JP4408384B2 - Method for manufacturing plastics polarizing lens body, plastics polarizing lens body, polarizing laminate and cover sheet used for manufacturing the lens body - Google Patents

Description

  The present invention relates to a method for producing a plastics polarizing lens body, a plastics polarizing lens body, a polarizing laminate and a covering sheet used for producing the lens body, and in particular, a plastics polarizing lens body having a high refractive index by a casting polymerization method, and The present invention relates to a method for producing a plastics polarizing lens body suitable for the production, a polarizing laminate and a covering sheet used for the production of the lens body.

  Conventionally, a plastic polarizing lens has (1) a method of manufacturing a lens by punching and bending a thick polarizing sheet (see Patent Document 1 below), and (2) a polarizing film bonded on a lens substrate. Later, it has been manufactured by a method of manufacturing a lens by attaching another lens base material thereon.

  The method (1) has been adopted as a method for producing a polycarbonate polarizing lens, but it has been virtually impossible to obtain a correction lens or a highly accurate plano lens (see Patent Document 1 below). reference). Further, the method (2) has a problem that productivity is low.

In order to solve the above-described problems, (3) a method of manufacturing a lens by integrating a resin as a lens substrate from the back side of a bent polarizing sheet by an injection molding technique (see Patent Document 2 below) ) And (4) A method for producing a lens by sandwiching a polarizing film with a polymerizable composition to produce a lens has been disclosed (see Patent Document 3 below).
The method (3) overcomes the drawbacks of the method (1), and a correction lens and a highly accurate plano lens can be obtained. Therefore, the method has already been adopted as a method for producing a polycarbonate polarizing lens (see below). (See Patent Document 2). The method (4) is a simple and effective method. In a system based on diethylene glycol bisallyl carbonate, triacetyl cellulose (hereinafter also referred to as “TAC”) is provided on both surfaces of a polarizing film of polyvinyl alcohol resin. There are known a method of using a laminated body and a method of applying an adhesive to a polarizing film prior to cast polymerization (see Patent Document 3 below).

Japanese Examined Patent Publication No. 7-94154 JP-A-8-52817 JP-A-1-232006

However, the method (3) has a problem that usable lens base materials are limited to polycarbonate polarizing lenses.
Even in the method (4), usable lens base materials are limited, and further, the base material and the polarizing film substrate or the polarizing laminate are peeled off at the time of polymerization, and the same peeling is likely to occur after the lens molding. There is a point.
That is, in the method (4), the system currently in practical use is only a system using diethylene glycol bisallyl carbonate, which is known by the name of CR-39, as a lens base material, as represented by a thiourethane resin. The method (4) has not been applied to a high refractive index lens. This is because, for example, the conditions for producing a high refractive lens by the casting polymerization method, such as the polymerization conditions for a thiourethane-based polymerizable composition, are generally considerably strict compared to the polymerization conditions for diethylene glycol bisallyl carbonate. Therefore, depending on various conditions during polymerization, the polarizing film may cause performance deterioration such as color tone fluctuation and polarization degree reduction, and the polarizing film or polarizing laminate may be affected by the polymerizable composition used for lens molding or its reactant. This is because of the poor adhesion between the lens substrate portion after the lens molding and the polarizing laminate or the polarizing film.

  Therefore, in order to produce plastics polarizing lenses with a high refractive index by cast polymerization with high productivity, development of polarizing films and polarizing laminates that can withstand various severe conditions during cast polymerization, and those films It is essential to find the right combination of laminate and lens precursor.

  The present invention has been made in view of the above, and relates to a method for manufacturing a plastics polarizing lens body, a plastics polarizing lens body, a polarizing laminate used for manufacturing the lens body, and a covering sheet, and in particular by a casting polymerization method. It is an object of the present invention to provide a plastics polarizing lens having a high refractive index, a method for manufacturing a plastics polarizing lens body suitable for manufacturing the same, a polarizing laminate and a covering sheet used for manufacturing the lens body.

  Therefore, the present inventors proceeded diligently in consideration of such a situation, the dye-based polarizing film appropriately treated with a specific metal compound and boric acid has excellent heat resistance and solvent resistance, and thiourethane type The inventors found that it exhibits very favorable characteristics in combination with a polymerizable composition, and developed a method for producing a polarizing film suitable for a lens made of thiourethane resin and a method for using the same (Japanese Patent Application No. 2004-42256). .

  Furthermore, it is not limited to the thiourethane-based polymerizable composition in Japanese Patent Application No. 2004-42256, and even when used in a versatile system such as CR-39, the adhesion between the lens substrate and the polarizing film is sufficient. In addition, as a result of further research into polarizing films and polarizing assemblies that can be easily processed before and after the processing of polarizing films for lens molding in the casting polymerization method, a transparent film is formed on at least one side of the polarizing film. Those that have been pasted together and coated with a specific acrylate or methacrylate polymerizable composition on the transparent film can be combined with a very wide range of lens polymerizable compositions, and can be bent and processed. It has been found that the management before and after is easy, and the present invention has been made.

That is, the method for producing a plastics polarizing lens body according to the first invention of the present invention is a method for producing a plastics polarizing lens body by a casting polymerization method using a sheet-like polarizing body having at least a polarizing sheet,
A sheet-like polarizer having at least one surface coated with a (meth) acrylate-based polymerizable composition is used.
The (meth) acrylate-based polymerizable composition preferably has UV curable properties. Examples of the (meth) acrylate-based polymerizable composition include a urethane (meth) acrylate-based polymerizable composition and a polyester (meth) acrylate-based composition. It is preferably at least one selected from a polymerizable composition and an epoxy (meth) acrylate polymerizable composition, and a urethane (meth) acrylate polymerizable composition and a polyester (meth) acrylate polymerizable composition It is more preferable that it is at least one selected from products. The thickness of the (meth) acrylate polymerizable composition film is preferably 2 μm or more and 13 μm or less.

The sheet-like polarizer used in the method for producing a plastics polarizing lens body of the present invention is preferably a polarizing laminate.
This polarizing laminate can be composed of a polarizing sheet and a transparent sheet that covers at least one surface of the polarizing sheet. In the polarizing laminate, the transparent sheet is preferably formed of any one selected from polycarbonate resin, cellulose resin, alicyclic polyolefin resin, and polyester resin.
The polarizing sheet of the plastics polarizing lens body is preferably formed of a polyvinyl alcohol resin.
In the polarizing laminate, the polarizing sheet preferably contains a dichroic dye, and is preferably treated with a metal compound and boric acid.

  The polymerizable composition used for the cast polymerization in the method for producing a plastics polarizing lens body of the present invention is selected from a thiourethane-based polymerizable composition, an episulfide-based polymerizable composition, and an allyl carbonate-based polymerizable composition. Any one of the above is preferable. The polymerizable composition more preferably contains a sulfur-containing polymerizable compound.

A plastics polarizing lens body according to a second aspect of the present invention is a plastics polarizing lens body including a sheet-like polarizing body having at least a polarizing sheet,
A (meth) acrylate-based resin layer is formed on at least one surface of the sheet-like polarizer, and a polymerizable resin layer is further laminated on at least the (meth) acrylate-based resin layer.
The (meth) acrylate-based resin layer is preferably formed by ultraviolet curing of a (meth) acrylate-based polymerizable composition film, and the (meth) acrylate-based resin layer is a urethane (meth) acrylate-based resin layer , A polyester (meth) acrylate-based resin layer, and an epoxy (meth) acrylate-based resin layer, and preferably a urethane (meth) acrylate-based resin layer and a polyester (meth) acrylate-based resin layer More preferably, it is at least one selected from the group consisting of: The thickness of the (meth) acrylate-based resin layer is preferably 2 μm or more and 13 μm or less.

The sheet-like polarizer used in the plastics polarizing lens body of the present invention is preferably a polarizing laminate.
This polarizing laminate can be composed of a polarizing sheet and a transparent sheet that covers at least one surface of the polarizing sheet. In the polarizing laminate, the transparent sheet is preferably formed of any one selected from polycarbonate resin, cellulose resin, alicyclic polyolefin resin, and polyester resin.
The polarizing sheet of the plastics polarizing lens body is preferably formed of a polyvinyl alcohol resin.
In the polarizing laminate, the polarizing sheet preferably contains a dichroic dye, and is preferably treated with a metal compound and boric acid.

