloxy group in the said molecule (it does not have an aromatic ring) (B2), as an alicyclic ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclo Monocyclic alicyclic rings such as dodecane ring; Decalin ring (perhydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenylene ring , Norbornane ring (bicyclo [2.2.1] heptane ring), isobonane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [6.2 .1.0 ^2,7 ] polycyclic alicyclic (crosslinked carbocyclic rings) such as undecane ring. As an alicyclic polycyclic alicyclic (crosslinked carbocyclic ring) is preferable. When (meth) acrylic acid ester having a polycyclic alicyclic (crosslinked carbocyclic ring) such as tricyclo [5.2.1.0 ^2,6 ] decane ring is used in the molecule, the heat resistance of the cured resin is improved, and the moisture absorption rate, thermal elastic modulus, The linear expansion coefficient can be reduced. Moreover, melt viscosity and dielectric constant can be reduced, and softening point, mechanical strength, and adhesiveness can be improved.

As a (meth) acrylic acid ester (however, it does not have an aromatic ring) (B2) which has an alicyclic and a (meth) acryloyloxy group in the said molecule, the compound represented by following formula (B2-1) is mentioned, for example. have.

In the above formula, ring Z ⁵ represents an alicyclic ring, Y ² and Y ³ are the same or different and represent a single bond or a linking group. The alicyclic of the said example is mentioned as alicyclic in ring Z <^5> . As ring Z <^5> , polycyclic alicyclic rings, such as a tricyclo [5.2.1.0 ^2,6 ] decane ring, are preferable.

Examples of the linking group for Y ² and Y ³ include a divalent hydrocarbon group, a carbonyl group (-CO-), an ether bond (-O-), an ester bond (-COO-), and an amide bond (-CONH-). , Carbonate bonds (-OCOO-), and groups in which a plurality of these bonds are mentioned. Divalent hydrocarbon group, methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene, tetramethylene group and the like in straight or branched chain alkylene group (e.g., C _{1 -10} alkylene group, preferably a C _{1 -6} alkyl group); 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylidene group, etc. Divalent alicyclic hydrocarbon group (especially bivalent cycloalkylene group); Examples in which a plurality of these are combined are exemplified. As the linking group for Y ² , Y ³ , in particular, a divalent hydrocarbon group (particularly an alkylene group), or one or two or more divalent hydrocarbon groups (particularly an alkylene group) and one or two or more oxygen atoms (-O- Groups to which are bonded are preferred.

Representative examples of the compound represented by formula (B2-1) include 1,4-cyclohexanedioldi (meth) acrylate, 1,4-cyclohexanedimethanoldi (meth) acrylate, and bicyclo [2.2.1]. Heptanedimethanoldi (meth) acrylate, 1,3-adamantanedioldi (meth) acrylate, 1,3-adamantanedimethanoldi (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane dimethanol di (meth) acrylate etc. are mentioned.

As (meth) acrylic acid ester (however, it does not have an aromatic ring) (B2) which has alicyclic and a (meth) acryloyloxy group in a molecule | numerator, cyclohexyl (meth) acrylate and cyclohexanemethanol (meth) acrylate, 1 Adamantanol (meth) acrylate, 1-adamantanemethanol (meth) acrylate, isobonyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanemethanol (meth) acrylate [= dicy Monofunctional (meth) acrylates such as clofentanil (meth) acrylate] and dicyclopentanyloxyethyl (meth) acrylate can also be used.

As (meth) acrylic acid ester (B3) which does not have an aromatic ring and an alicyclic ring in the said molecule, For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl Monofunctional (meth) acrylates such as (meth) acrylate, nonyl (meth) acrylate, and decyl (meth) acrylate; Ethylene glycol di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, neopentyl glycol (Meth) acrylate, polyethylene glycol di (meth) acrylate, tri (meth) acrylate of glycerin ethylene oxide adduct, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Polyfunctional (meth) acrylates, such as (meth) acrylate and dipentaerythritol poly (meth) acrylate, etc. are mentioned.

Although the ratio of the radically polymerizable compound (B) in the curable composition of this invention differs also according to the use of curable resin, etc., it is 0 to 90 weight% with respect to the whole curable composition (or the total amount of curable compound), Preferably it is 10 to 90 weight%, More preferably, it is about 15 to 80 weight%.

