JP2003160623A - Active energy ray curing type composition for optical part material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curing type composition for optical part materials which is excellent in adherability to a plastic base material, particularly polymethyl methacrylate, hardness and transparency and has suitable viscosity for the production of optical articles. <P>SOLUTION: The active energy ray curing composition for optical part materials is a polyurethane (meth)acrylate produced from a compound of molecular weight of at most 450 having two or more (meth)acryloyl groups (A), a compound having a molecular weight of at most 250 having one ethylene-based unsaturated group (B) and a monohydric alcohol having at least one or more diisocyanate, diol and (meth)acryloyl. In this case, a compound (C) in which the mole ratio of diisocyanate to diol is 3:2 to 21:20 is contained in the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray-curable composition for imparting various shapes to the surface of a plastic substrate and expressing an optical function. The composition of the present invention comprises: In addition to having an appropriate viscosity suitable for the production of optical members, the obtained cured product has excellent adhesiveness, hardness and transparency, and thus can be used particularly in the technical field of producing plastic optical members.

[0002]

2. Description of the Related Art Plastics having excellent transparency such as polymethylmethacrylate and polycarbonate are used for various optical members. Some of these optical members exert their functions by giving various shapes to the surface, and examples thereof include a light guide plate used for a lens sheet and a liquid crystal backlight or front light. To be

In recent years, active energy ray-curable compositions have been used in the production of optical members having various shapes on their surfaces, from the viewpoints of high production efficiency and ease of providing fine shapes. There are various methods for imparting various shapes to the surface of the transparent plastic, and examples thereof include a method of using a mold having various shapes and printing. Explaining the former method, for example, the active energy ray-curable composition is poured into a mold such as a nickel stamper having a fine shape, covered with transparent plastic from above, and cured by irradiating with active energy rays such as ultraviolet rays. Then, by removing from the stamper and transferring, it is possible to manufacture an optical member having a fine shape on the surface. On the contrary, there is also a method in which after coating the composition on the surface of a plastic substrate, a mold made of a transparent material having poor adhesion is covered and cured by irradiating active energy rays on the mold.

The active energy ray-curable composition used for the above-mentioned applications is required to have an optimum viscosity, and the physical properties of the cured product are the adhesion and hardness to the transparent plastic as the substrate. However, it is required to have excellent transparency and mold transferability. That is, the composition is processed into various shapes in order to exhibit an optical function, but since it is necessary to easily cast it into a mold, if the viscosity is too low, the composition often flows out of the mold. However, if the viscosity is high, foam bites or transfer from the mold will be poor. In addition, if the adhesion is insufficient, it becomes a problem in terms of durability and reliability as an optical material, and if the hardness is insufficient, it may cause scratches during assembly and use, and transparency However, it cannot be used as a material for an optical member that requires transparency.

[0005]

However, in the conventional active energy ray-curable composition, when the transparent plastic is polymethylmethacrylate, the adhesiveness is often insufficient, while the composition having excellent adhesiveness is used. On the contrary, the product was soft and had insufficient hardness. As a method of improving the adhesiveness, there is a method of incorporating a polymer into the composition. However, the composition is often insufficient in compatibility with the (meth) acrylate constituting the composition, and as a result, the transparency of the cured product is often decreased. In addition, there are conventional active energy ray-curable compositions in which the type and proportion of (meth) acrylate of each compounding component are adjusted so as to have a viscosity suitable for the production of optical articles. There is a problem that any one of adhesion, hardness and transparency is insufficient.

The present inventors have developed an active energy ray-curable composition for optical members, which has excellent adhesion to a plastic substrate, particularly polymethylmethacrylate, excellent hardness and transparency, and has a viscosity suitable for producing optical articles. He did a thorough study to find things.