  The polymerizable resin layer of the plastics polarizing lens body of the present invention is preferably any one selected from a thiourethane resin layer, an episulfide resin layer, and an allyl carbonate resin layer. The polymerizable resin layer is more preferably formed by cast polymerization of a polymerizable composition containing a sulfur-containing polymerizable compound.

A polarizing laminate according to a third aspect of the present invention is a polarizing laminate suitable for manufacturing a plastics polarizing lens body including at least a sheet-like polarizer having a polarizing sheet,
A (meth) acrylate-based polymerizable composition film is formed on at least one surface of the sheet-like polarizer.

The polarizing laminate may be composed of a polarizing sheet, a transparent sheet that covers at least one surface of the polarizing sheet, and the (meth) acrylate-based polymerizable composition film that covers the transparent sheet.
This transparent sheet is preferably formed of any one selected from polycarbonate resins, cellulose resins, alicyclic polyolefin resins, and polyester resins.
The polarizing sheet is preferably formed from a polyvinyl alcohol-based resin, preferably contains a dichroic dye, and is preferably treated with a metal compound and boric acid.

  The present invention is also a covering sheet used for producing the above polarizing laminate, in which a (meth) acrylate-based polymerizable composition film is formed on at least one side of the sheet-shaped polarizing body, and the single side of the transparent sheet Further, the present invention relates to a covering sheet obtained by coating a (meth) acrylate polymerizable composition.

  According to the method for producing a plastics polarizing lens body according to the present invention, it is possible to use a very wide range of the polymerizable composition for the lens, and it is easy to manage bending and before and after, particularly, A plastics polarizing lens body having a high refractive index can be provided with high productivity by the casting polymerization method.

Hereinafter, embodiments of the present invention will be described.
The manufacturing method of a plastics polarizing lens body according to the first aspect of the present invention is a manufacturing method of a plastics polarizing lens body by a casting polymerization method using a sheet-like polarizing body having at least a polarizing sheet, and at least one side is made of (Metal). ) A sheet-like polarizer coated with an acrylate polymerizable composition is used.
In this production method, a sheet-like polarizer in which one or both surfaces of the sheet-like polarizer are coated with a (meth) acrylate-based polymerizable composition can be used.
At least one surface of the sheet-like polarizer is coated with a (meth) acrylate-based polymerizable composition because the coating layer has a wide range of polymerizable compositions for various plastics polarizing lens bodies (hereinafter referred to as “for lens bodies”). This is because it has a high resistance to a “polymerizable composition” and has a property of adhering well. No other thermosetting composition or UV curable composition is found that has a good balance of adhesion and resistance.
Therefore, at least one surface of the sheet-like polarizer is coated with a (meth) acrylate polymerizable composition, and the polymerizable composition for a lens body and the (meth) acrylate polymerizable composition are polymerized by a cast polymerization method. If it carries out, it is possible to maintain the polarization | polarized-light characteristic of a polarizing body, and can provide the plastics polarizing lens body using the polymeric composition for very wide plastics polarizing lens bodies. In addition, a sheet-like polarizer having at least one surface coated with a (meth) acrylate-based polymerizable composition is easy to bend and manage before and after.
Here, the (meth) acrylate-based polymerizable composition refers to a polymerizable composition containing at least one of an acrylate-based polymerizable compound and a methacrylate-based polymerizable compound. In this composition, As the polymerizable compound, a (meth) acrylate-based polymerizable monomer and / or polymerizable oligomer is contained. In addition, the sheet-like polarizer refers to a sheet-like material having a polarizing property, for example, a polarizing sheet or the like having a polarizing property regardless of its thickness, such as a polarizing sheet, and a polarizing sheet. As described above, a polarizing laminate including a material having polarization itself can be used. In the case of the present invention, the casting polymerization method refers to a polymerization method in which the polymerizable composition for a lens body is polymerized after pouring the polymerizable composition for the lens body into a mold in which a sheet-like polarizer is incorporated. Say.

  The (meth) acrylate-based polymerizable composition used for forming the (meth) acrylate-based resin used in the method for producing the transparent plastic polarizing lens body is not particularly limited, and various (meth) acrylate-based polymerizable compositions are used. Things can be used. Such a (meth) acrylate-based polymerizable composition preferably has curability by irradiation with active energy rays from the viewpoint of curing time and safety, and the active energy rays are preferably ultraviolet rays. The (meth) acrylate polymerizable composition is preferably a mixed system of a (meth) acrylate polymerizable oligomer and a (meth) acrylate polymerizable monomer. As the polymerizable oligomer, a polyfunctional (meth) acrylate oligomer is preferable. For example, a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, and an epoxy (meth) acrylate oligomer are preferable. More preferred are (meth) acrylate oligomers and polyester (meth) acrylate oligomers.

The urethane (meth) acrylate oligomer is not particularly limited, and various urethane (meth) acrylate oligomers can be used. Such a urethane (meth) acrylate oligomer is an oligomer having a urethane bond and a (meth) acryl group in the structure, and is composed of a combination of polyisocyanate, polyol, hydroxy (meth) acrylate, and the like.
Polyisocyanates include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane. Although diisocyanate etc. are common, it is not limited to these. Examples of the polyol include polyether polyols obtained by adding propylene oxide or ethylene oxide to polyhydric alcohols, and polyester polyols such as adipate, polycaprolactone, and oligocarbonate.
Examples of the hydroxy (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) arylate, pentaerythritol tri (meth) acrylate, and the like. can give.

  Many urethane (meth) acrylate oligomers are commercially available and can be easily obtained. Examples of these urethane (meth) acrylate oligomers include a beam set 575, a beam set 551B, a beam set 550B, a beam set 505A-6, a beam set 504H, a beam set 510, a beam set 502H, a beam set 575CB, and a beam. Set 102 (above, trade name of urethane (meth) acrylate oligomer made by Arakawa Chemical Co., Ltd.), Photomer 6008, Photomer 6210 (above, trade name of urethane (meth) acrylate oligomer made by San Nopco), NK Oligo U-4HA, NK Oligo U-108A, NK Oligo U-1084A, NK Oligo U-200AX, NK Oligo U-122A, NK Oligo U-340A, NK Oligo U-324A, NK Oligo UA-100, NK Rigo MA-6 (above, trade name of urethane (meth) acrylate oligomer manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-1100, Aronix M-1200, Aronix M-1210, Aronix M-1310, Aronix M- 1600, Aronix M-1960 (above, product name of urethane (meth) acrylate oligomer made by Toagosei Co., Ltd.), AH-600, AT-606, UA-306H (above, Kyoeisha Chemical Co., Ltd. urethane (meth)) Trade name of acrylate oligomer), Kayrad UX-2201, Kayarad UX-2301, Kayarad UX-3204, Kayarad UX-3301, Kayarad UX-4101, Kayarad UX-6101, Kayarad UX-7101, Kayarad UX-4101 ( Above, Nippon Kayaku Co., Ltd. product name of urethane (meth) acrylate oligomer), purple light UV-1700B, purple light UV-3000B, purple light UV-3300B, purple light UV-3520TL, purple light UV-3510TL purple light UV-6100B, Violet UV-6300B, Violet UV-7000B, Violet UV-7210B, Violet UV-7550B, Violet UV-2000B, Violet UV-2250TL, Violet UV-2010B, Violet UV-2580B, Violet UV-2700B (above, Nippon Synthetic Chemical) (Trade name of urethane (meth) acrylate oligomer) manufactured by Kogyo Co., Ltd., Art Resin UN-9000PEP, Art Resin UN-9200A, Art Resin UN-9000H, Art Resin UN-1255, Art Resin UN-5200, Art Resin UN -2 111A, Art Resin UN-330, Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS Art Resin UN-6060P (above, urethane (meth) acrylate type manufactured by Negami Industrial Co., Ltd.) (Trade name of oligomers of Laromar UA19T, Laromer LR8949, Laromer LR8987, Laromar LR8983 (above, trade names of urethane (meth) acrylate oligomers manufactured by BASF), Diabeam UK6053, Diabeam UK6055, Diabeam UK6039, Beam UK6038, Diamond Beam UK6501, Diamond Beam UK6074, Diamond Beam UK6097 (Mitsubishi Rayon (Product name of urethane (meth) acrylate oligomer), Ebecryl 254, Ebecryl 264, Ebecryl 265, Ebecryl 1259, Ebecryl 4866, Ebecryl 1290K, Ebecryl 5129, Ebecryl 5129, Ebecryl 4833 Trade names of acrylate oligomers). These urethane (meth) acrylate-based polymerizable oligomers are polyfunctional urethane (meth) acrylate-based polymerizable oligomers from the viewpoint of solvent resistance, adhesion to a transparent sheet, and adhesion to a polymerizable composition. preferable. Among these polyfunctional urethane (meth) acrylate polymerizable oligomers, NK oligo U-4HA and Ebecryl 264 are preferable.

