JP5623190B2 - Plastic lens manufacturing method and plastic lens - Google Patents

Description

The present invention relates to the production method and plastic lens of the plastic lens having a composition distribution.

  In various optical systems such as a camera, an optical fiber imaging system, a copying machine, and a compact disc pickup optical system, a plurality of lenses are required to correct various aberrations such as spherical aberration and chromatic aberration. In particular, an optical system used under an imaging system or a white light source requires a larger number of lenses than a monochromatic optical system in order to correct chromatic aberration.

  Therefore, when a radial type refractive index distribution lens having a refractive index gradient in the radial direction from the optical axis is used in the lens medium, the effect particularly excellent in correcting chromatic aberration is exhibited. Therefore, the number of lenses for correcting chromatic aberration can be reduced, and the zoom lens can be miniaturized and enhanced in function such as wide angle and high magnification.

  The refractive index distribution of a plastic lens is formed by the composition distribution in the medium, such as the copolymerization ratio of two or more monomers having different refractive indexes, or the concentration distribution of inorganic fine particles having a refractive index different from the organic component of the matrix. can do.

  For example, as a method of forming a composition distribution in a plastic lens, a method is known in which a solid polymer is brought into contact with a monomer solution and the monomer is diffused into the polymer (for example, Patent Document 1). Patent Document 2).

Japanese Patent No. 03989035 Japanese Patent Laid-Open No. 7-40357

  The technique disclosed in Patent Document 1 is a method in which a polymer is photocured until it has self-shape retention, and then the polymer is swollen in the monomer to diffuse the monomer. Therefore, the degree of cure of the high molecular polymer is high and the diffusion of the monomer is slow. Therefore, it takes at least 17 days to diffuse the monomer to the center with a sample having a diameter of 20 mm. The obtained refractive index difference is about 0.02 between the central portion and the peripheral portion.

  In Patent Document 2, a pressure mechanism is required for the casting cell.

  In order to obtain a large refractive index difference, it is effective to form a concentration distribution of fine particles such as a metal oxide having a large refractive index. However, Patent Documents 1 and 2 do not disclose a method of forming a concentration distribution with fine particles in a method of manufacturing a plastic member having a composition distribution by using monomer diffusion.

The present invention has been made in view of such background art, and provides a plastic lens manufacturing method capable of obtaining a plastic lens having a composition distribution in a short time with a simple facility, with a small number of steps. To do.

Further, the present invention is to provide a plastic lens having a fabricated composition distribution in the method of manufacturing the plastic lens.

A method for producing a plastic lens having a composition distribution that solves the above-described problem is a first method in which a casting cell provided with a radiation irradiation surface is filled with a first radiation-polymerizable composition containing a first monomer capable of radiation polymerization . A filling step, a polymerization step of irradiating the radiation-irradiated surface of the casting cell, polymerizing a part of the first radiation-polymerizable composition to obtain a polymer of the first composition, and unpolymerized A removal step of removing the first radiation-polymerizable composition from the casting cell, and a second radiation-polymerizable composition containing a second monomer capable of radiation polymerization in the void of the casting cell generated by the removal. A second filling step of filling the composition and contacting the polymer of the first composition; and a total curing for curing the whole of the second radiation-polymerizable composition and the polymer of the first composition. of plastic lens having a step, a In the production method, the method includes a diffusion step of diffusing the second radiation polymerizable composition into the polymer of the first composition between the second filling step and the total curing step, The polymer of the first composition is a gel having a complex viscosity of 10 Pa · s or more and less than 10,000 Pa · s, and the second radiation polymerizable composition is liquid .

Plastic lenses to solve the above problems, a plastic lens produced by the production method of the plastic lens.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the plastic lens which can obtain the plastic lens which has composition distribution with a simple installation with few processes, and a short time can be provided.

In addition, according to the present invention, it is possible to provide a plastic lens having a composition distribution produced by the method for producing a plastic lens described above. Moreover, according to the present invention, a plastic lens having a fine particle concentration distribution can be obtained.

It is process drawing which shows one embodiment of the manufacturing method of the plastic lens of this invention. It is a figure which shows the refractive index distribution of the plastic lens obtained in the Example of this invention. It is a figure which shows distribution of the zirconium oxide microparticles | fine-particles of the plastic lens obtained in the Example of this invention. It is a figure which shows distribution of the zirconium oxide microparticles | fine-particles of the plastic lens obtained in the Example of this invention. It is a figure which shows distribution of the fluorescent X ray intensity derived from the silicon oxide microparticles | fine-particles of the plastic lens obtained in the Example of this invention. It is a figure which shows the transmittance | permeability profile of the gray scale mask used in the Example of this invention. It is a figure which shows the refractive index distribution of the plastic lens obtained in the Example of this invention. It is a figure which shows distribution of the zirconium oxide microparticles | fine-particles of the plastic lens obtained in the Example of this invention. It is a figure which shows the refractive index distribution of the plastic lens obtained in the Example of this invention. It is process drawing which shows the manufacturing method of the plastic lens of the comparative examples 1 and 2. It is a figure which shows the refractive index distribution of the plastic lens obtained in Example 8 of this invention ((a) Example 8-2 (b) Example 8-3 (c) Example 8-4). In Example 8 of this invention, it is a figure which shows the relationship between the exposure time of the irradiated ultraviolet-ray, and the complex viscosity of the polymer of a 1st composition.

Hereinafter, embodiments of the present invention will be described in detail. In the following description, “plastic member” may be used instead of “plastic lens”.

  The method for producing a plastic member having a composition distribution according to the present invention includes a step of filling a casting cell provided with a radiation irradiation surface with a first radiation-polymerizable composition containing a first monomer capable of radiation polymerization; Irradiating the irradiation surface of the casting cell with radiation, polymerizing a part of the first radiation-polymerizable composition to obtain a polymer of the first composition, and the unpolymerized first radiation. A step of removing the polymerizable composition from the casting cell, and filling the void of the casting cell generated by the removal with a second radiation polymerizable composition containing a second monomer capable of radiation polymerization. Diffusing in the casting cell; contacting the polymer of the first composition; diffusing the second radiation polymerizable composition into the polymer of the first composition; The second radiation-polymerizable composition and the first composition To further comprising a, and curing the whole of the polymer.

  A method for producing the plastic member of the present invention will be described with reference to the drawings. FIG. 1 is a process diagram showing an embodiment of a method for producing a plastic member of the present invention.