[0007]

As a result of various studies to solve the above-mentioned problems, the present inventors have found that an active energy ray-curable composition comprising three specific components can solve the above-mentioned problems. Heading, completed the present invention. The present invention will be described in detail below. In addition, in this specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, an acrylate or a methacrylate is represented as a (meth) acrylate, and acrylic acid or methacrylic acid is represented as a (meth) acrylic acid.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION 1. 2 (meth) acryloyl groups
Compound (A) having a molecular weight of 450 or less and having a molecular weight of 450 or less, which has two or more (meth) acryloyl groups (hereinafter simply referred to as component (A)) is essential in the composition of the present invention. The component (A) is mainly a component for imparting hardness to the cured product of the composition. If the molecular weight is more than 450, it becomes impossible to achieve both adhesion and hardness. As the component (A), various compounds can be used, and examples thereof include tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and hydroxypivalic acid. Neopentyl glycol esterified product di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra-acrylate, isocyanuric acid ethylene oxide 3 mol adduct di- or triacrylate, propylene glycol diglycidyl An ether (meth) acrylic acid 2 mol addition product etc. are mentioned.

As the component (A), acrylate is preferable because of its excellent curability.

A preferred blending ratio of the component (A) in the composition is 30 to 30 based on the total amount of the components (A) to (C).
80 parts by mass. If this ratio is less than 30 parts by mass, the hardness and adhesion may be insufficient, and if it is more than 80 parts by mass, the viscosity of the entire composition may be too low and the shape transferability may be deteriorated.

2. Molecules having one ethylenically unsaturated group
Compound (B) having an amount of 250 or less A compound having a molecular weight of 250 or less having one ethylenically unsaturated group [hereinafter simply referred to as component (B)] is essential in the composition of the present invention. The component (B) is mainly a component for imparting adhesion to the plastic substrate to the composition.
If the molecular weight exceeds 250, the adhesiveness will be reduced. Although various compounds can be used as the component (B), for example, (meth) acrylic acid dimer, 2-ethyl-hexyl (meth) acrylate, cyclohexyl acrylate, isobornyl (meth) acrylate, 2-
Methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth)
Acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylic acid, etc. are mentioned.

As the component (B), acrylate and N-vinylpyrrolidone are preferable from the viewpoint of excellent curability. Further, among these, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, N-vinylpyrrolidone, and the like are more preferable because they can exhibit strong adhesion.

A preferred blending ratio of the component (B) in the composition is 10 to 10 based on the total amount of the components (A) to (C).
40 parts by mass. When this ratio is less than 10 parts by mass, the adhesion may be insufficient, and when it exceeds 40 parts by mass, the hardness becomes insufficient and the viscosity becomes too low.
The shape transferability may deteriorate.

3. Polyurethane (meth) acrylate
(C) The composition of the present invention is a polyurethane (meth) acrylate prepared from a diisocyanate, a diol and a monohydric alcohol having at least one (meth) acryloyl group, and the molar ratio of diisocyanate to diol is 3:
A compound of 2 to 21:20 [hereinafter simply referred to as component (C)] is essential. If only the components (A) and (B) are used, the viscosity of the obtained composition will be too low and it will not be suitable for the production of optical articles. The component (C) is a component for increasing the viscosity of the obtained composition without lowering the adhesion, hardness and transparency of the cured product of the composition. As the diisocyanate in the component (C),
Various compounds can be used as long as they are compounds having two isocyanate groups, but it is preferable that the resulting urethane (meth) acrylate is a non-yellowing type, that is, one in which the isocyanate group is not directly bonded to the aromatic ring. .
Preferred examples include isophorone diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

In the component (C), the diol is
Various compounds can be used as long as they are compounds having two hydroxyl groups. For example, ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, diethylene glycol, tetraethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene glycol, polyester diol produced from adipic acid and neopentyl glycol, And polyester diol produced from adipic acid and ethylene glycol. Among these, it is preferable that the finally obtained component (C) does not crystallize in the composition and does not cause turbidity after curing, and specifically, those having no ester group are preferable. An example of a suitable diol is a diol composed of an alkylene oxide adduct having 2 to 4 carbon atoms (repeating units 1 to 5), and specific examples thereof include tripropylene glycol and tetramethylene glycol. Here, if the repeating unit is too large, the hardness of the cured product becomes low, which is not preferable.

In the component (C), the monohydric alcohol having one or more (meth) acryloyl groups is more preferably one having two or more (meth) acryloyl groups. When the number of (meth) acryloyl groups is 2 or more, the resulting composition has an increased amount of heat generated upon curing, and thus has excellent adhesiveness.