  The polyester (meth) acrylate oligomer is not particularly limited, and various polyester (meth) acrylate oligomers can be used. Such a polyester (meth) acrylate oligomer is synthesized by a dehydration condensation reaction of a polybasic acid, a polyhydric alcohol, and (meth) acrylic acid. For example, Aronix M-6100, Aronix M- 7100, Aronix M-8030, Aronix M-8060, Aronix M-8530, Aronix M-8050 (above, trade names of polyester (meth) acrylate oligomers manufactured by Toagosei Co., Ltd.), Laromer PE44F, Laromer LR8907, Laromer PE55F , Laromer PE46T, Laromer LR8800 (above, trade names of polyester (meth) acrylate oligomers manufactured by BASF), Ebecryl 80, Ebecryl 657, Ebecr l 800, Ebecryl 450, Ebecryl 1830, Ebecryl 584 (above, trade name of polyester (meth) acrylate oligomers manufactured by Daicel UCB Co., Ltd.), Photomer RCC13-429, Photomer 5018 (above, Sannopco Co., Ltd.) And a polyester (meth) acrylate oligomer product name). Among these polyester (meth) acrylate-based polymerizable oligomers, Ebecryl 80 is preferable.

  The epoxy (meth) acrylate oligomer is not particularly limited, and various epoxy (meth) acrylate oligomers can be used. Such an epoxy (meth) acrylate oligomer has a structure in which (meth) acrylic acid is added to an epoxy oligomer, and is a bisphenol A-epichlorohydrin type, a modified bisphenol A type, an amine modified type, a phenol novolak-epichlorohydrin type. , Aliphatic type and alicyclic type. For example, Laromer LR8986, Laromer LR8713, Laromer EA81 (above, trade names of epoxy (meth) acrylate oligomers manufactured by BASF), NK Oligo EA-6310, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA -6320, NK Oligo EA-7440, NK Oligo EA-6340 (above, trade name of epoxy (meth) acrylate oligomer manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 3700, Ebecryl 3200, Ebecryl 600 (above, Daicel U.C.) -Product name of an epoxy (meth) acrylate oligomer manufactured by B Co., Ltd. Among these epoxy (meth) acrylate-based polymerizable oligomers, NK oligo EA-1020 is preferable.

The (meth) acrylate polymerizable monomer is not particularly limited, and various (meth) acrylate polymerizable monomers can be used. Such (meth) acrylate polymerizable monomers include mono-, di- and poly (meth) acrylate compounds of aliphatic alcohols having 2 to 20 carbon atoms, diols and polyhydric alcohols, glycerin, trimethylolpropane, pentaerythritol. Poly (meth) acrylates of terminal hydroxy compounds having 30 or less carbon atoms including aliphatic ether bonds, ester bonds, carbonate bonds branched with polyhydric alcohols such as alicyclic compounds and aromatics in their skeletons Examples thereof include compounds having a group compound.
Specifically, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl acrylate, butanediol monoacrylate, polyethylene glycol (meth) acrylate, cyclopentenyl (meth) acrylate, cyclopentanyl (meth) acrylate, hexanediol (Meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclopentanyl di (meth) acrylate, hexanediol di (meth) ) Acrylate, isobornyl di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentylglycol (Meth) acrylate, neopentyl glycol di (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified neopentyl glycol di (meth) acrylate, PO-modified neopentyl glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tricyclode Canmethanol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) a Relate, it can be given PO-modified trimethylolpropane tri (meth) acrylate. Among these acrylate-based polymerizable monomers, 1,9-nonanediol di (meth) acrylate and PO-modified neopentyl glycol di (meth) acrylate are preferable.

  As the (meth) acrylate-based polymerizable compound contained in the (meth) acrylate-based polymerizable composition, a single (meth) acrylate-based polymerizable compound can be used, or two or more kinds of (meth) Acrylate polymerizable compounds can also be used in combination.

The various (meth) acrylate-based polymerizable compositions as described above can be used as a (meth) acrylate-based polymerizable oligomer and polymerizable monomer mixture.
In this case, the mixing ratio of the oligomer and the monomer is not particularly limited, but from the viewpoint of operability, the blending ratio of the (meth) acrylate polymerizable monomer is preferably in the range of 20 to 80% by weight of the monomer and the whole oligomer.

  Moreover, it is preferable that the film thickness of the said (meth) acrylate type polymeric composition is 2 micrometers or more and 13 micrometers or less. When the film thickness is less than 2 μm, the resistance and adhesiveness to the polymerizable composition described above are lowered, and when the film thickness exceeds 13 μm, problems such as generation of cracks during bending are likely to occur.

As a sheet-like polarizer used in the method for producing a plastics polarizing lens body of the present invention, for example, a polarizing sheet, such as a polarizing sheet, a polarizing sheet itself, regardless of its thickness, and a polarizing sheet, etc. Examples thereof include a polarizing laminate including one having polarization itself.
Here, the polarizing laminate refers to a polarizing laminate including a polarizing sheet.

As the polarizing sheet, various polarizing sheets conventionally referred to as a polarizing sheet, a polarizing film, a polarizing film substrate and the like can be used from the viewpoint of thickness and function. The polarizing sheet is preferably formed from a polycarbonate resin.
Specifically, a so-called polycarbonate (hereinafter, also referred to as “PC”) polarizing sheet used for injection molding is used as the polarizing sheet, and the surface is simply treated with a (meth) acrylate-based polymerizable composition. It can be used in the method for producing a plastics polarizing lens body of the present invention. In the case of a PC polarizing sheet, since it has been developed for injection molding, it has high heat resistance and is more preferable.

As the polarizing laminate, one comprising a polarizing sheet and a transparent sheet covering at least one surface of the polarizing sheet can be used. As this polarizing laminate, a transparent sheet in which one or both sides of a polarizing sheet are coated can be used.
By using a polarizing laminate in which at least one surface of the polarizing sheet is covered with a transparent sheet having a certain degree of heat resistance, the polarizing sheet can be prevented from being modified during cast polymerization.
Moreover, when this polarizing laminate is used as the polarizing sheet, the surface of a very common polarizing laminate is treated with a (meth) acrylate polymerizable composition or the surface is preliminarily (meth) acrylate polymerized. Since it becomes possible to use the coating sheet which consists of a transparent film film-processed with the property composition for polarizing laminated body manufacture, it is very efficient on manufacture.

The transparent sheet in the polarizing laminate is not particularly limited as long as it has a certain degree of heat resistance, and various transparent sheets can be used.
The transparent sheet is preferably formed of any one selected from polycarbonate resins, cellulose resins, alicyclic polyolefin resins, and polyester resins.
Specific examples of the transparent sheet include cellulose resin films such as cellulose acetate represented by TAC, propyl cellulose, and acetic acid / butyric acid cellulose, various acrylic resin films, polyethylene naphthalate (hereinafter, “PEN”). ), Polyethylene terephthalate (hereinafter referred to as “PET”), or a fluorene-based polyester (hereinafter referred to as “OKP”) resin film having excellent optical properties, “ARTON”, “ZEONOR”, “APEL”, etc. And alicyclic olefin-based polymers (hereinafter referred to as “APO”), various polycarbonate resins and the like.