[Cation and Radical Polymerizable Compound (C)]

As a cation and a radically polymerizable compound (C), if it is a compound which has a cationically polymerizable group and a radically polymerizable group in a molecule | numerator, there will be no restriction | limiting in particular, Various compounds can be used. These compounds can be used individually or in combination of 2 or more types. When such a cation and radically polymerizable compound (C) is compounded together with a cationically polymerizable compound (A) and a radically polymerizable compound (B) in a curing composition, the cation and radically polymerizable compound (C) Acts as a crosslinking agent between the cationic cured resin and the radical cured resin, and physical properties such as heat resistance and optical properties are often greatly improved.

As the cation and radically polymerizable compound (C), at least one cationically polymerizable group (especially an epoxy group, especially an alicyclic epoxy group) selected from an epoxy group, an oxetane group and a vinyl ether group, and at least one (meth) acryl The compound which has a diary [especially (meth) acryloyloxy group] is preferable. Examples of the alicyclic epoxy group include 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (represented by an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and the following formula (a). Or 9) days.

As a cation and a radically polymerizable compound (C), the compound which has alicyclic epoxy group in a molecule | numerator, especially the 3, 4- epoxy cyclocyclo [5.2.1.0] decane 8- (or 9) yl group represented by said Formula (a)] When used, the heat resistance of the cured resin can be remarkably improved, and the moisture absorption rate, the thermal elastic modulus, and the linear expansion coefficient can be reduced. Moreover, melt viscosity and dielectric constant can be reduced, and softening point, mechanical strength, and adhesiveness can be improved.

In addition, as a cation and a radically polymerizable compound (C), the reason similar to the case of (meth) acrylic acid ester in the said radically polymerizable compound (radical curable compound) (B) (radical polymerization and cationic polymerization as uniformly as possible) From the reason of advancing), a compound having at least one cationically polymerizable group (especially an epoxy group) selected from an epoxy group, an oxetane group and a vinyl ether group and at least one acryloyl group (particularly an acryloyloxy group) in a molecule This is preferred.

Especially as a cation and a radically polymerizable compound (C), the compound (C1) which has an epoxy group and a (meth) acryloyloxy group in a molecule is preferable, and the compound which has an epoxy group and an acryloyloxy group in a molecule is especially preferable. .

As a compound (C1) which has an epoxy group and a (meth) acryloyloxy group in a molecule | numerator, For example, (i) (meth) acrylic acid ester which has an alicyclic epoxy group, (ii) (meth) acrylic acid ester which has glycidyl group, etc. Can be mentioned. The alicyclic epoxy group is not particularly limited as long as it is an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting the alicyclic ring. As an alicyclic ring, For example, monocyclic alicyclic (3-15 membered, preferably 5-6 membered cycloalkane ring etc.), such as a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, and a cyclododecane ring; Decalin ring (perhydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenylene ring , Norbornane ring (bicyclo [2.2.1] heptane ring), isobonane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [6.2 .1.0 ^2,7 ] polycyclic (about 2-4 ring) alicyclic (crosslinked carbocyclic rings), such as an undecane ring, etc. are mentioned. As an alicyclic epoxy group, for example, an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (or 9) Diary etc. are mentioned. Examples of the alicyclic epoxy group include a crosslinked carbocyclic ring and an adjacent 2 constituting the crosslinked carbocyclic ring, such as a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (or 9) yl group represented by the formula (a). It is preferable that it is an alicyclic epoxy group which consists of an epoxy group comprised of two carbon atoms and an oxygen atom.

As a typical example of the compound (C1) which has an epoxy group and a (meth) acryloyloxy group in a molecule | numerator, the compound represented by following formula (C1-1) and (C1-2) is mentioned.

In the above formula, R ¹⁰ represents a hydrogen atom or a methyl group, Y ⁴ represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 1 or 2 or more carbon atoms and 1 or 2 or more oxygen atoms (-O -) a represents a group which combines, ring Z ⁶ represents an alicyclic epoxy group. As a C1-C10 alkylene group, linear or branched alkylene groups, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group, are mentioned, for example.

