TW201041846A - (Metha)acrylate resin, method of manufacturing the same, cured resin composition, cured article thereof, and plastic lens - Google Patents

Abstract

Provided is (metha)acrylate resin, which has high refractive index of cured article and has excellent heat resistance and wet resistance in cured article as an organic optical material, cured resin composition, cured article thereof, and plastic lens. A (metha)acrylate resin is cured by heating or irradiating active energy ray, characterized in that has binaphthalene skeleton in molecular structure and has a substituent represented by the formula (A) as a substituent on aromatic proton of the said binaphthalene skeleton. (wherein R1 is linear or branching alkenyl having 2 to 5 carbon atoms, R2 is hydrogen or methyl, 1 is repeating unit of 1 to 10 integer)

Description

201041846 VI. Description of the Invention: [Technical Field] The present invention relates to a method for forming a low viscosity and hardening by active energy rays and heating, and additionally having a high refractive index after hardening, and having high heat resistance And high-moisture-resistant hardened materials, and suitable for optical protective coatings, hard coating agents, anti-reflective films, spectacle lenses, optical fibers, optical waveguides, holograms, etc., optical components, other 稜鏡 lenses, Fresnel lenses A (meth) acrylate resin of a plastic lens such as a lenticular lens, a method for producing the same, a curable resin bismuth composition, and a cured product thereof. [Prior Art] Optical components such as optical protective coating agents, hard coating agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, and holograms are widely used in recent years because of their excellent processing and productivity. A resin material is used, and a resin material having a high refractive index is being sought from the viewpoint of downsizing and thinning of the optical component or adjusting the antireflection property. Conventionally, an acryl resin having an anthracene skeleton has been known as an optical material having a high refractive index as required. For example, a 2-functional type in which an acryl fluorenyl group is bonded to an alkoxy group by a stretching alkoxy group is known. The compound (refer to Patent Document 1, Patent Document 2, and Patent Document 3 below) or a compound obtained by reacting a condensed glycidyl ether containing a thin skeleton with acrylic acid or methacrylic acid (see Patent Document 4 below). However, in the case where the acrylate resin having the above-described fluorene skeleton is used alone as a polymerizable component, although the refractive index of the cured product becomes high, since the acrylate resin itself is solid, or at normal temperature, 201041846 A high-viscosity liquid of 3 00 0 Pa · S or more, so a large amount of a diluent having a low refractive index must be used, and thus the refractive index of the obtained cured product eventually becomes low. Further, the cured product of the acrylate resin having an anthracene skeleton is inferior in heat resistance and high moisture resistance, and the long-term reliability of the optical material is also inferior. Further, as the optical material having a high refractive index, a polyester resin having a binaphthol skeleton is known (see Patent Document 5 below). However, the polyester resin having such a binaphthol skeleton has a weight average molecular weight (Mw) of up to 1 Å, 〇〇〇1 〇〇, 〇〇〇, and is a solid thermoplastic resin at normal temperature, so It is suitable for use in active energy rays or thermosetting resins. Furthermore, in addition to poor solvent resistance, heat resistance and high moisture resistance, the long-term reliability of optical materials is also low. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] OBJECT OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION Therefore, the object of the present invention is to provide a cured product of an organic optical material having a high refractive index and excellent heat resistance and moisture resistance of a cured product. A (meth) acrylate resin, a curable resin composition, and a cured product having such properties. 201041846 In order to solve the above problems, the present inventors have found that a tetralina skeleton is contained in a molecular structure and an alkylene oxide having a (meth) propylene oxime group is introduced at the end. The compound which is a substituent on the aromatic nucleus of the binaphthyl skeleton has a low viscosity and a high refractive index of the cured product, and has excellent heat resistance and moisture resistance, and has completed the present invention. That is, the present invention relates to a (meth) acrylate resin having a tetralina skeleton in a molecular structure and having a substituent represented by the following structural formula (A) as the hydrazine a substituent on the aromatic nucleus of the naphthalene skeleton. Ο -^-〇-R1V-〇-C—C=CH2 Structural Formula (A) R2 (wherein R1 is a linear or branched alkyl group having 2 to 5 carbon atoms, R2 is a hydrogen atom or A methyl group, a 1 type repeating unit and an integer of 1 to 1 ). The invention further relates to a process for preparing a (meth) acrylate resin, which is characterized in that a binaphthols are reacted with an alkylene carbonate, and then The (meth) acrylated agent is reacted with the obtained reaction product. The present invention further relates to a curable resin composition characterized by the above (meth) acrylate resin (A) and a radical polymerization initiator ( B) as an essential component. The present invention further relates to a cured product obtained by curing an active energy ray or heating to cure the curable resin composition. The present invention further relates to a plastic lens which is hardened as described above. According to the present invention, it is possible to provide a cured product of an organic optical material having a high refractive index and excellent heat resistance and moisture resistance of the cured product (A) Acrylate A grease, a curable resin composition, and a cured product having such properties. Therefore, the (meth) acrylate resin of the present invention can be widely used for an optical protective coating agent, a hard coating agent, an antireflection film, and a spectacle lens.光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学 光学The resin of the group, specifically, has a binaphthyl skeleton in a molecular structure, and has a substituent represented by the following structural formula (A) as a substituent on the aromatic nucleus of the binaphthyl skeleton. Q -f〇-R1)-0-C—C=CH2 Structural Formula (A) 1 R2 (wherein Ri is a linear or branched alkyl group having 2 to 5 carbon atoms, and R 2 is a hydrogen atom. Or a methyl group, a 1 type repeating unit and an integer of 1 to 1 )) The (meth) acrylate resin has a heat-bonding property and a moisture-resistant property, and has an excellent heat resistance and moisture resistance, and can be used as an organic material. a material having a very high refractive index of 1.60 or more In addition, as a substituent on the biphinyl skeleton, an alkoxy group or a polyoxyalkylene group having an acryloxy group or a methacryloxy group at the terminal, a reactive functional group (201041846 methyl group) The degree of freedom of the propylene oxime group is high, and the heat resistance and moisture resistance of the cured product excellent in reactivity are also high. Here, the binaphthyl skeleton may be a 1,1-binaphthyl skeleton or a 1,2-linkage. From the viewpoint of so-called low viscosity and high refractive index, a dinaphthyl skeleton, a 2,2-dibinaphthyl skeleton, etc. are preferably a 1,1-dibina skeleton. The substituent represented by the following structural formula (A) of the substituent on the core is obtained by curing the (meth) acrylate resin of the present invention by irradiation with an active energy ray or heating. The structural part of the reactive base function. 〇-(-〇-R1-^-〇-C-C=CH2 Structural Formula (A) R2 (wherein R1 is a linear or branched alkyl group having 2 to 5 carbon atoms, R2 is hydrogen An atom or a methyl group, a repeating unit of 1 type and an integer of 1 to 10) The structural moiety is bonded to the biphenylnaphthalene structure by a (meth)acryloyloxy group through a monoalkoxy group or a polyoxyalkylene group. Therefore, the degree of freedom of the (meth)acryloxy group as a reactive functional group is increased, and the reactivity is excellent, and the heat resistance and moisture resistance of the cured product are increased. Specifically, the above-described structure herein The R1 in the formula (A) may, for example, be an ethyl group, an exopropyl group, an exoisopropyl group, a butyl group, a 4-methyl-exetylene group, a pernylpentyl group or the like. The point at which the refractive index of the (meth) acrylate resin itself becomes high is preferably an alkyl group selected from the group consisting of an exoethyl group, an exopropyl group and an exo isopropyl group. The substituent represented by (A) is a perylene group constituting the resin in the (meth) acrylate resin per 1 mole, and is contained in an average of 1.5 to 4.0, 201041846. In some cases, it is preferable that the heat resistance and the moisture resistance are high. In particular, the refractive index of the (meth) acrylate resin itself is increased, and the above structural formula is contained in a ratio of 1.5 to 1.98. The substituent represented by (A) is preferred. When the integer " of 1 to 10 in the above structural formula (A) exceeds 10, the refractive index of the (meth) acrylate resin itself becomes low, The refractive index of the cured product of the object of the present invention cannot reach a sufficient level. In the present invention, the average value of '1' is higher than the range of 1.0 to 3.0 based on the point at which the refractive index of the (meth) acrylate resin itself becomes high. In particular, it is preferably in the range of l.〇~l.5, especially preferably substantially 1. Such a (meth) acrylate resin has the use of 1, bis-naphthol as a starting material, and a ring. Oxidation of the phenolic hydroxyl group in the bis-naphthol, followed by the molecular structure obtained by the (meth) propylene oximation of the hydroxyl group formed by the alkylation of the alkylene group, based on heat resistance and moisture resistance It is preferable in terms of a hardened material having excellent properties and a high refractive index. Such an i, 1-linked The (meth) acrylate resin in which naphthol is a starting material, for example, has a molecular structure represented by the following general formula (1) ^. X3 X2