  A casting cell 3 in which a gasket 2 is provided between a pair of optical glasses 1 is prepared. A first radiation polymerizable composition 4 containing a first monomer capable of radiation polymerization is filled between the gaskets of the casting cell 3 provided with a light irradiation surface made of the optical glass 1 (FIG. 1 (a). )).

  A part of the first radiation-polymerizable composition 4 in the casting cell is irradiated with a radiation 10 such as light on a part of the light irradiation surface formed by providing the shield 5 on the casting cell. Is polymerized to obtain a polymer 6 of the first composition (FIG. 1B).

  Unpolymerized first radiation-polymerizable composition is removed from the casting cell (FIG. 1 (c)).

  The void 7 of the casting cell generated by the removal is filled with a second radiation-polymerizable composition 8 containing a second monomer capable of radiation polymerization and brought into contact with the polymer 6 of the first composition. (FIG. 1 (d)).

  The second radiation polymerizable composition is allowed to stand for a predetermined time to diffuse into the polymer of the first composition (FIG. 1 (e)).

  The whole of the second radiation-polymerizable composition and the polymer of the first composition diffused in the casting cell is cured by irradiation or heating (FIG. 1 (f)).

  The cured product is taken out from the casting cell to obtain a plastic member 9 having a composition distribution (FIG. 1 (g)).

  Hereinafter, the raw material used with the manufacturing method of this invention is demonstrated.

(First radiation polymerizable composition)
The first radiation-polymerizable composition (A) is composed of a radiation-sensitive polymerization initiator (c) and a radiation-polymerizable first monomer (d). The first radiation polymerizable composition may contain fine particles (e), a photosensitizer (f), and a thermal polymerization initiator (g).

  Examples of the first monomer (d) include a radical polymerizable monomer or a cationic polymerizable monomer.

  As the radical polymerizable monomer, a compound having at least one acryloyl group or methacryloyl group is preferable.

  As the cationic polymerizable monomer, a compound having at least one vinyl ether group, epoxy group or oxetanyl group is preferable.

As a monofunctional (meth) acrylic compound having one acryloyl group or one methacryloyl group, for example,
Phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4 -Phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, (meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2-bromophenoxyethyl (meta) ) Acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, and a phenochrome modified with multiple moles of ethylene oxide and propylene oxide. Xyl (meth) acrylate, polyoxyethylene nonyl phenyl ether (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( (Meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, Toxidiethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol ( (Meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylami , N, N-dimethylaminopropyl (meth) acrylamide include, but are not limited to.

As a commercial item of a monofunctional (meth) acryl compound, for example,
Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (above, manufactured by Toagosei), LA, IBXA, 2-MTA, HPA, Biscote # 150, # 155, # 158, # 190, # 192, # 193, # 220, # 2000, # 2100, # 2150 (above, manufactured by Osaka Organic Chemical Industry), light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A (manufactured by Kyoeisha Chemical), KAYARAD TC110S, R-564, R- 128H (above, Nippon Kayaku), NK ester AMP-10G, AMP-20G (above, Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (Hitachi Chemical Co., Ltd.), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (above, Daiichi Kogyo) (Manufactured by Pharmaceutical), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (manufactured by Kojin), and the like, but are not limited thereto.

As a polyfunctional (meth) acryl compound having two or more acryloyl groups or methacryloyl groups, for example,
Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylolpropane tri (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloyloxy) isocyanurate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, EO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, EO, Examples thereof include, but are not limited to, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane.

  These can be used alone or in combination of two or more. In the above, (meth) acrylate means acrylate and its corresponding methacrylate, (meth) acryloyl group means acryloyl group and its corresponding methacryloyl group, EO indicates ethylene oxide, and is EO-modified. These compounds have an ethylene oxide group block structure. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

As a commercial item of a polyfunctional (meth) acryl compound, for example,
Iupimer UV SA1002, SA2007 (Mitsubishi Chemical), Biscote # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (above, Osaka Organic Chemical) Manufactured by Kogyo Co., Ltd.), light acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A KAYARAD PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (above, Nippon Kayaku), Aronix M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (above, Ltd. 亞 synthesis), Ripoxy VR-77, VR-60, VR-90 (manufactured by Showa High Polymer)
However, it is not limited to these.

As a compound having one vinyl ether group, for example,
Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, di- Cyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl Examples thereof include, but are not limited to, vinyl ether and phenoxy polyethylene glycol vinyl ether.

As a compound having two or more vinyl ether groups, for example,
Divinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylol Ethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide adduct Methylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Examples thereof include polyfunctional vinyl ethers such as addition dipentaerythritol hexavinyl ether and propylene oxide addition dipentaerythritol hexavinyl ether, but are not limited thereto.

As a compound having one epoxy group, for example,
Phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxide decane, epi Examples include, but are not limited to, chlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, and 3-vinylcyclohexene oxide.

As a compound having two or more epoxy groups, for example,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A Diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5 , 5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene Oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate , Methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthalic acid Dioctyl, epoxyhexahydrophthalic acid di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylo Rupane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2 , 5,6-diepoxycyclooctane and the like, but not limited thereto.

As a compound having one oxetanyl group, for example,
3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3 -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- 3-Oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl ( 3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3- Ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl) -3- Xetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether and the like can be mentioned, but not limited thereto.

Examples of the compound having two or more oxetanyl groups include:
3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1 , 4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl- 3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3 -Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Licyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipe Taerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ) Ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, Such as O-modified bisphenol F (3- ethyl-3-oxetanylmethyl) polyfunctional oxetane such as ethers including but not limited to.

  The first monomer (d) component is preferably used in combination of a monofunctional monomer and a polyfunctional monomer.

  The radiation-sensitive polymerization initiator (c) is a radiation-sensitive radical generator when the first monomer (d) component is a radical polymerizable monomer, and when the first monomer (d) component is a cationic polymerizable monomer. It is a radiation sensitive acid generator.

  A radiation-sensitive radical generator is a compound capable of initiating radical polymerization by generating a chemical reaction upon irradiation with radiation, such as charged particle beams such as infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and electron beams. It is.

As such a compound, for example,
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 2,4,5-triarylimidazole dimer, such as 2,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. Mer;
Benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chloro Benzophenone derivatives such as benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone;
Aromatics such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Ketone derivatives;
2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, Quinones such as 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone;
Benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether;
Benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, propylbenzoin;
Benzyl derivatives such as benzyldimethyl ketal;
Acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane;
N-phenylglycine derivatives such as N-phenylglycine;
Acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone;
Thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone:
Xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one,
Examples include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. These can be used alone or in combination of two or more.

