JPH0959535A - Active energy beam curing type resin composition, its cured product and fresnel lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a specific urethane acrylate, capable of providing high refractive index type cured coating film excellent in coating workability, physical properties of coating film and economical efficiency, compared with a conventional composition and therefore suitable as a raw material for thin fresnel lens. SOLUTION: This compound contains a urethane acrylate comprising (A) an organic isocyanate having two or more isocyanate groups capable of reacting with hydroxy groups (preferably tolylene diisocyanate), (B) a polyol having two or more hydroxyl groups and >=300 molecular weight (preferably polycaprolactone) and (C) a (meth)acrylate monomer having both of hydroxyl group and aromatic ring. A compound of formula I [R<1> is H or methyl; R<2> is H or a 1-10C alkyl; R<3> to R<5> are each H, phenyl, etc.; (a) is 0-20] etc., is preferably used as the component C. Furthermore, the composition is preferably further blended with a compound of formula II [* exhibits an (un)saturation; R<6> and R<7> are H or a lower alkyl; R<8> and R<9> are each H or methyl; (n) is 1-10].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray-curable resin composition containing a urethane acrylate having a specific structure and having excellent physical properties, a cured product thereof, and a thin Fresnel lens comprising the cured product.

[0002]

2. Description of the Related Art Active energy ray-curable resins that cure with active energy rays such as ultraviolet rays or electron beams have excellent productivity and are widely used due to the increasing awareness of environmental problems in recent years. Widely used in the field. Among them, in the field of molding resin, it is possible to reduce the product cost because the number of molds is smaller than that of the conventional hot pressing method, and it is possible to lower the molding temperature and shorten the molding time. Therefore, it has advantages in terms of product performance and cost, and is particularly noticed and used. On the other hand, in a field lens of a projector, a focus glass of a camera, a projection television, etc., a Fresnel lens that transmits parallel rays by cutting fine annular zones on the surface of a plastic plate is used. Fresnel lenses used in these fields are required to be particularly thin, and in view of their function and moldability, the refractive index of the resin composition that can be used is 1.4.
It is required that the resin composition has a hardness of 7 or more, is rapidly cured by ultraviolet rays during molding, and has appropriate flexibility from the viewpoint of physical properties such as scratch resistance and restoration property.

As such a molding resin having a high refractive index, a resin containing a sulfur-containing compound is used in JP-A-5-247256 and JP-B-6-25232. No. 117348 uses halogen-containing compounds other than bromine and fluorine,
Japanese Unexamined Patent Publication (Kokai) No. 5-65318 proposes one using an aromatic ring-containing acrylate monomer. However, the compounds disclosed in the above publications are not satisfactory in that the raw materials are limited to special ones, and the scratch resistance and the restoring property are satisfactory. Under these circumstances, an active energy ray-curable resin composition that is a high-refractive-index cured product having excellent coating workability without using a special compound, its cured product, and a Fresnel lens using the cured product Development is desired.

[0004]

As a result of intensive studies on urethane acrylates, the present inventors have found that specific urethane acrylates can be cured by active energy rays.
The active energy ray-curable resin composition is excellent in coating film workability and coating film physical properties, and it is found that the cured product has a high refractive index and a Fresnel lens can be easily obtained from the cured product. The invention was completed.

That is, the present invention relates to an organic isocyanate having at least two isocyanate groups capable of reacting with a hydroxyl group (a), a polyol having at least two hydroxyl groups in a molecule and having a molecular weight of at least 300 (b) and at least 1
The present invention provides an active energy ray-curable resin composition containing a urethane acrylate composed of one hydroxyl group and (meth) acrylate monomer (c) having at least one aromatic ring. Further, the (meth) acrylate monomer (c) having at least one hydroxyl group and at least one aromatic ring is a compound selected from the following general formulas (1) to (5): An energy ray curable resin composition is provided. Further, the compound represented by the general formula (6) is added in an amount of 5 to 40 parts by weight based on 100 parts by weight of the urethane acrylate.
The present invention provides the active energy ray-curable resin composition, which is contained by weight. Also, urethane acrylate 1
The present invention provides the active energy ray-curable resin composition containing 1 to 10 parts by weight of a photopolymerization initiator with respect to 00 parts by weight. Furthermore, the refractive index at 25 ° C is 1.4
It provides a cured product of the active energy ray-curable resin composition, which is 7 or more. In addition, the present invention provides a Fresnel lens characterized by laminating the cured product on a cured product of a thermoplastic resin having a haze of 10% or less. Further, the present invention provides a Fresnel lens characterized in that the thermoplastic resin is polymethylmethacrylate. Hereinafter, the present invention will be described in detail.