The polarizing sheet of the plastics polarizing lens body is basically not particularly limited as long as it has a certain degree of heat resistance, and various polarizing sheets can be used. The polarizing sheet is preferably formed from a polyvinyl alcohol resin.
The polyvinyl alcohol-based resin can be used as long as a general polyvinyl alcohol-based film is used without any particular limitation. Specific examples of such polyvinyl alcohol resins include, for example, polyvinyl alcohol resins, poly (ethylene-vinyl acetate) copolymer resins, polyvinyl butyral resins, and polyvinyl acetal resins. Of these polyvinyl alcohol resins, polyvinyl alcohol resins are preferable.

  As the polarizing sheet, one using a dichroic dye is preferable because of excellent heat resistance. For example, in the case of the polyvinyl alcohol resin, it can be dyed by immersing the resin in a dichroic dye solution at room temperature to 50 ° C. under heating.

  Examples of the dye used for the production of the polarizing sheet include chrysophenine (C.I. 24895), chloranthin fast red (C.I. 28160), Sirius yellow (C.I. 29000), and benzoperpurine (C.I. 23500), Direct First Red (C.I. 23630), Brilliant Blue B (C.I. 24410), Chlorazole Black BH (C.I. 22590), Direct Blue 2B (C.I. 22610), Direct Sky Blue (C.I. 24400), Diamine Green (C.I. 30295), Solophenyl Blue 4GL (C.I. 34200), Direct Copper Blue 2B (C.I. 24185), Nippon Brilliant Violet BKconc (C I.27885), Congo Head (C.I.22120), A Sid Black (C.I.20470), and the like, can be selected and used two or more colors of dye according to the purpose from among these dyes. In parentheses, Color Index No. described in “New Edition Dye Handbook” edited by Organic Synthesis Association (Maruzen Co., Ltd., 1970) is used. showed that.

If the polarizing sheet is further treated with a metal compound and boric acid, it has excellent heat resistance and solvent resistance, which is preferable.
Specifically, the polarizing sheet dyed in the dichroic dye solution is stretched during or after being immersed in a mixed solution of the metal compound and boric acid, or dyed and stretched in the dichroic dye solution. The polarizing sheet can be treated by a method of immersing the polarizing sheet in a mixed solution of a metal compound and boric acid.

  As the metal compound, even if it is a transition metal belonging to any one of the fourth period, the fifth period, and the sixth period, there is one in which the heat resistance and solvent resistance effect are confirmed in the metal compound. However, metal salts such as acetates, nitrates, and sulfates of fourth-period transition metals such as chromium, manganese, cobalt, nickel, copper, and zinc are preferable in terms of price. Among these, compounds of nickel, manganese, cobalt, zinc and copper are more preferable because they are inexpensive and have excellent effects.

  Examples of the metal compound include manganese acetate (II) tetrahydrate, manganese acetate (III) dihydrate, manganese nitrate (II) hexahydrate, manganese sulfate (II) pentahydrate, and cobalt acetate. (II) tetrahydrate, cobalt nitrate (II) hexahydrate, cobalt sulfate (II) heptahydrate, nickel acetate (II) tetrahydrate, nickel nitrate (II) hexahydrate, nickel sulfate (II) hexahydrate, zinc acetate (II), zinc sulfate (II), chromium nitrate (III) nonahydrate, copper acetate (II) monohydrate, copper nitrate (II) trihydrate, Examples include copper (II) sulfate pentahydrate. Any one of these metal compounds may be used alone, or a plurality of them may be used in combination.

The content of the metal compound and boric acid in the polarizing sheet is 0.2 to 20 mg as a metal in the metal compound per 1 g of the polarizing sheet from the viewpoint of imparting heat resistance and solvent resistance to the polarizing sheet. Is preferable, and 1 to 5 mg is more preferable. The content of boric acid is preferably 0.3 to 30 mg as boron, and more preferably 0.5 to 10 mg. The composition of the treatment liquid used for the treatment is set so as to satisfy the above content, and generally, the concentration of the metal compound is 0.5 to 30 g / L, and the boric acid concentration is 2 to 20 g / L. preferable.
Analysis of the metal and boron content contained in the polarizing sheet can be performed by atomic absorption spectrometry.

  The immersion conditions in the immersion step with the metal compound and boric acid are usually from room temperature to 50 ° C. for 5 to 15 minutes. The conditions of the heating process after immersion are 70 degreeC or more, Preferably it heats at the temperature of 90-120 degreeC for 1 to 120 minutes, Preferably it is 5 to 40 minutes.

  The transparent sheet and the polarizing sheet in the polarizing laminate can be bonded and laminated with an adhesive. Examples of the adhesive include thermosetting adhesives such as acrylic resins, urethane resins, epoxy resins, and urethane acrylate resins, and UV curable adhesives.

  Lamination of the transparent sheet to the polarizing sheet is generally performed in a sandwich form on both sides of the polarizing sheet. Depending on the application, it may be laminated only on one side, and the polarizing sheet may be exposed on one side.

The coating with the coating film of the (meth) acrylate polymerizable composition on the transparent sheet can be performed after the polarizing laminate is formed, or the transparent sheet on which the (meth) acrylate polymerizable composition has been previously coated. Can be bonded to a sheet-like polarizer to form a polarizing laminate.
In any case, coating of a (meth) acrylate polymerizable composition on a transparent sheet is possible by a very general coating method such as spin coating, dipping, flow coating, roll coater, or curtain coating. is there.

In the method for producing a plastics polarizing lens body of the present invention, at least one surface of the sheet-like polarizing body coated with a (meth) acrylate-based polymerizable composition is a very wide range of polymerizable compositions for lens substrates. It is possible to mold the lens in combination. As such a polymerizable composition for a lens body, since almost all polymerizable compositions for lens base materials currently available on the market can be used as they are, it is very useful. Specifically, not only a polymerizable composition for a high refractive index lens body such as a thiourethane-based polymerizable composition and an episulfide-based polymerizable composition, but also a highly versatile polymerizable composition such as CR39. It can be used.
Moreover, as such a polymerizable composition for a lens body, a polymerizable composition containing a sulfur-containing polymerizable compound is preferable.

The thiourethane-based polymerizable composition (including a copolymer and a polymer mixture) is composed of a combination of isocyanate and thiol.
Examples of the iso (thio) cyanate combined with such a thiourethane resin composition include the following compounds. For example, diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, Lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl ether diisocyanate, 3- (2'-isocyanatocyclohexyl) propyl isocyanate, tris ( Phenyl isocyanate) thiophosphate, isopropylidene-bis (cyclohexyl) Cyanate), 2,2′-bis (4-isocyanatoenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ′, 4′-triisocyanate-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diisocyanatobiphenyl, 4,4′-diisocyanato-3,3 ′ -Dimethylbiphenyl, dicyclohexylmethane-4,4'-diisocyanate, 1,1'-methylenebis (4-isocyanatobenzene), 1,1'-methylenebis (3-methyl-4-isocyanatobenzene), m-xylylene diene Isocyanate, p-xylylene diisocyanate, 1, -Bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) benzene, 2,6 -Bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) tetrahydrothiophene, bis (isocyanatomethyl) thiophene, 2,5-diisocyanatomethylnorbornene, bis (isocyanate) Natomethyl) adamantane, 3,4-diisocyanateselenophan, 2,6-diisocyanate-9-selenabicyclononane, bis (isocyanatomethyl) selenophan, 3,4-diisocyanate-2,5-diselenolane, dimer acid diisocyanate 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-bis (isocyanatomethyl-4-isocyanate-2- Thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanato-2-thiapropyl) -1,4-dithiane, 1,3,5-triisocyanatocyclohexane, 1,3,5-tris ( Isocyanatomethyl) cyclohexane, bis (isocyanatomethylthio) methane, 1,5-diisocyanate-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatoethylthio) propane, 1,2,3 -(Isocyanatomethylthio) propane, 1,1,6,6-tetrakis (isocyanatomethyl) -2,5-dithiahexane, 1,1,5, Examples include 5-tetrakis (isocyanatomethyl) -2,4-dithiapentane, 1,2-bis (isocyanatomethylthio) ethane, 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane, and the like. . Further, dimers of these polyisocyanates by a bullet type reaction, cyclized trimers of these polyisocyanates, adducts of these polyisocyanates and alcohol or thiol, and the like can be mentioned. Furthermore, the compound which changed a part or all of the isocyanate group of the said polyisocyanate into the isothiocyanate group can be mentioned. These can be used alone or in combination of two or more.