  Examples of commercially available radiation-sensitive radical generators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur l116, 1173 (above, Ciba Japan), Lucirin TPO, LR8883, LR8970 (above, manufactured by BASF), Ubekrill P36 (manufactured by UCB), and the like, but are not limited thereto.

  A radiation-sensitive acid generator is a compound capable of initiating cationic polymerization by generating a chemical reaction upon irradiation with radiation, such as charged particle beams such as infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and electron beams. It is. Examples of such compounds include, but are not limited to, onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, and the like. In the present invention, it is preferable to use an onium salt compound.

Examples of onium salt compounds include:
Examples include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like. Specific examples of the onium salt compound include bis (4-t-butylphenyl) iodonium perfluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, and bis (4-t-butylphenyl). Iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium pyrenesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium p- Toluene sulfonate, bis (4-tert-butylphenyl) iodonium benzene sulfonate, bis (4-tert-butylphenyl) iodonium 10-camphor sulfonate, bis (4-tert-butylphenyl) iodonium n-oct Sulfonate, diphenyliodonium perfluoro-n-butanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyl Iodonium benzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octanesulfonate, triphenylsulfonium perfluoro-n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfone , Triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, diphenyl ( 4-t-butylphenyl) sulfonium perfluoro-n-butanesulfonate, diphenyl (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, diphenyl (4-t-butylphenyl) sulfonium 2-trifluoromethylbenzenesulfonate, diphenyl ( 4-t-butylphenyl) sulfonium pyrenesulfonate, diphenyl (4-t-butylphenyl) L) sulfonium n-dodecylbenzenesulfonate, diphenyl (4-t-butylphenyl) sulfonium p-toluenesulfonate, diphenyl (4-t-butylphenyl) sulfoniumbenzenesulfonate, diphenyl (4-t-butylphenyl) sulfonium 10-camphor Sulfonate, diphenyl (4-t-butylphenyl) sulfonium n-octanesulfonate, tris (4-methoxyphenyl) sulfonium perfluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxy Phenyl) sulfonium 2-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium pyrenesulfonate, tris (4-methoxy) Phenyl) sulfonium n-dodecylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium p-toluenesulfonate, tris (4-methoxyphenyl) sulfoniumbenzenesulfonate, tris (4-methoxyphenyl) sulfonium 10-camphorsulfonate, tris (4- Methoxyphenyl) sulfonium n-octane sulfonate and the like, but are not limited thereto.

  Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include, but are not limited to, phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like.

  Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of the sulfonic acid ester compound include α-methylol benzoin perfluoro-n-butane sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin 2-trifluoromethylbenzene sulfonate, and the like. Not.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) ) Naphthylimide, N- (10-camphorsulfonyloxy) s Synimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-Methylphenylsulfonyloxy) phthalimide, N- (4-methylpheny Sulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N -(2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2, 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (4-fluorophenyl) phthalimide, N- (4-fluorophenyl) Sulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bi Chlo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyl) Examples include, but are not limited to, oxy) naphthylimide.

      Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, (cyclohexyl) Examples include, but are not limited to, sulfonyl) (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and the like.

  Of these radiation-sensitive acid generators, onium salt compounds are preferred. In this invention, an acid generator can be used individually or in mixture of 2 or more types.

  The mixing ratio of the radiation-sensitive polymerization initiator (c) component is 0.01% by mass or more and 10% by mass or less, preferably 0.1% with respect to the total amount of the first radiation-polymerizable composition (A) of the present invention. It is from 3% by mass to 3% by mass. If it is less than 0.01% by mass, the curing rate may decrease and the reaction efficiency may decrease. On the other hand, when it exceeds 10 mass%, it may be inferior in the point of the hardening characteristic and handleability of a radiation sensitive polymerizable composition, and the mechanical characteristic and optical characteristic of hardened | cured material.

  A photosensitizer (f) can be added to the first radiation-polymerizable composition (A) of the present invention. By adding a photosensitizer, a composition distribution can be formed with a smaller exposure amount. Here, the photosensitizer is a compound that is excited by absorbing light of a specific wavelength and has an interaction property with the radiation-sensitive polymerization initiator (c) component, and includes a coumarin derivative, a benzophenone derivative, a thioxanthone derivative, Examples include, but are not limited to, anthracene derivatives, carbazole derivatives, and perylene derivatives. Examples of the interaction include energy transfer and electron transfer from the photosensitizer in the excited state. The molar extinction coefficient of the photosensitizer (f) component with respect to the exposure wavelength is preferably larger than the molar extinction coefficient of the radiation sensitive polymerization initiator (c) component.

(Second radiation-polymerizable composition)
As the second radiation polymerizable composition (B), a second radiation polymerizable composition (C) containing a second monomer (d1) capable of radiation polymerization is used.

  As the second radiation polymerizable composition (C), the same composition as the first radiation polymerizable composition (A) is used. In this case, the second radiation-polymerizable composition (C) and the first radiation-polymerizable composition (A) have different monomers and compositions, and have different physical properties such as optical physical properties and electrical physical properties after curing. Is used.

  At least one of the first radiation-polymerizable composition and the second radiation-polymerizable composition in the present invention can contain fine particles (e). The material constituting the fine particles (e) used in the present invention is not particularly limited as long as it is transparent to irradiation light described later and can be uniformly dispersed in the radiation-sensitive polymerizable composition. An inorganic material or an organic-inorganic composite material can be used. The surface may be modified.

As a material constituting the fine particles (e), for example,
Titanium oxide (TiO ₂ ), titanium hydroxide, zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), aluminum oxide (Al ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), tin oxide (SnO ₂₎ ), Antimony oxide (Sb ₂ O ₅ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ), indium tin oxide (ITO), indium oxide (In ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ), oxidation Gadonium (Gd ₂ O ₃ ), hafnium oxide (HfO ₂ ), erbium oxide (Er ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ), cerium oxide (CeO ₂ ), dysprosium oxide (Dy ₂ O ₃ ), oxide magnesium (MgO), iron oxide _{(Fe 2 O} 3), iron hydroxide (Fe _{(OH) 3),} gallium oxide _{(Ga 2 O} 3), hydroxide Gallium (Ga _{(OH) 3),}
And mixed oxides and mixed hydroxides thereof, but are not limited thereto. From the viewpoint of stability, aluminum oxide, titanium oxide, niobium oxide, tin oxide, zinc oxide, silicon oxide, indium oxide, zirconium oxide, tantalum oxide, lanthanum oxide, gadonium oxide, hafnium oxide, erbium oxide, neodymium oxide, oxidation Cerium, dysprosium oxide, and mixed oxides and hydroxides thereof are used.

