JP4523325B2 - Manufacturing method of plastic light control lens body - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method for manufacturing a plastics light control lens body, a plastics light control lens body, a coated sheet sheet light control body and a covering sheet used for manufacturing the lens body, and in particular, a high refractive index plastic by a casting polymerization method. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic lens body, a method for producing a plastics photochromic lens body suitable for manufacturing the same, and a coated sheet-like light control body and a covering sheet used for manufacturing the lens body.

  In recent years, a lens made of a resin has come to be used for a spectacle lens because it is lighter than a glass lens and has high safety in terms of resistance to cracking. Along with this, the demand for imparting additional functions that have been conventionally applied to glass lenses also to resin lenses has increased, and in particular, when strong light hits, the transmission of the light is suppressed. There is a strong demand to have a characteristic of being colored or discolored and disappearing when placed in a dark place, that is, a photochromic characteristic (also referred to as “light control”).

  Conventionally, plastics photochromic lenses (also referred to as “plastic photochromic lenses”) having photochromic characteristics have been manufactured mainly by a so-called in-vibration method (see Patent Document 1 below). However, this method is difficult to apply to systems other than diethylene glycol bisallyl carbonate (hereinafter abbreviated as “CR-39”) known under the name of CR-39.

  Therefore, as a method applicable to systems other than CR-39, (1) a method of providing a coating layer containing a photochromic dye (also referred to as “light control dye”) on the lens surface (see Patent Document 2 below) ), And (2) a method in which a photochromic dye is directly contained in a lens substrate (see Patent Document 3 below). In addition, a method has been proposed in which (3) a laminate having a photochromic function is produced and a polymerization composition serving as a lens substrate is polymerized from both sides of the laminate (see Patent Document 4 below).

  However, the method (1) has a drawback that the contrast between colored and non-colored is hardly set to a sufficient level due to the limit of the coating thickness (see Patent Document 1 below). The method (2) has a problem that it is difficult to achieve sufficient contrast and response time. The method (3) is only an idea and has not been put into practical use.

  In order to solve the above-mentioned problems, in the method of manufacturing a lens by injection molding, a method of using a laminate in which a photochromic layer is sandwiched between polycarbonate resins to form a polycarbonate photochromic lens is applied to a light control lens. Is considered. In addition, since excellent photochromic laminates have been developed (see Patent Documents 5 and 6 below), this method is actually being adopted.

US Pat. No. 5,130,353 JP-A 63-178193 Japanese Patent Laid-Open No. 7-253633 JP-A-61-236521 International Publication No. 01/77723 Pamphlet International Publication No. 01/77740 Pamphlet

  However, there is a problem that the material is limited even in the method of making a polycarbonate photochromic lens using a laminate in which the photochromic layer is sandwiched between the above polycarbonate resins, and a method for producing a photochromic lens by a casting polymerization method However, as a method having high productivity at present, only a system using diethylene glycol bisallyl carbonate, known as CR-39, as a lens base material is known.

  Therefore, manufacturing of plastics light control lenses using high refractive index lenses represented by thiourethane-based polymer compositions requires a completely different approach from that of CR-39 currently used. Therefore, it is indispensable to develop light control films and light control laminates that can withstand various severe conditions during cast polymerization and to find an appropriate combination of these films or laminates and lens precursors.

  The present invention has been made in view of the above, and relates to a method for manufacturing a plastics light control lens body, a plastics light control lens body, a coated sheet-like light control body used for manufacturing the lens body, and a covering sheet. In particular, a plastics light control lens having a high refractive index by a casting polymerization method, a method for manufacturing a plastics light control lens body suitable for manufacturing the same, and a coating sheet sheet light control body and a covering sheet used for manufacturing the lens body are provided. The task is to do.