[0006]

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[0007]

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[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The "organic isocyanates (a) having at least two isocyanate groups capable of reacting with a hydroxyl group" used in the present invention include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate,
Examples include diisocyanates such as xylylene diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1,6-hexamethylene diisocyanate, and isocyanurates such as hexamethylene diisocyanate trimers and isophorone diisocyanate trimers. . Among these, tolylene diisocyanate and xylylene diisocyanate are particularly preferable.

Examples of the "polyol (b) having two or more hydroxyl groups in one molecule and a molecular weight of 300 or more" include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetraethylene glycol, polycaprolactone and polybutyrolactone. Lactone polyester polyols, polycarbonate polyols, and the like. Among these, polycaprolactone and polybutyrolactone are particularly preferable. The molecular weight of the polyol (b) having two or more hydroxyl groups in one molecule is preferably 300 or more, and particularly preferably 500 to 1000. When the molecular weight is less than 300, the flexibility of the urethane acrylate decreases, and the coating film physical properties of the composition decrease.

"At least one hydroxyl group and at least one
The (meth) acrylate monomer (c) having one aromatic ring is not particularly limited as long as it is a compound having both one reactive hydroxyl group and one aromatic ring in one molecule. By having both a reactive hydroxyl group and an aromatic ring, a resin composition having a high refractive index after curing can be obtained. Particularly preferred are the compounds represented by the general formulas (1) to (5).

The "compound represented by the general formula (1)" is 2-hydroxyethyl-2-phenyl (meth) acrylate, 2-hydroxypropyl-2-phenyl (meth) acrylate, 2-hydroxybutyl-2. -Phenyl (meth) acrylate, 2-hydroxybutyl-2-
(2,4,6-tribromophenyl) (meth) acrylate, 2-hydroxybutyl-2- (4-methylphenyl) (meth) acrylate, or styrene oxide and ε-caprolactone-modified (meth) acrylic acid Examples include reaction products. Of these, 2-hydroxyethyl-2-phenyl acrylate is particularly preferable.

The "compound represented by the general formula (2)" includes 2-hydroxypropyl-3-benzoate (meth) acrylate, 2-hydroxybutyl-4-benzoate (meth) acrylate and 2-hydroxypropyl-3. -(2,4,6-tribromobenzoate) (meth) acrylate, 2-hydroxypropyl-3- (4
-Phenylbenzoate) (meth) acrylate, or a reaction product of glycidyl (meth) acrylate and ε-caprolactone-modified benzoic acid. Of these, particularly preferred is 2-hydroxypropyl-3.
A benzoate acrylate.

The "compound represented by the general formula (3)" includes 3-hydroxy-4-benzoate-cyclohexylmethyl (meth) acrylate, or 3,4-epoxycyclohexylmethyl (meth) acrylate and ε-.
Examples thereof include reaction products with caprolactone-modified benzoic acid. Of these, particularly preferred is a reaction product of 3,4-epoxycyclohexylmethyl acrylate and ε-caprolactone-modified benzoic acid.

The "compound represented by the general formula (4)" includes 2-hydroxypropyl-2- (meth) acryloyloxyethyl phthalate and 2-hydroxyethyl-2.
-(Meth) acryloyloxyethyl phthalate, 4-
Examples thereof include hydroxybutyl-2- (meth) acryloyloxyethyl phthalate. Of these, 2-hydroxyethyl-2-acryloyloxyethyl phthalate is particularly preferable.