  When the particle size of the fine particles is large, the irradiation light is scattered, so fine particles sufficiently smaller than the wavelength of the irradiation light must be used. Also, in the case of a plastic member that requires transparency, such as an optical lens, there is a problem that the transmittance decreases due to the influence of light scattering if the particle size is large. Therefore, the average particle size of the fine particles used in the present invention is 50 nm or less, preferably 20 nm or less. Although it depends on the intended plastic member, a narrow particle size distribution is preferable.

  In order to uniformly disperse the fine particles in the polymerizable composition, it is preferable that the surface is chemically modified at the time of fine particle preparation, or a treatment such as addition of a dispersant is performed after the fine particle preparation. The fine particles can be used alone, in a mixture, or in a complex. In addition, a material having a photocatalytic reaction such as titanium oxide may be subjected to a treatment such as coating the surface with a silicon compound or the like as necessary in order to prevent the resin from being decomposed by the reaction.

  The content of the fine particles varies depending on the target optical performance and mechanical characteristics, and also varies depending on the types of the fine particles used, the first monomer, and the second monomer (d) component. On the other hand, 1 mass% or more and 99 mass% or less, Preferably 1 mass% or more and 70 mass% or less are preferable. The fine particles to be dispersed are not limited to a single kind, and plural kinds of fine particles may be dispersed.

  It is preferable that the first radiation-polymerizable composition (A) and the second radiation-polymerizable composition (B) are liquid. Moreover, it is preferable that it is liquid at the time of injection | pouring and removal. If it is solid at room temperature and atmospheric pressure, it may be injected or removed while heating or pressurizing as necessary.

  The first radiation-polymerizable composition (A) is preferably encapsulated in a casting cell that is transparent to radiation irradiated on at least one surface. The inner surface of the casting cell may be spherical, aspherical or flat and can be selected according to the intended device.

  The casting cell can be produced by providing a gap with a spacer such as a gasket between two substrates, at least one of which is transparent to the irradiation light. The casting cell is fixed with a clip with a spring as necessary, and the radiation polymerizable composition (A) is injected into the gap using a syringe or the like. Examples of the transparent substrate include known materials such as quartz, glass, silicone resin, fluororesin, acrylic resin, polycarbonate resin, transparent resin such as polyimide, sapphire, diamond, and the like. In order to facilitate the removal step of the first radiation-polymerizable composition (A) and the injection step of the second radiation-polymerizable composition (B), which will be described later, a syringe after injection of the radiation-polymerizable composition (A) It is preferable to leave the needle pierced.

  In order to facilitate mold release after curing the first radiation-polymerizable composition (A) and the second radiation-polymerizable composition (B), the surface of the casting cell is treated with a mold release agent. It is preferable. The release agent treatment is performed by applying a release agent such as a fluororesin, a silicone resin, or a fatty acid ester by spraying, dipping, spin coating, or the like, and heating as necessary. Excess release agent may be removed by solvent cleaning or wiping.

  The radiation to be irradiated is selected according to the sensitivity wavelength of the first radiation-polymerizable composition (A) to be used, but ultraviolet light having a wavelength of about 200 to 400 nm, X-rays, electron beams, etc. are appropriately selected. Are preferably used. Ultraviolet light is particularly preferred because a wide variety of photosensitive compounds having sensitivity to ultraviolet light are readily available as the first monomer (c) component. Examples of the light source that emits ultraviolet light include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a low-pressure mercury lamp, a Deep-UV lamp, a carbon arc lamp, a chemical lamp, a metal halide lamp, and a xenon lamp, and an ultra-high pressure mercury lamp is particularly preferable. One or more of these radiations can be used.

  A part of the casting cell is irradiated with radiation to cure a part of the first radiation-polymerizable composition (A) in the cell. As a method of irradiating a part, a part of the casting cell may be covered with a shielding member, or irradiation may be performed while scanning with beam-shaped radiation.

  The degree of polymerization of the first radiation-polymerizable composition (A) can be controlled by the radiation dose. A dose distribution may be provided in the radiation irradiation region.

  For example, the irradiation dose of the radiation irradiated to the radiation irradiation surface of the casting cell is not constant, the irradiation dose of the radiation irradiated to the radiation irradiation surface of the casting cell is lower as the outer periphery, or It is preferable that the irradiation amount of the radiation irradiated to the radiation irradiation surface of the casting cell is higher as the outer circumference is increased.

  Since the diffusion rate is determined by viscosity, cross-linking density, etc., the diffusion behavior can be controlled by giving an irradiation dose distribution. That is, the refractive index distribution profile can be controlled.

  Examples of a method for providing an irradiation distribution include a method in which a gray scale mask having different radiation transmittances is placed on a cell, a method in which a shielding member is moved during radiation irradiation, and a method in which beam-shaped radiation is scanned. However, it is not limited to these.

  The degree of polymerization of the first radiation-polymerizable composition (A) by radiation polymerization is as follows. The first radiation-polymerizable composition is a non-polymerized liquid using a syringe needle from the casting cell at the irradiated / non-irradiated interface. When the product (A) is separated, a minimum degree of polymerization is preferred so that the irradiated portion, that is, the cured portion does not collapse. Moreover, the minimum polymerization degree of the grade which does not collapse | disintegrate also in the removal process mentioned later and the injection | pouring process of a 2nd radiation polymerizable composition (B) is preferable.

  The degree of cure of the polymer (polymer A) of the first radiation-polymerizable composition (A) produced by irradiation with radiation will be described.

  The complex viscosity of the polymer A is desirably 10 Pa · s or more and less than 10,000 Pa · s. When the complex viscosity is less than 10 Pa · s, when the unpolymerized liquid first radiation-polymerizable composition (A) is separated from the casting cell using a syringe needle, the irradiated portion, that is, the cured portion is collapsed. When the complex viscosity is 10,000 Pa · s or more, the progress of diffusion is slow in the leaving step described later.

  The complex viscosity can be measured with a dynamic viscoelasticity measuring device (for example, viscoelasticity measuring device MCR-301 manufactured by Anton Paar Japan Co., Ltd.).