  Therefore, the present inventors have made extensive studies in view of such circumstances, and are not limited to CR-39, and even when used in a highly versatile system such as a thiourethane-based polymerizable composition, a lens substrate and a light control film As a result of further studies on light-controlling films and light-control integrated bodies that have sufficient adhesiveness and can be easily processed before and after light-control film processing for lens molding in the casting polymerization method. A transparent film is pasted on at least one side of the film, and the transparent film is coated with a specific acrylate or methacrylate polymerizable composition. It was found that they can be combined, and bending and management before and after that are easy, and the present invention has been made.

That is, the method for manufacturing a plastics light control lens body according to the first aspect of the present invention is a method for manufacturing a plastics light control lens body by a casting polymerization method using at least a sheet-shaped light control body having a light control sheet. And
It is characterized by using a sheet-like light-regulating body having at least one surface coated with a (meth) acrylate-based polymerizable composition.
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-based polymerizable composition. The thickness of the (meth) acrylate polymerizable composition film is preferably 2 μm or more and 13 μm or less.

It is preferable that the sheet-like light control body used in the method for producing a plastics light control lens body of the present invention is a light control laminate.
This light control laminated body can be comprised from the light control sheet and the transparent sheet which coat | covers at least one surface of this light control sheet. In the light control laminate, the transparent sheet is preferably formed of at least one selected from polycarbonate resin, cellulose resin, alicyclic polyolefin resin, and polyester resin.
It is preferable that the light control sheet | seat which the said plastics light control lens body has is formed from a polyurethane-type resin. In the light control laminate, the polyurethane resin of the light control sheet preferably contains at least one light control dye selected from a spirobenzopyran derivative, a naphthopyran derivative, and a spirooxazine derivative, and is further treated with a curing agent. It is preferable.

  The polymerizable composition for the lens body used in the cast polymerization in the method for producing a plastics light control lens body of the present invention preferably contains a sulfur-containing polymerizable compound, and in particular, a thiourethane-based polymerizable compound. It is preferable to contain at least one selected from a compound and an episulfide polymerizable compound. Further, as the polymerizable composition for the lens body, an allyl carbonate-based polymerizable composition is also preferable.

A plastics light control lens body according to a second invention of the present invention is a plastics light control lens body including a sheet-shaped light control body having at least a light control sheet,
A sheet-shaped light control member, a (meth) acrylate-based resin layer laminated on at least one surface of the sheet-shaped light control member, and a lens-body polymerizable resin laminated on at least the (meth) acrylate-based resin layer It consists of layers.
The (meth) acrylate-based resin layer is preferably formed by ultraviolet curing of a (meth) acrylate-based polymerizable composition film. As the (meth) acrylate-based resin layer, a urethane (meth) acrylate-based resin layer It is preferably at least one selected from a polyester (meth) acrylate resin layer and an epoxy (meth) acrylate resin layer. The thickness of the (meth) acrylate-based resin layer is preferably 2 μm or more and 13 μm or less.

It is preferable that the sheet-like light control body used in the plastics light control lens body of the present invention is a light control laminate.
This light control laminated body can be comprised from the light control sheet and the transparent sheet which coat | covers at least one surface of this light control sheet. In the light control laminate, the transparent sheet is preferably formed of at least one selected from polycarbonate resin, cellulose resin, alicyclic polyolefin resin, and polyester resin.
It is preferable that the light control sheet | seat which the said plastics light control lens body has is formed from a polyurethane-type resin. In the light control laminate, the polyurethane resin preferably contains at least one light control pigment selected from spirobenzopyran derivatives, naphthopyran derivatives, and spirooxazine derivatives, and is further treated with a curing agent. preferable.

  The polymerizable resin layer for the lens body of the plastic light control lens body of the present invention is preferably a polymerizable resin layer formed by cast polymerization of a polymerizable composition for a lens body containing a sulfur-containing polymerizable compound. Among these, a polymerizable resin layer formed by cast polymerization of a polymerizable composition for a lens body containing at least one selected from a thiourethane-based polymerizable compound and an episulfide-based polymerizable compound is more preferable. . Moreover, it is also preferable that it is a polymerizable resin layer formed by cast polymerization of an allyl carbonate-based polymerizable composition.