In the thiourethane-based polymerizable composition, examples of the thiol compound to be combined include the following compounds. For example, methylthiol, ethylthiol, n-propylthiol, n-butylthiol, allylthiol, n-hexylthiol, n-octylthiol, n-decylthiol, n-dodecylthiol, n-tetradecylthiol, n-hexa Decylthiol, n-octadecylthiol, cyclohexylthiol, isopropylthiol, tert-butylthiol, tert-nonylthiol, tert-dodecylthiol, benzylthiol, 4-chlorobenzylthiol, methylthioglycolate, ethylthioglycolate, n-butyl Thioglycolate, n-octyl thioglycolate, methyl (3-mercaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate) ), N-butyl (3-mercaptopropionate), 2-ethylhexyl (3-mercaptopropionate), n-octyl (3-mercaptopropionate), 2-mercaptoethanol, 3-mercaptopropanol, 2- Mercaptopropanol, 2-hydroxypropylthiol, 2-phenyl-2-mercaptoethanol, 2-phenyl-2-hydroxyethylthiol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, etc. Monothiols, methanedithiol, methanetrithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3- Trimercaptopropane, 1,4-dimercaptobutane 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, bis (2,3-dimercaptopropyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, 1,5-dimercapto-3 -Oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1 , 3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,4-bis (mer Captomethyl) -1,5-dimercapto-3-thiapentane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-bis (mercaptomethyl) -1 , 11-dimercapto-3,6,9-trithiaundecane, 5,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 1,2,7-trimercapto- 4,6-dithiaheptane, 1,2,9-trimercapto-4,6,8-trithianonane, 1,2,8,9-tetramercapto-4,6-dithianonane, 1,2,10,11-tetramercapto -4,6,8-trithiaundecane, 1,2,12,13-tetramercapto-4,6,8,10-tetrathiaundecane, 1,1,1-tris (mercap) Methyl) propane, tetrakis (mercaptomethyl) methane, tetrakis (4-mercapto-2-thiable) methane, tetrakis (7-mercapto-2,5-dithiaheptyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-methylpropionate), trimethylolpropane tris (2-mercaptoacetate) ), Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis 2-mercaptoacetate), 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercaptomethyl) Cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 2,5-bis (mercaptoethyl) -1-thian, 1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercapto Phenyl) ether, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4-mer) Ptophenyl) propane, bis (4-mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, 2,5-dimercapto-1,3,4 Thiadiazole, 3,4-thiophenedithiol, 1,2-dimercapto-3-propanol, 3,4-thiophenedithiol, 1,2-dimercapto-3-propanol, 1,3-dimercapto-2-propanol, glyceryl thioglycolate 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, etc. , And dimers to 20-mers thereof Can be mentioned. Furthermore, the compound which changed some or all of the thiol group of the said polythiols into the alcohol group can be mentioned. In addition, thiophenol, 4-tert-butylphenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, It has an unsaturated group such as 2-hydroxythiophenol, 3-hydroxythiophenol, thiophenols such as 4-hydroxythiophenol, allylthiol, 2-vinylbenzylthiol, 3-vinylbenzylthiol, 4-vinylbenzylthiol, etc. Mention may be made of thiophenols having an unsaturated group such as thiols, 2-vinylthiophenol, 3-vinylthiophenol, 4-vinylthiophenol.
These thioalcohols can be used alone or in combination of two or more.

  Specific examples of the monomer used in the episulfide polymerizable composition include, for example, ethylene sulfide, propylene sulfide, cyclohexene sulfide, styrene sulfide, thioglycidol, 1,1-bis (epithioethyl) methane, tetrakis (β-epithio). Propyl) methane, 1,1,1-tris (β-epithiopropyl) propane, 1,3- or 1,4-bis (epithioethyl) cyclohexane, 2,5-bis (epithioethyl) -1,4-dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, methylthioglycidyl ether, bis (β-epithiopropyl) ether, 1,2-bis (β-epithiopropyloxy) ethane , Tetrakis (β-epithio Propyloxymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, bis [4- (β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β -Epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2,5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 1,3 -Or 1,4-bis (β-epithiopropyloxy) benzene, 1,3- or 1,4-bis (β-epithiopropyloxymethyl) benzene, bis [4- (β-epithiopropyloxy) Phenyl] methane, 2,2-bis [4- (β-epithiopropyloxy) phenyl] propane, bis [4- (β-epithiopropyloxy) Enyl] sulfide, bis [4- (β-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (β-epithiopropyloxy) biphenyl, bis (β-epithiopropyl) sulfide, bis (β- Epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β -Epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1,4-bis (β-epithiopropylthio) butane, 1,5-bis (β-epithiopropylthio) ) Pentane, 1,6-bis (β-epithiopropylthio) hexane, bis (β-epithiopropylthioethyl) sulfide, tetrakis (β-epithio) (Lopylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) -3- Thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1,8-bis (β-epithiopropylthio) -4 -(Β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3,6- Dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2 , 4,5-Tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) 3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl]- 3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1, 11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epi Opropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-[(2-β-epithiopropylthioethyl) thiomethyl] -3 , 6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 2, 5-bis (epithiopropylthiomethyl) -1,4-dithiane, 2,4,6-tris (epithiopropylthiomethyl) -1,3,5-dithiane, 1,3- or 1,4-bis (Β-epithiopropylthio) benzene, 1,3- or 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2 -Bis [4- (β-epi Opropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropyl) Thio) biphenyl, bis (β-epithiopropyl) selenide, bis (β-epithiopropyl) diselenide, bis (β-epithiopropyl) telledo, bis (β-epithiopropyl) ditelledo, vinylphenylthioglycidyl ether, And vinyl benzyl thioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, allyl thioglycidyl ether, and the like. Furthermore, one or more hydrogen atoms of the thiirane ring of the above listed compounds are substituted with a methyl group. And episulfide compounds. Among these, preferred specific examples include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,4-bis (β-epithiopropylthio) butane, 1,5-bis (Β-epithiopropylthio) pentane, 1,6-bis (β-epithiopropylthio) hexane, bis (β-epithiopropylthioethyl) sulfide may be mentioned.

  As the monomer used for the CR-39 polymerizable composition (including a copolymer and a polymer mixture), an allyl derivative such as an allyl carbonate of an aliphatic or aromatic polyol is preferable, and diethylene glycol bis (allyl carbonate). ) (CR-39) is the most common, but other examples include ethylene glycol bis (allyl carbonate), diethylene glycol bis (2-methylallyl carbonate), ethylene glycol bis (2-chloroallyl carbonate), triethylene. Glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), propylene glycol bis (2-ethylallyl carbonate), 1,3-butenediol bis (allyl carbonate), 1,4-butene All bis (2-bromoallyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethylallyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylene bisphenol A bis (allyl carbonate), etc. Can be mentioned. These allyl carbonates can be used alone or in combination of two or more.

Integration of the polymerizable composition to be a lens substrate and the sheet-like polarizer having at least one surface coated with a (meth) acrylate-based polymerizable composition can be performed by a general casting polymerization method.
That is, using a glass mold having a structure in which the polymerizable composition for a lens body can be injected from at least one of the upper and lower sides of a sheet-like polarizer coated with the (meth) acrylate-based polymerizable composition. The polymerization may be performed under conditions suitable for the polymerizable composition.
Therefore, in the case of a sheet-like polarizer coated on one side with a (meth) acrylate-based polymerizable composition, only the coated surface of the sheet-like polarizer may be integrated with the polymerizable composition for a lens body, Both surfaces of the coated surface of the sheet-like polarizer and the surface on which the sheet-like polarizer is exposed may be integrated with the polymerizable composition for a lens body. Moreover, in the case of a sheet-like polarizer having both surfaces coated with a (meth) acrylate-based polymerizable composition, the both surfaces are usually integrated with the polymerizable composition for a lens body, but only one side is integrated. May be used.

