JP2855424B2 - Actinic ray curable composition for optical article, and optical article - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition for cast polymerization which is rapidly cured by irradiation with actinic rays such as ultraviolet rays. Ru is molded Furenerure
Lens sheet, lenticular lens sheet, prism sheet
Actinic radiation curable set suitable for the production of lens sheets such as sheet
It relates to a product and a lens sheet . 2. Description of the Related Art Conventionally, a curable composition comprising an oligomer (prepolymer) having a (meth) acrylate terminal, a reactive monomer and a photopolymerization initiator has been used at room temperature without using a solvent which has an adverse effect on the human body. It is widely used in paints, inks, coatings, electric materials, image forming fields, and the like because it has the advantage of curing in a short time. [0003] However, the photocurable composition as described above is used for coating,
It is limited to the field of coating represented by painting, and the thickness of these coating films is extremely thin, ranging from several μm to several hundred μm. This is due to the fact that the irradiation light is absorbed and scattered by the photoinitiator, powder and the like contained in the composition and cannot reach the inside, and a composition having a deep curability of several mm to several cm has been found. Not. As an attempt to improve the deep curing property, a method of using a thermal catalyst such as azobisisobutyronitrile and benzoyl peroxide in combination has also been proposed. Yellow coloring, optical distortion, and stress distortion occur, and are particularly important when molding optical components. [0004] The present inventors have developed a lens system.
Depth curability described above in over preparative, transparency, optical distortion, mechanical residual strain, the result of intensive studies yellowing of improvement, the use of a particular initiator, found that these problems can be improved, the present invention Reached. Namely, it is an aspect of the present invention, hydrin
Roxyl, glycidyl or amino group-containing (meth) a
Having two or more isocyanate groups in the molecule with acrylate
Reaction product (A) with an isocyanate compound
30 to 99% by weight , 1 to 70% by weight of a reactive diluent monomer (B) having a boiling point of 100 ° C. or more, and 2-hydroxy-2
At least one photoinitiator (C) selected from -methyl-1-phenylpropan-1-one and hydroxycyclohexylphenyl ketone , with the component (A) and the component (B)
0.01 to 3 parts by weight based on 100 parts by weight
Lens sheet for actinic radiation curable compositions comprising a, and the lens sheet obtained by curing it. Hereinafter, the present invention will be described in detail. The terminal (meth) acryloyl group-containing oligomer (A) which is the first component of the present invention includes a hydroxyl group, glycidyl group or amino group-containing (meth) acrylate and an isocyanate compound having two or more isocyanate groups in a molecule. A ring-opening reaction product of (meth) acrylic acid and an epoxy compound having at least one epoxy group in a molecule, a polyester of a polyhydric alcohol and a polybasic acid, and a (meth) acrylic acid Polyester (meth) acrylate, (meth) acrylic acid and a polyfunctional hydroxyl compound or hydroxyl group
Examples thereof include an esterification reaction product between a glycidyl group or a halogen-containing (meth) acrylate and a polyvalent carboxyl compound and a transesterification reaction product between various (meth) acrylates and a polyhydric hydroxyl compound. Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxyethyl (meth) acrylate.