The coating film sheet-shaped light control member according to the third aspect of the present invention is a coating film sheet-shaped light control member suitable for manufacturing a plastics light control lens body including a sheet-shaped light control member having at least a light control sheet. And
It consists of a sheet-like light control body, and the (meth) acrylate type polymeric composition film | membrane coat | covered on the at least single side | surface of this sheet-like light control body.

The sheet-like light control body is preferably a light control laminate comprising a light control sheet and a transparent sheet that covers at least one surface of the light control sheet.
This transparent sheet is preferably formed of at least one selected from polycarbonate resins, cellulose resins, alicyclic polyolefin resins, and polyester resins.
The light control sheet is preferably formed of a polyurethane resin, and the polyurethane resin preferably contains at least one light control dye selected from spirobenzopyran derivatives, naphthopyran derivatives, and spirooxazine derivatives. Further, it is preferable that the film is further treated with a curing agent.

  The present invention is also a covering sheet used for producing the above-mentioned coated sheet-shaped light control body, in which a (meth) acrylate-based polymerizable composition film is laminated on at least one surface of the sheet-shaped light control body. The present invention relates to a coated sheet comprising a transparent sheet and a (meth) acrylate-based polymerizable composition film coated on one side of the transparent sheet.

  According to the method for producing a plastic light control lens body according to the present invention, it is possible to use a very wide range of the polymerizable composition for lenses, and it is easy to bend and manage before and after, particularly, The plastics light control 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 method for manufacturing a plastics light control lens body according to the first aspect of the present invention is a method for manufacturing a plastics light control lens body by a casting polymerization method using at least a sheet-shaped light control body having a light control sheet, It is characterized by using a sheet-like light control body having one surface coated with a (meth) acrylate-based polymerizable composition.
In this production method, a sheet-shaped light control body in which one or both surfaces of the sheet-shaped light control body are coated with a (meth) acrylate-based polymerizable composition can be used.

  The at least one surface of the sheet-shaped light control body is coated with a (meth) acrylate-based polymerizable composition because the coating layer has a wide range of polymerizable compositions for various plastics light control lens bodies (hereinafter, “ This is because it has a high resistance to a “polymerizable composition for a lens body” and a good adhesion property. By this coating treatment, the polymerizable composition for a lens body is polymerized while maintaining transparency, and a polymerizable resin layer for a lens body can be formed. No other thermosetting composition or UV curable composition is found that has a good balance of adhesion and resistance.

  Accordingly, if at least one surface of the sheet-shaped light control body is coated with a (meth) acrylate-based polymerizable composition and the polymerizable composition for a lens body is polymerized by a casting polymerization method, the light control of the light control body is performed. The characteristics can be maintained, and a plastics photochromic lens body using a polymerizable composition for a very wide range of plastics photochromic lens bodies can be provided. Moreover, the sheet-shaped light control body which coat | covered at least one surface with the (meth) acrylate type polymeric composition is easy to bend and control before and after that.

  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. Moreover, a sheet-like light control body means the sheet-like thing which has light control property. For example, the light control sheet | seat which has various thickness, the light control laminated body containing these light control sheets, etc. can be mentioned. Here, as described above, the dimming property refers to a characteristic that colors or discolors so as to suppress the transmission of strong light when it hits, and the color disappears when placed in a dark place. In the case of the present invention, the casting polymerization method is a polymerization method of polymerizing the polymerizable composition for a lens body after pouring the polymerizable composition for the lens body into a mold in which a sheet-like dimmer is incorporated. That means.

  The (meth) acrylate-based polymerizable composition used for forming the (meth) acrylate-based resin used in the method for producing the transparent plastic light control lens body is not particularly limited, and various (meth) acrylate-based polymerizable properties. A composition 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.

  Examples of the polyisocyanate include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl. Although methane 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 a polyhydric alcohol, 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 be mentioned.

  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 5833, 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 produced 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 And 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.

  Examples of the sheet-shaped light control body used in the method for producing the plastics light control lens body of the present invention include light control sheets having various thicknesses, and light control laminates including these light control sheets. it can. Here, the light control laminate refers to a laminate having a light control property including a light control sheet.