The plastics polarizing lens body according to the second aspect of the present invention is a plastics polarizing lens body including at least a sheet-like polarizing body having a polarizing sheet, and a (meth) acrylate-based resin layer on at least one surface of the sheet-like polarizing body. Further, a polymerizable resin layer is laminated on at least the (meth) acrylate resin layer.
In this plastics polarizing lens body, a single-sided or double-sided (meth) acrylate-based resin layer of a sheet-like polarizing body is laminated and further formed only on the (meth) acrylate-based resin layer, or ( A polymerizable resin layer for the lens body is laminated on the (meth) acrylate-based resin layer and the other surface.
Since this plastics polarizing lens body is manufactured by coating at least one surface of a sheet-like polarizing body with a (meth) acrylate-based polymerizable composition, the sheet-like polarizing body of the plastics polarizing lens body is manufactured at the time of manufacture. It is not denatured even under severe conditions. Therefore, the plastics polarizing lens body of the present invention includes a plastics polarizing lens body composed of a wide variety of lens base materials including those having a high refractive index characteristic.

  Specific examples of the plastics polarizing lens body of the present invention include, for example, plastics polarizing lenses, plastics polarizing lens windows for automobiles and houses, polarizing lens windows, sun visors, ski goggles, windshields for airplanes and motorcycles, and the like. be able to. Among these, it is preferable to use as a plastics polarizing lens.

The significance of the “sheet-like polarizing body having at least a polarizing sheet” in the plastics polarizing lens body of the present invention is “the sheet-like polarizing body having at least a polarizing sheet” in the method for producing a plastics polarizing lens body according to the first invention of the present invention. The meaning of “body” is the same.
In addition, the meaning of “the (meth) acrylate-based resin layer is formed on at least one surface” means “the (meth) acrylate-based polymerizable composition on at least one surface” in the method for producing a plastics polarizing lens body according to the first invention of the present invention. The same applies to the meaning of “coating film” except for the following points. That is, the film of the (meth) acrylate-based polymerizable composition before polymerization is shown in the first invention, whereas the layer of the (meth) acrylate-based resin after polymerization is shown in the second invention.
Further, “(meth) acrylate-based” and “sheet-like polarizer” also have the same significance as in the first invention.

An example of a plastics polarizing lens body in the case where the sheet-like polarizing body in the plastics polarizing lens body of the present invention is a polarizing laminate is schematically shown in FIG.
In FIG. 1, a transparent sheet 2 is bonded to both surfaces of a polarizing sheet 1 to form a sheet-like polarizing body that is a polarizing laminate. The (meth) acrylate resin layer 3 covers both surfaces of the sheet-like polarizer. Furthermore, a plastics polarizing lens body is formed by laminating a polymerizable resin layer 4 for a lens body on these (meth) acrylate resin layers.

The polarizing laminate according to the third aspect of the present invention is a polarizing laminate suitable for manufacturing a plastics polarizing lens body including at least a sheet-like polarizer having a polarizing sheet, and is formed on at least one surface of the sheet-like polarizer ( A (meth) acrylate-based polymerizable composition film is formed.
The polarizing laminate of the present invention can be obtained by coating the surface of a very common polarizing laminate or by using a transparent film whose surface has been previously treated for the production of a polarizing laminate. Easy to manufacture. By performing casting polymerization using the polarizing laminate as it is, the plastics polarizing lens body of the present invention can be obtained, so that it is useful as an intermediate product of the plastics polarizing lens body of the present invention.
The polarizing laminate of the present invention can be composed of a polarizing sheet, a transparent sheet that covers at least one surface of the polarizing sheet, and the (meth) acrylate-based polymerizable composition film that covers the transparent sheet.

The significance of the “sheet-shaped polarizer having at least a polarizing sheet” in the polarizing laminate of the present invention is “the sheet-shaped polarizer having at least a polarizing sheet” in the method for producing a plastics polarizing lens body according to the first aspect of the present invention. The meaning is the same as
Further, the meaning of “formation of (meth) acrylate-based polymerizable composition film on at least one surface” means “(meth) acrylate-based polymerization on at least one surface” in the method for producing a plastics polarizing lens body according to the first invention of the present invention. The meaning is the same as the meaning of “coating film”.
Further, “(meth) acrylate-based” and “sheet-like polarizer” also have the same significance as in the first invention.

Specific examples of the polarizing laminate of the present invention include, for example, a polarizing film sandwiched on both sides with triacetyl cellulose as a general polarizing laminate.
In addition, as described above, after producing a polarizing sheet by a normal method, both sides are laminated in a sandwich with an optical transparent resin typified by an alicyclic polyolefin-based resin film such as ARTON, ZEONOR, APEL, etc. Can do.

  An example of the polarizing laminate of the present invention is schematically shown in the figure. A polarizing sheet 1 and a transparent sheet 2 excluding the polymerizable resin layer 4 and the (meth) acrylate resin layer 3 for the lens body in FIG. The laminated body which consists of is mentioned.

The present invention also provides a polarizing laminate in which a (meth) acrylate-based polymerizable composition film is formed on at least one surface of the sheet-shaped polarizing body and is coated with the (meth) acrylate-based polymerizable composition. The coating sheet is characterized in that a (meth) acrylate polymerizable composition is coated on one side of a transparent sheet.
Since the polarizing laminate can be obtained simply by adhering this covering sheet to a sheet-like polarizer such as an existing polarizing sheet, the covering sheet of the present invention is very useful.
Specifically, as described above, a so-called PC polarizing sheet used for injection molding can be used as a polarizing sheet, and a coated sheet whose surface is coated with a (meth) acrylate polymerizable composition can be exemplified. . In the case of a PC polarizing sheet, since it has been developed for injection molding, it has high heat resistance and is more preferable.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention does not receive a restriction | limiting at all to the following examples.
<Measurement method>
The following methods were used to measure and calculate the transmittance, polarization degree, and coating thickness of the plastics polarizing lenses produced in the following Examples and Comparative Examples.
(A) Transmittance The transmittance was measured using a spectrophotometer (manufactured by JASCO Corporation).
(B) Polarization degree Polarization degree (P) was calculated | required from following Formula.
P (%) = √ ((H ₀ −H ₉₀ ) / (H ₀ + H ₉₀ )) × 100
Parallel transmittance (H ₀ ): light transmittance when two polarizing plates are superposed so that their molecular orientation axes are parallel, orthogonal transmittance (H ₉₀ ): two polarizing plates in their molecular orientation The light transmittance when superposed so that the axes are vertical) is an average value obtained by correcting the visibility in the visible region of 400 nm to 700 nm.
(C) Thickness of the coating film The thickness measurement of the coating film was performed using a multilayer film thickness measuring apparatus DC-8200 (manufactured by Gunze Co., Ltd.).

<Example 1 to Example 3>
(A) Production of Polarizing Film Substrate (1) (Polarizing Sheet in the Present Invention) 0.25 g of chloranthin fast red (C.I. 28160) polyvinyl alcohol (Kuraray Co., Ltd., trade name: Kuraray Vinylon # 750) / L, chrysophenine (C.I. 24895) 0.18 g / L, solophenyl blue 4GL (C.I. 34200) 1.0 g / L and sodium sulfate 10 g / L and stained at 35 ° C. for 3 minutes Then, it was stretched 4 times in the solution.
Subsequently, this dyed film was immersed in an aqueous solution containing 2.5 g / L of nickel acetate and 6.6 g / L of boric acid at 35 ° C. for 3 minutes.
Next, the film was dried at room temperature for 3 minutes while being kept in tension, and then heat-treated at 70 ° C. for 3 minutes to obtain a polarizing film substrate (1).
In addition, the optical characteristic of the obtained polarizing film board | substrate was the visibility correction | amendment transmittance | permeability T (vis.) = 19.3% in the whole visible region, and the polarization degree P = 99.8%.
The nickel content in the film substrate was 1.2 mg / g, and the boron content was 1.3 mg / g.