The shape obtained a gel-like polymer so as not to collapse, the exposure amount at the wavelength 365 nm, 0.01 mJ / cm ² or more 1000000mJ / cm ² or less, preferably 0.1 mJ / cm ² or more 100000mJ / cm ² or less And

The non-irradiated portion of the unpolymerized first radiation-polymerizable composition (A) is removed from the casting cell. If the syringe needle used for injection remains, it is preferable to suck out the unpolymerized first radiation-polymerizable composition (A) from the syringe needle. You may remove, heating or pressurizing as needed.
Since the radiation-polymerizable composition (A) in contact with the end surface of the gel is in a liquid state, the end surface of the gel is not damaged when separated.

  A syringe containing the second radiation-polymerizable composition (B) is attached to a syringe needle, and the void inside the casting cell produced by the removal has physical properties different from those of the first radiation-polymerizable composition (A). The liquid second radiation-polymerizable composition (B) is filled. You may inject | pour, heating or pressurizing as needed.

  After filling with the second radiation polymerizable composition (B), the casting cell is allowed to stand for a predetermined time. During the standing step, exchange of materials occurs by diffusion between the polymerized radiation-polymerizable composition (A) and the polymerizable composition (B), and a composition distribution is obtained. The lower the degree of polymerization, the faster the diffusion. For the purpose of accelerating diffusion, heating, electric field application, and magnetic field application may be performed during the leaving step, or the casting cell may be rotated. In the step of diffusing the second radiation polymerizable composition into the polymer of the first composition, it is preferable to heat the casting cell to a temperature higher than room temperature (23 ° C.).

  After the standing step, irradiation or / and heating is performed to stop the diffusion of the material, and the polymerized radiation-polymerizable composition (A) and polymerizable composition (B) are cured. The radiation described above can be used for the radiation irradiation. Heating can be performed using a known apparatus such as an oven or a hot plate. It is preferable to cure sufficiently so as to obtain mechanical properties and environmental stability.

  The cured products of the first radiation polymerizable composition and the second radiation polymerizable composition preferably have different refractive index wavelength dispersions.

  The cured product is taken out from the casting cell to obtain a plastic member having a composition distribution as a target product.

  Hereinafter, the present invention will be described in detail with specific examples.

  (D1) 90 parts by weight of benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts by weight of trimethylolpropane triacrylate (manufactured by Sigma Aldrich Japan), and (c1) a photoradical generator (Irgacure 184, manufactured by Ciba Japan) ) Radiation polymerizable composition (A1) consisting of 0.1 parts by weight was prepared.

  As component (d2), 90 parts by weight of methyl methacrylate (manufactured by Sigma-Aldrich Japan) and 10 parts by weight of trimethylolpropane triacrylate (manufactured by Sigma-Aldrich Japan), as a component (c2), a photo radical generator (Irgacure 184, A polymerizable composition (B2) comprising 0.1 part by weight of Ciba Japan) was prepared.

  The refractive index of the cured product of benzyl methacrylate is 1.568, the refractive index of the cured product of trimethylolpropane triacrylate is 1.509, and the refractive index of the cured product of methyl methacrylate is 1.490.

  Two disc-shaped optical glasses having a diameter of 70 mm and a thickness of 5 mm are spray-coated with die-free aerosol type GA-6010 (manufactured by Daikin Industries) as a release agent, and an excess release agent is applied with a cleaning cloth for optical equipment. Wiped off.

  A circular O-ring made of fluorine rubber with a diameter of 35 mm and a thickness of 1.5 mm is sandwiched in the center between the two optical glasses, and fixed at two opposite positions with a spring clip. A type cell was used. Using a disposable syringe, the radiation-polymerizable composition (A1) was injected into the casting cell while being careful not to leave bubbles.

As a radiation irradiation light source, a UV light source EX250 (manufactured by HOYA CANDEO OPTRONICS CORPORATION) equipped with a 250 W ultra-high pressure mercury lamp was used. An iris diaphragm (manufactured by Edmund Optics Japan Co., Ltd.) having a minimum opening diameter of 2 mm and a maximum opening diameter of 50 mm was used as a light shield. An ultraviolet transmission visible absorption filter (UTVAF-50S-36U) and a frost type diffusion plate (DFSQ1-50C02-800) (both manufactured by Sigma Kogyo Co., Ltd.) were interposed between the light source and the light shielding object. The illuminance on the optical glass surface on the irradiation side of the casting cell was 10 mW / cm ² at a wavelength of 365 nm.

  Irradiation was performed for 300 seconds with respect to the center of the casting cell with an iris diaphragm having an opening diameter of 20 mm.

  An empty disposable syringe was attached to the syringe needle, and the uncured radiation-polymerizable composition (A1) was sucked out. Next, a disposable syringe filled with the polymerizable composition (B1) was attached to the syringe needle, and the polymerizable composition (B1) was immediately injected into the casting cell. The casting cell was left at room temperature for 4 hours.

  After irradiating the entire surface of the casting cell for 1 hour using the above light source and optical system, the optical glass was peeled off to obtain a flat cured product.

  The refractive index distribution at a wavelength of 524.3 nm was evaluated using a light-tracking type refractive index distribution measuring device (Index Profile Analyzer: IPA5-C, manufactured by Advanced Technology Co., Ltd.). The result is shown in FIG. In the range of about 27 mm in diameter, a continuous refractive index profile reaching about 0.056 was obtained.

  75 parts by weight of benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as component (d3), 25 parts by weight of zirconium oxide having an average particle size of 7 nm (manufactured by Sumitomo Osaka Cement) as component (e3), and a photoradical generator (Irgacure as component (c3)) A radiation polymerizable composition (A3) consisting of 0.1 part by weight of 184, manufactured by Ciba Japan) was prepared.

  As component (d4), 90 parts by weight of benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts by weight of trimethylolpropane triacrylate (manufactured by Sigma-Aldrich Japan), photoradical generator (Irgacure 184, Ciba Japan) as component (c4) A polymerizable composition (B4) consisting of 0.1 parts by weight was prepared. The refractive index of the component (e3) zirconium oxide is 2.17.

  As in Example 1, a casting cell filled with the radiation polymerizable composition (A3) was prepared.

Using the same light source and optical system as in Example 1, the illuminance was 30 mW / cm ² , the aperture diameter of the iris diaphragm was 16 mm, and the central portion of the casting cell was irradiated for 50 seconds.