Addition products of monoepoxy compounds such as hydroxybutyl (meth) acrylate and butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate and (meth) acrylic acid, and polyethylene glycol and polypropylene glycol (meth) And acrylic acid monoesters. Specific examples of the isocyanate compound having at least two isocyanate groups in the molecule include aliphatic, aromatic or alicyclic isocyanates such as tetramethylene diisocyanate, hexamethyldiisocyanate, trimethylhexamethylene diisocyanate, and dimer. Acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenyl methane diisocyanate, m-phenylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, biphenyl diisocyanate, and the like. At least two active hydrogen atoms such as hydroxyl groups, carboxyl groups, and water Compounds having at least two isocyanate groups in the molecule obtained by reaction of a compound of or the diisocyanate compounds trimeric 5 mer, or the like can also be used. The urethanization reaction between the hydroxyl group-containing (meth) acrylate and these isocyanates is carried out by a known method, for example, by mixing a mixture of a hydroxyl group-containing (meth) acrylate with a catalyst such as dibutyltin dilaurate at 50 ° C. in the presence of an isocyanate compound. It can be produced by dropping under conditions of ~ 90 ° C. Specific examples of epoxy compounds having at least one epoxy group in the molecule include aromatic and alicyclic compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolak glycidyl ether, and cresol novolak glycidyl ether. Group epoxy compounds, glycidyl esters of aliphatic polycarboxylic acids, and dimers to pentamers of these epoxy compounds can be used. The reaction of these epoxy compounds with (meth) acrylic acid or an adduct of a hydroxyl group-containing (meth) acrylate with a dicarboxylic anhydride such as phthalic anhydride can be carried out in a known manner, for example, by reacting an epoxy compound with (meth) acrylic acid. Catalysts such as tertiary amino compounds such as dimethylaminoethyl methacrylate, mixtures with quaternary amine salts,
It can be produced by heating a mixture with a secondary amine salt to 60C to 110C. Specific examples of the polyester acrylate include ethylene glycol, 1,4-butanediol,
Polyhydric alcohols such as 6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, and polypropylene glycol and polyhydric alcohols such as phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, and terephthalic acid A condensation reaction product of a polyester obtained from a basic acid and (meth) acrylic acid is exemplified. The reaction between these polyhydric alcohols and polybasic acid is carried out by heating at 200 ° C. in the presence of a catalyst such as dibutyltin oxide to obtain a polyester, which is further subjected to a condensation reaction of (meth) acrylic acid at 100 ° C. Can be manufactured. In addition, bisphenol A, bisphenol F
Or oligo (meth) acrylate obtained by esterifying bisphenol S with ethylene oxide or propylene oxide in an amount of n mol and (meth) acrylic acid. These oligomers (A) having a terminal (meth) acryloyl group can be used alone or in combination of two or more. The reactive diluent monomer (B) having a boiling point of 100 ° C. or more, which is the second component of the present invention, serves as a reactive diluent for the oligomer (A) having a terminal (meth) acryloyl group. The composition for casting polymerization has a resin viscosity range of 3000 to 50 which can be poured into the mold.
Although it is desirable that the viscosity does not exceed 00 cps, in the case of a photocurable composition, it is also possible to lower the viscosity by heating to an acceptable range, for example, about 100 ° C. You can go beyond the width. Specific examples of the diluent monomer (B) include:
Methyl methacrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) Lauryl acrylate, sterial (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- (meth) acrylate
Hydroxybutyl, glycidyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate, phenylglycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, phenylcellosolov (meth)
Acrylate, N-vinyl-2-pyrrolidone (meth) acrylate, dicyclopentenyl (meth) acrylate,
Mono (meth) acrylic compounds such as biphenyl (meth) acrylate, glycidyl (meth) acrylic acid (meth) acryl, 2-hydroxyethyl (meth) acryloyl phosphate, styrene, vinyltoluene, chlorostyrene, divinylbenzene, 1- Monovinyl compounds such as vinyl naphthalene and 2-vinyl naphthalene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol (meth) ) Acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylol pantri (meth) acrylate, neopentyl glyco Distearate (meth) acrylate,
1,6-hexamethylene di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Polyfunctional (meth) acrylic compounds such as tris (meth) acryloxyethyl isocyanurate are exemplified. In addition, allyl compounds such as diethylene glycol bisallyl carbonate, diallyl phthalate, dimethallyl phthalate and allyl methacrylate can also be used. These diluent monomers can be used alone or in combination of two or more. In the third component of the present invention, 2-hydroxy-2
