WO2010095475A1 - (meth)acrylate resin and process for producing same, and curable resin composition, cured object obtained therefrom, and plastic lens - Google Patents

Abstract

A (meth)acrylate resin which gives, as an organic optical material, a cured object having a high refractive index and having excellent heat resistance and moisture resistance; a curable resin composition; a cured object obtained from the composition; and a plastic lens. A (meth)acrylate resin characterized by having a binaphthalene skeleton in the molecular structure and having a substituent represented by structural formula (A) as a substituent on the aromatic nuclei of the binaphthalene skeleton is cured by heating or irradiation with actinic energy rays. (In the formula, R¹ is a linear or branched C_2-5 alkylene; R² is a hydrogen atom or methyl; and l, indicating the number of repeating units, is an integer of 1-10.)

Description

(Meth) acrylate resin, production method thereof, curable resin composition, cured product thereof, and plastic lens

The present invention has a low viscosity and is cured by irradiation with active energy rays or heating. After curing, the cured product has a high refractive index and high heat resistance and high moisture resistance. (Meth) acrylate resin suitable for overcoat agent, hard coat agent, antireflection film, spectacle lens, optical component such as optical fiber, optical waveguide, hologram, and other plastic lens such as prism lens, Fresnel lens, lenticular lens, and production method thereof The present invention relates to a curable resin composition and a cured product thereof.

In recent years, resin materials have been widely used for optical parts such as optical overcoat agents, hard coat agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, and holograms because of their excellent processing and productivity. Therefore, a resin material having a high refractive index is demanded from the viewpoint of miniaturization and thinning of optical components, or adjustment of antireflection properties.
Conventionally, an acrylate resin having a fluorene skeleton has been known as an optical material having a high refractive index that meets such requirements. For example, a bifunctional compound in which an acryloyl group is bonded to a fluorene skeleton via an alkyleneoxy group (see below) Patent Literature 1, Patent Literature 2, and Patent Literature 3), and compounds obtained by reacting diglycidyl ether containing a fluorene skeleton with acrylic acid or methacrylic acid (see Patent Literature 4 below) are known.

However, when the acrylate resin having a fluorene skeleton described above is used alone as a polymerizable component, the refractive index of the cured product becomes high, but the acrylate resin itself is solid or has a high value of 3000 Pa · S or more at room temperature. Since it is a viscous liquid, it is necessary to use a large amount of a diluent having a low refractive index, so that the refractive index of the resulting cured product eventually becomes low. In addition, the cured product of the acrylate resin having a fluorene skeleton is inferior in heat resistance and high moisture resistance, and inferior in the long-term reliability of the optical material.

A polyester resin having a binaphthol skeleton is known as an optical material having a high refractive index (see Patent Document 5 below).
However, since the polyester resin having such a binaphthol skeleton has a high weight average molecular weight (Mw) of 10,000 to 100,000 and is a solid thermoplastic resin at room temperature, it can be used for active energy rays or thermosetting resins. In addition, it was inferior in solvent resistance, heat resistance and high moisture resistance, and the long-term reliability of the optical material was low.

Japanese Patent No. 3130555 JP 2007-84815 A International Publication Number WO2005 / 033061 Japanese Patent Laid-Open No. 03-106918 JP 2002-332345 A

Therefore, the problem to be solved by the present invention is a (meth) acrylate resin, a curable resin composition, which has a high refractive index in a cured product as an organic optical material, and is excellent in heat resistance and moisture resistance of the cured product, And it is providing the hardened | cured material which has such performance.

As a result of diligent studies to solve the above problems, the present inventors have a binaphthalene skeleton in the molecular structure and an alkylene having a (meth) acryloyloxy group at the end as a substituent on the aromatic nucleus of the binaphthalene skeleton. It has been found that a compound having an oxy group introduced itself has a low viscosity and a high refractive index of a cured product, and can further have excellent heat resistance and moisture resistance, and the present invention has been completed.

That is, the present invention has a binaphthalene skeleton in the molecular structure, and the following structural formula (A) as a substituent on the aromatic nucleus of the binaphthalene skeleton.

(Wherein R ¹ is a linear or branched alkylene group having 2 to 5 carbon atoms, R ² is a hydrogen atom or a methyl group, and l is an integer of 1 to 10 as a repeating unit.)
It has a substituent represented by (meth) acrylate resin characterized by the above-mentioned.
The present invention further relates to a method for producing a (meth) acrylate resin, characterized in that a binaphthol is reacted with an alkylene carbonate, and then a (meth) acrylate agent is reacted with the obtained reaction product.
The present invention further relates to a curable resin composition comprising the (meth) acrylate resin (A) and the radical polymerization initiator (B) as essential components.
The present invention further relates to a cured product obtained by curing the curable resin composition by irradiation with active energy rays or heating.
The present invention further relates to a plastic lens obtained by molding and curing the curable resin composition.

According to the present invention, a (meth) acrylate resin, a curable resin composition, which has a high refractive index in a cured product as an organic optical material, and is excellent in heat resistance and moisture resistance of the cured product, and such performance are combined. A cured product can be provided.

Therefore, the (meth) acrylate resin of the present invention can be widely applied to optical parts such as optical overcoat agents, hard coat agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, holograms, and prism lenses.

FIG. 1 is a ¹³ C-NMR spectrum of the hydroxyl group-containing compound (a) obtained in Example 1. FIG. 2 is a ¹³ C-NMR spectrum of the (meth) acrylate resin (A) obtained in Example 1.

The (meth) acrylate resin of the present invention means a resin having an acryloyloxy group or a methacryloyloxy group. Specifically, the (meth) acrylate resin has a binaphthalene skeleton in the molecular structure and has an aromatic nucleus on the binaphthalene skeleton. As a substituent of the following structural formula (A)

(Wherein R ¹ is a linear or branched alkylene group having 2 to 5 carbon atoms, R ² is a hydrogen atom or a methyl group, and l is an integer of 1 to 10 as a repeating unit.)
It has the substituent represented by these. Since the (meth) acrylate resin has a binaphthalene skeleton, it has excellent heat resistance and moisture resistance, and is an organic material having a very high refractive index of 1.60 or more. Moreover, since it has an alkyloxy group or polyoxyalkylene group having an acryloyloxy group or a methacryloyloxy group as a substituent on the binaphthalene skeleton, the degree of freedom of the (meth) acryloyloxy group which is a reactive functional group is Higher reactivity and better heat resistance and moisture resistance of the cured product.

Examples of the binaphthalene skeleton include a 1,1-binaphthalene skeleton, a 1,2-binaphthalene skeleton, a 2,2-binaphthalene skeleton, and the like. Is preferred.