As Y ⁴ , in particular, a single bond, an alkylene group having 1 to 6 carbon atoms, an alkyleneoxy group having 1 to 6 carbon atoms (an oxygen atom right end), and a plurality of alkyleneoxy groups having 1 to 6 carbon atoms (for example, 2 to 6) It is preferable that it is a polyalkyleneoxy group (terminal oxygen atom right end) couple | bonded with about 20).

The following compounds are mentioned as a more specific example of a compound represented by Formula (C1-1).

In the above formula, R ¹⁰ and Y ⁴ are the same as above.

(Meth) acrylic acid glycidyl etc. are mentioned as a specific example of a compound represented by a formula (C1-2).

The proportion of the cation and radically polymerizable compound (C) in the curable composition of the present invention is, for example, 0 to 70% by weight, preferably 5 to 50, based on the entire curable composition (or the total amount of the curable compound). Wt%, more preferably about 8-40 wt%.

[Combination of cationically polymerizable compound (A), radically polymerizable compound (B), cation and radically polymerizable compound (C)]

In the curable composition of this invention, the combination of a cationically polymerizable compound (A), a radically polymerizable compound (B), and a cation and a radically polymerizable compound (C) can be suitably selected according to the use of cured resin, etc.

When the cured resin is used for optical applications such as lenses, optical properties (light transmittance, refractive index, Abbe's number, etc.) and physical properties [heat resistance (high glass transition point), moisture absorption rate, linear expansion coefficient, curing resistance shrinkage, etc.] In order to improve, the following combinations (i) and (ii) are preferable.

(i) Epoxy compound (A1) which has an aromatic ring and an epoxy group in a molecule | numerator, (meth) acrylic acid ester (B1) which has an aromatic ring and a (meth) acryloyloxy group in a molecule | numerator, an epoxy group and a (meth) acryloyl jade in a molecule | numerator Combination of Compounds (C1) with Timing

(ii) an epoxy compound having an alicyclic ring and an epoxy group (but not having an aromatic ring) in the molecule (A2), and a (meth) acrylic acid ester having an alicyclic ring and a (meth) acryloyloxy group in the molecule (wherein the aromatic ring Combination) (B2) and compound (C1) having an epoxy group and a (meth) acryloyloxy group in the molecule

In the combination of said (i), as an epoxy compound (A1) which has an aromatic ring and an epoxy group in a molecule | numerator, a polyfunctional epoxy compound is preferable, Especially, said formula (A1-1), a formula (A1-2), a formula (A1) The compound represented by -3) [in particular, the compound represented by Formula (A1-3)] is preferable. Moreover, as (meth) acrylic acid ester (B1) which has an aromatic ring and a (meth) acryloyloxy group in a molecule | numerator, polyfunctional (meth) acrylate is preferable, Especially, said formula (B1-1), a formula (B1- The compound represented by 2) [especially the compound represented by Formula (B1-1)] is preferable. Moreover, as a compound (C1) which has an epoxy group and a (meth) acryloyloxy group in a molecule, especially the compound represented by said Formula (C1-1), Formula (C1-2) [especially with Formula (C1-1) Compound to be represented] is preferable.

In the combination of the above (i), in the blending ratio of (A1), (B1) and (C1), (A1) is 10 to 70% by weight relative to the curable composition (or the total amount of the curable compound) (particularly 30 To 50% by weight), (B1) is 10 to 70% by weight (particularly 30 to 50% by weight), and (C1) is 1 to 50% by weight (particularly 10 to 30% by weight). The ratio of the total amount of (A1), (B1) and (C1) to the total amount of the curable compound is, for example, at least 60% by weight, preferably at least 80% by weight, more preferably at least 90% by weight.