Various monohydric alcohols having at least one (meth) acryloyl group can be used.
As the monohydric alcohol having one (meth) acryloyl group, 2-hydroxyethyl (meth) acrylate,
2-Hydroxypropyl (meth) acrylate and the like can be mentioned. As the monohydric alcohol having two or more (meth) acryloyl groups, pentaerythritol tri (meth) alcohol can be mentioned.
Ethylene oxide 3 of acrylate, trimethylolpropane di (meth) acrylate and isocyanuric acid
Di (meth) acrylate, which is a molar addition product, and the like can be mentioned.

In the component (C) used in the present invention, the molar ratio of diisocyanate to diol is 3: 2 to 21: 2.
Must be 0. When the ratio of diisocyanates exceeds 3, the effect of the component (C) obtained to increase the viscosity of the entire composition becomes small, and when the ratio of diisocyanates is less than 21, the composition ratio approaches 1: 1. Since it is too high, a high-molecular-weight substance which impairs transparency is produced.

As the method for producing the component (C), a conventional method usually employed in the production of urethane (meth) acrylate may be used. The preferred method is as follows. That is, a solution composed of a divalent isocyanate, a polymerization inhibitor and a catalyst is stirred, and a reaction is performed while dropping a divalent alcohol into the solution to produce a urethane prepolymer having an isocyanate group, and then the reaction solution is further (meth) A monohydric alcohol having at least one acryloyl group is charged and reacted.
In this case, the reaction is carried out by dissolving the component (A) or (B) that does not contain a functional group that reacts with an isocyanate group, more specifically, the component (A) or (B) that does not contain a hydroxyl group in the reaction solution. The method is preferred. According to this method, when the component to be obtained is only the component (C), the viscosity may be too high and stirring may not be possible, and a uniform reaction solution may not be obtained, but (A) or (B) By dissolving the components in advance, it is possible to reduce the reaction liquid to a viscosity at which stirring is possible and obtain a uniform reaction product. At this time, the charged amount of the monohydric alcohol should be at least higher than the number of moles of isocyanate groups remaining when all the diisocyanates and diols have reacted. The reaction temperature is 3
The temperature is preferably 0 to 100 ° C.

The weight average molecular weight of the component (C) is preferably 1,000 to 50,000, more preferably 1,000 to 50,000.

As the component (C), acrylate is preferable because of its excellent curability.

The preferable blending ratio of the component (C) in the composition is 10 to 10 based on the total amount of the components (A) to (C).
It is 50 parts by mass. When this ratio is less than 10 parts by mass, the viscosity of the composition becomes too low, and the cured product is likely to crack. On the contrary, if it exceeds 50 parts by mass, the viscosity becomes too high.

[0023] 4. Active energy ray curing type assembly for optical members
Composition The composition of the present invention essentially contains the components (A) to (C). The method for producing the composition of the present invention is as described above.
It can be obtained by stirring and mixing components (A) to (C) and, if necessary, other components according to a conventional method.

The composition of the present invention preferably has a viscosity of 500 to 5,000 mPa · s at 25 ° C. This makes the composition easier to cast into a mold in the production of optical articles, and the cured product is more suitable for the production of optical articles without chewing bubbles or the like.

The composition of the present invention includes the above (A) to (C).
It is preferable that all of the components are acrylates because of excellent curability. Further, in this case, it is more preferable that the acrylic equivalent of the entire composition is high. Specifically, the acrylic equivalent is preferably 4 meq / g or more, more preferably 5 meq / g or more.
It is not less than meq / g. The upper limit of the acrylic equivalent is not particularly limited, but is preferably 9 meq / g or less. If the acrylic equivalent exceeds 9 meq / g, the cured product may crack.

Usually, an active energy ray-curable composition having a large acrylic equivalent has a high curing shrinkage, which causes a decrease in adhesion. The composition of the present invention is considered to attack the surface of the plastic substrate by the low molecular weight component and the heat generated during curing, thereby exhibiting strong adhesion, and this effect is large enough to exceed the influence of curing shrinkage. . Therefore, the composition of the present invention has excellent adhesion even if the acrylic equivalent is large.