Further, the following structural formula (A), which is a substituent on the aromatic nucleus of the binaphthalene skeleton

(Wherein R ¹ is a linear or branched alkylene group having 2 to 5 carbon atoms, R ² is a hydrogen atom or a methyl group, and l is an integer of 1 to 10 as a repeating unit.)
The substituent represented by is a structural site that functions as a reactive group when the (meth) acrylate resin of the present invention is cured by irradiation with active energy rays or heating. Since the (meth) acryloyloxy group is bonded to the binaphthalene structure via a monoalkyloxy group or a polyoxyalkylene group, the structural site has a degree of freedom of the (meth) acryloyloxy group that is a reactive functional group. It becomes high and the reactivity is excellent, and the heat resistance and moisture resistance of the cured product become high.

Here, specific examples of R ¹ in the structural formula (A) include ethylene, n-propylene, isopropylene, butylene, 4-methyl-n-butylene, and n-pentene. Among these, an alkylene group selected from the group consisting of ethylene, n-propylene and isopropylene is particularly preferred from the viewpoint that the refractive index of the (meth) acrylate resin itself is high.

The substituent represented by the structural formula (A) is contained in a ratio of 1.5 to 4.0 on average per mole of the binaphthalene skeleton constituting the resin in the (meth) acrylate resin. From the viewpoint of improving the refractive index of the (meth) acrylate resin itself, it is preferably contained in a ratio of 1.5 to 1.98.

The value of l in the structural formula (A) is an integer of 1 to 10, but when it exceeds 10, the refractive index of the (meth) acrylate resin itself is lowered, and the refractive index in the cured product intended by the present invention is reduced. The rate will not reach a sufficient level. In the present invention, since the refractive index of the (meth) acrylate resin itself is high, the average value of l is in the range of 1.0 to 3.0, particularly in the range of 1.0 to 1.5. It is particularly preferable that the number is substantially 1.

Such a (meth) acrylate resin uses 1,1-binaphthol as a starting material, converts a phenolic hydroxyl group in the 1,1-binaphthol to alkylene oxide, and then converts the hydroxyl group generated as a result of the alkylene oxide to (meta) It is preferable that it has a molecular structure obtained by acryloyloxylation from the viewpoint of obtaining a cured product having excellent heat resistance and moisture resistance and a high refractive index. Examples of such (meth) acrylate resins starting from 1,1-binaphthol include, for example, the following general formula (1)

(Wherein X ¹ to X ¹² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and A ¹ and A ² are carbon atoms. A linear or branched alkylene group having 2 to 5 atoms, Y ¹ and Y ² are a hydroxyl group, an acryloyloxy group, or a methacryloyloxy group, n and m are repeating units, each having 1 to 10 (However, at least one of Y ¹ and Y ² is an acryloyloxy group or a methacryloyloxy group.)
The thing which has the molecular structure represented by these is mentioned.

Here, in the general formula (1), the structural sites represented by A ¹ and A ² correspond to R ¹ in the structural formula (A), specifically, ethylene, n-propylene. Isopropylene, butylene, 4-methyl-n-butylene, n-pentene and the like. Among these, an alkylene group selected from the group consisting of ethylene, n-propylene and isopropylene is particularly preferred from the viewpoint that the refractive index of the (meth) acrylate resin itself is high.

In the general formula (1), m or n represents a repeating unit corresponding to l in the structural formula (A). Furthermore, examples of the halogen atom constituting X ¹ to X ¹² in the general formula (1) include a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, A propyl group, t-butyl group, cyclohexyl group, octyl group, linear or branched alkyl group such as decyl group, and an aralkyl group formed by reacting the binaphthalene skeleton with a benzylating agent. There may be. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, butoxy group, octyloxy group, decyloxy group and the like. Here, when halogen atoms constituting X ¹ to X ¹² are used, the refractive index of the acrylate resin itself is increased, but it is difficult to apply to applications requiring non-halogenation. On the other hand, when a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is used, the viscosity of the acrylate resin can be further reduced.

Among such (meth) acrylate resins represented by the above general formula (1), the following molecular structure is preferable from the viewpoint of high heat resistance, high moisture resistance, and high refractive index, which are the effects of the present invention. The thing which has.

Here, in the structural formulas represented by the above formulas (1) to (21), as in the general formula (1), Y ¹ and Y ² represent a hydroxyl group, an acryloyloxy group, or a methacryloyloxy group, and n And m is an integer of 1 to 10 as a repeating unit. However, at least one of Y ¹ and Y ² is an acryloyloxy group or a methacryloyloxy group.

In the acrylate resin represented by the general formula (1), those having a halogen atom as X ¹ to X ¹² in the formula can further increase the refractive index of the acrylate resin itself as described above. Application to applications requiring halogenation becomes difficult. On the other hand, those having a high degree of freedom in the structure itself such as linear alkyl groups or alkoxy groups as X ¹ to X ¹² are effective in reducing the viscosity of the acrylate resin, but the refractive index is represented by the general formula (1 ), All of X ¹ to X ¹² are relatively lower than those in which all are hydrogen atoms. Therefore, X ¹ to X ¹² in the above general formula (1) are each independently a hydrogen atom or a carbon atom number of 1 from the viewpoint of compatibility of both properties of refractive index and viscosity, difficulty in synthesis, and cost. It is preferably an alkyl group of 1 to 3, particularly preferably all of which are hydrogen atoms. Therefore, in the acrylate resin represented by the general formula (1), A ¹ and A ² are alkylene groups selected from the group consisting of ethylene, n-propylene, and isopropylene, and X ¹ to X ¹² are all A (meth) acrylate resin that is a hydrogen atom is preferred.

Furthermore, Y ¹ and Y ² in the general formula (1) represent a functional group selected from a hydroxyl group, an acryloyloxy group, and a methacryloyloxy group as described above, and ^one of Y ¹ and Y ² , or Both are acryloyloxy groups or methacryloyloxy groups. In the present invention, among acryloyloxy groups and methacryloyloxy groups, acryloyloxy groups are particularly preferred because the refractive index of the (meth) acrylate resin itself is high. .