(B) Transparent film (2) (transparent sheet in the present invention)
A polycarbonate sheet having a thickness of 300 μm (Mitsubishi Gas Chemical Co., Ltd., retardation value 4,800) was used as the transparent film (2).

(C) Adhesive composition (3)
An adhesive composition (3) was prepared by using 25 parts by weight of diphenylmethane-4,4′-diisocyanate and 100 parts by weight of ethyl acetate as a solvent with respect to 100 parts by weight of polypropylene glycol (M = 900).
(D) (Meth) acrylate-based polymerizable composition (4)
60 parts by weight of 1,9-nonanediol acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name: Biscote # 215), 37 parts by weight of polyfunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: U-4HA) (Meth) acrylate-based polymerizable composition using 3 parts by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (polymerization initiator manufactured by Ciba Specialty Chemicals, trade name: Darocur 1173) A product (4) was prepared.

(E) Manufacture of coated polarizing laminate The adhesive composition (3) was applied to one side of the polarizing film substrate (1) obtained in (a) using a bar coater # 24 and dried at room temperature for 5 minutes. Then, the polycarbonate sheet (2) was laminated with a laminator (manufactured by Mitsushi Corporation) under the condition of a nip pressure of 4.0 kg / cm ² G.
Subsequently, the polycarbonate sheet was bonded together on the other side in the same manner.
Apply the (meth) acrylate-based polymerizable composition (4) to the outermost layer on one side of this laminate using a bar coater # 24, and cover it with a polyethylene film (Toray Synthetic Film Co., Ltd., 50 μm), The polyethylene film was irradiated with ultraviolet rays on the condition of 2200 mJ / cm ² . The other surface was subjected to the same treatment to obtain a polarizing laminate coated with a (meth) acrylate polymerizable composition.
It was confirmed that the thickness of both coating surfaces after curing was 5-7 μm.

(F) Manufacture of plastics polarizing lens by cast polymerization (f-1) Bending of coated polarizing laminate The coated polarizing laminate obtained in (e) is punched into a circle, 140 ° C, Vacuum molding was performed for 5 minutes under an atmosphere of 3 mmHg to obtain a lens-shaped bent product having a curvature radius R = 87.2 mm.
(F-2) Cast polymerization (f-2-1) Cast polymerization using thiourethane-based polymerizable composition This bent product is cut to a diameter of 60 mm and placed in a glass mold having a diameter of 60 mm. A thiourethane-based polymerizable composition comprising 39.55 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), 30.45 parts by weight of m-xylylene diisocyanate and 0.035 parts by weight of dibutyltin dilaurate on the top and bottom of the processed product. The temperature was raised from 30 ° C. to 100 ° C. at a rate of 3.5 ° C./hour, and the temperature was further raised from 100 ° C. to 120 ° C. at a rate of 20 ° C./hour. Polymerization was carried out under the condition of maintaining the time.
A plastics polarizing lens with good transparency in which the coated polarizing laminate and the thiourethane resin as the lens substrate were firmly integrated was obtained. The color tone of the obtained lens is not significantly changed visually as compared with the polarizing film substrate before polymerization, and T (vis.) = 19.9% and P = 99 in the characteristic evaluation with a spectrophotometer. It was confirmed that there was no significant change in polarization characteristics before and after polymerization.

(F-2-2) Cast polymerization using episulfide-based polymerizable composition 95 parts by weight of bis (β-epithiopropyl) sulfide, 5 parts by weight of bis (2-mercaptoethyl) sulfide, tetra-n-butylphosphonium An episulfide polymerizable composition was prepared by mixing 0.05 parts by weight of bromide.
As polymerization conditions, the temperature is raised from 20 ° C. to 100 ° C. at a rate of 4 ° C./hour, the temperature is further raised from 100 ° C. to 120 ° C. at a rate of 20 ° C./hour, and then kept at 120 ° C. for 3 hours The same operation as (f-2-1) was performed except that.
In this case as well, a good plastics polarizing lens was obtained, and the polarization characteristics were T (vis.) = 19.8% and P = 99.8%, and it was confirmed that there was almost no change before and after polymerization.

(F-2-3) Cast polymerization using CR-39 As a polymerizable composition for a lens body, 150 parts by weight of diethylene glycol bisallyl carbonate and 5 parts by weight of diisopropyl peroxycarbonate were mixed to prepare CR-39. did.
As the polymerization conditions, (f-2) except that 30 ° C. was maintained for 10 hours, then the temperature was increased from 30 ° C. to 100 ° C. at a rate of 7 ° C./hour, and further 100 ° C. was maintained for 1 hour. The same operation as in -1) was performed.
In this case as well, a good plastics polarizing lens was obtained, and the polarization characteristics were T (vis.) = 19.5% and P = 99.8%, and it was confirmed that there was almost no change before and after polymerization. The optical characteristics of each lens were as shown in Table 1 below and were good.

<Example 4 to Example 6>
1,9-nonanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester NOD-N), polyfunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: U-4HA) ) 40 parts by weight, 3 parts by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (polymerization initiator manufactured by Ciba Specialty Chemicals, trade name: Darocur 1173), and (meth) An acrylate polymerizable composition was prepared.
The other operations were the same as in Examples 1 to 3. The thickness of the coating film of the outermost layer of the obtained polarizing laminate was 6-9 μm.
In any combination with the polymerizable composition for a lens body, a good plastics polarizing lens was obtained, and the optical characteristics of each lens were as shown in Table 2 below, which were good.

<Example 7 to Example 9>
PO modified neopentyl glycol diacrylate (manufactured by Sannopco, trade name: Photomer 4127-SN) 48 parts by weight, trifunctional urethane acrylate oligomer (manufactured by Daicel UCB, trade name: Ebecryl 264) 49 parts by weight, benzophenone (polymerization initiator, 3 parts by weight of Wako Pure Chemical Industries, Ltd.) was mixed to prepare a (meth) acrylate polymerizable composition.
The other operations were the same as in Examples 1 to 3. The coating layer thickness of the outermost layer of the obtained polarizing laminate was 4 to 6 μm.
In any combination with the polymerizable composition for a lens body, a good plastics polarizing lens was obtained, and the optical characteristics of each lens were as shown in Table 3 below, which were good.

<Example 10 to Example 12>
Except for using urethane acrylate paint UT-001 (manufactured by Nippon B Chemical Co., Ltd.) as the acrylate polymerizable composition, the same operations as in Examples 1 to 3 were performed. The thickness of the coating film of the outermost layer of the obtained polarizing laminate was 6 to 8 μm.
In any combination with the polymerizable composition for a lens body, a good plastics polarizing lens was obtained, and the optical characteristics of each lens were as shown in Table 4 below, which were good.

<Example 13 to Example 15>
45 parts by weight of PO-modified neopentyl glycol diacrylate (manufactured by Sannopco, trade name: Photomer 4127-SN), 30 parts by weight of tetrafunctional polyester acrylate oligomer (trade name: Ebecryl 80, manufactured by Daicel UCB), trifunctional urethane acrylate oligomer ( 20 parts by weight of Daicel UCB, trade name: Ebecryl 264) and 5 parts by weight of benzophenone (polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed to prepare a (meth) acrylate polymerizable composition.
The other operations were the same as in Examples 1 to 3. The thickness of the coating film of the outermost layer of the obtained polarizing laminate was 7 to 9 μm.
In any combination with the polymerizable composition for a lens body, a good plastics polarizing lens was obtained, and the optical characteristics of each lens were as follows.

<Example 16 and Example 17>
70 parts by weight of 1,9-nonanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester NOD-N), bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer EA) -1020) 30 parts by weight, 2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (polymerization initiator manufactured by Ciba Specialty Chemicals, trade name: Darocur 1173), A (meth) acrylate polymerizable composition was prepared.
The other operations were the same as in Examples 1 and 3. The coating layer thickness of the outermost layer of the obtained polarizing laminate was 6 to 9 μm.
In any combination with the polymerizable composition for a lens body, a good plastics polarizing lens was obtained, and the optical characteristics of each lens were as shown in Table 6 below, which were good.