According to the curable composition of the combination of said (i), any of an optical characteristic and a physical characteristic are excellent, and the light transmittance (400 nm) of the cured resin obtained is 80% or more (preferably 85% or more), The internal transmittance (400 nm) is, for example, 85% or more (preferably 90% or more), the refractive index (589 nm) is, for example, 1.55 or more (preferably 1.60 or more), and the Abbe number is, for example, 35 or less. (Preferably 30 or less), and it can be a cured resin excellent in optical characteristics having high transparency and resolution. Moreover, water absorption is 2 weight% or less (preferably about 1 weight%), for example, a glass transition point is 100 degreeC or more (preferably 120 degreeC or more), and a linear expansion coefficient is 120 ppm, for example. / K or less (preferably 100 ppm / K or less), the curing shrinkage rate is, for example, 10% or less (preferably 8% or less), and can be a resin having excellent effects in terms of moldability and moisture resistance. . Moreover, even if this cured resin is placed under high temperature conditions (for example, about 260 degreeC), light transmittance, refractive index, and Abbe's number hardly change, and shape does not change, either.

In the combination of said (ii), as an epoxy compound which has an alicyclic and an epoxy group in a molecule | numerator (but it does not have an aromatic ring) (A2), a polyfunctional epoxy compound is preferable, Especially, said formula (A2-1), a formula The compound represented by (A2-2) [in particular, the compound represented by Formula (A2-2)] is preferable. Moreover, as (meth) acrylic acid ester (however, it does not have an aromatic ring) (B2) which has alicyclic and a (meth) acryloyloxy group in a molecule | numerator, polyfunctional (meth) acrylate is preferable, Especially, the said formula ( The compound represented by B2-1) is preferable. Moreover, as a compound (C1) which has an epoxy group and a (meth) acryloyloxy group in a molecule, especially the compound represented by said Formula (C1-1), Formula (C1-2) [especially with Formula (C1-1) Compound to be represented] is preferable.

In the combination of the above (ii), as a compounding ratio of (A2), (B2), and (C1), with respect to curable composition (or total amount of curable compound), (A2) is 10-70 weight% (especially 30 To 50% by weight), (B2) is 10 to 70% by weight (particularly 30 to 50% by weight), and (C1) is 1 to 50% by weight (particularly 10 to 30% by weight). The ratio of the total amount of (A2), (B2) and (C1) to the total amount of the curable compound is, for example, at least 60% by weight, preferably at least 80% by weight, more preferably at least 90% by weight.

According to the curable composition of the combination of said (ii), any of an optical characteristic and a physical characteristic are excellent, and the light transmittance (400 nm) of the cured resin obtained is 80% or more (preferably 85% or more), The internal transmittance (400 nm) is, for example, 85% or more (preferably 90% or more), the refractive index (589 nm) is, for example, 1.45 or more (preferably 1.50 or more), and the Abbe number is, for example, 45 or more. (Preferably 50 or more), and it can be cured resin excellent in the optical characteristic which has high transparency and resolution. Moreover, water absorption is 2 weight% or less (preferably about 1 weight%), for example, a glass transition point is 100 degreeC or more (preferably 120 degreeC or more), and a linear expansion coefficient is 120 ppm, for example. / K or less (preferably 100 ppm / K or less), the curing shrinkage rate is, for example, 10% or less (preferably 8% or less), and can be a resin having excellent effects in terms of moldability and moisture resistance. . Moreover, even if this cured resin is placed under high temperature conditions (for example, about 260 degreeC), the light transmittance, refractive index, and Abbe's number do not change for the most part, and shape does not change, either.

The refractive index of the lens varies depending on the wavelength of light, and a phenomenon (chromatic aberration) occurs in which a shift (smearing or blurring) occurs in the image. In order to reduce the influence of chromatic aberration, a normal lens has a structure that corrects chromatic aberration by combining a high Abbe's lens resin and a low Abbe's lens resin. As for the glass of the lens used for a camera, glass is divided into two according to Abbe's number, and generally, what has an Abbe number of 50 or less is called flint glass and the thing of 50 or more is called crown glass.

In this invention, the lens (low Abbe number lens resin) which consists of hardened | cured material (curable resin) of the curable composition which consists of said combination (i), and the hardened | cured material (curable resin) which consists of a combination of said (ii) By using a combination of lenses (high Abbe's lens resin), a high resolution lens (lens unit) having very small chromatic aberration can be obtained.

[Other Ingredients]

The curable composition of this invention may contain the cationic polymerization initiator, the hardening | curing agent, the hardening accelerator, the radical polymerization initiator, the photosensitizer, and various additives according to the kind etc. of the curable compound to be used.