The composition used in the present invention includes (A) to
In addition to the component (C), a compound having two or more (meth) acryloyl groups having a molecular weight of more than 450 can be further blended. The compounding ratio of the compound having two or more (meth) acryloyl groups is preferably within 30 parts by mass from the viewpoint of adhesion.

Further, various antioxidants such as 2,6-di-tert-butyl-4-methylphenol may be added for the purpose of reducing the deterioration and coloration of the cured product. The preferred blending ratio of the antioxidant is from (A) to
It is 0 to 1 part by mass based on the total amount of the component (C).
If this ratio exceeds 1 part by mass, curability may be deteriorated or bleeding may occur.

In the present invention, when the active energy rays are ultraviolet rays or visible rays, it is preferable to add a generally used photopolymerization initiator in order to make the photocurability of the composition sufficient. . Further, a sensitizer may be used in combination with the photopolymerization initiator, if necessary.

Although various kinds of photopolymerization initiators can be used, those having excellent thermal stability and little coloring after curing are preferable. Specifically, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (IRGACURE 907 manufactured by Ciba Specialty Chemicals), benzyl dimethyl ketal (IRGA manufactured by Ciba Specialty Chemicals). Cure 651),
1-hydroxycyclohexyl phenyl ketone (Ciba
Specialty Chemicals Irgacure 18
4), diethoxy acetophenone (First Cure DEAP manufactured by Fast Chemical), 2-hydroxy-2
-Methyl-1-phenylpropan-1-one (Darocur 117 manufactured by Ciba Specialty Chemicals)
3), 4- (2-hydroxyethoxy) phenyl (2-
Hydroxy-2-propyl) ketone (Irgacure 2959 manufactured by Ciba Specialty Chemicals) and 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 369 manufactured by Ciba Specialty Chemicals) and other acetophenone-based photopolymerization initiators; benzophenone, methyl o-benzoylbenzoate, 4 -Benzophenone-based photopolymerization initiators such as -phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide and 2,4,6-trimethylbenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,2 6
-Dimethoxybenzoyl) -2,4,4-trimethyl-
Examples thereof include acylphosphine oxide-based photopolymerization initiators such as pentylphosphine oxide.

Specific examples of the sensitizer used in combination with the above photopolymerization initiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4 -Isoamyl dimethylaminobenzoate,
4,4-dimethylaminobenzophenone, 4,4-diethylaminobenzophenone and the like can be mentioned.

The preferred blending ratio of the photopolymerization initiator is 0.1 to 10 parts by mass based on the composition. If it is less than 0.1 part by mass, the effect of promoting the initiation of polymerization becomes insufficient,
If the amount exceeds 10 parts by mass, the components that are truly necessary for the cured product may be reduced to deteriorate the physical properties of the cured product, or the cured product may be colored.

The composition of the present invention is suitable for producing an optical member. Specific examples of the optical member include lenses such as Fresnel lenses and lenticular lenses, and components of a light guide plate used as components of a liquid crystal display device. The method of using the composition of the present invention is not particularly limited, but the composition is poured into a mold having a specific fine shape according to the purpose of use, and the surface of the plastic substrate is covered with the composition. A method of irradiating with active energy rays, or conversely, a method of coating a composition on the surface of a plastic substrate, covering a mold made of a transparent material with poor adhesion, and irradiating with active energy rays from above Is mentioned. At this time, the composition may be preheated to an appropriate temperature.

Examples of the plastic substrate include various plastics used for optical members, such as polymethylmethacrylate, polycarbonate, polystyrene and methylmethacrylate-styrene copolymer.

In order to strengthen the adhesion of the composition of the present invention to a plastic substrate, when surface treatment such as corona treatment is not performed, after the composition and the plastic substrate are contacted with each other, Is preferably heated to 60 ° C to 80 ° C. If the temperature is lower than 60 ° C, the adhesion may be insufficient, and if the temperature is higher than 80 ° C, the plastic substrate may be deformed by heat.

Examples of active energy rays include electron rays, visible rays and ultraviolet rays, and ultraviolet rays are preferable because the apparatus used is inexpensive and the cured product obtained has excellent various physical properties. .