Moreover, the (meth) acrylate resin represented by the general formula (1) can be used as a mixture of various compounds satisfying the general formula (1). At this time, the hydroxyl group constituting Y ¹ and Y ² in the general formula (1) in the (meth) acrylate resin (hereinafter abbreviated as “hydroxyl group (y1)”), acryloyloxy group or The ratio of yloxy group (hereinafter abbreviated as “(meth) acryloyl group (y2)”) can be arbitrarily adjusted. In the present invention, the ratio of the hydroxyl group (y1) to the (meth) acryloyl group (y2) is preferably in the range of 75/25 to 1/99 in terms of molar ratio (y1 / y2). That is, when the amount of (meth) acryloyl group (y2) is more than 75/25 in terms of molar ratio (y1 / y2), the curability by active energy rays or heating is improved, and the liquid temperature is normal. It becomes a (meth) acrylate resin and has a sufficiently low viscosity. On the other hand, when the amount of the (meth) acryloyl group (y2) is lower than 1/99 in the molar ratio (y1 / y2), the crystallinity of the (meth) acrylate resin itself can be moderately suppressed. The viscosity at can be reduced.

As described above, the structural parts represented by A ¹ and A ² in the general formula (1) are carbon such as ethylene, n-propylene, isopropylene, butylene, 4-methyl-n-butylene, n-pentene and the like. Although it is a linear or branched alkylene group having 2 to 5 atoms, it is possible to arbitrarily adjust the abundance ratio thereof in the present invention. For example, ethylene (hereinafter referred to as this) in the (meth) acrylate resin can be adjusted. Is abbreviated as “ethylene group (a1)”), the refractive index of the (meth) acrylate resin itself increases. On the other hand, the presence of an appropriate amount of another structure, that is, an alkylene group having 3 to 5 carbon atoms (hereinafter abbreviated as “alkylene group having 3 to 5 carbon atoms (a2)”) allows (meth) Crystallization of the acrylate resin can be suppressed, and the viscosity can be reduced. Therefore, in the present invention, the molar ratio (a1 / a2) between the ethylene group (a1) and the alkylene group (a2) having 3 to 5 carbon atoms is in the range of 50/50 to 98/2. The (meth) acrylate resin is preferable because it is liquid at room temperature and has a low viscosity, and the refractive index of the (meth) acrylate resin itself is high.
Further, as described above, since the alkylene group (a2) having 3 to 5 carbon atoms is preferably n-propylene or isopropylene (hereinafter abbreviated as “C3 alkyl”), the ethylene group (a1 ) And C3 alkyl (ethylene group (a1) / C3 alkyl) is preferably in the range of 50/50 to 98/2.

In the above general formula (1), m and n are integers of 1 to 10 representing repeating units. From the viewpoint of increasing the refractive index of the (meth) acrylate resin itself, m and n are respectively averages thereof. It is preferably in the range of 1.0 to 3.0, particularly preferably in the range of 1.0 to 1.5, and particularly preferably substantially 1.

The (meth) acrylate resin described in detail above has a viscosity of not more than 3000 Pa · s at 25 ° C., and it has good fluidity and wide application range for various applications. It is preferable because the amount of diluent used can be reduced. In particular, the range of 1000 to 100 Pa · s is preferable from the standpoint that this effect is remarkable.

As described above, the (meth) acrylate resin itself has a high refractive index. Specifically, the (meth) acrylate resin has a refractive index of 1.55 or more, and a refractive index of 1.60 or more depending on the selection of the molecular structure. Become a material.

The method for producing the (meth) acrylate resin described in detail above is to obtain a compound having a hydroxyl group by reacting binaphthols with an alkylene oxide, a halogenoalkanol, or an alkylene carbonate, and then the resulting reaction product having a hydroxyl group. A desired (meth) acrylate resin can be obtained by reacting a product with a (meth) acrylate agent.

Here, examples of the binaphthols that can be used include those having a binaphthalene structure corresponding to the general formula (1), specifically, the following structural formula (2)

(Wherein X ¹ to X ¹² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms)
The thing represented by is mentioned.

Among these, X ¹ to X ¹² in the above general formula (1) are each independently a hydrogen atom or carbon from the viewpoints of compatibility of both properties of refractive index and viscosity, difficulty in synthesis, and cost. An alkyl group having 1 to 3 atoms is preferable, and all of them are particularly preferably hydrogen atoms. Therefore, in the acrylate resin represented by the general formula (1), A ¹ and A ² are alkylene groups selected from the group consisting of ethylene, n-propylene, and isopropylene, and X ¹ to X ¹² are all A (meth) acrylate resin that is a hydrogen atom is preferred.

In the step of reacting the above binaphthols with alkylene oxide, halogenoalkanol, or alkylene carbonate, for example, as a method of reacting binaphthols with alkylene oxide, a temperature condition of 100 to 200 ° C. in the presence of an alkali catalyst is used. And a method of subjecting an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to a polyaddition reaction.

Next, as a method of reacting binaphthols with halogenoalkanols, halogenoalkanols such as 2-chloroethanol, 3-chloro-2-propanol and 2- (2-chloroethoxy) ethanol are added to the binaphthols in the presence of an alkali catalyst. A method of reacting under a temperature condition of 100 to 200 ° C. is mentioned below.

Next, the method of reacting the binaphthols with the alkylene carbonate specifically includes the method of reacting the binaphthols with the alkylene carbonate in the presence of an alkali catalyst or an acid catalyst at a temperature of 80 to 200 ° C.

In each of the above methods, the method of reacting binaphthols with alkylene oxide is difficult to adjust the repeating unit 1 in the above structural formula (A), and the method of reacting binaphthols with halogenoalkanol is as follows: In addition, there is a problem that the reaction kettle is corroded because acid substances such as hydrochloric acid are by-produced. On the other hand, the method of reacting binaphthols with alkylene carbonate is easy to adjust the repeating unit 1 and is advantageous for production on an industrial scale without causing the formation of corrosive substances. It is preferable. Hereinafter, a method of reacting the binaphthols with alkylene oxide will be described in detail.

The alkylene carbonate used in the method of reacting binaphthols with alkylene carbonate may be any alkylene group having 2 to 5 carbon atoms, such as ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. As described above, as A ¹ and A ^{2 in} the general formula (1), ethylene, n-propylene, and isopropylene have a high (meth) acrylate resin refractive index and a low resin viscosity. Therefore, ethylene carbonate and propylene carbonate are preferable as the alkylene carbonate. Here, in order to adjust the molar ratio of C2 alkyl to C3 alkyl (C2 alkyl / C3 alkyl) in the (meth) acrylate resin in the range of 50/50 to 98/2, the ratio of ethylene carbonate to propylene carbonate It is preferable to use the (molar ratio) in such a ratio that the former / the latter is 50/50 to 98/2.

The reaction ratio between the binaphthols and the alkylene carbonate is not particularly limited, and the higher the equivalent ratio of the alkylene carbonate to the hydroxyl group of the binaphthols, the more preferable is the value of 1 in the structural formula (A). The values of m and n in the general formula (1) are increased. As described above, the value of l in the structural formula (A) and the values of m and n in the general formula (1) are integers of 1 to 10, and in order to adjust to this range, the hydroxyl group of the binaphthols It is preferably in the range of 1 to 10 equivalents of alkylene carbonate with respect to 1 equivalent.