The "compound represented by the general formula (5)" includes 2,4-diphenyl-4-methyl-1,2-epoxypentane and (meth) acrylic acid or ε-caprolactone-modified (meth). Examples include reaction products with acrylic acid. Among these, particularly preferred is a reaction product of 2,4-diphenyl-4-methyl-1,2-epoxypentane and acrylic acid.

In the compounds represented by the above general formulas (1) to (3) and (5), one chemical equivalent of the epoxy group in the corresponding raw material and the carboxyl group in the corresponding raw material are 0.8 to 1.
It is obtained by reacting at 2 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents. The reaction temperature at this time is preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C. A catalyst may be used to accelerate the reaction, and specific examples of the catalyst include benzylmethylamine, triethylamine, benzyltrimethylammonium chloride and the like. The amount used is preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight.

The active energy ray-curable resin composition of the present invention preferably contains "a compound represented by the general formula (6)". This is because it is possible to further improve the breaking strength of the cured product of the active energy ray-curable resin composition. Specific examples thereof include reaction products of modified bisphenol A type compounds such as bisphenol A ethylene oxide adducts and bisphenol A propylene oxide adducts with (meth) acrylic acid.
In the formula, * represents saturated or unsaturated, and R ⁶ , R ⁷
Each independently represent hydrogen or a lower alkyl group, and R ⁸ and R ⁹
Each independently represent hydrogen or a methyl group, and n represents an integer of 1 to 10. In the reaction product of the modified bisphenol A type compound and (meth) acrylic acid, (meth) acrylic acid is preferably 0.8 to 1.2 chemical equivalents, preferably 1 chemical equivalent of the terminal hydroxyl group of the modified bisphenol A type. Is 0.
It can be obtained by reacting at a ratio of 9 to 1.1 chemical equivalents. The reaction temperature is preferably 60 to 150 ° C, particularly preferably 80 to 120 ° C. A catalyst may be used to accelerate the reaction, and specific examples of the catalyst include benzylmethylamine, triethylamine, benzyltrimethylammonium chloride and the like. The amount used is preferably 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight. The compound represented by the general formula (6) is 5 per 100 parts by weight of urethane acrylate.
It is preferable to contain -40 parts by weight, and particularly preferably 10-30 parts by weight. If it is less than 5 parts by weight, the effect of the addition is not seen, and if it exceeds 40 parts by weight, the viscosity of the entire composition may be too low.

As the "photopolymerization initiator" which can be blended in the active energy ray-curable resin composition of the present invention, benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone and 2,2-dimethoxy-2 can be used.
-Phenylacetophenone, 2,2-diethoxy-2-
Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone,
2-Methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, N,
N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-
Butylanthraquinone, 1-chloroanthraquinone, 2
-Amyl anthraquinone, 2-amino anthraquinone,
2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone and the like can be mentioned. These may be used alone or in combination of two or more. Further, as such a photopolymerization initiator, known conventional photopolymerization initiation aids such as N, N-dimethylaminobenzoic acid ethyl ester, triethanolamine and triethylamine may be used alone or in combination of two or more kinds. You can The content of the photopolymerization initiator is 1 to 10 parts by weight based on 100 parts by weight of the urethane acrylate,
Particularly, it is preferably in the range of 3 to 6 parts by weight.

In the present invention, for the purpose of adjusting the viscosity of the composition and improving the physical properties of the coating film, any ethylenically unsaturated monomer (compounds represented by the general formulas (1) to (5) are excluded. ) Can be used. Specific examples of the ethylenically unsaturated monomer include styrene, (meth) acrylonitrile, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth). ) Acrylate, 2-chlorostyrene, phenoxyethyl (meth) acrylate, (meth) acrylic acid,
2-hydroxyethyl (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned. These may be used alone or in combination of two or more.