[0037]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples. However, the present invention is not limited to these examples.

Abbreviations used in the examples MANDA: diacrylate of esterified product of hydroxypivalic acid and neopentyl glycol (molecular weight: 31
2), KAYARAD MANDA M313, manufactured by Nippon Kayaku Co., Ltd .: Di- or triacrylate of ethylene oxide 3 mol adduct of isocyanuric acid (di-form: tri-form =
3: 7) (molecular weight: di-form 369, tri-form 423), Toagosei Co., Ltd. Aronix M-313 M305: pentaerythritol tri or tetraacrylate (tri-form: tetra-form = 6: 4) (molecular weight: tri-form) 298, tetra body 352), Aronix M-305 M309 manufactured by Toagosei Co., Ltd .: trimethylolpropane triacrylate (molecular weight: 296), Aronix M manufactured by Toagosei Co., Ltd.
-309 THFA: Tetrahydrofurfuryl acrylate (molecular weight: 156), Viscoat # manufactured by Osaka Organic Chemical Industry Co., Ltd.
150 HEA: 2-hydroxyethyl acrylate (molecular weight:
116), Toagosei Co., Ltd. HPA: 2-hydroxypropyl acrylate (molecular weight: 130), Osaka Organic Chemical Industry Co., Ltd. HPA BR106: Polymer based on methacrylic acid ester, Mitsubishi Rayon Co., Ltd. Knall BR resin #
106 Dc1173: 2-Hydroxy-2-methyl-1-phenylpropan-1-one, Ciba Specialty Chemicals KK Darocurure 1173, equivalent to photopolymerization initiator

Production Example 1 (Polyurethane acrylate C
Production of -1) In a separable flask equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a gas introducing tube, 74.7 g (0.34 mol) of isophorone diisocyanate, 2,6-di-t.
0.24 g of ert-butyl-4-methylphenol, 140 g of MANDA, which is the component (A), and 0.40 g of dibutyltin dilaurate were charged, and the mixture was stirred while blowing air through the gas introduction pipe, and 55.3 g (0) of tripropylene glycol was added thereto. (.29 mol) was added dropwise over 20 minutes. After completion of dropping, the mixture was reacted at 70 ° C. for 3 hours and then M3
130 g (0.11 equivalent of hydroxyl group) of 13 was added all at once.
This was reacted at 80 ° C. for 2 hours, and after confirming that the peak derived from isocyanate disappeared by IR, it was extracted. The viscosity of the mixture containing the polyurethane acrylate C-1 which is the component (C) of the product and the unreacted component (A) MANDA was 124 Pa · s at 25 ° C.
This is referred to as product 1.

Production Example 2 (Polyurethane acrylate C
-2) 111.0 g (0.50 mol) of isophorone diisocyanate and 2,6-di-t were placed in the same flask as in Production Example 1.
ert-butyl-4-methylphenol 0.15 g,
243 g of MANDA as the component (A) and 0.68 g of dibutyltin dilaurate were charged and stirred while blowing air through the gas introduction tube, and 76.8 g (0.40 mol) of tripropylene glycol was added dropwise to this over 20 minutes. After completion of dropping, the mixture was reacted at 70 ° C. for 2 hours and then M3
121 g of 05 (0.26 equivalent of hydroxyl group) was added dropwise over 30 minutes. This was reacted at 80 ° C. for 5 hours, and after confirming that the peak derived from isocyanate disappeared by IR, it was extracted. Polyurethane acrylate C-2 which is the component (C) of the product and M which is the unreacted component (A)
The mixture containing AND has a viscosity of 21.5 Pa at 25 ° C.
It was s. This is referred to as product 2.