A cationic polymerization initiator is an initiator (curing catalyst; acid generator) which releases the substance which starts cationic polymerization by heating or light. As a cationic polymerization initiator, a thermal cationic polymerization initiator is preferable. The compounding quantity of a cationic polymerization initiator is 0-15 weight% with respect to the whole cation curable composition, Preferably it is 0.01-10 weight%. By mix | blending in this range, hardened | cured material with favorable heat resistance, transparency, weather resistance, etc. can be obtained.

As said cationic polymerization initiator, For example, an aryldiazonium salt [for example, PP-33, Asahi Den Cargo Co., Ltd. product], an aryl iodonium salt, an arylsulfonium salt [for example, FC-509, 3M Manufacture], UVE1014 [GE manufacture], CP-66, CP-77 [manufactured by Asahi Denka Kogyo Co., Ltd.], SI-60L, SI-80L, SI-100L, SI-110L [Sanshin Chemical Co., Ltd.] KK Co., Ltd.] and an allen-ion complex (for example, CG-24-61 Shivagaigi Co., Ltd. product) are mentioned. In addition, a system of a metal such as aluminum or titanium, a chelate compound of acetoacetic acid ester or diketone, and silanol or phenol is also used. Examples of the chelate compound include aluminum trisacetyl acetonate, aluminum trisacetoacetate and the like. Examples of the silanol or phenols include triphenylsilanol, bisphenol S, and the like.

An acid anhydride can be used as a hardening | curing agent. As an acid anhydride, what is generally used for hardening of an epoxy compound can be used, It is preferable that it is liquid at normal temperature, Specifically, For example, methyltetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, dodecenyl anhydride Succinic acid, methyl endo methylene tetrahydro phthalic anhydride, etc. are mentioned. In addition, solid acid anhydrides such as phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylcyclohexenedicarboxylic acid anhydride, and the like at room temperature within a range that does not adversely affect the impregnation of the curable composition of the present invention. Can be used. When using a solid acid anhydride at normal temperature, it is preferable to melt | dissolve in a liquid acid anhydride at normal temperature, and to use as a liquid mixture at normal temperature. Although the compounding quantity of a hardening | curing agent changes also with the kind and quantity of the cation curable compound in a cation curable composition, it is 0-60 weight% with respect to the whole cation curable composition, for example, Preferably it is about 5-40 weight%.

A hardening accelerator is a compound which has a function which promotes hardening reaction, when an acid anhydride is used as a hardening agent. The curing accelerator is not particularly limited as long as it is generally used. Examples thereof include diazabicyclo undecene-based curing accelerators (1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or salts thereof), Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminemethyl) phenol, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole Organic phosphine compounds such as imidazoles and triphenylphosphine, tertiary amine salts, quaternary ammonium salts, phosphonium salts, metal salts such as tin octylate and zinc octylate. Among these, a diazabicyclo undecene type hardening accelerator is preferable. The compounding quantity of a hardening accelerator is 0-5 weight%, Preferably it is about 0.05-3 weight% with respect to the whole cation curable composition. When there is too little compounding quantity, the hardening promoting effect may become inadequate, and when too large, the color in hardened | cured material may deteriorate.

As a radical polymerization initiator (radical generator), a well-known and common thing can be used as a photo- or thermal radical polymerization initiator. As a typical radical photopolymerization initiator, For example, benzoin benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- [4- (methylthio) Acetophenones such as phenyl] -2-morpholino-propane-1-one and 2-benzyl-2-dimethylamine-1- (4-morpholinophenyl) -butan-1-one; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertarybutylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone and 2,4-isopropyl thioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Xanthones; 1,7-bis (9-acridinyl) heptane etc. are mentioned.

Representative thermal radical polymerization initiators include, for example, organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkylperesters, dialkylperoxides, perketals, ketoneperoxides and alkylhydroperoxides. Etc. can be mentioned. As a specific example of these thermal polymerization initiators, dibenzoyl peroxide, t-butyl perbenzoate, azobisisobutyronitrile, etc. are mentioned, for example.