General formula (1) 201041846 (In the formula, χι~χι 2 is an independent hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 1 carbon atom, or an alkoxy group having 1 to 10 carbon atoms, Α1, Α2 a linear or branched alkyl group having 2 to 5 carbon atoms, a γ, Υ 2 hydroxy group, a propylene oxy group, or a methacryloxy group, η and m repeating units, respectively, and 1 to 1 An integer of 〇. However, at least one of γι and Y2 is an acryloxy group or a methacryloxy group. Here, in the general formula (1), the structural positions represented by Α1 and Α2 correspond to the above structural formula. Specific examples of the Ri in (Α) include an ethyl group, a fluorenyl group, an isopropyl group, a butyl group, a 4-methyl-exetylene group, and a pentyl group. Among these, in particular, based on the point that the refractive index of the (meth) acrylate resin itself becomes high, it is preferably from the group consisting of an exoethyl group, an exopropyl group, and an exo isopropyl group. Selected alkylene. Further, in the general formula (1), m or η represents a repeating unit corresponding to 1 in the above structural formula (Α). In addition, examples of the halogen atom constituting Χ^Χ12 in the general formula (1) include a chlorine atom and an iodine atom, and a hydrocarbon group having a carbon number of 1 to 1 除了 in addition to a methyl group, an ethyl group, a propyl group, and a third group. In addition to the alkyl group such as a butyl group, a cyclohexyl group, a octyl group, a linear or a branched fluorenyl group, an aralkyl group formed by reacting a benzylating agent with the above-described biphthyl skeleton may also be used. base. Further, examples of the alkoxy group having 1 to 1 ring carbon atoms include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, and a decyloxy group. Here, in the case of using a halogen atom constituting χι~χι2, although the refractive index of the acrylic resin itself is increased, it is difficult to apply to applications requiring non-halogenation. On the other hand, in the case of using a hydrocarbon group having 1 to 1 ring of carbon atoms or an alkoxy group having 1 to 10 carbon atoms, the viscosity of the acrylic resin can be further reduced. -10-201041846 Among the (meth) acrylate resins represented by the above general formula (1), it is based on the points of high heat resistance, high moisture resistance, and high refractive index which are effects of the present invention. Particularly preferred are those having the following molecular structure. 〇

〇-CH2CH2)n γΐ 〇-CH2CH2-|___y2 〇-CH2CH2CH2|_y1 〇-〇Η2〇Η2〇Η2)__ν2 (1) (3)

Ch3 o-ch2ch4^—y1 ch3 o-ch2ch^—Y2 (5)

O-CHzCHaCHzCHz^—Yi 0-CH2CH2CH2CH2)-_y2 ch3 o-ch2ch2ch^-y1 ch3 o-ch2ch2ch-)^-y2 CH3 o-ch2ch2ch2ch4^-y1 CH3 (6) o—ch2ch2ch2ch-)—Y2 m (2) (4)

G

(8) (10) -11- (12) 201041846

Ο

(13) (15) (17)

(14) (16) (18)

(20)

Here, in the structural formulas represented by the above formulas (1) to (21), in the same manner as in the general formula (1), Υ1 and Υ2 represent a hydroxyl group, an acryloxy group, or a methacryloxy group, η and m is a repeating unit and is an integer from 1 to 10. However, at least one of Υ1 and Υ2 -12- 201041846 is an acryloxy group or a methacryloxy group. In the acrylic resin represented by the above general formula (1), in the formula, XhX12 has a halogen atom, and although the refractive index of the acrylic resin itself can be further increased as described above, it is applied to applications requiring non-halogenation. It has become difficult. Further, x^x12 is a linear alkyl group or an alkoxy group, and although the viscosity of the acrylic resin having a high degree of freedom in the structure itself is low, it is effective, but in the general formula (1), χι~ When χΐ2 is all hydrogen atoms, the refractive index is lower than the comparison. For this reason, x^x12 in the above general formula (1) is independent of hydrogen atoms or carbon atoms 1 to 3 in terms of both the refractive index and the viscosity of the two properties, the ease of synthesis, and the cost. The alkyl group is preferred, and particularly all of them are hydrogen atoms. Therefore, in the acrylic resin represented by the above general formula (1), it is preferred that the oxime 1, Α2 is an alkyl group selected from the group consisting of an exoethyl group, a propyl group and an exo isopropyl group, and all of χι~χΐ2 are selected. It is a (meth) acrylate resin of a hydrogen atom. Further, γι and Υ2 in the above general formula (1) are as described above, and represent a functional group selected from a trans group, an acryloxy group, and a methacryloxy group, and one of Ογι and Υ2. 'or both of them are acryloxy or methacryloxyl'. In the context of the present invention, propylene is exemplified by decyloxy and methacrylic decyloxy, especially from (meth) acrylate resin. The point at which the refractive index itself becomes high is preferably propylene oxy group. Further, the (meth) acrylate resin represented by the above general formula (1) can be used as a mixture of various compounds satisfying the general formula (1). In this case, the radicals constituting Υ1 and Υ2 in the above general formula (1) which are occupied by the (meth) acrylate resin (hereinafter, 'slightly referred to as "hydroxyl (y"), and acrylic acid-13-201041846 oxygen The ratio of the group or the methacryloxy group (hereinafter, abbreviated as "(meth) acrylonitrile group (y2)") can be arbitrarily adjusted. In the present invention, the hydroxyl group (yi) and the (meth) group The ratio of acrylonitrile (y2) is preferably in the range of 75/25 to 1/99 in terms of molar ratio (yl/y2). That is, the amount of (meth)acryl fluorenyl (y2) is In the case where the ear ratio (yl/y2) is more than 75/25, in addition to the active energy ray or the hardenability by heating, the (meth) acrylate resin at room temperature is formed and the viscosity is also On the other hand, in the case where the amount of (meth) acrylonitrile (y2) is less than 1/99 in terms of molar ratio (yl/y2), it is moderately suppressed (methyl). The crystallinity of the acrylate resin itself can reduce the viscosity at normal temperature. As described above, the structural parts represented by A1 and A2 in the above general formula (1) are extended to the ethyl group and the extension. a linear or branched alkyl group having 2 to 5 carbon atoms, such as n-propyl, isopropyl, butyl, 4-methyl-exetylene, and pentyl, but optionally in the present invention It is possible to adjust the ratio of the existence of these, for example, the ratio of the ethylidene group (hereinafter, abbreviated as "extended ethyl group") which is occupied by the (meth) acrylate resin is higher. The (meth) acrylate resin itself has a high refractive index, and another structure, that is, an alkyl group having 3 to 5 carbon atoms (hereinafter, abbreviated as "carbon number 3 to 5" The alkylene group (a2)" is present in an appropriate amount, and the crystallization of the (meth) acrylate resin can be suppressed, and the viscosity can be reduced. Therefore, in the present invention, the ethyl group (al) and the carbon atom are 3 When the molar ratio (al/a2) of the alkylene group (a2) of ~5 is in the range of 50/50 to 98/2, the (meth) acrylate resin is liquid at normal temperature and the viscosity is also low. The point 'further from the point that the refractive index of the (meth) acrylate resin itself becomes higher. -14- 201041846 The alkylene group (a2) having 3 to 5 carbon atoms is preferably an extended propyl group or an extended isopropyl group (hereinafter, abbreviated as "C3 alkyl group"), and the above-mentioned ethyl group (al) The molar ratio (extended ethyl (al)/C3 alkyl group) to the C3 alkyl group is preferably in the range of 50/50 to 98/2. Further, m and η in the above general formula (1) represent repeats. The integer of 1 to 10 of the unit is preferably in the range of 1.0 to 3.0, particularly 1.0 to 1.5, based on the fact that the refractive index of the (meth) acrylate resin itself is high. In particular, it is preferably substantially 1. The (meth) acrylate resin described above has a viscosity at 300 ° C of 300 ° Pa·s or less, and is excellent in fluidity and is suitable for various applications. Further, it is preferable to reduce the amount of the diluent used as the low refractive index substance used in the viscosity adjustment. In particular, from the viewpoint that the effect becomes remarkable, it is preferably in the range of 1000 to 100 Pa·s. The (meth) acrylate resin is a material having a high refractive index as described above, specifically, a refractive index of 1.55 or more. By selecting a molecular structure, a material having a refractive index of 1.60 or more can be formed. The method for producing a (meth) acrylate resin as described above, wherein a binaphthol, an alkylene oxide, a halogenated alkanol or a alkylene carbonate is reacted to obtain a compound having a hydroxyl group, and then, The (meth) acrylated agent is reacted with a reaction product having the obtained hydroxyl group to obtain a desired (meth) acrylate resin. In the case of the binaphthol which is obtained by the above formula (2), the binaphthyl structure which is obtained by the above formula (1) is exemplified. -15- 201041846 X3 X2