  As in Example 1, the uncured radiation-polymerizable composition (A3) was sucked out.

  In the same manner as in Example 1, the polymerizable composition (B4) was immediately injected into the casting cell.

  Example 2-1 The casting cell was left at room temperature for 2 hours. Example 2-2: The casting cell was left in an oven maintained at 80 ° C. for 2 hours. Example 2-3: The casting cell was left in an oven maintained at 80 ° C. for 24 hours.

  Similarly to Example 1, after irradiating the entire surface of the casting cells of Examples 2-1 to 2-3 with ultraviolet rays for 1 hour, the optical glass was peeled off to obtain a flat cured product.

  Using an energy dispersive micro fluorescent X-ray analyzer μEDX-1300 (manufactured by Shimadzu Corp.) capable of elemental analysis of a 50 μmφ region, the peak intensity of fluorescent X-rays derived from zirconium atoms (15.85 keV) is 0.2 mm. By mapping at intervals, the composition distribution on the irradiation side surface of the cured product was observed. The result is shown in FIG.

  Zirconium oxide particles are eluted from the cured product of the radiation-polymerizable composition (A3) by diffusion, and the concentration of zirconium oxide particles is 0% by volume (0% by weight) over the range of 1.6 to 3.6 mm near the gel interface. A distribution varying continuously from 1 to 5.0% by volume (25% by weight) was obtained. The behavior of increasing the diffusion distance by heating to 80 ° C. was observed.

  (D5) 90 parts by weight of benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts by weight of trimethylolpropane triacrylate (manufactured by Sigma-Aldrich Japan), and (c5) a photoradical generator (Irgacure 184, manufactured by Ciba Japan) A radiation-polymerizable composition (A5) comprising 0.1 part by weight was prepared.

  90 parts by weight of benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as the component (d6), 0.1 parts by weight of a photo radical generator (Irgacure 184, manufactured by Ciba Japan) as the component (c6), A polymerizable composition (B6) comprising 10 parts by weight of zirconium oxide (manufactured by Sumitomo Osaka Cement) was prepared.

  As in Example 1, a casting cell filled with the radiation-polymerizable composition (A5) was prepared.

Using the same light source and optical system as in Example 1, the illuminance was 10 mW / cm ² , the aperture diameter of the iris diaphragm was 16 mm, and the center portion of the casting cell was irradiated for 450 seconds.

  As in Example 1, the uncured radiation-polymerizable composition (A5) was sucked out.

  In the same manner as in Example 1, the polymerizable composition (B6) was immediately injected into the casting cell.

  Example 3-1: The casting cell was left at room temperature for 4 hours. Example 3-2: The casting cell was left in an oven maintained at 80 ° C. for 4 hours.

  Similarly to Example 1, after irradiating the entire surface of the casting cells of Examples 3-1 to 3-2 with ultraviolet rays for 1 hour, the optical glass was peeled off to obtain a flat cured product.

  Similar to Example 2, the composition distribution on the irradiation side surface of the cured product was observed. The result is shown in FIG.

  With respect to the cured product of the radiation-polymerizable composition (A5), zirconium oxide particles penetrated from the polymerizable composition (B6) by diffusion, and the concentration of the zirconium oxide particles was 0% by volume (0% over a range of 3.6 mm). A distribution varying continuously from (wt%) to 1.9 vol% (10 wt%) was obtained.

  (D7) 90 parts by weight of benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts by weight of trimethylolpropane triacrylate (manufactured by Sigma-Aldrich Japan), and (c7) a photoradical generator (Irgacure 184, manufactured by Ciba Japan) A radiation polymerizable composition (A7) consisting of 0.1 part by weight was prepared.

  (D8) Highlink NanO G 130-31 (manufactured by Clariant Japan, isobornyl acrylate dispersion of silica fine particles, silica content 30% by weight) and trimethylolpropane triacrylate (manufactured by Sigma Aldrich Japan) 10 weights Part, a polymerizable composition (B8) comprising 0.1 part by weight of a photoradical generator (Irgacure 184, manufactured by Ciba Japan) as a component (c8) was prepared.

  As in Example 1, a casting cell filled with the radiation polymerizable composition (A7) was prepared.

Using the same light source and optical system as in Example 1, the illuminance was 10 mW / cm ² , the aperture diameter of the iris diaphragm was 16 mm, and the center portion of the casting cell was irradiated for 450 seconds.

  As in Example 1, the uncured radiation-polymerizable composition (A7) was sucked out.

  In the same manner as in Example 1, the polymerizable composition (B8) was immediately injected into the casting cell.

  Example 4-1 The casting cell was left at room temperature for 144 hours. Example 4-2: The casting cell was left at room temperature for 4 hours. Example 4-3: The casting cell was left in an oven maintained at 50 ° C. for 4 hours. Example 4-4: The casting cell was left in an oven maintained at 80 ° C. for 4 hours.

  Similarly to Example 1, after irradiating the entire surface of the casting cells of Examples 4-1 to 4-4 with ultraviolet rays for 1 hour, the optical glass was peeled off to obtain a flat cured product.

  Similarly to Example 2, the fluorescence X-ray intensity distribution derived from the silicon oxide fine particles on the irradiation side surface of the cured product was observed. The result is shown in FIG. Distribution in which silicon oxide particles permeate by diffusion from (B) to the cured product of (A), and the fluorescent X-ray intensity derived from silicon oxide particles continuously changes over a range of 3.0 to 7.0 mm. was gotten.

  As in Example 1, a casting cell filled with the radiation-polymerizable composition (A1) was prepared.

  A photomask with a diameter of 50 mm having a circular transparent portion with a diameter of 20 mm at the center was prepared. The light-shielding material of the photomask is chromium, the base material is quartz, the transmittance of the light-shielding portion is 0.01% or less at a wavelength of 365 nm, and the transmittance of the transparent portion is 98%.

  A gray scale mask having the transmittance profile shown in FIG. 6 was prepared. The shade material of the gray scale mask is Inconel, and the base material is quartz.

Example 5-1 The photomask was placed in the center of the casting cell, and using the same light source and optical system as in Example 1, the illuminance was 30 mW / cm ² and irradiation was performed for 300 seconds.

Example 5-2: The photomask and the grayscale mask are installed in this order in the center of the casting cell, and the illuminance is set to 30 mW / cm ² using the same light source and optical system as in Example 1. Irradiation was performed for 300 seconds.