Commercially available products of the radical polymerization initiator include Irgacure (registered trademark) 184 (1-hydroxycyclohexylphenyl ketone) and Irgacure (registered trademark) 500 (1-hydroxycyclo), which are available from Ciba, for example, as a radical photopolymerization initiator. Hexylphenyl ketone, benzophenone), and other photopolymerization initiators of the Irgacure (registered trademark) type; Darocur (registered trademark) 1173, 1116, 1398, 1174, and 1020 (available from Merck).

Although the compounding quantity of a radical polymerization initiator changes with kinds, amounts, etc. of the radically polymerizable compound in a cation curable composition, it is about 0.1-20 weight% with respect to the whole cation curable composition, for example.

It is preferable to use a photosensitizer in combination with a photoinitiator. As a photosensitizer, a well-known conventional thing can be used as a photosensitizer, For example, N, N- dimethylamine benzoic acid ethyl ester, N, N- dimethylamine benzoic acid isoamyl ester, pentyl-4- dimethylamine benzo Tertiary amines such as ate, triethylamine and triethanolamine; and the like can be given. These photosensitizers can be used 1 type or in combination with 2 or more types. Although content of a photosensitizer is not specifically limited, For example, it is about 0.1 to 5 weight% with respect to the whole cation curable composition.

As an additive which may be added to the cation curable composition of this invention, an organosiloxane compound, a metal oxide particle, a rubber particle, a silicone- or fluorine-type antifoamer, a silane coupling agent, a filler, a plasticizer, a leveling agent, an antistatic agent, A mold release agent, a flame retardant, a coloring agent, antioxidant, a ultraviolet absorber, an ion adsorption body, a pigment, etc. are mentioned. The compounding quantity of these various additives is 5 weight% or less with respect to the whole cation curable composition, for example. Although the cation curable composition of this invention may contain the solvent, when too much, foaming may generate | occur | produce in cured resin, Preferably it is 10 weight% or less with respect to the whole cation curable composition, Especially 1 weight% or less.

The cationically curable composition of the present invention includes, for example, a predetermined amount of a cationically polymerizable compound and the specific organic sulfur compound, a radically polymerizable compound, a cationic polymerization initiator, a curing agent, a curing accelerator, and a radical polymerization initiator added as necessary. And a photosensitizer, various additives, etc. are mix | blended, and it prepares by stirring and mixing, removing a bubble under vacuum as needed. The temperature at the time of stirring and mixing is about 10-60 degreeC, for example. A well-known apparatus, for example, a rotating revolving mixer, a single screw or a multi screw extruder, a planetary mixer, a kneader, a dissolver, etc. can be used for stirring and mixing.

The cationic curable composition of the present invention is particularly suitable for optical applications (optical materials applications), opt device applications, display device applications, electrical / electronic component materials applications, etc., because a cured resin hardly yellowed even at high temperatures is obtained by curing. Can be used.

The hardened | cured material of this invention can be obtained by hardening the said cation curable composition. As a method of hardening, a suitable method can be selected by a well-known hardening method according to the kind etc. of the curable compound in a curable composition. For example, the said cationically curable composition can be put into the metal mold | die according to the shape of hardened | cured material, irradiated and hardened | cured by an active energy ray (for example, ultraviolet-ray), and it can heat, and a desired hardened | cured material can be obtained. Moreover, desired hardened | cured material can also be obtained only by heating. In addition, when using an ultraviolet-ray as an active energy ray, the irradiation amount is about 1000-4000mJ / cm < ² >, for example. Moreover, although heating temperature changes also with kinds of curable compound, it is 80-200 degreeC, Preferably it is about 110-160 degreeC. In addition, after removing a hardened | cured material from a metal mold | die, you may perform postcure (baking).

As mentioned above, since the yellowing is remarkably suppressed also in the high temperature of about 260 degreeC as mentioned above, it is used suitably as an optical member. As the optical member, for example, a lens for imaging of a camera (vehicle mounted camera, digital camera, PC camera, mobile phone camera, surveillance camera, etc.), spectacle lens, filter, diffraction grating, prism, light guide, light Beam condenser lens, light diffusing lens, cover glass for display device, photo sensor, photo switch, LED, light emitting element, optical waveguide, optical splitter, optical fiber adhesive, substrate for display element, substrate for color filter, substrate for touch panel, And a display protective film, a display backlight, a light guide plate, an antireflection film, and the like.