In the formula (2), in the formula, χΐ~χΐ2 means an independent hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 1 ring of carbon atoms, or an alkoxy group having 碳10 to 10 carbon atoms. In particular, based on the combination of the refractive index and the viscosity, the ease of synthesis, and the cost, the Χ^Χ12 in the above general formula (1) preferably has independent hydrogen atoms or carbon atoms of 1~. The alkyl group of 3 is particularly preferably a hydrogen atom. Therefore, the acrylic resin represented by the above general formula (1) is preferably an alkyl group selected from the group consisting of an exoethyl group, an exo-propyl group and an exo-isopropyl group, and all of the groups are selected from the group consisting of an exoethyl group, an exo-propyl group and an exo-isopropyl group. A (meth) acrylate resin of a hydrogen atom. In the step of reacting the above-mentioned binaphthols, an alkylene oxide, a halogenated alkanol or an alkylene carbonate, for example, a method of reacting with a binaphthol and an alkylene oxide is exemplified by a basic catalyst. In the presence of the present invention, an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide is subjected to a polymerization reaction at a temperature of 100 to 200 ° C. Next, as a method of reacting a binaphthol with a halogenated alkanol, 2-chloroethanol and 3-chloro are used in the presence of a basic catalyst at a temperature of 100 to 200 ° C. A method of reacting a halogenated alkanol such as benzyl-2-propanol or 2-(2-chloroethoxy)ethanol with a binaphthol. -16- 201041846 Next, a method for reacting a binaphthol with a alkylene carbonate is specifically a temperature of 80 to 200 ° C in the presence of a basic catalyst or an acid catalyst. A method of reacting binaphthols with alkylene carbonate. In the above respective methods, a method of reacting a binaphthol with an alkylene oxide, the adjustment of the repeating unit 1 in the above structural formula (A) is difficult, and in addition, the binaphthol and the halogenated alkanol are reacted. This method causes problems such as corrosion of the reaction vessel due to generation of an acidic substance such as hydrochloric acid. On the other hand, the method of reacting the binaphthols with the alkylene carbonate is easy to adjust the above-mentioned repeating unit 1, and also does not cause the formation of corrosive substances, which is advantageous in industrial scale production. It is better. Hereinafter, the method of reacting the binaphthols with alkylene oxide will be described in detail. The alkylene carbonate used in the method of reacting the binaphthols with the alkylene carbonate may be an alkylene group having a carbon number, and examples thereof include ethyl carbonate and propyl carbonate. , butyl carbonate, amyl carbonate, etc., but as described above, based on the point that the (meth) acrylate resin has a high refractive index and the resin viscosity is low, as the general formula (1) A 1 and The A2^ is preferably an ethyl group, a propyl group or an isopropyl group. Therefore, the alkylene carbonate is preferably an ethyl carbonate or a propyl carbonate. Here, in order to adjust the molar ratio (C2 alkyl/C3 alkyl group) of the C2 alkyl group and the C3 alkyl group in the (meth) acrylate resin to the range of 50/50 to 98/2, it is preferred to make The ratio of ethyl carbonate to propylene carbonate (mole ratio) is the ratio of 50/50 to 98/2 in the former and the latter is not particularly limited. The more the equivalent ratio of the alkylene carbonate to the hydroxyl group in the binaphthols is increased, the first one of the structural formula (A) in the above -17-201041846, that is, the general formula (1) in the preferred embodiment. The m and η in the middle become larger. As described above, after 1 in the above structural formula (A), the enthalpy of m and η in the above general formula (1) is an integer of 1 to 1 ,, and in order to adjust the range, it is relative to the binaphthol. The hydroxyl group in the class is preferably 1 equivalent of the alkylene carbonate in the range of 1 to 1 〇 equivalent. Further, the enthalpy of 1 in the above structural formula (Α), and m in the above general formula (1) It is based on the point that the refractive index of the (meth) acrylate resin itself becomes high, and the average is 1. 〇 to 3.0, especially 1.0 to 1.5, and it is preferably 1 in the substantial 〇, in order to adjust The range is preferably in the range of 1 to 5 equivalents, particularly 1 to 3 equivalents, per equivalent of the hydroxyl group of the binaphthols. As the alkylene carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, amyl carbonate or the like can be used. The catalyst in the reaction of the above method 3) may be either a basic catalyst or an acid catalyst, and is preferably an alkaline catalyst based on the point that the reaction proceeds rapidly and the impurities are less. The basic catalyst may, for example, be potassium hydroxide, sodium hydrogen hydride, cesium hydroxide, magnesium oxide, sodium carbonate or potassium carbonate. Among them, potassium hydroxide or sodium hydroxide is preferred. The case of using an acid catalyst is not particularly limited, and examples thereof include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like, and among them, p-toluenesulfonic acid is preferred. The catalyst is used in a proportion of 0.001 to 0.1 equivalent of the catalyst based on 1 equivalent of the hydroxyl group of the polynaphthol. The above reaction can be carried out even in the absence of a solvent, and in the case of use, it is preferable to use, for example, toluene or xylene, in addition to the organic solvent other than the alcohol solvent which hinders the reaction. Further, the reaction temperature is preferably in the range of 80 to 200 -18 to 201041846 °c as described above, and is preferably in the range of 100 to 180 °C in order to allow the reaction to proceed well and the amount of impurities to be small. Then, the hydroxyl group-containing compound thus obtained is specifically obtained by reacting the following general formula (3) with a (meth) acrylate forming agent to obtain a desired (meth) acrylate resin.