In addition, the value of l in the structural formula (A) and the values of m and n in the general formula (1) are 1.0 to 1.0 on average because the refractive index of the (meth) acrylate resin itself is high. It is preferably 3.0, particularly 1.0 to 1.5, and more preferably 1, but in order to adjust to such a range, 1 to 5 equivalents of alkylene carbonate per 1 equivalent of hydroxyl group of binaphthols. It is preferably in the range of ˜5 equivalents, particularly in the range of 1 to 3 equivalents.

As alkylene carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. can be used.

The catalyst in the reaction of the method 3) may be either an alkali catalyst or an acid catalyst, but is preferably an alkali catalyst from the viewpoint that the reaction proceeds rapidly and impurities are reduced. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate and the like, among which potassium hydroxide and sodium hydroxide are preferable. The acid catalyst is not particularly limited, and examples thereof include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like. Among them, p-toluenesulfonic acid is preferable. The catalyst is preferably used in an amount of 0.001 to 0.1 equivalent of catalyst with respect to 1 equivalent of hydroxyl group of polynaphthol.

The above reaction proceeds even without solvent, but when used, it is preferable to use other organic solvents such as toluene and xylene other than alcohol solvents that inhibit the reaction. Further, the reaction temperature is preferably in the range of 80 to 200 ° C. as described above, and more preferably in the range of 100 to 180 ° C., since the reaction proceeds well and the impurities are reduced.

Next, the hydroxyl group-containing compound thus obtained is specifically represented by the following general formula (3)

(Wherein X ¹ to X ¹² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and A ¹ and A ² are carbon atoms. A linear or branched alkylene group having 2 to 5 atoms, n and m are repeating units and are integers of 1 to 10, provided that at least one of Y ¹ and Y ² is an acryloyloxy group or a methacryloyloxy group; The desired (meth) acrylate resin can be obtained by reacting with a (meth) acrylate agent.

Here, as the (meth) acrylate agent, (meth) acrylic acid such as acrylic acid and methacrylic acid; (meth) acrylic acid halogen such as acrylic acid chloride and methacrylic acid chloride; methyl acrylate, methyl methacrylate, acrylic acid Examples include alkyl (meth) acrylates such as ethyl and ethyl methacrylate. Of these, halogens (meth) acrylates cause by-products such as hydrochloric acid during reaction to cause corrosion problems in the reaction kettle, and when alkyl (meth) acrylates are used, by-product alcohol is removed. (Meth) acrylic acid is preferable because it is necessary to carry out a dealcoholization treatment.

The reaction between the hydroxyl group-containing compound and (meth) acrylic acid can be carried out, for example, by performing a dehydration reaction in an organic solvent such as toluene, benzene, cyclohexane, n-hexane, n-heptane and the like in the presence of an acid catalyst. . Examples of the acid catalyst used here include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and the like. In addition, it is preferable to use a polymerization inhibitor (for example, hydroquinone, p-methoxyphenol, methylhydroquinone, etc.) in order to prevent polymerization during the reaction.

The reaction ratio between the hydroxyl group-containing compound and (meth) acrylic acid is preferably such that (meth) acrylic acid is 0.75 to 0.99 equivalents per hydroxyl group equivalent of the hydroxyl group-containing compound. The reaction temperature is preferably 60 to 120 ° C., and the reaction time is preferably 3 to 20 hours.

The curable resin composition of the present invention comprises a (meth) acrylate resin described in detail above (hereinafter, the (meth) acrylate resin is abbreviated as “(meth) acrylate resin (A)”), a radical polymerization initiator ( And B) as essential components.

Examples of the radical polymerization initiator (B) used here include a photopolymerization initiator and a thermal polymerization initiator. Specific examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, 2-methylbenzoin, benzophenone, Michler's ketone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, benzoylbenzoic acid, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthiophenyl)]-2-morpholino) propane-1, 2-chlorothioxanthone, 2,4 -Diethylthioki Cantonal, 2,4-diisopropyl thioxanthone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.

These photopolymerization initiators can be used alone or as a mixture of two or more. The amount used is preferably such that the photopolymerization initiator is 0.01 to 30 parts by weight with respect to 100 parts by weight of the (meth) acrylate resin (A), particularly preferably 0.01 to 20 parts by weight. Or less. When the blending range is less than this range, the polymerization rate becomes slow and the curing becomes insufficient. On the other hand, if this range is exceeded, the refractive index will drop.

These photopolymerization initiators can be used in combination with a photopolymerization accelerator such as amines. Examples include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like. The use ratio of these photopolymerization accelerators is in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerization initiator, the polymerization rate is high, and the refractive index of the cured product is high. This is preferable.

Next, as the thermal polymerization initiator, known peroxide initiators and azobis initiators can be used. Specifically, as the peroxide initiator, ketone peroxide initiators such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexane ketone peroxide, acetylacetone peroxide, isobutyl peroxide, diacyl peroxide initiators such as m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, α-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, 2,4,4 Hydroperoxides such as trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide Id initiator, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumylper Dialkyl peroxide initiators such as oxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di- (t-butylperoxy) butane, 4,4- Peroxyketal initiators such as di-t-butylperoxyvaleric acid-n-butylester, 2,4,4-trimethylpentylperoxyphenoxyacetate, α-cumylperoxyneodecanoate, t-butylper Alkyl perester initiators such as oxybenzoate and di-t-butylperoxytrimethylodipate, di-t-methoxybutyl -Peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, percarbonate-based initiators such as bis (4-t-butylcyclohexyl) peroxydicarbonate and diisopropylperoxydicarbonate, and other acetylcyclohexylsulfonylperoxydi Examples of the azobis initiator include 1,1′-azobiscyclohexane-1-carbonitrile and 2,2′-azobis. -(2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (methylisobutyrate), α, α ' -Azobis- (isobutyronitrile), 4,4'-azobis- (4 Shianobarein acid).

These thermal polymerization initiators can be used alone or as a mixture of two or more. The amount used is such that the thermal polymerization initiator is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylate resin (A), the polymerization rate is fast, and the curing is This is preferable from the viewpoint of increasing the refractive index of the object.

In addition to the (meth) acrylate resin (A) and the radical polymerization initiator (B) described above, the curable resin composition of the present invention further includes a radical polymerizable monomer as a diluent for adjusting the viscosity of the composition. The body (C) or other organic solvent (D) can be used in combination. In the present invention, among these diluents, the radically polymerizable monomer (C) is particularly preferable because the cured product has good heat resistance and moisture resistance.