Production Example 3 (Polyurethane acrylate C
Production of -3) In a flask similar to Production Example 1, 111.0 g (0.50 mol) of isophorone diisocyanate and 2,6-di-t were added.
ert-butyl-4-methylphenol 0.15 g,
198 g of M309 which is the component (A) and 0.47 g of dibutyltin dilaurate were charged, and the mixture was stirred while blowing air through the gas introduction tube, and 76.8 g (0.40 mol) of tripropylene glycol was added dropwise thereto over 20 minutes. . After completion of dropping, the mixture was reacted at 70 ° C. for 2 hours and then M3
05 (109 g (hydroxyl group: 0.23 equivalent)) was added dropwise over 30 minutes. This was reacted at 80 ° C. for 4 hours, and after confirming that the peak derived from isocyanate disappeared by IR, it was extracted. Polyurethane acrylate C-3 which is the component (C) of the product and M which is the unreacted component (A)
The mixture containing 309 has a viscosity of 150 Pa · s at 25 ° C.
Met. This is referred to as product 3.

Comparative Production Example 1 (Production of Polyurethane Acrylate C'-1) In a flask similar to that of Production Example 1, 799.2 g (3.60 mol) of isophorone diisocyanate, 0.70 g of hydroquinone monomethyl ether, and 0.1 of phenothiazine.
4 g, 1.4 g of dibutyltin dilaurate and 600 g of THFA as the component (B) were charged and stirred while blowing air through the gas introduction pipe. Neopentyl glycol (187.2 g, 1.80 mol) was added to the mixture, and the mixture was reacted at 60 ° C. for 1 hour. Then, HEA 422.2 g (3.
(64 mol) was added dropwise over 1 hour, and the mixture was reacted at 80 ° C. for 2 hours. After confirming that the peak derived from isocyanate disappeared by IR, it was extracted. Is a product,
Polyurethane acrylate C'-1 and unreacted (B)
The mixture containing the component THFA has a viscosity of 3 at 25 ° C.
It was 4.5 Pa · s. The polyurethane acrylate C′-1 is a polyurethane acrylate having a molar ratio of divalent isocyanate to dihydric alcohol of 2: 1 and different from the component (C) of the present invention. This is referred to as Comparative Product 1.

Comparative Production Example 2 (Production of Urethane Acrylic Adduct) In the same flask as in Production Example 1, 666 g (3.00 mol) of isophorone diisocyanate, 0.72 g of hydroquinone monomethyl ether, and 2.89 g of dibutyltin dilaurate were charged. Stir while blowing air through the gas introduction tube, and add HPA 788 g (6.06 mol) thereto.
Was added dropwise over 1.5 hours. After the completion of the dropping, 0.72 g of hydroquinone monomethyl ether was added, and the mixture was reacted at 80 ° C. for 2 hours, and after confirming that the peak derived from isocyanate disappeared by IR, it was extracted. Obtained 2
The viscosity of the urethane acryl adduct having a number of acryloyl groups (molecular weight 482) was 21.3 Pa · s at 50 ° C. This is called IPDA.

Comparative Production Example 3 (with a molecular weight of 45 as a diluent)
No acrylate of 0 or less is used) 240 g of IPDA was charged into the same flask as in Production Example 1, and the temperature was raised to 70 ° C. while stirring while blowing air through the gas introduction tube. To this was charged 0.24 g of 2,6-di-tert-butyl-4-methylphenol, 31.4 g (0.142 mol) of isophorone diisocyanate, and 0.40 g of dibutyltin dilaurate, and then 23.3 g (0 of tripropylene glycol). .121 mol)
Was added dropwise over 20 minutes. After the dropping was completed, the reaction was carried out at 80 ° C. for 2 hours, and then HPA 105.5 g (0.812 mo
I) was prepared in a batch. Let this react for another 30 minutes,
After confirming that the peak derived from isocyanate disappeared by IR, it was extracted. The product, polyurethane acrylate C-4 and the unreacted (A) 'component, I
The mixture containing PDA has a viscosity of 17.5 Pa at 25 ° C.
It was s. This is referred to as Comparative Product 2.

Example 1 75 parts of the product 1 obtained in Production Example 1, 25 parts of HPA and 5 parts of Dc1173 as a photopolymerization initiator were mixed by stirring according to a conventional method to prepare an active energy ray-curable composition. Was manufactured.
Using the obtained composition, the viscosity according to the following evaluation method,
Adhesion, pencil hardness and transparency were evaluated. The results are shown in Table 2.