<Example 18>
One side of the polarizing film substrate was exposed, and on the other side, a laminate similar to the laminate of Example 1 was obtained in the same manner as in Example 1.
A plastic of thiourethane resin is prepared by performing the processing from bending to polymerization in the same manner as in (f-2-1) of Example 1 so that the coated PC side of the laminate is convex. A polarized lens was made.
Also in this case, a plastics polarizing lens having good transparency in which the polarizing laminate and the lens base material were firmly integrated was obtained. Further, the color tone of the obtained plastics polarizing lens is not significantly changed visually as compared with the polarizing film substrate before polymerization, and T (vis.) = 19.7 is also evaluated by the spectrophotometer. %, P = 99.8%, and it was confirmed that there was no significant change in polarization characteristics before and after polymerization.

<Example 19>
(F-2-2) of Example 1 except that a fluorene polyester resin OKP4 film (manufactured by Osaka Gas Chemical Co., Ltd., press-molding the resin at 280 ° C. to create a sheet of about 200 μm) was used as the transparent sheet. A thiourethane resin lens was prepared under the same conditions as in 1). The obtained plastics polarizing lens was confirmed to have no significant change in polarization characteristics before and after polymerization at T (vis.) = 19.8% and P = 99.8%.

<Example 20>
Using a TAC film (manufactured by Konica Minolta Opto Co., Ltd., thickness: 80 μm) as a transparent sheet, an episulfide resin lens was produced under the same conditions as in Example 1 except that the bending temperature was 95 ° C. It was confirmed that the obtained lens had no significant change in polarization characteristics before and after polymerization at T (vis.) = 19.7% and P = 99.8%.

<Example 21>
The same operation as in Example 18 was performed using APEL (trade name: APL6509T, thickness: 200 μm, manufactured by Mitsui Chemicals, Inc.) as the transparent sheet. A thiourethane resin lens was produced under the same conditions as in Example 1 except that the bending temperature was 80 ° C. It was confirmed that the obtained plastics polarizing lens had no significant change in polarization characteristics before and after polymerization at T (vis.) = 19.9% and P = 99.8%.

<Comparative Example 1>
A polarizing laminate was produced in the same manner as in Example 1.
Without processing the surface of this laminate, it was bent in the same manner as (f-1) in Example 1, and an attempt was made to mold an episulfide resin lens in the same manner as (f-2-2) in Example 1. It was.
Only a cloudy lens was obtained, and it was found that the surface of the laminate was affected.

<Comparative example 2>
The same operation as in Example 20 was performed, and an episulfide resin lens was molded in the same manner as in Example 1 (f-2-2) without any treatment on the TAC surface.
The polymerizable resin as the lens substrate and the TAC sheet did not adhere.

<Comparative Example 3>
The same operation as in Example 21 was performed without any treatment on the surface of APEL. The lens molding of thiourethane resin was attempted in the same manner as in Example 1 (f-2-1).
The polymerizable resin as the lens substrate and the apel did not adhere.

<Comparative example 4>
The same operation as in Example 19 was performed without any treatment on the surface of OKP4.
Only a cloudy lens was obtained, and it was found that the surface of the laminate was affected.

  The method for producing a plastics polarizing lens body according to the present invention is useful for the production of plastics polarizing lens bodies using a very wide range of lens substrates, and is quite simple. Since the optical properties of the polarizing sheet used in the plastics polarizing lens body to be used are not impaired, a high-refractive-index plastics polarizing lens body having high productivity can be provided.

It is the figure which showed typically an example of the plastics polarizing lens body in case the sheet-like polarizing body in the plastics polarizing lens body of this invention is a polarizing laminated body.

Explanation of symbols

1 Polarizing sheet 1
2 Transparent sheet 2
3 (Meth) acrylate resin layer 3
4 Polymerizable resin layer 4

Claims (22)

A method for producing a plastics polarizing lens body by a casting polymerization method using a sheet-shaped polarizer having at least a polarizing sheet,
A sheet-shaped polarizer having at least one surface coated with a (meth) acrylate-based polymerizable composition, and the polymerizable composition used for the casting polymerization is a thiourethane-based polymerizable composition and an episulfide-based polymerizable composition. Any one type chosen , The manufacturing method of the plastics polarizing lens body characterized by the above-mentioned.   The method for producing a plastics polarizing lens body according to claim 1, wherein the (meth) acrylate-based polymerizable composition has ultraviolet curable properties.   The (meth) acrylate-based polymerizable composition is at least any selected from a urethane (meth) acrylate-based polymerizable composition, a polyester (meth) acrylate-based polymerizable composition, and an epoxy (meth) acrylate-based polymerizable composition. The method for producing a plastics polarizing lens body according to claim 1 or 2, wherein the plastics polarizing lens body is one type.   4. The method according to claim 1, wherein the (meth) acrylate-based polymerizable composition is at least one selected from a urethane (meth) acrylate-based polymerizable composition and a polyester (meth) acrylate-based polymerizable composition. A method for producing a plastics polarizing lens body according to claim 1.   5. The method for producing a plastics polarizing lens body according to claim 1, wherein a film thickness of the (meth) acrylate-based polymerizable composition is 2 μm or more and 13 μm or less.   The method for producing a plastics polarizing lens body according to any one of claims 1 to 5, wherein the sheet-like polarizing body is a polarizing laminated body.   The method for producing a plastics polarizing lens body according to claim 6, wherein the polarizing laminate is composed of a polarizing sheet and a transparent sheet covering at least one surface of the polarizing sheet.   The plastics polarizing lens body according to claim 7, wherein the transparent sheet is formed of any one selected from polycarbonate resin, cellulose resin, alicyclic polyolefin resin, and polyester resin. Manufacturing method.   The method for producing a plastics polarizing lens body according to any one of claims 1 to 8, wherein the polarizing sheet is formed of a polyvinyl alcohol-based resin.   The method for producing a plastics polarizing lens body according to any one of claims 1 to 9, wherein the polarizing sheet contains a dichroic dye.   The method for producing a plastics polarizing lens body according to claim 10, wherein the polarizing sheet is further treated with a metal compound and boric acid.   A plastics polarizing lens body including at least a sheet-like polarizing body having a polarizing sheet,
  A (meth) acrylate-based resin layer is formed on at least one surface of the sheet-shaped polarizer, and a polymerizable resin layer is further laminated on at least the (meth) acrylate-based resin layer;
  The plastics characterized in that the polymerizable resin layer is formed by cast polymerization of a polymerizable composition containing any one selected from a thiourethane-based polymerizable composition and an episulfide-based polymerizable composition. Polarized lens body.   The plastics polarizing lens body according to claim 12, wherein the (meth) acrylate-based resin layer is formed by ultraviolet curing of a (meth) acrylate-based polymerizable composition film.   13. The (meth) acrylate-based resin layer is at least one selected from a urethane (meth) acrylate-based resin layer, a polyester (meth) acrylate-based resin layer, and an epoxy (meth) acrylate-based resin layer. Or a plastics polarizing lens body according to 13;   The said (meth) acrylate type resin layer is at least any one chosen from a urethane (meth) acrylate type resin layer and a polyester (meth) acrylate type resin layer, The any one of Claims 12-14 Plastics polarized lens body.   The plastics polarizing lens body according to any one of claims 12 to 15, wherein a thickness of the (meth) acrylate-based resin layer is 2 µm or more and 13 µm or less.   The plastics polarizing lens body according to any one of claims 12 to 16, wherein the sheet-like polarizing body is a polarizing laminated body.   The plastics polarizing lens body according to claim 17, wherein the polarizing laminated body includes a polarizing sheet and a transparent sheet that covers at least one surface of the polarizing sheet.   The plastics polarizing lens body according to claim 18, wherein the transparent sheet is formed of any one selected from a polycarbonate resin, a cellulose resin, an alicyclic polyolefin resin, and a polyester resin. .   The plastics polarizing lens body according to any one of claims 12 to 19, wherein the polarizing sheet is formed of a polyvinyl alcohol-based resin.   The plastics polarizing lens body according to any one of claims 12 to 20, wherein the polarizing sheet contains a dichroic dye.   The plastics polarizing lens body according to claim 21, wherein the polarizing sheet is further treated with a metal compound and boric acid.

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