The urethane acrylate used in the present invention is the above-mentioned "organic isocyanate (a) having at least two isocyanate groups capable of reacting with a hydroxyl group",
Known are "polyol (b) having a molecular weight of 300 or more having two or more hydroxyl groups in one molecule" and "(meth) acrylate monomer (c) having at least one hydroxyl group and at least one aromatic ring". It can be obtained by reacting by a method. As an example, the temperature is 6 at normal pressure.
React at 0-90 ° C. Further, it is desirable to use a catalyst for accelerating the reaction, and specific examples thereof include dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfide and dibutyltin dibutoxide. The amount of the catalyst effective for the reaction between the hydroxyl group and the isocyanate group is preferably 50 to 5000 ppm, particularly preferably 250 to 1000 ppm. The reaction is usually
This is repeated until the concentration of the residual isocyanate falls below a predetermined concentration.

The active energy ray-curable resin composition of the present invention gives a cured product having a different refractive index depending on the combination of constituent units of urethane acrylate which is an essential component, the content of the constituent components and the blending ratio of other optional components. be able to. Additivity is established in the refractive index of the composition, and "refractive index of mixture = Σ (refractive index of each raw material × weight%) / 100".

The cured product of the present invention preferably has a refractive index at 25 ° C. of 1.47 or more, particularly 1.50 or more. If the refractive index of the cured product is lower than 1.47, the cured product must be made thicker for use as an optical component, which is not practical. The cured product of the present invention has a sufficiently high refractive index and is capable of forming a flexible coating film. Therefore, the cured product comes into contact with the hands of workers or other products during transportation or post-processing after curing. Even after that, no marks are left on the surface, and the restorability is good.

The cured product of the active energy ray-curable resin composition of the present invention can be obtained by curing by irradiation with ultraviolet rays or electron beams according to a conventional method. The irradiation conditions when using ultraviolet rays are a mercury lamp and a metal halide lamp, and the curing energy is 100 to 1000 mJ / c.
m ² is preferred. Further, the irradiation condition when using an electron beam is as follows:
A dose of 5 Mrad is preferred. Irradiation is generally performed in a resin mold.

A Fresnel lens can be obtained from the active energy ray-curable resin composition of the present invention and a thermoplastic resin having a haze of 10% or less according to JIS K7105.

The Fresnel lens can be manufactured according to the following. First, the active energy ray-curable resin composition of the present invention is applied to a resin mold of a Fresnel lens in which a groove is formed in a ring shape, and the active energy ray-curable resin composition layer having a thickness of 100 to 500 μm (hereinafter, “ It is called "A layer".)
And Then, a substrate having a thickness of 50 μm to 3 mm and made of a thermoplastic resin having a haze of 10% or less (hereinafter referred to as “B layer”) is brought into close contact with the A layer. Then, in that state, an active energy ray of, for example, 400 mJ / cm ² is irradiated toward the A layer from the B layer by a high pressure mercury lamp or the like.
Cure the layer. Thereafter, the resin mold of the Fresnel lens is peeled off to obtain a Fresnel lens having a thickness of 150 μm to 3.5 mm.

Similarly, a lenticular lens can be obtained by using a resin mold of the lenticular lens. Specifically, the active energy ray curable resin composition of the present invention is applied to a resin mold of a lenticular lens on which minute kamaboko-shaped irregularities are formed to a thickness of 100 to 500 μm, and an active energy ray curable resin layer is applied. (Hereafter, "C layer"
Called. ). Then, in this state, the C layer is irradiated with an active energy ray of, for example, 400 mJ / cm ² by a high pressure mercury lamp or the like to cure the C layer. Then, the resin mold of the lenticular lens is peeled off to obtain the lenticular lens.

A transmission screen can be obtained from the Fresnel lens of the present invention and the lenticular lens described above. Specifically, the active energy ray-curable resin composition of the present invention is applied to a resin mold for a lenticular lens on which minute kamaboko-shaped irregularities are formed, and a thickness of 100 to 50 is applied.
The C layer has a thickness of 0 μm. In addition, B of the Fresnel lens
The layer side is laminated on the C layer, and in this state, the C layer is cured by irradiating an active energy ray of 400 mJ / cm ² from above the A layer with a high pressure mercury lamp or the like. After that, the resin screen of the lenticular lens is peeled off to obtain a transmissive screen. In addition, it is also possible to manufacture a lenticular lens in advance, and use the concavo-convex surface of the lenticular lens and the A layer having the ring-shaped groove of the Fresnel lens manufactured previously to face each other and use it as a transmission screen.