General formula (3) (In the formula, Χΐ-Χ1 2 is an independent hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an A1, A2 carbon atom. a linear or branched alkyl group of 2 to 5, η and m repeating units and an integer of 1 to 1 。. However, at least one of Y1 and Y2 is an acryloyloxy group or a methyl group. Propylene oxime). Examples of the (meth)acrylic acid esterifying agent herein include (meth)acrylic acid such as acrylic acid and methacrylic acid; (meth)acrylic acid halide such as acrylonitrile chloride or methacrylium chloride; methyl acrylate; An alkyl (meth)acrylate such as methyl methacrylate, ethyl acrylate or ethyl methacrylate. Among these, there is a problem that the reaction vessel is corroded by the generation of an acidic substance such as hydrochloric acid during the reaction, and in the case of using an alkyl (meth)acrylate, it is necessary to remove the alcohol produced by the secondary generation. The alcohol (meth)acrylic acid halide is preferably (meth)acrylic acid. -19- 201041846 The reaction of the above-mentioned hydroxyl group-containing compound with (meth)acrylic acid is exemplified by, for example, in an organic solvent such as toluene, benzene, cyclohexyl, Zhengjiyuan, and Zhenggeng, and under an acid catalyst. It is carried out by carrying out a dehydration reaction. Examples of the acid catalyst used herein include sulfuric acid, p-toluene acid expansion, and methanesulfonic acid. Further, in the reaction, it is preferred to use a polymerization inhibitor (for example, hydroquinone, p-methoxyphenol, methylhydroquinone or the like) for preventing polymerization. Further, the reaction of the above hydroxyl group-containing compound with (meth)acrylic acid The ratio is preferably 1 equivalent to the hydroxyl group of the hydroxyl group-containing compound, so that the (meth)propionate is in a ratio of 〇75 to 0.99 equivalent. Further, the reaction temperature is preferably from 6 Ο to 120 ° C, and the reaction time is preferably from 3 to 20 hours. The curable resin composition of the present invention is a (meth) acrylate resin (hereinafter, this (meth) acrylate resin is abbreviated as "(meth) acrylate resin (A)"), A radical polymerization initiator is used as an essential component.