The radical polymerizable monomer (C) used here is a (meth) acrylate monomer such as a monofunctional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, or a trifunctional or higher polyfunctional (meth) acrylate monomer. And vinyl monomers such as styrene, methylstyrene, halogenated styrene, and divinylbenzene.

Examples of the monofunctional (meth) acrylate monomer include acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydro Furfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) ) Acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Data) acrylate, o- phenylphenol polyethoxy (meth) acrylate, and the like.

Examples of bifunctional (meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and tricyclodecanedi. Methanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate,
Examples thereof include ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate monomer include tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of hydroxypentylglycolate dipentylglycol, trimethylolpropane tri (meth) acrylate, trimethylolpropane poly Examples thereof include ethoxytri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.

Among these, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate are particularly effective as a diluent in a curable resin composition because of the effect of reducing the viscosity of the composition and maintaining a high refractive index of the cured product. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Monofunctional or bifunctional (meth) acrylate monomers such as pentenyloxyethyl (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, and divinylbenzene are preferred. Particularly, phenoxyethyl (meth) acrylate, o Phenylphenol polyethoxy (meth) acrylate, and those selected from the group consisting of divinylbenzene is preferable from the point where the high refractive index of the cured product is excellent in dilution capability.

On the other hand, examples of the organic solvent (D) include methyl ethyl ketone, carbitol acetate, butyl cellosolve acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and solvent naphtha.

The diluent sufficiently exhibits the effect of reducing the viscosity of the composition, and can maintain the refractive index of the cured product at a high level in a mass ratio of [(meth) acrylate resin / diluent] of 90/10 to It is preferably used at a ratio of 30/70, particularly 80/20 to 40/60.

In the curable resin composition of the present invention, additives such as a silane coupling agent, a polymerization inhibitor, and a leveling agent can be added as long as the original characteristics are not changed for further performance improvement. Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.

Examples of the polymerization inhibitor that can be used here include hydroquinone monomethyl ether, methyl hydroquinone, t-butylcatechol, p-benzoquinone, 2,5-t-butyl-hydroquinone, and phenothiazine. Examples of the leveling agent include “Modaflow” manufactured by Monsanto.

The method of curing the curable resin composition of the present invention described in detail is that the curable resin composition is applied or molded to a substrate according to the purpose and application, and then irradiated with active energy rays or heated. The method of doing is mentioned.

Here, when it hardens | cures by irradiation of an active energy ray, an electron beam, an ultraviolet-ray, visible light etc. are mentioned as this active energy ray. When an electron beam is used as the active energy beam, a Cochloft Walton type accelerator, a bandegraph type electron accelerator, a resonant transformer type accelerator, an insulated core transformer type, a dynamitron type, a linear filament type, a high frequency type, etc. The curable resin composition of the present invention can be cured using a generator. When ultraviolet rays are used as the active energy ray, they can be cured by irradiation with a mercury lamp such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp or a low pressure mercury lamp, a xenon lamp, a carbon arc, a metal height lamp or the like. In this case, the amount of ultraviolet light exposure is preferably in the range of 0.1 to 1000 mJ / cm ² .

On the other hand, when cured by heating, it can be cured by heating to a temperature range of 60 to 250 ° C.

Since the curable resin composition of the present invention described in detail above has performances such as high refractive index, high heat resistance, and high moisture resistance, plastic lenses such as spectacle lenses, digital camera lenses, Fresnel lenses, and prism lenses. It can be applied to various optical materials such as optical overcoat agent, hard coat agent, antireflection film, optical fiber, optical waveguide, hologram, prism lens, LED sealing material, solar cell coating material and the like.

Among these, in particular, it can be preferably applied to a plastic lens because of its high refractive index in the cured product and excellent heat resistance and moisture resistance of the cured product, and is particularly useful as a prism lens for a liquid crystal substrate.

Here, the prism lens for a liquid crystal substrate has a plurality of fine prism-shaped portions on one side of a sheet-like molded body, and usually has a prism surface on the back side (light source side) of the liquid crystal display element and on the element side. Further, the sheet-like lens is used so that the light guide sheet is arranged on the back surface thereof, or the prism lens is a sheet-like lens having a function of the light guide sheet.
Here, the prism portion of the prism lens preferably has a prism apex angle θ in the range of 70 to 110 ° from the viewpoint of excellent light-collecting properties and improved luminance, and particularly in the range of 75 to 100 °. In particular, the range of 80 to 95 ° is particularly preferable.

Also, the prism pitch is preferably 100 μm or less, and particularly preferably in the range of 70 μm or less from the viewpoint of preventing the generation of moiré patterns on the screen and further improving the definition of the screen. Further, the height of the unevenness of the prism is determined by the value of the prism apex angle θ and the prism pitch, but is preferably in the range of 50 μm or less. In addition, the sheet thickness of the prism lens is preferably thick from the viewpoint of strength, but optically it is preferably thin in order to suppress light absorption. From the viewpoint of these balances, the sheet thickness is in the range of 50 μm to 1000 μm. preferable.

In order to produce the prism lens described above from the curable resin composition of the present invention, for example, the curable resin composition is applied to a molding die such as a mold or a resin die on which a prism pattern is formed, and the resin composition After smoothing the surface, a method of producing by irradiating and curing a transparent base material and irradiating active energy rays can be mentioned.

Here, as long as the transparent base material is highly transparent, a material having a thickness of 3 mm or less is preferable in consideration of the transparency of the active energy ray, the handleability, and the like. Examples of the material for the transparent substrate include acrylic resins, polycarbonate resins, polyester resins, polystyrene resins, fluorine resins, polyimide resins, synthetic resins such as a mixture of these polymers, and glass.

The prism sheet formed on the transparent substrate thus obtained can be used as it is, but the transparent substrate may be peeled off and used as a single prism portion. When using with the prism part formed on a transparent substrate, it is important from the viewpoint of weather resistance and durability that the interface is adequately bonded. It is preferable to perform the treatment.

On the other hand, when the transparent substrate is used after being peeled off, it is preferable that the transparent substrate can be peeled relatively easily, and the surface of the transparent substrate is preferably subjected to a surface treatment with silicone or a fluorine-based release agent.

In the following, embodiments of the present invention will be described in more detail with reference to synthesis examples, but the present invention is not limited thereto.
1) Viscosity: Measured at 25 ° C. using an E type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.).
2) ¹³ C-NMR: NMR “GSX270” manufactured by JEOL Ltd.
3) FD-MS: Double convergence type mass spectrometer “AX505H (FD505H)” manufactured by JEOL Ltd.