○ Evaluation Method-Viscosity The obtained composition was measured for viscosity at 25 ° C. with an E-type viscometer. Moreover, the obtained results were judged in the following two stages. ◯: 500 to 5,000 mPa · s, ×: viscosity outside the range on the left

Adhesiveness Polymethylmethacrylate base material (Engineering Test Service Co.) was coated with the composition to 30 μm with a bar coater, heated in a dryer at 70 ° C. for 10 minutes, and then irradiated with ultraviolet rays to give the composition. Was cured. UV irradiation conditions are
A 160 W / cm condensing type high-pressure mercury lamp (one lamp), a mercury lamp height of 10 cm, a conveyor speed of 10 m / min, and the number of passes was made tack-free, and two more passes were made. With respect to the obtained cured film, according to the test method of JIS K-5400, the cellophane tape was peeled off, and the adhesion was evaluated by the following three grades by the remaining squares in 100 squares. ◯: 100, Δ: 99 to 81, x: 80 or less

[Hardness] Regarding the cured film obtained by the above adhesion test, JIS
According to the test method of K-5400, the pencil hardness was measured by the hand scraping method. Moreover, the obtained results were judged in the following three stages. ○: H or more, Δ: F, ×: HB or less

1 part of the transparent composition in a 10 cc glass sample bottle having a diameter of 2 cm
Take 0 cc and cover, 80 W / cm condensing type high pressure mercury lamp (one lamp), mercury lamp height 13 cm, conveyor speed 10
Ultraviolet irradiation was performed under the condition of m / min, and a total of 10 passes were made while changing the irradiation surface. The transparency of the obtained cured product was visually evaluated in the following three stages. ○: Completely transparent, △: Slightly turbid, ×: White turbid

Comprehensive judgment Based on all the results obtained above, judgment was made in the following three stages. ◯: ○ in all items, Δ: There is no x in any item, but there is Δ, ×: There is x in any item.

Examples 2 to 4 An active energy ray-curable composition was produced in the same manner as in Example 1 except that the components and proportions shown in Table 1 were used.
The obtained composition was used and evaluated in the same manner as in Example 1. In the case of Example 2 only, the coated substrate was placed in a cell having a glass upper surface and replaced with nitrogen gas, followed by irradiation with ultraviolet rays to cure the substrate. The results are shown in Table 2.

[0052]

[Table 1]

[0053]

[Table 2]

Comparative Examples 1 to 5 Active energy ray-curable compositions were produced in the same manner as in Example 1 except that the components and proportions shown in Table 3 were used.
The obtained composition was used and evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

The active energy ray-curable resin composition for optical members of the present invention has excellent adhesion to plastic substrates, especially polymethylmethacrylate, and excellent physical properties such as hardness and transparency. It has a viscosity suitable for manufacturing a member and can be suitably used for manufacturing an optical member.

Claims (6)

[Claims] 1. A compound (A) having two or more (meth) acryloyl groups and a molecular weight of 450 or less, a compound (B) having one molecular weight of 250 or less and having one ethylenically unsaturated group, and a diisocyanate, a diol and (meth). An optical system comprising a polyurethane (meth) acrylate produced from a monohydric alcohol having at least one acryloyl group, the compound (C) having a molar ratio of diisocyanate and diol of 3: 2 to 21:20. Active energy ray curable composition for members. 2. The composition comprises 30 to 80 parts by mass of the component (A), 10 to 40 parts by mass of the component (B), and 10 to 50 parts by mass of the component (C). The active energy ray-curable composition for optical members according to claim 1. 3. The composition has a viscosity of 500 to 5 at 25 ° C.
The active energy ray-curable composition for optical members according to claim 1 or 2, which has a viscosity of 000 mPa · s. 4. The diol as the component (C) has 2 to 4 carbon atoms.
Alkylene oxide adduct of (repeating units 1 to 5)
The active energy ray-curable composition for an optical member according to any one of claims 1 to 3, wherein the monohydric alcohol is a compound having two or more acryloyl groups. 5. The active energy ray-curable composition for optical members according to claim 1, wherein all of the components (A), (B) and (C) are acrylates. 6. The active energy ray-curable composition for an optical member according to claim 5, which has an acrylic equivalent of 4 meq / g or more.