In the case of a combination of at least one photoinitiator (C) selected from -methyl-1-phenylpropan-1-one and hydroxycyclohexylphenyl ketone, by mixing with the components (A) and (B), It is not yellowed by actinic rays such as ultraviolet rays, is quickly cured, and gives a cured product with good deep curability and surface hardness. For this reason, the actinic ray-curable composition of the present invention using the photoinitiator (C) is useful for producing optical articles and optical lenses, such as optical parts and optical lenses, which require excellent transparency, surface hardness, and precision. Particularly suitable as a material. When a molded product is produced by casting polymerization, an ultraviolet absorber is often used in combination to improve the weather resistance. In this case, too, the ultraviolet absorber and the two types of photoinitiators are used. Since the polymerization of the agent (C) can be carried out with a smaller amount of actinic rays than in the past, a molded article can be produced by cast polymerization with good productivity in an inexpensive high-pressure mercury lamp facility, and thus it is preferable. In the present invention, the first component (meth) acryloyl group-containing oligomer (A) 30 to 9
9% by weight, more preferably 50 to 90% by weight, and the second component, a reactive diluent monomer (B) having a boiling point of 100 ° C. or more, 1 to 70% by weight, more preferably 10 to 50% by weight. Is preferred. Further, the photoinitiator (C) as the third component is preferably added in an amount of 0.005 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the components (A) and (B). It is in the range of 01 to 3 parts by weight. When the amount of the terminal (meth) acryloyl group-containing oligomer (A) is less than 30% by weight, the activity to ultraviolet rays tends to decrease, and the hardness, abrasion resistance, heat resistance and impact resistance of the cured product tend to decrease. If the photoinitiator (C), which is the third component of the present invention, is less than 0.005 parts by weight, the activity to actinic rays tends to decrease. I ca n’t,
It is not preferable in terms of cost. In carrying out the present invention, after mixing the terminal (meth) acryloyl group-containing oligomer (A) and the reactive diluent monomer (B) having a boiling point of 100 ° C. or more, the photoinitiator (C) is mixed. Is preferred. In order to polymerize and cure the monomer mixture by irradiation of ultraviolet rays, ultraviolet rays having a wavelength of 2,000 to 8,000 angstroms are preferable, and the irradiation atmosphere is sufficient in ordinary air. As a light source, a known chemical lamp, xenon lamp, low-pressure mercury lamp, high-pressure mercury lamp, or the like can be applied. In the present invention, in addition to the above-described polymerization and curing method by irradiation with ultraviolet rays, it is also possible to apply a known polymerization and curing method by irradiation with X-rays, electron beams, visible rays, and the like. In practicing the present invention, when performing polymerization, various ultraviolet curable monomers, oligomers, other copolymerizable monomers, and monomers for preventing polymerization shrinkage as long as the curing of the present invention is not impaired. Non-reactive substances, such as polyethylene glycol, polypropylene glycol, polyethylene glycol, monoalkyl ether, polypropylene glycol monoalkyl ether, ethylene oxide or propylene oxide adduct of bisphenol A, ethylene oxide or propylene oxide adduct of tetrabromobisphenol A, and the like. Further, various peroxides, yellowing inhibitors such as triphenylphosphine, ultraviolet absorbers, blue ink dyes and the like may be added. Hereinafter, the present invention will be described in more detail by way of examples. In the examples, “parts” means “parts by weight”. The evaluation of the physical properties in the examples was measured according to the methods described below. (1) Depth of cure: inner diameter 8 m / m, outer diameter 10 m / m, length 50 m / m
m, the resin composition was poured into a polyethylene test tube, and the upper part was covered with a transparent polyester film.
The cured product was taken out by irradiating ultraviolet rays for about 30 seconds from above with a high-pressure mercury lamp having a height of 70 cm and measuring the side hardness with a Shore-D hardness meter to measure the length up to a portion having a hardness of 70 or more. (2) Surface hardness: measured according to JIS-K5400,
The pencil hardness was described. (3) Coloring: The cured product was judged by visual comparison with a Gardner colorimetric standard tube. <Synthesis of oligomer> (Production of urethane dimetal acrylate) Trimethylhexamethylene diisocyanate 210 was placed in a three-necked flask.