Example

EMBODIMENT OF THE INVENTION Below, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples.

Example 1

Epoxy compound [2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane addition product, It is contained in the compound represented by said formula (A2-2). Become; 30 weight part of Daicel Chemical Co., Ltd. make, brand name "EHPE3150", and the compound represented by (meth) acrylic acid ester [tricyclo [5.2.1.0 ^2,6 ] decane dimethanol diacrylate and the said Formula (B2-1) Included in; (Meth) acrylic acid ester [epoxylated dicyclopentenyl acrylate (= 3,4-epoxytricyclo [5.2.1.0 ^2, ]) which has 50 weight part of Daicel Cytec company make, brand name "IRR214K", and an epoxy group ⁶ ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate, which are included in the compound represented by formula (C1-1) above; 20 parts by weight of a high school company, trade name "E-DCPA"], 1 part by weight of an acid generator (arylsulfonium salt-based acid generator; acid Aprosa, trade name "CPI-100P"), and a radical generator (aceto 1 weight part of phenone radical generators, the Ciba-Geigy company make, brand name "Igacure 184", and a decanthiol (organic sulfur compound; C ₁₀ H ₂₁ SH) in 1 weight part, and it is a rotating revolution type. The uniform and transparent curable composition (optical material composition liquid) was obtained by stirring and mixing with a mixer. By applying a release agent to the mold made of a glass-made flask of which the deposition thickness of 0.5mm.

Subsequently, ultraviolet rays (irradiation amount; 2,600 mJ / cm ² ) were irradiated to the cast optical material composition solution to produce a cured resin, and the produced cured product was heated at 160 ° C. for 1 hour in an air atmosphere, and the thickness was 0.5 mm. A plate-like transparent and uniform cured resin was obtained. This cured resin could be easily released from the mold of glass. The obtained cured resin was used for evaluation mentioned later.

Example 2

A cured resin was obtained in the same manner as in Example 1 except that 1,10-decanedithiol (HS-C ₁₀ H ₂₁ -SH) was used instead of decanthiol.

Example 3

A cured resin was obtained in the same manner as in Example 1 except that didecyl sulfide (n-decyl sulfide; C ₁₀ H ₂₁ -SC ₁₀ H ₂₁ ) was used instead of decanthiol.

Example 4

A cured resin was obtained in the same manner as in Example 1 except that didecylzisulfide [(C ₁₀ H ₂₁ -S-) ₂ ] was used instead of decanthiol.

Comparative Example 1

Cured resin was obtained like Example 1 except not mix | blending an organic sulfur compound.

Comparative Example 2

1 weight part of a hindered phenolic antioxidant (Ciba Specialty Chemicals make, brand name "Irg1010") instead of compounding an organic sulfur compound, and phosphorus antioxidant (made by Sanko Corporation, brand name "HCA") instead of 1 A weight part was mix | blended and it carried out similarly to Example 1, and obtained cured resin.

The viscosity measurement of the curable composition obtained by the Example and the comparative example, the general characteristic of the cured resin obtained by the Example, and the comparative example, and the heat test (evaluation of yellowing resistance under reflow conditions) were performed on the following methods and conditions. The results are shown in Table 1. In addition, in Table 1, "-" in the comparative example 2 shows that it is unevaluated.

(1) Viscosity

The viscosity of the curable composition measured the viscosity in 25 degreeC of rotational speed (D) = 20 / s using the R / S rheometer (The Physica company make, brand name "PHYSICA UDS200 / Paar").

(2) the shape of the resin surface

The presence or absence of the stria of the resin surface of cured resin was visually investigated. In addition, a stria means an optically heterogeneous state and points out the wrinkles and the shaking observed from the cured resin surface.

(3) internal transmittance

The internal transmittance of cured resin was computed by the following formula | equation.

Internal transmittance (400 nm) = light transmittance at 400 nm / (1-r) ²

r = {(n-1) / (n + 1)} ²

n is the refractive index at 400 nm. The light transmittance at 400 nm was measured using a spectrophotometer (manufactured by Hitachi High Technologies, trade name "U-3900"), and the refractive index used the value of the refractive index at 400 nm measured by the following method (4). .