Example 1
To a 5 L four-necked flask equipped with a stirrer, thermometer, Dean-Stark trap and condenser were added 858 g (3 mol) of binaphthol, 634 g (7.2 mol) of ethylene carbonate and 24 g of 48% by mass potassium hydroxide at 170 ° C. For 4 hours. Thereafter, 1500 g of methyl isobutoxy ketone was added and dissolved, 1000 g of water was added, stirring was stopped, and the lower layer was discarded. Further, 1000 g of water was added, stirring was stopped, and the lower layer was discarded. Thereafter, the solvent was removed at 150 ° C. to obtain 1050 g of a resin having a melting point of 108 ° C. by DSC measurement. This resin was measured by mass spectrum (FD-MS), and a peak of M = 374 was confirmed. From the measurement result of ¹³ C-NMR shown in FIG. It was confirmed to be compound (a).

Next, in a 1 L four-necked flask equipped with a stirrer, thermometer, condenser and decanter, 187 g (0.5 mol) of the hydroxyl group-containing compound (a), 200 g of toluene, 72 g (1.0 mol) of acrylic acid, p -Toluenesulfonic acid (15 g) and hydroquinone (1 g) were added, and dehydration reaction was carried out at 80-100 ° C for 10 hours.

Next, the reaction liquid was cooled, charged with 200 g of toluene and 100 g of a 20% aqueous sodium hydroxide solution, the stirring was stopped, and the lower layer was discarded. Subsequently, it was washed twice with 20% sodium chloride and 100 g of an aqueous solution. Thereafter, the solvent was removed at 100 ° C. to obtain 200 g of a resin. When this resin was measured by mass spectrum, peaks of M = 482 and M = 428 were confirmed, and from the measurement result of ¹³ C-NMR shown in FIG. 2, the compound represented by the following structural formula (α) It confirmed that it was an acrylate resin (A) which is a mixture of ((alpha)) and the compound ((beta)) represented by following structural formula ((beta)).

From the gas chromatograph (each isolated and calculated by the internal standard method), the ratio of the compound (α) to the compound (β) [molar ratio of (α) / (β)] is 90/10. The acryloyloxy group / hydroxyl molar ratio was confirmed to be 95/5. This acrylate resin has a refractive index of 1.63 and a viscosity measured by an E-type viscometer of 460 Pa.s. s.

(Curability evaluation)
Next, 80 parts by mass of the obtained acrylate resin (A), 20 parts by mass of phenoxyethyl acrylate, and 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator were used. The blended composition was applied to a glass plate using a bar coater (No. 20), and then irradiated with a high-pressure mercury lamp of 120 W / cm ^{2 in} an air atmosphere at a dose of 100 mJ / cm ² to be curable. Evaluated. Evaluation was judged according to the following criteria.
○: Curing (no tack)
×: Uncured (with tackiness)
Table 1 shows the curability results together with the properties of the acrylate resin (A).

Example 2
Except having changed the usage-amount of acrylic acid into 61 g (0.85 mol), it carried out similarly to Example 1 and obtained 190 g of acrylate resin (B). From the gas chromatograph (each isolated and calculated by the internal standard method), the ratio of the compound (α) to the compound (β) [molar ratio of (α) / (β)] is 60/40, and acryloyl It was confirmed that the oxy group / hydroxyl group was 80/20 (molar ratio). This acrylate resin has a refractive index of 1.64 and a viscosity measured by an E-type viscometer of 490 Pa.s. s.
(Curability evaluation)
The curability was evaluated in the same manner as in Example 1 except that the acrylate resin (A) was changed to the acrylate resin (B). Table 1 shows the curability results together with the properties of the acrylate resin (B).

Example 3
Except having changed the usage-amount of acrylic acid into 86 g (1.2 mol) and having changed reaction time into 12 hours, it carried out similarly to the synthesis example 1, and obtained acrylate resin (C) 205g. From the gas chromatograph (each isolated and calculated by the internal standard method), the ratio of the compound (α) to the compound (β) [molar ratio of (α) / (β)] is 99/1, and the acryloyloxy group / It was confirmed that the hydroxyl group was 99.5 / 0.5 (molar ratio). This acrylate resin has a refractive index of 1.63 and a viscosity measured by an E-type viscometer of 440 Pa.s. s. The acrylate resin crystallized when left at 25 ° C. for 2 hours.
(Curability evaluation)
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). Table 1 shows the curability results together with the properties of the acrylate resin (C).

Example 4
Except having changed the usage-amount of acrylic acid into 58 g (0.80 mol) and changing reaction time into 6 hours, it carried out similarly to Example 1 and obtained 185g of acrylate resin (D). From the gas chromatograph (isolated and calculated by the internal standard method), the ratio of the compound (α) to the compound (β) [molar ratio of (α) / (β)] was 40/60, and acryloyl group / It was confirmed that the hydroxyl group was 70/30 (molar ratio). This acrylate resin has a refractive index of 1.65 and a viscosity measured by an E-type viscometer of 510 Pa. s.
(Curability evaluation)
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). Table 1 shows the curability results together with the properties of the acrylate resin (D).

Example 5
286 g (1 mol) of binaphthol, 190 g (2.16 mol) of ethylene carbonate, 24 g (0.24 mol) of propylene carbonate, 48 mass in a 2 L four-necked flask equipped with a stirrer, thermometer, Dean-Stark trap and condenser 8 g of an aqueous potassium hydroxide solution was added and reacted at 170 ° C. for 4 hours. Thereafter, 500 g of methyl isobutoxy ketone was added and dissolved, 300 g of water was added, stirring was stopped, and the lower layer was discarded. Further, 300 g of water was added, stirring was stopped, and the lower layer was discarded. Thereafter, the solvent was removed at 150 ° C. to obtain 340 g of a resin.

Next, 187 g of resin, 200 g of toluene, 86 g of acrylic acid (1.2 mol), 15 g of p-toluenesulfonic acid, hydroquinone obtained in a 1 L four-necked flask equipped with a stirrer, thermometer, condenser and decanter 1 g was added and dehydration reaction was carried out at 80-100 ° C. for 10 hours. Next, the reaction liquid was cooled, charged with 200 g of toluene and 100 g of a 20% aqueous sodium hydroxide solution, the stirring was stopped, and the lower layer was discarded. Subsequently, it was washed twice with 20% sodium chloride and 100 g of an aqueous solution. Thereafter, the solvent was removed at 100 ° C. to obtain 201 g of an acrylate resin (E). Further, from the measurement result of ¹³ C-NMR, it was confirmed that the molar ratio of ethyleneoxo group / propyleneoxo group was 90/10. This acrylate resin has a refractive index of 1.63 and a viscosity measured with an E-type viscometer of 465 Pa.s. s.
(Curability evaluation)
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). Table 2 shows the results of curability together with the properties of the acrylate resin (E).