  Similarly to Example 1, uncured radiation-polymerizable composition (A1) was sucked out from the casting cells of Examples 5-1 to 5-2.

  In the same manner as in Example 1, the polymerizable composition (B2) was immediately injected into the casting cells of Examples 5-1 to 5-2.

  As in Example 1, the casting cells of Examples 5-1 to 5-2 were left at room temperature for 4 hours.

  Similarly to Example 1, after irradiating the entire surface of the casting cells of Examples 5-1 to 5-2 with ultraviolet rays for 1 hour, the optical glass was peeled off to obtain a flat cured product.

  Similarly to Example 1, the refractive index distribution at a wavelength of 524.3 nm of the cured products of Examples 5-1 to 5-2 was evaluated. The result is shown in FIG.

  Application of a gray scale mask has been shown to yield different refractive index profile.

A casting cell filled with the radiation polymerizable composition (A3) was prepared in the same manner as in Example 2.
Example 6-1: The same photomask as that of Example 5 is placed in the center of the casting cell, and the light source and optical system similar to those of Example 1 are used. The illuminance is 30 mW / cm ² and the irradiation is performed for 50 seconds. Went.

Example 6-2: The same photomask as in Example 5 and the same gray scale mask as in Example 5 are installed in the center of the casting cell in this order, and the same light source and optical system as in Example 1 are used. The illuminance was 30 mW / cm ² and irradiation was performed for 50 seconds.

  Similarly to Example 1, uncured radiation-polymerizable composition (A3) was sucked out from the casting cells of Examples 6-1 to 6-2.

  In the same manner as in Example 1, the polymerizable composition (B4) was immediately injected into the casting cells of Examples 6-1 to 6-2.

  As in Example 1, the casting cells of Examples 6-1 to 6-2 were left at room temperature for 144 hours.

  Similarly to Example 1, after irradiating the entire surface of the casting cells of Examples 6-1 to 6-2 with ultraviolet light for 1 hour, the optical glass was peeled off to obtain a flat cured product.

  Similarly to Example 2, the fluorescent X-ray intensity distribution of the fluorescent X-rays (15.85 keV) derived from zirconium atoms on the irradiation side surface of the cured product was observed. The result is shown in FIG.

  In any of Examples 6-1 to 6-2, the zirconium oxide particles were eluted from the cured product of the radiation polymerizable composition (A3) by diffusion, and the concentration of the zirconium oxide particles was 0% by volume (0% by weight) near the gel interface. ) To 5.0% by volume (25% by weight). By applying the gray scale mask, the behavior of increasing the diffusion distance was observed, and different density distribution profiles were obtained.

  As component (d9), 72 parts by weight of tetrafluoropropyl methacrylate (manufactured by Osaka Organic Chemical), 18 parts by weight of methyl methacrylate (manufactured by Sigma-Aldrich Japan) and 10 parts by weight of trimethylolpropane triacrylate (manufactured by Sigma-Aldrich Japan) A polymerizable composition (B9) comprising 0.1 part by weight of a photoradical generator (Irgacure 184, manufactured by Ciba Japan) as a component (c9) was prepared.

  As in Example 1, a casting cell filled with the radiation-polymerizable composition (A1) was prepared.

Example 7-1: The same photomask as in Example 5 was placed in the central portion of the casting cell, using a light source and an optical system as in Example 1, the illuminance and 30 mW / cm ^2, irradiation 300 seconds Went.

Example 7-2: The same photomask as in Example 5 and the same gray scale mask as in Example 5 are installed in the center of the casting cell in this order, and the same light source and optical system as in Example 1 are used. The illuminance was 30 mW / cm ² and irradiation was performed for 300 seconds.
Similarly to Example 1, uncured radiation-polymerizable composition (A1) was sucked out from the casting cells of Examples 7-1 to 7-2.

  In the same manner as in Example 1, the polymerizable composition (B9) was immediately injected into the casting cells of Examples 7-1 to 7-2.

  As in Example 1, the casting cells of Examples 7-1 to 7-2 were left at room temperature for 4 hours.

  Similarly to Example 1, after irradiating the entire surface of the casting cells of Examples 7-1 to 7-2 with ultraviolet rays for 1 hour, the optical glass was peeled off to obtain a flat cured product.

  Similarly to Example 1, the refractive index distribution at a wavelength of 524.3 nm of the cured products of Examples 7-1 to 7-2 was evaluated. The result is shown in FIG.

  Application of a gray scale mask has been shown to yield different refractive index profile. In addition, a larger refractive index difference was obtained by applying a gray scale mask.

  The reason why the large refractive index difference was obtained is that the degree of curing of the gel cured product of the radiation polymerizable composition (A1) was low and the concentration of the component (B9) at the gel end was high. It is done.

  First, as in Example 1, a casting cell filled with the radiation polymerizable composition (A1) was prepared. As in Example 5, a photomask with a diameter of 50 mm having a circular transparent portion with a diameter of 20 mm at the center was prepared.

  Next, the exposure time was changed as follows, and the radiation polymerizable composition (A1) was exposed to ultraviolet rays.

(Example 8-1)
The photomask was placed at the center of the casting cell, and using the same light source and optical system as in Example 1, the illuminance was 30 mW / cm ² and exposure was performed for 150 seconds.

(Example 8-2)
The photomask was placed in the center of the casting cell, and using the same light source and optical system as in Example 1, the illuminance was 30 mW / cm ² and exposure was performed for 200 seconds.

(Example 8-3)
The photomask was placed in the center of the casting cell, and using the same light source and optical system as in Example 1, the illuminance was 30 mW / cm ² and exposure was performed for 300 seconds.

(Example 8-4)
The photomask was placed in the center of the casting cell, and using the same light source and optical system as in Example 1, the illuminance was 30 mW / cm ² and exposure was performed for 350 seconds.

  Next, as in Example 1, the uncured radiation-polymerizable composition (A1) was sucked out from the casting cells of Examples 8-1 to 8-4. The gel in the casting cell of Example 8-1 collapsed.

  Moreover, like Example 1, the polymeric composition (B2) was rapidly inject | poured in the casting cell of Example 8-2 to Example 8-4. Similarly to Example 1, the casting cells of Examples 8-2 to 8-4 were left at room temperature for 4 hours. Similarly to Example 1, the entire casting cells of Examples 8-2 to 8-4 were exposed to ultraviolet rays for 1 hour, and then the optical glass was peeled off to obtain a flat cured product. In the same manner as in Example 1, the refractive index distribution at a wavelength of 524.3 nm of the cured products of Examples 8-2 to 8-4 was evaluated. The results are shown in FIGS. 11 (a) to 11 (c). The longer the exposure time, the flatter the refractive index profile at the center of the sample. From this, it can be said that the longer the exposure time, the slower the diffusion of the polymerizable composition (B2) into the gel.