The radical polymerization initiator (B) used herein may, for example, be a photopolymerization initiator or a thermal polymerization initiator. As a photopolymerization initiator, specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, 2-methylbenzoin, diphenyl Ketone, rice ketone, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, benzamidine benzoic acid, 4-benzylidene-4'-methyldiphenyl sulphide Ether, 3,3,-dimethyl-4-ylmethoxydiphenyl ketone, 1-(4-deca-phenylphenyl-2-hydroxy-2-methylpropanone, hydroxycyclohexylbenzene Ketone, 2-hydroxy-2-methylphenylpropanone, 2-methyl-[4-(methylthiophenyl)]-2- morpholino)propane-; 1, 2-chloro Oxime, 2,4-diethyloxysulfonium, 2,4-diisopropyloxysulfonium, 2,4,6_3-20- 201041846 methylbenzene diphenyl Phosphine and the like. These photopolymerization initiators can be used individually, and can also be used as a mixture of 2 or more types. The amount of the photopolymerization initiator is preferably from 0.01 to 30 parts by weight, based on 1 part by weight of the (meth) acrylate resin (A), and particularly preferably 20 parts by weight. the following. When the blending range is below this range, the polymerization rate becomes slow and becomes insufficiently hardened. Conversely, above this range, a decrease in refractive index is caused. Further, among these photopolymerization initiators, a photopolymerization accelerator such as an amine can be used. For example, 2-dimethylaminoethyl benzoate, dimethylamino acetophenone, p-dimethylamino benzoic acid ethyl, p-dimethylamino benzoic acid isoamyl Wait. When the ratio of use of the photopolymerization accelerator is in the range of 0.1 to 100 parts by weight based on 100 parts by weight of the photopolymerization initiator, it is preferred that the polymerization rate is high and the refractive index of the cured product becomes high. Next, as the thermal polymerization initiator, a well-known peroxide initiator and an azobis initiator can be used. Specific examples of the peroxide oxime initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexane ketone peroxide, and peroxidation. a ketone peroxide initiator such as acetoacetone; isobutyl peroxide, m-chlorobenzhydryl peroxide, 2,4-dichlorobenzhydryl peroxide, α-甲Dimercapto peroxide initiator such as benzylidene peroxide, bis-3,5,5-trimethylhexyl peroxide; 2,4,4-trimethylpentyl- a hydroperoxide initiator such as 2-hydroperoxide, diisopropylbenzene hydroperoxide, I hydroperoxide or tert-butyl hydroperoxide; dimercapto peroxide, 2, 5--21- 201041846 Dimethyl-2,5-di(t-butylperoxy)hexane, iota, 3_bis(t-butylperoxyisopropyl)benzene, tert-butyl a dialkyl peroxide initiator such as mercapto peroxide; 1, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di-( Peroxyl such as t-butylperoxy)butane, 4,4-di-t-butylperoxy-acid butyl oxalate Ketal initiator; 2,4,4-trimethylpentylperoxyphenoxyacetate, α-mercaptoperoxy neodecanoate, tert-butylperoxybenzoate An alkyl perester initiator such as di-t-butylperoxytrimethyl adipate; di-tertiary methoxybutylperoxy dinonate carbonate, di-2-ethyl Percarbonate-based initiators such as hexyl-peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, etc.; The cyclohexylsulfonyl peroxydicarbonate, the third butylperoxyallyl carbonate, and the like, and the azobis-based initiator system specifically includes 1,1'-azo. Bicyclohexane-1-carbonitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-di Methylvaleronitrile), 2,2'-azobis-(methyl isobutyrate), .〇:, '--azobis-(isobutyronitrile), 4,4'-azobis- (4-cyanovaleric acid) and the like. Ο These thermal polymerization initiators can be used singly or in combination of two or more kinds. When the amount of the thermal polymerization initiator is in the range of 0.1 to 1 part by weight based on 100 parts by weight of the (meth) acrylate resin (Α), the polymerization rate is rapid and the cured product is based on the polymerization rate. It is preferable that the refractive index becomes higher. In addition to the above-mentioned (meth) acrylate resin (Α) and a radical polymerization initiator (Β), the curable resin composition of the present invention can be used as a diluent in order to adjust the viscosity of the composition. Base polymerizable monomer (C) -22- 201041846 or other organic solvent (D). In the present invention, among these diluents, the free radical polymerizable monomer (C) is particularly preferred because the heat resistance and moisture resistance of the cured product are good. The radical polymerizable monomer (C) used herein may, for example, be a monofunctional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, or a trifunctional or higher polyfunctional (meth) group. A (meth) acrylate monomer such as an acrylate monomer; a vinyl monomer such as styrene, methyl styrene, halogenated styrene or divinyl benzene. Examples of the monofunctional (meth) acrylate monomer herein include propylene sulfenyl porphyrin, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and a ring. Hexane-1,4-dimethanol mono(meth)acrylate, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid phenoxyethyl ester, (meth)acrylic acid phenylpolyethoxylate, 2-Hydroxy-3-phenoxypropyl (meth)acrylate, p-nonylphenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, tribromophenoxy (meth)acrylate Ethyl ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, o-phenylphenol (^) Ethoxylate and the like. Examples of the bifunctional (meth) acrylate monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-fluorene. Diol di(meth)acrylate, tricyclodecyl dimethanol (meth) acrylate, bisphenol A polyethoxy di(meth) acrylate, bisphenol a polypropoxy di(meth) acrylate Ester, bisphenol F polyethoxy di(meth) acrylate, ethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, and the like. Examples of the trifunctional or higher polyfunctional (meth) acrylate monomer include -23-201041846 bis(acryloxyethyl)isocyanate, neopentyltetrakis(meth)acrylate. , dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentyltetraol hexa(meth) acrylate, tripentenol pentoxide (methyl) Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxylate of ε-caprolactone adduct of acrylate, hydroxypivalic acid neopentyl glycol Tris(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, and the like. Among these, in particular, as a dilute release agent in the curable resin composition, based on the effect of reducing the viscosity of the composition and maintaining the high refractive index of the cured product, acryloyl porphyrin is preferred. , (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid phenoxyethyl ester, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (methyl) a monofunctional or bifunctional (meth) acrylate monomer such as phenyl phenol polyethoxylate or divinyl benzene; based on the point that the dilution ability is excellent and the refractive index of the cured product becomes high at the same time Preferably, it is selected from the group consisting of phenoxyethyl (meth)acrylate, o-phenylphenol poly(ethoxy) acrylate, and divinylbenzene. On the other hand, examples of the organic solvent (D) include methyl ethyl ketone, carbitol acetate, butyl cellosolve acetate, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. , solvent naphtha, etc. The above-mentioned diluent is based on the point that the viscosity of the composition can be sufficiently reduced, and at the same time, the refractive index of the cured product is maintained at a high level, with [( -24- 201041846 methyl) acrylate resin / diluent j The mass ratio is preferably 90/10 to 30/70, and particularly preferably 80/20 to 40/60. The curable resin composition of the present invention can be modified in order to improve the performance, and an additive such as a decane coupling agent, a polymerization inhibitor or a leveling agent can be added without changing the original characteristics. The sand chamber coupling agent to be used may, for example, be r-methacryloxypropyltrimethoxydecane, r-(2-aminoethyl)aminopropyltrimethoxydecane, ortho-hydrogenthio group. Propyltrimethoxydecane, and the like. The polymerization inhibitor which can be used herein may, for example, be hydroquinone monomethyl ether, methylhydroquinone, tert-butyl catechin, p-benzoquinone, 2,5-t-butyl-hydroquinone or brown. Tillage and so on. Further, the leveling agent may, for example, be "MODAFLOW" of MONSANTO Co., Ltd., or the like. The method of curing the curable resin composition of the present invention, which is described in detail, may be a method in which the curable resin composition is applied or molded onto a substrate in accordance with the purpose and use, and then the active energy ray is irradiated or heated. Here, in the case where the active energy ray is irradiated and hardened, the active energy ray system may be an electron beam, an ultraviolet ray, a visible ray or the like. In the case of using an electron beam as the active energy line, a Cockcroft-Walton accelerator, a Van de Graaff accelerator, a resonant transformer type accelerator, or the like can be used. An electron beam generating device such as an insulated core transformer type, a high frequency high voltage accelerator (Dynamitron) type, a linear filament type, and a high frequency type is used to cure the curable resin composition of the present invention. In addition, when ultraviolet rays are used as the active energy ray, it can be hardened by irradiation with a mercury lamp such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide mercury lamp, or the like. . The exposure amount of the ultraviolet ray at this time is preferably in the range of 〇1 to 1〇〇〇inj/Cm2. On the other hand, in the case where it is hardened by heating, it can be hardened by heating in a temperature range of 60 to 250 °C. The curable resin composition of the present invention described in detail above has properties such as high refractive index, high heat resistance, and high moisture resistance, and thus can be applied to a spectacle lens, a lens for a digital camera, a Fresnel lens, and an edge. Various optical materials such as a plastic lens such as a mirror lens, an optical protective coating agent, a hard coating agent, an antireflection film, an optical fiber, an optical waveguide, a hologram, a krypton lens, a LED sealing material, and a coating material for a solar cell. Among these, in particular, based on the fact that the refractive index of the cured product is high and the heat resistance and moisture resistance of the cured product are excellent, it is preferably applied to a plastic lens, in particular, as a liquid crystal substrate. useful. Here, the prism lens for a liquid crystal substrate has a plurality of fine 稜鏡-shaped portions on one surface of the sheet-shaped molded body, and is usually used on the back surface (light source side) of the liquid crystal display element, on the element side. The sheet lens used for arranging the light guide sheet on the back side of the crucible surface, or the sheet lens having the side effect of the light guide sheet function. Here, the shape of the crotch portion of the 稜鏡 lens is at an angle of 0 to 70-110. In the case of the range, it is preferable that the light collection property is excellent and the brightness is improved, particularly in the range of 75 to 100°, particularly 80 to 95. The range is particularly good. -26- 201041846 In addition, the pitch of the crucible is preferably l〇〇/zm or less, especially in the range of 70° or less, based on the point that the ripple pattern of the screen can be prevented and the fineness of the screen is further improved. The words are better. Further, the height of the concave convex portion in the crucible is determined by the angle between the angle 0 of the dome angle and the pitch of the crucible, and is preferably in the range of 50/zm or less. Further, the thickness of the sheet of the 稜鏡 lens is preferably thicker from the strength surface, and is preferably optically smaller in order to suppress light absorption, and based on these balance points, it is preferably 5 〇βπι~1 The range of 〇〇〇νιη. The bismuth lens produced by the curable resin composition of the present invention, for example, by applying the curable resin composition to a mold for forming a ruthenium pattern or a resin mold or the like, and using a resin After smoothing the surface of the composition, a transparent substrate is placed and irradiated with an active energy ray to cure it. Here, when the transparent substrate has high transparency, it is preferably 3 mm or less in consideration of the permeability of the active energy ray or the workability. Further, examples of the material of the transparent substrate include synthetic resins such as an acrylic resin, a fluorene polycarbonate resin, a polyester resin, a polystyrene resin, a fluororesin, a polyimide resin, a mixture of such polymers, or the like. The ruthenium formed on the transparent substrate thus obtained may be used as it is, or the transparent substrate may be peeled off to be used in a state in which the enamel portion is separated. In the case where the crotch portion is directly formed on the transparent substrate, the bonding of the interface is important in terms of weather resistance and durability, and it is preferable to perform plasma treatment on the transparent substrate or the like. Adhesion improvement treatment. -27- 201041846 On the other hand, in the case where the transparent substrate is peeled off, it is preferable to peel off relatively easily, and it is preferred to subject the surface of the transparent substrate to a surface treatment with a polyfluorene oxide and a fluorine-based release agent. EXAMPLES Hereinafter, the present invention will be described in more detail by way of Synthesis Examples, but the present invention is not limited thereto. 1} Viscosity: Measured at 25 ° C using an E-type viscometer ("TV-2 0-shaped" conical plate type manufactured by Toki Sangyo Co., Ltd.) O 2) 13C-NMR: NMR manufactured by Nippon Electronics Co., Ltd. "GSX270

J 3) FD-MS: Double Focused Mass Spectrometer "AX505H (FD505H)" manufactured by JEOL Ltd. Example 1 4 port of 5L equipped with a mixer, thermometer, Dean-Stark separator, and condenser To the flask, 858 g (3 mol) of binaphthol, 634 g (7.2 mol) of ethyl carbonate, and 24 g of 48% by mass of potassium hydroxide were added, and the mixture was reacted at 170 ° C for 4 hours. Then, 500 g of dissolved methyl isobutoxyketone I was added, water was added to 1000 g, stirring was stopped, and the lower layer was discarded. An additional 100 g of water was added, the stirring was stopped and the lower layer was discarded. Then, solvent removal was carried out at 150 ° C to obtain a resin of 1 〇 5 0 g of a melting point of 1 〇 8 t as determined by D S C . When the resin was measured by mass spectrometry (FD-MS), the peak of m = 374 was confirmed, and the result of 1 3 C-NMR shown in Fig. 1 was confirmed to be a hydroxyl group-containing compound represented by the following structural formula ( a). -28- 201041846

O-ch2ch2oh o-ch2ch2oh Next, the above-mentioned hydroxyl group-containing compound (a) 187 g (0.5 mol), toluene 200 g, and acrylic acid 72 g were added to a 4-liter flask equipped with a stirrer, a thermometer, a condenser, and a decanter. 1.0 mol), 15 g of p-toluenesulfonic acid, 1 g of hydroquinone, and dehydration reaction was carried out at 80-100 ° C for 1 hour.