The thermoplastic resin that can be used as the B layer preferably has a haze of 10% or less for the purpose of use. Specifically, synthetic resins such as polymethylmethacrylate, polystyrene, and polycarbonate, or copolymers thereof can be used. Among these, polymethylmethacrylate and polystyrene are preferable.

[0029]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. “%” Indicates “% by weight” unless otherwise indicated.

(Measurement Method) Evaluations in the examples were carried out by the following methods. (1) UV curability: 200μ of each sample on a glass plate
m high pressure mercury lamp 120W / cm × 5
m / min. It was irradiated with ultraviolet rays at × 2Pass and it was judged by touching with a finger whether the coating film was cured. The judgment criteria are ○ ・ ・
・ No tack on the coating surface, △ ... Slight tack on the coating surface, × ... Tack on the coating surface. (2) Refractive index of coating film: The refractive index of a coating film cured by UV under the conditions of (1) was measured at 25 ° C. with an Appe type refractometer. (3) Elongation at break (%): A tensile test was performed using a free film obtained by peeling the coating film cured by UV under the conditions of (1) from a glass plate. Distance between chucks 10 cm,
The distance between marked lines is 6 cm, the pulling speed is 100 mm / min. (4) Breaking strength (kg / mm ² ): A tensile test was carried out using a free film obtained by peeling a coating film cured by UV under the conditions of (1) from a glass plate. Chuck distance 10 cm, marked line distance 6 cm, pulling speed 100 mm / m
in. (5) Scratch resistance: A coating film surface cured by UV under the conditions of (1) has a width of 10 mm obtained by polishing the tip with sandpaper.
A metal piece having a thickness of 0.2 mm was rubbed vertically for a length of 30 mm, and the presence or absence of scratches was observed. Judgment criteria are: ○: no damage on the coating surface, △: 5 or less scratches on the coating surface, × ・
..6 or more scratches on the surface of the coating film. (6) Restorability: 30 kg / cm of a 5 mm diameter metal rod with a flat tip on the surface of the coating film cured by UV under the conditions of (1)
^It was pressed at a pressure of ² for 5 seconds, and the time until the trace disappeared was measured. The judgment criteria are: ◎ ... disappears instantly, ○ ・
..Disappearing within 30 seconds, △ ... Disappearing within 60 seconds, ×
... It takes 60 seconds or more to disappear.

(Synthesis Example 1) A soaker, which is immersed in an oil bath,
240 g (2 mol) of styrene oxide (“STO” manufactured by Daicel Chemical Industries, Ltd.) and 0.5 g of triethylamine were charged into a reaction vessel equipped with a thermometer, an addition funnel and a dry air supply port, and the temperature was raised. When the temperature inside the reaction vessel reached 90 ° C, 144 g (2 mol) of acrylic acid was added from the addition funnel.
Was slowly added. After the addition was completed, the oxirane concentration was 0.
Aging until the content is 5% or less, 2-hydroxyethyl-2
-Phenyl acrylate was obtained.

(Synthesis Example 2) In place of styrene oxide in Synthesis Example 1, 284 g (2 mol) of glycidyl methacrylate and 244 g (2 mol) of benzoic acid instead of acrylic acid.
2-Hydroxypropyl-3-benzoate methacrylate was obtained in the same manner as in Synthesis Example 1 except that.

(Synthesis Example 3) In place of the glycidyl methacrylate of Synthesis Example 2, 392 g (2 mol) of 3,4-epoxycyclohexylmethyl methacrylate ("Cyclomer M100" manufactured by Daicel Chemical Industries, Ltd.) was used. Operating in the same manner as in Synthesis Example 2, 3-hydroxy-4-
Benzoate-cyclohexylmethylmethacrylate was obtained.