(4) refractive index

The refractive index of cured resin measured the refractive index of 589 nm in 25 degreeC using the refractometer (the product made from Metricon, brand name "Model 2010") by the method based on JISK7142.

(5) linear expansion coefficient

The coefficient of linear expansion of the cured resin was measured using a TMA measuring device (manufactured by SII Nanotechnology Co., Ltd., product name "TMA / SS100") at a temperature increase rate of 5 ° C / min and a measurement temperature range of 30 ° C to 250 ° C. The gradient of the straight line on the low temperature side was shown as the linear expansion coefficient.

(6) modulus of elasticity

The elastic modulus of cured resin measures a dynamic viscoelasticity characteristic at a temperature increase rate of 5 ° C / min and a measurement temperature range of -30 ° C to 270 ° C using a solid viscoelasticity measuring device (manufactured by T.A. Instruments, trade name "RSAIII"). The elasticity modulus in 25 degreeC was read.

(7) glass transition temperature

As for the glass transition temperature of cured resin, it heats from -50 degreeC to 250 degreeC by preprocessing (heating rate 20 degree-C / min, using differential scanning calorimetry apparatus (The product made by T.A. Instruments, brand name "Q2000"), And a cooling rate of 20 deg. C / min, cooling from 250 deg. C to -50 deg. C), and then measured at a heating rate of 20 deg. C / min and a measurement temperature range of -50 deg.

(8) water absorption

The water absorption of cured resin was measured by the method based on JISK7209.

(9) Heat resistance test (evaluation of yellowing resistance under reflow conditions)

After three successive heat tests in which the cured resin was previously heated to 270 ° C. for 1 minute in an air atmosphere, the transmittance at 400 nm and the refractive index at 400 nm of the cured resin provided for the heat test were measured, and then The transmittance was calculated.

The yellowing resistance under reflow conditions was evaluated by making the yellowing rate the reduction rate of the internal transmittance computed by the following formula | equation.

In addition, a yellowing rate of 3% or less has high transparency even after a heat test, and can be used suitably as optical materials, such as a lens.

% Reduction of internal transmittance = (internal transmittance before heat test-internal transmittance after heat test) / (internal transmittance before heat test)

In comparison with Examples 1-4 and Comparative Example 1, the heat resistance test by organic sulfur compounds, such as a thiol compound and a sulfide compound, specifically, the yellowing inhibitory effect under reflow conditions is recognized. In addition, it is recognized from the comparison with Comparative Example 2 that organic sulfur compounds such as thiol compounds and sulfide compounds have a higher yellowing inhibitory effect under heat resistance tests than conventional antioxidants. Therefore, the cured resin obtained from the curable resin composition which mix | blended organic sulfur compounds, such as a thiol compound and a sulfide compound, has high transparency even after a heat test, and is suitable for various uses, such as an optical use, such as a lens unit, an opt device use, etc. suitably. Can be used.

According to the curable composition of this invention, since hardening resin which is excellent in yellowing resistance which is hard to yellow even under high temperature can be obtained by hardening, it is especially suitable for various uses, such as the use of optical members, such as a lens, and an opt device. .

Claims (8)

A curable composition comprising a cationically polymerizable compound and at least one organic sulfur compound selected from a thiol compound, a dithiol compound, a sulfide compound, and a disulfide compound. The curable composition of Claim 1 whose boiling point of an organic sulfur compound is 100 degreeC or more. The curable composition according to claim 1 or 2, wherein the cationic polymerizable compound is at least one compound selected from an epoxy compound, an oxetane compound, and a vinyl ether compound. The curable composition according to any one of claims 1 to 3, further comprising a radically polymerizable compound. The curable composition of Claim 4 whose radically polymerizable compound is a (meth) acrylic acid ester compound. The curable composition according to any one of claims 1 to 5, further comprising a compound having a cationic polymerizable group and a radical polymerizable group in the molecule. Cured resin obtained by hardening | curing the curable composition of any one of Claims 1-6. The optical member which consists of cured resin of Claim 7.