(Complex viscosity)
Next, the relationship between the ultraviolet exposure time and the complex viscosity for the radiation polymerizable composition (A1) was examined using a dynamic viscoelasticity measuring apparatus (MCR-301 manufactured by Anton Paar) having an ultraviolet irradiation mechanism. The illuminance of ultraviolet rays was 30 mW / cm ² at a wavelength of 365 nm. The relationship between exposure time and complex viscosity is shown in FIG.

  As a result, in Example 8-1, the complex viscosity was 4 Pa · s, in Example 8-2, 697 Pa · s, in Example 8-3, 1750 Pa · s, and in Example 8-4, 39700 Pa · s.

(Summary)
It was found that the gel collapsed in Example 8-1 because the complex viscosity was too low. In Examples 8-2 to 8-4, it was found that the longer the exposure time, the slower the diffusion progresses because the longer the exposure time, the higher the complex viscosity.

<Comparative Example 1>
FIG. 10 shows a method for manufacturing the plastic member of Comparative Example 1.

  A plastic member was produced using the same radiation-polymerizable composition (A1) and polymerizable composition (B2) as in Example 1.

  A spacer 22 was sandwiched between two optical glasses 21 similar to those in Example 1 to form a casting cell 23. The radiation polymerizable composition (A1) was injected into the casting cell using a disposable syringe.

In the same manner as in Example 1, the radiation-polymerizable composition (A1) was irradiated with radiation on the entire area under conditions of 10 mW / cm ² and 300 seconds, and the polymer 26 of the gel-like polymerizable composition (A1) was obtained. Obtained.

  When the spacer 22 in the casting cell 23 was to be removed, the polymer 26 collapsed.

<Comparative example 2>
FIG. 10 shows a method for manufacturing the plastic member of Comparative Example 1.

  A plastic member was produced using the same radiation-polymerizable composition (A1) and polymerizable composition (B2) as in Example 1.

  A spacer 22 was sandwiched between two optical glasses 21 similar to those in Example 1 to form a casting cell 23. The radiation polymerizable composition (A1) was injected into the casting cell using a disposable syringe.

In the same manner as in Example 1, the radiation-polymerizable composition (A1) was irradiated with radiation over the entire area under the conditions of 10 mW / cm ² and 1800 seconds, and the polymer 26 of gel-like polymerizable composition (A1) was obtained. Obtained.

  The spacer 22 in the casting cell 23 was removed, the void 27 was provided outside the polymer 26 of the polymerizable composition (A1), the spacer 25 was installed, and the casting cell 23 was assembled.

  Next, the polymerizable composition (B1) 28 was injected into the void 27 of the casting cell 23 using a syringe needle, and contacted with the polymer 26 of the gel-like polymerizable composition (A1). The casting cell was left at room temperature for 4 hours. After irradiating the entire surface of the casting cell with radiation, the optical glass was peeled off to obtain a plastic member 29 made of a flat cured product.

  The refractive index distribution of the obtained plastic member was measured by the same method as in Example 1. However, no significant refractive index distribution occurred at the polymer 26 site.

  In the present invention, a plastic member having a composition distribution can be obtained in a short time with a simple facility, with a small number of processes, so that a camera, an optical fiber imaging system, a copying machine, a compact disk pickup optical system, etc. It can utilize for the manufacturing method of this lens.

DESCRIPTION OF SYMBOLS 1 Optical glass 2 Gasket 3 Casting cell 4 1st radiation polymerizable composition 5 Shielding object 6 Polymer of 1st composition 7 Cavity 8 2nd radiation polymerizable composition 9 Plastic member 10 Radiation

Claims (10)

A first filling step of filling a casting cell provided with a radiation irradiation surface with a first radiation polymerizable composition containing a first monomer capable of radiation polymerization; and irradiating the radiation irradiation surface of the casting cell with radiation. A polymerization step of polymerizing a part of the first radiation-polymerizable composition to obtain a polymer of the first composition, and removing the unpolymerized first radiation-polymerizable composition from the casting cell. A removal step to be performed, and a void of the casting cell generated by the removal is filled with a second radiation-polymerizable composition containing a second monomer capable of radiation polymerization, and the polymer of the first composition In a method for producing a plastic lens , comprising: a second filling step for contacting; and a total curing step for curing the whole of the second radiation-polymerizable composition and the polymer of the first composition .
A diffusion step of diffusing the second radiation polymerizable composition into the polymer of the first composition between the second filling step and the full curing step;
The polymer of the first composition is a gel having a complex viscosity of 10 Pa · s or more and less than 10,000 Pa · s,
A method for producing a plastic lens having a composition distribution, wherein the second radiation-polymerizable composition is liquid . The method for producing a plastic lens according to claim 1, wherein the first radiation-polymerizable composition is liquid. The process for producing a plastic lens according to claim 1 or 2 wherein at least one of the first radiation polymerizable composition and the second radiation polymerizable composition is characterized by containing fine particles. Plastic lens according to any one of claims 1 to 3, wherein a cured product of each different refractive index wavelength dispersion of the first radiation polymerizable composition and the second radiation polymerizable composition Production method. The method of manufacturing a plastic lens according to any one of claims 1 to 4 , wherein an irradiation amount of radiation irradiated to a radiation irradiation surface of the casting cell is not constant. 6. The method of manufacturing a plastic lens according to claim 5 , wherein the irradiation amount of the radiation irradiated to the radiation irradiation surface of the casting cell is such that the irradiation amount is lower toward the outer periphery. 6. The method of manufacturing a plastic lens according to claim 5 , wherein the irradiation amount of the radiation irradiated to the radiation irradiation surface of the casting cell is higher toward the outer periphery. 8. The casting cell is heated to a temperature higher than room temperature in the step of diffusing the second radiation-polymerizable composition into the polymer of the first composition. A method for producing a plastic lens according to any one of the items. Method for producing the inner surface of the casting cell is spherical, the plastic lens according to any one of claims 1 to 8, characterized in that a non-spherical surface or plane. Produced plastic lens manufacturing method for a plastic lens according to any one of claims 1 to 9.