Example 6
Except having changed into 127 g (1.44 mol) of ethylene carbonate and 98 g (0.96 mol) of propylene carbonate, it carried out similarly to Example 5 and obtained 203 g of acrylate resin (F). Further, from the measurement result of ¹³ C-NMR, it was confirmed that the molar ratio of ethyleneoxo group / propyleneoxo group was 60/40. This acrylate resin has a refractive index of 1.62 and a viscosity measured by an E-type viscometer of 480 Pa.s. s.
(Curability evaluation)
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). Table 2 shows the curability results together with the properties of the acrylate resin (F).

Example 7
Except having changed into ethylene carbonate 209g (2.38 mol) and propylene carbonate 2g (0.02 mol), it carried out similarly to Example 5 and obtained acrylate resin (G) 206g. Further, from the measurement result of ¹³ C-NMR, it was confirmed that the molar ratio of ethyleneoxo group / propyleneoxo group was 99/1. This acrylate resin has a refractive index of 1.63 and a viscosity measured by an E-type viscometer of 455 Pa.s. s. The acrylate resin crystallized when left at 25 ° C. for 2 hours.
(Curability evaluation)
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). Table 2 shows the curability results together with the properties of the acrylate resin (G).

Example 8
Except having changed into 95 g (1.08 mol) of ethylene carbonate and 135 g (1.32 mol) of propylene carbonate, it carried out similarly to Example 5 and obtained 206 g of acrylate resin (H). Further, NMR confirmed that ethyleneoxo group / propyleneoxo group = 45/55 (molar ratio). The acrylate resin (H) has a refractive index of 1.61 and a viscosity measured by an E-type viscometer of 510 Pa. s.
(Curability evaluation)
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). Table 2 shows the curability results together with the properties of the acrylate resin (H).

As described above, when it was in the range of acryloyl group / hydroxyl group = 75/25 to 99/1 (molar ratio), it became liquid at room temperature and had good curability. On the other hand, when the ratio of the hydroxyl group is less than this range, the crystallinity becomes high, and crystallization occurred when left at room temperature for 2 hours.

As described above, when the ratio of ethyleneoxo group / propyleneoxo group was in the range of ethyleneoxo group / propyleneoxo group = 50/50 to 98/2 (molar ratio), it became liquid at normal temperature. However, when the ratio of propylene oxo was less than this range, the crystallinity was high, and crystallization occurred upon standing at room temperature for 2 hours.

Comparative Example 1
Compound (a) 187 g (0.5 mol), terephthalic acid 83 g (0.5 mol), dibutyltin obtained in Example 1 in a 1 L four-necked flask equipped with a stirrer, thermometer, condenser and decanter Esterification was performed by adding 0.7 g of oxide and gradually heating from 190 ° C. to 230 ° C. under a reduced pressure of 5 to 10 Torr while stirring. After extracting a predetermined amount of water out of the system, the temperature was increased and the pressure was gradually reduced, and the temperature of the heating tank was reached to 280 ° C. and the degree of pressure reduction to 133.322 Pa or less while removing the generated water. After maintaining this condition for 1 hour, the reaction product was extruded into water to obtain 210 g of a polyester resin (I). The refractive index of this resin was 1.67. The E type viscometer could not be measured because it was solid.

Comparative Example 2
The following structural formula

The refractive index of the fluorene type acrylate represented by the formula (acrylate resin (J), “Ogsol EA-0200” manufactured by Osaka Gas Chemical Company) was 1.59. The E type viscometer could not be measured because it was semi-solid.

Comparative Example 3
The following structural formula

The refractive index of the fluorene type epoxy acrylate represented by the formula (acrylate resin (K), “ASF-400” manufactured by Nippon Steel Chemical Co., Ltd.) was 1.58. The E type viscometer could not be measured because it was solid.

Examples 9 to 12 and Comparative Examples 4 to 6
The following method using acrylate resins (A), (B), (E), (F), fluorene type acrylate resin (J), fluorene type epoxy acrylate resin (K), and polyester resin (I) of Comparative Compound 1 A coating film was prepared and evaluated in various ways. The results are shown in Table 3.

(Creation of cured coating film of acrylate resin (A), (B), (E), (F), (J) or (K))
80 parts by mass of an acrylate resin (A), (B), (E), (F), (J) or (K), 20 parts by mass of phenoxyethyl acrylate, Iragacure 184 (3 parts) as a photopolymerization initiator , Ciba Specialty Chemicals) was applied to a glass plate using a bar coater (No. 20). Next, it irradiated with the irradiation amount of 500 mJ / cm < ² > using the 120 W / cm < ² > high pressure mercury lamp in air atmosphere, and obtained the cured coating film.

(Adjustment of coating film using polyester resin (I))
The polyester resin (I) was heated to 150 ° C. and melted, and applied to a glass plate using a bar coater (No. 20).

(Solvent resistance)
The coating film obtained by preparing the coating film was rubbed 50 times with a cotton swab (manufactured by Johnson) containing methyl ethyl ketone, and the change of the coating film was visually observed. Evaluation was judged as follows.
Evaluation ○: No change ×: Change such as cloudiness and peeling (heat resistance)
The coating film obtained by preparing the coating film was placed in a 125 ° C. drier and held for 150 hours. The change of the coating film after holding was visually observed. Evaluation was judged as follows.
Evaluation ○: No change △: Change in hue only, no change in shape ×: Change in hue and shape (moisture resistance)
The coating film obtained by preparing the coating film was placed in a constant temperature and humidity machine at 85 ° C. and a humidity of 85% and held for 300 hours. The change of the coating film after holding was visually observed. Evaluation was judged as follows.
Evaluation ○: No change △: Change in hue only, no change in shape ×: Change in hue and shape

As described above, it was confirmed that the acrylate resin of the present invention has a low viscosity and a high refractive index, and the cured product after light irradiation is excellent in a high refractive index, solvent resistance, heat resistance, and moisture resistance.