(Synthesis Example 4) In a reaction vessel equipped with a hot water jacket, a stirrer, a thermometer, an addition funnel and a nitrogen supply port,
2,4-diphenyl-4-methyl-1-pentene 472
g (2 mol) was charged, the temperature was raised to 50 ° C., and then peracetic acid 1
67 g (2.2 mol) was dropped into the reactor over 1 hour, and the mixture was aged for 4 hours. Cool to 30 ° C,
Washing with water was repeated until the acid value of the reaction product became 1 mgKOH / g or less. Then, the reaction product was dried under reduced pressure to remove volatile components to obtain 2,4-diphenyl-4-methyl-1,2-epoxypentane. Next, Synthesis Example 1
In place of styrene oxide, 252 g of 2,4-diphenyl-4-methyl-1,2-epoxypentane (1
Mol), and the same operation as in Synthesis Example 1 gave 2-hydroxy-2,4-diphenyl-4-methyl-pentyl acrylate.

(Synthesis example 5) The mixture was immersed in an oil bath, stirred,
Isophorone diisocyanate (IPDI) 444 was added to a reaction vessel equipped with a thermometer, addition funnel and dry air supply port.
g (2 mol), dibutyltin dilaurate (DBTDL)
0.5 g was charged and the temperature was raised. When the inside of the reaction vessel reached 70 ° C., 530 g (1 of polycaprolactone (manufactured by Daicel Chemical Industries, Ltd., “Placcel 205”, polycaprolactone diol having a molecular weight of 530) of polycaprolactone) was added from the addition funnel.
Mol) was added slowly. After the addition was completed, aging was carried out until the residual isocyanate concentration reached a theoretical value to produce a polycaprolactone urethane prepolymer. Then, 2-hydroxyethyl-2-acryloyloxyethyl phthalate ("Viscote 2308" manufactured by Osaka Organic Industry Co., Ltd.) 616
g (2 mol) was added. After the completion of the addition, aging was carried out until the residual isocyanate concentration became 0.1% or less to obtain urethane acrylate (Synthesis example 5).

(Synthesis Example 6) In place of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5, 384 g (2 mol) of 2-hydroxyethyl-2-phenyl acrylate obtained in Synthesis Example 1 was used. A urethane acrylate (Synthesis Example 6) was obtained in the same manner as in Synthesis Example 5 except for the above.

(Synthesis Example 7) In place of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5, 528 g (2 mol) of 2-hydroxypropyl-3-benzoate methacrylate obtained in Synthesis Example 2 was used. A urethane acrylate (Synthesis Example 7) was obtained in the same manner as in Synthesis Example 5 except for the above.

Synthesis Example 8 Instead of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5, 636 g (2) of 3-hydroxy-4-benzoate-cyclohexylmethyl methacrylate obtained in Synthesis Example 3 was used.
A urethane acrylate (Synthesis Example 8) was obtained in the same manner as in Synthesis Example 5 except that the amount was changed to mol.

(Synthesis Example 9) 2-hydroxy-2,4-diphenyl-4-methyl-pentyl acrylate obtained in Synthesis Example 4 was used in place of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5. 648 g (2
A urethane acrylate (Synthesis Example 9) was obtained in the same manner as in Synthesis Example 5 except that the amount was changed to mol.

Synthesis Example 10 Tolylene diisocyanate 34 was used in place of the isophorone diisocyanate in Synthesis Example 5.
In the same manner as in Synthesis Example 5, except that 8 g (2 mol) was used,
Urethane acrylate (Synthesis example 10) was obtained.

(Synthesis Example 11) A urethane acrylate (Synthesis Example 11) was obtained in the same manner as in Synthesis Example 5 except that 336 g (2 mol) of hexamethylene diisocyanate was used instead of the isophorone diisocyanate in Synthesis Example 5.