Next, the reaction liquid was cooled, and 200 g of toluene and 20% aqueous sodium hydroxide solution were fed, and stirring was stopped, and the lower layer was discarded. Then, it was washed twice with 20% sodium chloride and 1 g of an aqueous solution. Then, solvent removal was carried out at 100 ° C to obtain a resin of 200 g. When the resin was measured by mass spectrometry, the peaks of Μ = 4 8 2 and Μ = 428 were confirmed, and the results of 13C-NMR measurement shown in Fig. 2 were confirmed to be the compounds represented by the following structural formula (α). And a mixture of the compound (/3) represented by the following structural formula (0000), an acrylate resin (Α).

0 II o-ch2ch2o-c-ch=ch2 0 II o-ch2ch2o-c-ch=ch2 Constructive (α)

O-ch2ch2〇h ο 〇-CH2CH2〇-C-CH=CH2 Structural formula (0) In addition, according to gas chromatography (isolated separately and calculated according to internal standard method -29- 201041846), compound (α) and The ratio of the compound (dot) [molar ratio of (α)/(/3)] was 90/10, and it was confirmed that the molar ratio of the acryloxy group/hydroxy group was 95/5. The acrylate resin had a refractive index of 1.63 and a viscosity of 460 Pa.s as measured by a Ε-type viscometer. (Evaluation of Curability) Next, 80 parts by mass of the obtained acrylate resin (A) and 20 parts by mass of phenoxyethyl acrylate were blended as a photopolymerization initiator using a bar coater (No. 20). 3-hydroxycyclohexyl phenyl ketone ("IRGACURE 184" manufactured by Ciba Specialty O Chemicals) was applied to a glass plate, and then a 120 W/cm2 high-pressure mercury lamp was used in an air atmosphere, and The irradiation amount of 〇m J/cm 2 was irradiated to evaluate the hardenability. The evaluation is judged based on the following criteria. 〇: hardening (non-stickiness) X: uncured (viscosity) The results of the hardenability are shown together with the properties of the acrylate resin (A) in Table 1.实施 Example 2 In the same manner as in Example 1, except that the amount of acrylic acid used was changed to 61 g (0.85 mol), 19 〇g of the acrylate resin (B) was obtained. According to gas chromatography (isolated separately and calculated according to the internal standard method), it can be confirmed that the ratio of the compound (α ) to the compound (θ ) [the molar ratio of (α ) / (々) is 6 0/40, Further, the acryloxy group/passage group is 8 〇/2 〇 (mole ratio). The acrylate resin has a refractive index of 1.64, and the viscosity measured by a Ε-type viscometer is 490 Pa.s ° -30- 201041846 (hardness evaluation) except that the acrylate resin (A) is changed to an acrylate. The curability was evaluated in the same manner as in Example 1 except for the resin (B). The results of the curability and the properties of the acrylate resin (B) are shown in Table 1. Example 3 The amount of acrylic acid used was changed to 86 g (1.2). In the same manner as in Synthesis Example 1, except that the reaction time was changed to 12 hours, 205 g of an acrylate resin (C) was obtained, which was obtained by gas chromatography (isolated separately and calculated according to the internal standard method). It was confirmed that the ratio [U)/(々) of the compound (α) to the compound (^) was 99/1, and the acryloxy group/hydroxy group was 99.5/0.5 (mole ratio). The acrylate resin had a refractive index of 1.63 and a viscosity of 440 Pa·s as measured by an E-type viscometer. Further, the acrylate resin was crystallized after standing at 25 ° C for 2 hours. (Evaluation of Curability) The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (C). The results of the hardenability are shown in Table 1 together with the properties of the acrylate resin (C). (Example 4) 185 g of an acrylate resin (D) was obtained in the same manner as in the Example except that the amount of the acrylic acid used was changed to 58 g (0.80 mol) and the reaction time was changed to 6 hours. According to gas chromatography (isolated separately and calculated according to internal standard method), it can be confirmed that the ratio of compound (α) to compound ($) [(〇:) / (cold) molar ratio] is 40/60 ' Further, acrylonitrile group/hydroxy group = 70/30 (mole ratio). The acrylate resin had a refractive index of us of 510 Pa.s as measured by an ε-31-201041846 type viscometer. (Evaluation of Curability) The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (D). The results of the curability were shown together with the properties of the acrylate resin (D). Table 1. Example 5 In a 4-liter 4-neck flask equipped with a stirrer, a thermometer, a Dean-Stark separator, and a condenser, 238 g (l mol) of binaphthol and 190 g of acetamethylene carbonate were added ( 2.16 moles, 24 g of propyl carbonate (0.24 mol), 8 g of a 48% by mass aqueous potassium hydroxide solution, and allowed to react at 170 ° C for 4 hours. Then, 500 g of dissolved methyl isobutoxy ketone was added. 300 g of water was added, stirring was stopped, and the lower layer was discarded. 300 g of water was further added, stirring was stopped, and the lower layer was discarded. Then, solvent removal was carried out at 150 ° C to obtain 340 g of a resin. Next, a mixer, a thermometer, a condenser, and a tilting were installed. In a 1-L 4-neck flask of a separator, 187 g of the obtained resin, 200 g of toluene, 86 g of acrylic acid (1.2 mol), 15 g of p-toluenesulfonic acid, and hydroquinone lg were added, and 10 hours at 80-100 ° C for 10 hours. Dehydration reaction. Then, the reaction solution is cooled, and toluene 2 is fed. 0 § and 20% aqueous sodium hydroxide solution 100 mesh, stirring was stopped and the lower layer was discarded. Next, washing was carried out twice with 20% sodium chloride and 100 g of an aqueous solution. Then, solvent removal was carried out in 10 CTC to obtain an acrylate resin ( E) 201 g. Further, based on the measurement results of 1 3 C - NMR, it was confirmed that the molar ratio of the ethoxylated/extended propoxy group was 90/10. The refractive index of the acrylate resin was 1.63, and the yttrium-type viscometer was used. The measured viscosity was 465 Pa.s. (Evaluation of the curability) -32-201041846 The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (E). The results are shown in Table 2 together with the properties of the acrylate resin (E). Example 6 Example 5 except that it was changed to 127 g (1.44 mol) of ethyl carbonate and 98 g (0.96 mol) of propyl carbonate. The same procedure was carried out to obtain an acrylate resin (F) of 2 0 3 g. Further, from the measurement results of 1 3 C - NMR, it was confirmed that the molar ratio of the exoethoxy group to the propenyloxy group was 60/40. The ester resin has a 〇 refractive index of 1.62 and a viscosity of 4 measured by a Ε-type viscometer. 80 Pa.s (Evaluation of Curability) - The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (F). The result of the curability was compared with the acrylate resin (F). The properties are shown in Table 2. Example 7 The same procedure as in Example 5 was carried out except that 209 g (2.38 mol) of ethylene carbonate and 2 g (0.0 2 mol) of propylene carbonate were changed to obtain acrylic acid. Oxime ester resin (G) 2 0 6 g. Further, from the measurement results of 1 3 c - N M R , it was confirmed that the molar ratio of the exoethoxy group to the propenyloxy group was 99/1. The acrylate resin had a refractive index of 1.63 and a viscosity of 455 Pa.s as measured by a Ε-type viscometer. Further, the acrylate resin was crystallized after standing at 25 ° C for 2 hours. (Evaluation of Curability) The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (G). The results of the hardenability are shown in Table 2 together with the properties of the acrylate resin (G). -33-201041846 Example 8 An acrylate resin was obtained in the same manner as in Example 5 except that it was changed to 95 g (1.08 mol) of ethyl carbonate and 135 g (l·32 mol) of propylene carbonate. H) 206g. Further, it was confirmed by NMR that the ethoxy group / propenyloxy group = 45/55 (mole ratio). The acrylate resin (H) had a refractive index of 1.61 and a viscosity of 5 lOPa.s as measured by an E-type viscometer. (Evaluation of Curability) The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (H). The results of the hardenability are shown in Table 2 together with the properties of the acrylate resin (H). Table 1