Examples 13 to 16, Comparative Examples 7 to 9
Active energy ray cured product using acrylate resins (A), (B), (E), (F), fluorene-type acrylate resin (J) of comparative compound 1 and fluorene-type epoxy acrylate resin (K) of comparative compound 2 A coating film was prepared by the following method using the polyester resin (I) obtained in Comparative Example 1, and various evaluations were performed in the same manner as in Example 12. The results are shown in Table 4.
(Creation of cured coating film of acrylate resin (A), (B), (E), (F), (J) or (K))
80 parts by mass of acrylate resin (A), (B), (E), (F), (J) or (K), 20 parts by mass of phenoxyethyl acrylate, 3 parts by mass of methyl ethyl ketone peroxide as a thermal polymerization initiator The composition containing was applied to a glass plate using a bar coater (No. 20). Next, it was put into a dryer at 100 ° C. and held for 4 hours to obtain a cured coating film.
(Adjustment of coating film using polyester resin (I))
The polyester resin (I) was heated to 150 ° C. and melted, and applied to a glass plate using a bar coater (No. 20).

As described above, it was confirmed that the acrylate resin of the present invention has a low viscosity and a high refractive index, and the cured product after heat curing is excellent in a high refractive index, solvent resistance, heat resistance, and moisture resistance.

Examples 17 to 22 and Comparative Examples 10 to 11
A varnish-like composition was prepared according to the formulation shown in Table 5 below, and the liquid refractive index and viscosity of the composition were measured by the following method. Then, a cured coating film was produced in the same manner as in Example 12. The solvent resistance, heat resistance, and moisture resistance were evaluated.
Moreover, the cured film A and the board | substrate B with a cured film were manufactured by the following method using each composition, and transparency and adhesiveness were evaluated. Furthermore, the release property from a metal mold | die was evaluated by the following method using this composition. The results are shown in Table 5.

[Production of cured film A]
The composition prepared according to the composition shown in Table 5 below was placed between a chrome-plated metal plate and a transparent untreated PET film, the thickness was adjusted, and a UV light of 500 mJ / cm ² was applied to the transparent substrate using a high-pressure mercury lamp. After being irradiated and cured from the side, a cured film (hereinafter abbreviated as “cured film A”) was taken out from the metal plate and the transparent substrate.

[Manufacture of substrate B with cured film]
The composition prepared in accordance with the composition shown in Table 5 below was placed between a chrome-plated metal plate and a transparent surface adhesion-treated PET film, and then the thickness was adjusted. Using a high-pressure mercury lamp, UV light of 500 mJ / cm ² was used as a transparent base. After being cured by irradiation from the material side, only the metal plate was peeled off to obtain a substrate with a cured film (hereinafter abbreviated as “substrate B with cured film”).

[Liquid refractive index]
It applied directly to the prism of an Abbe refractometer, and the refractive index (D-line of 589.3 mm) was measured at 25 ° C.
[viscosity]
Viscosity was measured at 25 ° C. with an E-type rotational viscometer.
[Hardened material refractive index]
The cured film A was adhered to the Abbe refractometer prism with 1-bromonaphthalene, and the refractive index (D line of 589.3 mm) was measured at 25 ° C.
[transparency]
Using the cured film A, the light transmittance in the wavelength region of 400 to 900 nm was measured. A film showing a transmittance of 85% or more in all regions was marked with ◯, and a light transmittance less than that was marked with ×.
[Adhesion]
Using the substrate B with a cured film, the adhesion between the base material and the cured film layer was measured in accordance with JIS K5400.
[Releasability]
The composition adjusted according to the composition shown in Table 5 below was placed between the chrome-plated prism mold and the transparent surface adhesion-treated PET film, the thickness was adjusted, and UV light of 500 mJ / cm ² was made transparent with a high-pressure mercury lamp. After being cured by irradiation from the material side, when the mold was released from the mold, the one in which the composition did not remain in the mold was marked with ◯, and the remaining one was marked with x.

In Table 5, “phenoxyethyl acrylate” is “Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd., and “OPPEA” is o-phenylphenol ethylene oxide modified acrylate (“Aronix TO-1463” manufactured by Toagosei Co., Ltd.). “Photoinitiator” is 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals).

Claims (11)

1. In addition to having a binaphthalene skeleton in the molecular structure, as a substituent on the aromatic nucleus of the binaphthalene skeleton, the following structural formula (A)
   

   

   
   (Wherein R ¹ is a linear or branched alkylene group having 2 to 5 carbon atoms, R ² is a hydrogen atom or a methyl group, and l is an integer of 1 to 10 as a repeating unit.)
   (Meth) acrylate resin characterized by having the substituent represented by these.
2. The following general formula (1)
   

   

   
   (Wherein X ¹ to X ¹² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and A ¹ and A ² are carbon atoms. A linear or branched alkylene group having 2 to 5 atoms, Y ¹ and Y ² are a hydroxyl group, an acryloyloxy group, or a methacryloyloxy group, n and m are repeating units, each having 1 to 10 (However, at least one of Y ¹ and Y ² is an acryloyloxy group or a methacryloyloxy group.)
   The (meth) acrylate resin of Claim 1 which has the molecular structure represented by these.
3. The (meth) acrylate resin according to claim 1 or 2, which is liquid at 25 ° C.
4. The (meth) acrylate resin is a mixture of various compounds represented by the general formula (1), and the hydroxyl group (y1) and acryloyl in Y ¹ and Y ² of the general formula (1) The (meth) acrylate resin according to claim 2, wherein the ratio with the oxy group or methacryloyloxy group (y2) is in the range of 75/25 to 99/1 in terms of molar ratio (y2 / y1).
5. The (meth) acrylate resin is a mixture of various compounds represented by the general formula (1), and A ¹ and A ^{2 in} the structural formula (1) are each independently an ethylene group ( a1) and an alkylene group having 3 to 5 carbon atoms (a2), and the ethylene group (a1) and the alkylene group having 3 to 5 carbon atoms (a2) The (meth) acrylate resin according to claim 2, wherein the molar ratio (a1 / a2) is in the range of 50/50 to 98/2.
6. The (meth) acrylate resin according to any one of claims 1 to 5, which has a viscosity at 25 ° C of 3000 Pa · s or less.
7. It is characterized by reacting binaphthols with alkylene oxide, halogenoalkanol, or alkylene carbonate to obtain a compound having a hydroxyl group, and then reacting the resulting reaction product having a hydroxyl group with a (meth) acrylate agent. A method for producing (meth) acrylate resin.
8. A curable resin composition comprising the (meth) acrylate resin (A) according to any one of claims 1 to 6 and a radical polymerization initiator (B) as essential components.
9. The curable resin composition according to claim 8, further comprising a radical polymerizable monomer (C) in addition to the (meth) acrylate resin (A) and the radical polymerization initiator (B).
10. A cured product obtained by curing the curable resin composition according to claim 9 by irradiation with active energy rays or heating.
11. A plastic lens obtained by molding and curing the curable resin composition according to claim 9.

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