(Synthesis Example 12) A urethane acrylate (Synthesis Example 12) was prepared in the same manner as in Synthesis Example 5, except that 524 g (2 mol) of methylene bis (4-cyclohexyl isocyanate) was used instead of the isophorone diisocyanate in Synthesis Example 5. Got

(Synthesis Example 13) A urethane acrylate (Synthesis Example 13) was prepared in the same manner as in Synthesis Example 5, except that 508 g (2 mol) of 4,4-diphenylmethane diisocyanate was used instead of the isophorone diisocyanate in Synthesis Example 5.
I got

(Synthesis Example 14) Instead of polycaprolactone in Synthesis Example 5, polyethylene glycol (average molecular weight 6) was used.
A urethane acrylate (Synthesis Example 14) was obtained in the same manner as in Synthesis Example 5 except that 600 g (1 mol) of 00) was used.

(Synthesis Example 15) Polycarbonate diol (“PCL CD-205” manufactured by Daicel Chemical Industries, Ltd.) having a molecular weight of about 5 was used instead of polycaprolactone in Synthesis Example 5.
00 polycarbonate diol, HO- (CH ₂ ) _6-
[OCO (CH ₂ ) ₆ O] _n —H, n = 2 to 3) 50
Except for 0 g (1 mol), in the same manner as in Synthesis Example 5,
Urethane acrylate (Synthesis example 15) was obtained.

Synthesis Example 16 Hydroxyethyl acrylate (HEA) 23 was used in place of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5.
A urethane acrylate (Synthesis Example 16) was obtained in the same manner as in Synthesis Example 5 except that the amount was 2 g (2 mol).

(Synthesis Example 17) Instead of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5, ε-caprolactone modified 2-hydroxyethyl acrylate (“PCL F manufactured by Daicel Chemical Industries, Ltd.”) was used.
A-2 ") 688 g (2 mol), but in the same manner as in Synthesis Example 5, a urethane acrylate (Synthesis Example 17) was obtained.

Synthesis Example 18 Instead of 2-hydroxyethyl-2-acryloyloxyethyl phthalate in Synthesis Example 5, pentaerythritol triacrylate ("PETIA" manufactured by Daicel-UCB Co., Ltd.) 696 g
A urethane acrylate (Synthesis Example 18) was obtained in the same manner as in Synthesis Example 5 except that (2 mol) was used.

(Examples 1 to 17 and Comparative Examples 1 to 4) Table-
The resin composition having the composition as shown in 1 (numerical values indicate parts by weight) was blended, and the physical properties of the cured coating film obtained by UV-curing them were evaluated.

[Table 1]

[0050]

According to the active energy ray-curable resin composition obtained by the present invention, a high-refractive-index type cured coating film having excellent coating workability, coating film physical properties and economical efficiency as compared with the conventional ones can be obtained. And can be used in the field of resin molding. Since the cured product obtained from the active energy ray-curable resin composition of the present invention has a high refractive index, a Fresnel lens can be obtained using this.

Claims (7)

[Claims] 1. An organic isocyanate having at least two isocyanate groups capable of reacting with a hydroxyl group (a), 1
Containing a polyol (b) having a molecular weight of 300 or more having two or more hydroxyl groups in the molecule and a urethane acrylate composed of at least one hydroxyl group and (meth) acrylate monomer (c) having at least one aromatic ring. An active energy ray-curable resin composition characterized by the above. 2. At least one hydroxyl group and at least one
The active energy ray-curable resin composition according to claim 1, wherein the (meth) acrylate monomer (c) having one aromatic ring is a compound selected from the following general formulas (1) to (5). Stuff. Embedded image 3. The active energy ray-curable resin composition according to claim 1, which contains 5 to 40 parts by weight of the compound represented by the general formula (6) with respect to 100 parts by weight of urethane acrylate. Embedded image 4. A photopolymerization initiator is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of urethane acrylate.
The active energy ray-curable resin composition according to any one of 1 to 3. 5. The cured product of the active energy ray-curable resin composition according to claim 1, which has a refractive index at 25 ° C. of 1.47 or more. 6. A Fresnel lens comprising the cured product of claim 5 laminated on a cured product of a thermoplastic resin having a haze of 10% or less. 7. A Fresnel lens, wherein the thermoplastic resin according to claim 6 is polymethylmethacrylate.