Example 1 2 3 4 Acrylate Resin Properties Acrylate Resin ABCD Acrylhydrazine/Hydroxyl, Mohr 95/5 80/20 99.5/0.5 70/30 Refractive Index 1.63 1.64 1.63 1.65 Viscosity (mPa.s, 25 ° C } 460 490 440 510 Hardenability 〇〇^ 〇X As described above, in the case of acrylonitrile/hydroxyl=75/25~99/1 (mole ratio), it is liquid at room temperature, and hardenability is also On the other hand, in the case where the ratio of the hydroxyl group is smaller than the range, the crystallinity becomes high and crystallizes after standing for 2 hours at normal temperature. -34- 201041846 Table 2 ______ Example 5 6 7 8 Acrylate resin Properties acrylate resin EFG 醯 propylene fluorenyl / propenoxy, molar ratio 90/10 60/40 99/1 45/55 refractive index 1.63 1.62 1.63 1.61 viscosity (mPa.s, 25 ° ci 465 480 455 500 hardening As described above, in the case where the ratio of the ethoxy group/exet propoxy group is in the range of ethoxy group / propenoxy group = 50/50 to 98/2 (mole ratio), The normal temperature is liquid. However, the ratio of the propoxyl group is less than the range, and the crystallinity is high, and it is placed at normal temperature. Crystallization after 2 hours. Comparative Example 1 In a 4-neck flask equipped with a stirrer, a thermometer, a condenser, and a decanter, 187 g (0.5 mol) of the compound (a) obtained in Example 1 and p-benzene were added. 83 g (0.5 mol) of dicarboxylic acid and 7 g of dibutyltin oxide, and the temperature was gradually heated from 19 CTC to 2 30 ° C under stirring at a reduced pressure of 5 to 10 Torr to carry out esterification. After the water is pumped out of the system, the temperature is gradually increased and decompressed, and the generated water is drawn while the temperature of the heating bath reaches 280 ° C, and the degree of pressure reduction reaches 1 33.322 Pa or less. After the condition is maintained for 1 hour, The reactant was extruded into water to obtain 210 g of a polyester resin (I). The refractive index of the resin was 167. Further, since it was a solid, the E-type viscometer could not be measured. Comparative Example 2 The following structural formula -35- 201041846

The refractive index of the fluorene type acrylate (acrylic resin (j), "OGSOL EA-0200" manufactured by Osaka Gas Chemical Co., Ltd.) was 1.59. Moreover, since it is a semi-solid, it cannot be measured by a Ε-type viscometer. Comparative example 3

The following structural formula

The refractive index of the bismuth type epoxy acrylate (acrylic resin (ASF-400) manufactured by Nippon Steel Chemical Co., Ltd.) was 1.58. Moreover, since it is a solid, the Ε-type viscometer cannot be measured.