And 0.2 part of hydroquinone monomethyl ether, and a mixture of 273 parts of 2-hydroxyethyl methacrylate and 0.5 part of dibutyltin dilaurate was added dropwise over 3 hours while stirring at 60 ° C. After the completion of the dropwise addition, the reaction was further continued at 70 ° C. for 3 hours to obtain urethane diacrylate. (Production of epoxy diacrylate) A three-necked flask was charged with 378 parts of bisphenol A type epoxy resin (Epicoat 828, Yuka Shell Epoxy Co., Ltd.), 144 parts of acrylic acid, and 5 parts of benzyltrimethylammonium chloride. The mixture was stirred and reacted at 5 ° C. for 5 hours and at 100 ° C. for 10 hours to obtain an epoxy diacrylate. (Production of Polyester Acrylate) A three-necked flask was charged with 44 parts of adipic acid, 25 parts of 1,6-hexanediol, 30 parts of triethylene glycol, and 0.1 part of dibutyltin oxide. For 5 hours. 11 parts of acrylic acid, p
-0.5 parts of toluenesulfonic acid was added at 90 ° C for 3 hours,
The reaction was carried out while distilling off water under reduced pressure to obtain a polyester acrylate. <Production of an actinic ray-curable composition> (Example 1) The above urethane dimethacrylate (UDM)
A) 30 parts of trimethylolpropane trimethacrylate and 0.5 part of 2-hydroxy-2-methyl-1-phenylpropan-1-one were mixed with 70 parts of A) to obtain an actinic ray-curable composition. This resin composition was injected into a polyethylene test tube having an inner diameter of 8 m / m and a length of 60 m / m, the upper part was covered with a polyester film, and the side was covered with aluminum foil so that light could be irradiated only from the upper part. The test tube was irradiated with ultraviolet rays from the upper opening for about 30 seconds with a high-pressure mercury lamp of 80 W / cm, and the cured product was taken out, and the curing depth, surface hardness and Gardner color number were measured. The results are as shown in Table 1. The cured product was colorless and transparent, and the surface hardness was 4H in pencil hardness. (Examples 2 to 9, Comparative Examples 1 to 11) In the same manner as in Example 1, a composition was prepared using the components (A), (B) and (C) shown in Table 1, The performance of each cured product was evaluated. The results obtained are shown in Table 1. [Table 1] The abbreviations in Table 1 are as follows. UDMA: urethane dimethacrylate obtained by reacting trimethylhexamethylene diisocyanate with 2-hydroxyethyl methacrylate EDA: epoxy acrylate obtained by reacting bisphenol type epoxy resin with acrylic acid PEA: adipic acid / 1,6- Polyester acrylate obtained by reacting hexanediol / triethylene glycol / acrylic acid TMPM: trimethylolpropane trimethacrylate THFA: tetrahydrofurfuryl methacrylate ST: styrene Oi 1: 2-hydroxy-2-methyl-1-phenylpropane 1-one Oi 2: hydroxycyclohexylphenyl ketone Oi 3: acetophenone Oi 4: diethoxyacetophenone Oi 5: benzophenone Oi 6: 2,2-dimethoate C-2-phenylacetophenone Oi 7: 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone Oi 8: 2-chlorothioxanthone Oi 9: isopropylthioxanthone Oi10: isobutylbenzoin ether Oi11 isopropyl benzoin ether Oi12: benzoin ethyl ether Oi13: as detailed benzoin methyl ether [0029] [effect of the invention above, the actinic ray curable composition of the present invention is excellent in depth curability, and the resulting therefrom the cured product has no optical distortion and mechanical residual strain, is excellent in surface hardness and transparency, full transparency, it is required precision
Rennel lens sheet, lenticular lens sheet,
An excellent effect can be exerted on a lens sheet such as a rhythm sheet obtained by a casting polymerization method using actinic rays such as ultraviolet rays.

Continuation of front page                   (56) References JP-A-59-87124 (JP, A)                 JP-A-61-194401 (JP, A)                 JP-A-59-161422 (JP, A)                 JP-A-61-14210 (JP, A)                 JP-A-61-14212 (JP, A)                 JP-A-62-104817 (JP, A)                 JP-A-63-199302 (JP, A)                 JP-A-62-258401 (JP, A)                 Journal of Radiat               ion Curing, (July 1984)               Pages 4-8

Claims (1)

(57) [Claims] Contains hydroxyl group, glycidyl group or amino group
(Meth) acrylate and two or more isocyanates in the molecule
Reaction with an isocyanate compound having a phosphate group
30-99% by weight of the reaction product (A), 1-70% by weight of a reactive diluent monomer (B) having a boiling point of 100 ° C. or more, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxycyclohexylphenyl At least one photoinitiator (C) selected from ketones is used in an amount of 0.01 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
An actinic ray-curable composition for a lens sheet comprising about 3 parts by weight . 2. A lens obtained by curing the curable composition according to claim 1.
Sheet .