Examples 9 to 12 and Comparative Examples 4 to 6 The acrylate-type acrylate resin (J) and the oxime-type epoxy acrylate using the acrylate resins (A), (B), (E), (F), and Comparative Compound 1 were used. The resin (I) and the polyester resin (I) were formed into a coating film by the following method and various evaluations were carried out. The results are shown in Table 3. (Preparation of hardened coating film of acrylate resin (A), (B), (E), (F) '(J) or (κ)) Blending acrylic acid using a bar coater (No. 20) 80 parts by mass of acrylate resin of ester resin (A), -36-201041846 (B), (E), (F), (J) or (K), 20 parts by mass of phenoxyethyl acrylate, as photopolymerization The composition of IRAGACURE 184 (3 parts, manufactured by Ciba Specialty Chemicals) of the initiator was applied to a glass plate. Next, a 120 W/cm2 high-pressure mercury lamp was used in an air atmosphere, and irradiated with an irradiation amount of 500 mJ/cm2 to obtain a hardened coating film. (Adjusting the coating film using the polyester resin (I)) The polyester resin (I) was heated and melted at 150 ° C, and applied to a glass plate using a bar coating machine (No. 20). (Solvent resistance) After the coating film obtained by the coating film was rubbed back and forth for 50 times with a cotton rod (manufactured by Johnson Co., Ltd.) containing no methyl ethyl ketone, the change of the coating film was visually observed. The evaluation is judged as follows. Evaluation 〇: No change X: Change in haze, peeling, etc. ^ (Heat resistance) The film obtained by coating the film was placed in a dryer at 125 ° C for 1 to 50 hours. The change of the coating film after the retention was visually observed. The evaluation is judged as follows. Evaluation 〇: No change △: Only the hue changes, the shape does not change X: The hue and shape change -37- 201041846 (moisture resistance) The film obtained in the film production is placed at 85 ° C, humidity 85% The constant temperature and humidity machine is kept for 300 hours. The change of the coating film after the retention was visually observed. The evaluation is judged as follows. Evaluation 〇: No change △: only the hue changed, the shape did not change X: hue and shape changed 〇 Table 3 Example Comparative Example 9 10 11 12 4 5 6 Acrylate resin ABEFIJK Coating refractive index 1.64 1.65 1.64 1.63 1.67 1.59 1.58 Solvent resistance 〇〇〇〇X 〇〇Heat resistance 〇〇〇〇X Δ Δ Moisture resistance 〇〇〇〇X Δ Δ As described above, the acrylate resin of the present invention can be confirmed to have low viscosity and high refractive index. And the cured product after light irradiation is excellent in high refractive index, solvent resistance, heat resistance, and moisture resistance. Example 1 3 to 16 and Comparative Examples 7 to 9 using acrylate resin (A), (B), (E), (F), comparative compound 1 acrylate resin (J), comparative compound 2 The active energy ray-cured material of the bismuth type epoxy acrylate resin (K) and the polyester resin (I) obtained in Comparative Example 1 were used to form a coating film by the following method, and various types were produced in the same manner as in Example 12. Evaluation. The results are shown in Table 4. (Preparation of hardened coating film of acrylate resin (A), (B), (E), (F), (J) or (K)} -38- 201041846 Using bar coater (No. 2 0) 80 parts by mass of acrylate resin of acrylate resin (A), (B), (E), (F), (J) or (K), 20 parts by mass of phenoxyethyl acrylate, as heat A composition of 3 parts by mass of methyl ethyl ketone peroxide as a polymerization initiator was applied to a glass plate, and then placed in a dryer at 1 ° C for 4 hours to obtain a cured coating film. Coating film of ester resin (1) The polyester resin (I) was heated and melted at 150 ° C, and applied to a glass plate using a bar coater (No. 20). Ο Table 4 Example Comparative Example 13 14 15 16 7 8 9 Acrylate resin ABEFIJK Coating refractive index 1.64 1.65 1.64 1.63 1.67 1.59 1.58 Solvent resistance 〇〇〇〇X 〇〇Heat resistance 〇〇〇〇X Δ Δ Moisture resistance 〇〇〇〇X Δ Δ The acrylate resin of the present invention can be confirmed to have a low viscosity, a high refractive index, and a cured product after heat hardening is a high refractive index. It is excellent in solvent resistance, heat resistance, and moisture resistance. Example 1 7 to 2 2 and Comparative Example 1 0 to 1 1 The varnish-like composition was adjusted according to the following Table 5, and the following method was used. The liquid refractive index and the viscosity of the composition were measured, and then a cured coating film was produced in the same manner as in Example 12, and solvent resistance, heat resistance, and moisture resistance were evaluated. Further, each composition was used, and the following method was used. The cured film A and the substrate B with the cured film were produced to evaluate transparency and adhesion. Further, the composition was used and the release film-39-201041846 property from the mold was evaluated by the following method. Table 5. [Manufacture of hardened film A] After the composition adjusted according to the combination of the following Table 5 was inserted between the chrome-plated metal plate and the transparent surface untreated PET film, the thickness was adjusted, and the high-pressure mercury lamp was used from the transparent base. After the material side is irradiated with ultraviolet rays of 500 mJ / cm 2 and hardened, the cured film is removed from the metal plate and the transparent substrate (hereinafter, it is abbreviated as "hardened film A"). [Substrate B with hardened film Manufacturing] After the composition adjusted according to the following Table 5 was inserted between the swarf-treated metal plate and the transparent surface-adhered PET film, the thickness was adjusted, and a high-pressure mercury lamp was used to irradiate ultraviolet rays of 500 mJ/cm 2 from the transparent substrate side. After the hardening, only the metal plate is peeled off to obtain a substrate with a cured film (hereinafter, abbreviated as "substrate B with a cured film"). [Liquid refractive index] Directly applied to the crucible of the Abbe refractometer The measurement of the refractive index at 25 ° C (D line of 5 8 9.3 mm) was carried out. 〇 [Viscosity] The viscosity at 25 ° C was measured with an E-type rotary viscometer. [Refractive Index Refractive Index] The cured film A was adhered to a crucible of an Abbe refractometer by using 1-bromo naphthalene, and the refractive index at 25 ° C (D line of 589.3 mm) was measured. [Transparency] Using the cured film A, the light transmittance in the wavelength range of 400 to 900 nm is measured, and in all fields, the transmittance of 85% or more is set to 〇' wear--40-201041846. Set to X. [Adhesiveness] The adhesion between the substrate and the cured film layer was measured in accordance with JIS K5400 using the substrate B to which the cured film was attached, and was set to X when all the components remained, and X was set to be the same. [Removing property] Between the chrome-plated enamel mold and the transparent surface-adhering PET film, the composition adjusted according to the blending of the following Table 5 was inserted, and the Ο thickness was adjusted, and the high-pressure mercury lamp was used from the transparent substrate side. After the ultraviolet rays of 500 mj/cm 2 were irradiated and cured, the film was removed from the mold, and the composition was left in the mold, and the residue was set to X. -41- 201041846 Table 5 Example Comparative Example 17 18 19 20 21 22 10 11 Composition Acrylate Resin (VIII) 65 40 60 70 50 75 — — Acrylate Resin (J) — One — One — — 30 70 Phenoxy B Acrylate Ester 35 — — — — — — — OPPEA — 60 40 30 — — 70 30 Diphenyl methacrylate — — — — 50 25 — — Photoinitiator 4 4 4 4 4 4 4 4 Clear varnish liquid refractive index 1.586 1.597 1.607 1.612 1.597 1.612 1.576 1.608 Viscosity (mPa.s, 25°〇1000 1200 4900 9800 1100 12000 1300 Cannot measure the hardened material evaluation result Hardener refractive index 1.625 1.635 1.633 1.633 1.635 1.630 1.611 Can not measure transparency〇〇〇〇〇〇 〇Cannot measure the adhesion 〇〇〇〇〇〇〇 Can not measure the release property 〇〇〇〇〇〇〇 Can not measure the solvent resistance 〇 Δ 不能 X Can not measure the heat resistance 〇 Δ 不能 X Can not measure resistance Wet 〇Δ 〇〇〇〇X cannot be measured. In Table 5, "phenoxyethyl acrylate" is a Kyungwon Chemical Co., Ltd. "LIGHT ACRYLATE Ρ Ο - A", "Ο PPEA" is an o-phenyl oxime ethylene oxide modified acrylate ("ARONIXTO-1463" manufactured by Toagosei Co., Ltd.), and a "photoinitiator" 1-hydroxy ring. Hexyl phenyl ketone (Ciba Specialty -42- 201041846

Chemicals "IRGACURE 184"). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a UC-NMR spectrum of the hydroxyl group-containing compound (a) obtained in Example 1. Fig. 2 is a 13C-NMR spectrum of the (meth) acrylate resin (A) obtained in Example 1. [Main component symbol description] te. 〇 -43-

Claims (1)

201041846 VII. Patent application scope: 1. A (meth) acrylate resin characterized in that it has a binaphthyl skeleton in a molecular structure and has a substituent represented by the following structural formula (A) as the quinone. Substituents on the aromatic nucleus of the skeleton, Ο / 1\ II ten o-r1)j~o-c_?=ch2 Structural formula (a) R2 (wherein R1 is a linear chain of 2 to 5 carbon atoms or a branched alkyl group, R 2 is a hydrogen atom or a methyl group, and a repeating unit of 1 is an integer of 1 to 1 }. 〇 2. A (meth) acrylate resin according to claim 1 of the patent range, Having the molecular structure shown by the following general formula (1), - (1) (In the formula, χι~χΐ2 are independent hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, or alkoxy groups having 1 to 10 carbon atoms, Ai, Α2 carbon atoms a linear or branched alkyl group of 2 to 5, a hydrazine, a hydrazine 2 hydroxy group, a propylene methoxy group, or a methacryloxy group, a η and m repeating unit, and each of which is 1 to 1 Å. Integer: wherein at least one of Y1 and Y2 is an acryloxy group or a methacryloxy group). 3. The (meth) acrylate resin according to claim 1 or 2, which is liquid at 25 °C. -44- 201041846 4. The (meth) acrylate resin of the second aspect of the patent application, wherein the (meth) acrylate resin is a mixture of the various compounds represented by the above formula (1), and The ratio of the hydroxyl group (y 1) in Y1 and Y2 of the general formula (1) to the acryloxy group or the methacryloxy group (y 2) is 75/25 in terms of the molar ratio (y2/yl). Range of ~99/1. 5. The (meth) acrylate resin according to claim 2, wherein the (meth) acrylate resin is a mixture of the various compounds represented by the above general formula (1), and the above structural formula (1) Ai and A2 are each independently selected from the group consisting of an ethyl group (al) and an alkyl group (a2) having a carbon number of 3 to 5, and the aforementioned ethyl group (a 1) and the foregoing The molar ratio (al/a2) of the alkylene group (a2) having 3 to 5 carbon atoms is in the range of 50/50 to 98/2. 6. The (meth) acrylate resin according to any one of claims 1 to 5, wherein the viscosity at 25 ° C is 3,000 Pa «s or less. 7. A process for producing a (meth) acrylate resin, characterized in that a binaphthol, an alkylene oxide, a halogenated alkanol or a alkylene carbonate is reacted to obtain a compound having a hydroxyl group, followed by The (meth) acrylated agent is reacted with a reaction product having the obtained hydroxyl group. 8. A curable resin composition characterized by using (meth) acrylate resin (A) and a radical polymerization initiator (B) as any one of items 1 to 6 of the patent application range as an essential component . 9. The curable resin composition of claim 8 which contains a radical polymerizable monomer in addition to the (meth) acrylate resin (A) and the radical polymerization initiator (B) described above. (C). -45- 201041846 1 硬化. A cured product obtained by hardening a curable resin composition as disclosed in claim 9 by irradiation with an active energy ray or heating. A plastic lens formed by forming and hardening a curable resin composition according to claim 9 of the patent application. -46 -