  As the light control sheet, various light control sheets conventionally called a light control sheet, a light control film, a light control film substrate and the like can be used from the viewpoint of thickness and function. The light control sheet is preferably formed from a polyurethane resin.

As said light control laminated body, what is comprised from the light control sheet and the transparent sheet which coat | covers at least one surface of this light control sheet can be used. As this light control laminated body, what the transparent sheet coat | covered the single side | surface or both surfaces of the light control sheet can be used.
By using the light control laminate in which at least one surface of the light control sheet is covered with a transparent sheet having a certain degree of heat resistance, it is possible to prevent the light control sheet from being modified during the casting polymerization.
Further, when this light control laminate is used as the light control sheet, the surface of a very general light control laminate is treated with a (meth) acrylate polymerizable composition, or the surface is preliminarily (meth) Since it becomes possible to use the coating sheet which consists of a transparent film film-processed with the acrylate polymeric composition for light control laminated body manufacture, it is very efficient on manufacture.

The transparent sheet in the light control laminate is not particularly limited as long as it has a certain level of heat resistance, and various transparent sheets can be used.
The transparent sheet is preferably formed of at least 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”, “Zconoa”, “APEL”, etc. And alicyclic olefin-based polymers (hereinafter referred to as “APO”), various polycarbonate resins, and the like (WO02 / 99513).

The light control sheet in the light control laminate is basically not particularly limited as long as it has a certain degree of heat resistance, and various light control sheets can be used. This light control sheet is preferably formed of a polyurethane resin.
The polyurethane resin is not particularly limited as long as it is a polyurethane resin having a certain degree of heat resistance. Among them, a two-component thermosetting polyurethane resin composed of a polyurethane prepolymer and a curing agent is preferable.

A preferred example of the polyurethane prepolymer is a compound obtained by reacting a diisocyanate compound and a polyoxyalkylene diol at a certain ratio and having an isocyanate group at both ends.
Examples of the diisocyanate compound used in the polyurethane prepolymer include diphenylmethane-4,4′-diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, lysine isocyanate, and water. An added xylylene diisocyanate may be mentioned, and among them, diphenylmethane-4,4′-diisocyanate is preferable.
Examples of the polyoxyalkylene diol used in the polyurethane prepolymer include polypropylene glycol, polyethylene glycol, and polyoxytetramethylene glycol. Among them, polypropylene glycol having a degree of polymerization of 5 to 30 is preferable.
The molecular weight of the polyurethane prepolymer is 500 to 5000 in terms of number average molecular weight, preferably 1500 to 4000, more preferably 2000 to 3000. Here, the number average molecular weight means an average molecular weight determined by a method such as a terminal group quantification method, a boiling point raising method, a freezing point depression method, an osmotic pressure method, and gel permeation chromatography.

The curing agent is not particularly limited as long as it is a compound having two or more hydroxyl groups. Examples of these compounds include polyurethane polyol, polyether polyol, polyaster polyol, acrylic polyol, polybutadiene polyol, and polycarbonate polyol. Among these, a polyurethane polyol having a hydroxyl group at a terminal obtained from a specific isocyanate and a specific polyol is preferable, and a polyurethane polyol having a hydroxyl group at least at both terminals derived from a diisocyanate compound and a polyol is more preferable.
Examples of the diisocyanate compound include diphenylmethane-4,4′-diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, lysine isocyanate, and hydrogenated xylylene diisocyanate. Among them, tolylene diisocyanate is preferable.
Examples of the polyol include those obtained by reacting trimethylolpropane or the like with ethylene oxide or propylene oxide, and among them, a polypropylene glycol derivative having a polymerization degree of 5 to 30 is preferable.
The molecular weight of these curing agents is 500 to 5,000 in terms of number average molecular weight, preferably 1500 to 4000, and more preferably 2000 to 3000.

  In these polyurethane prepolymers and curing agents, solvents such as ethyl acetate and tetrahydrofuran can be used for viscosity adjustment. The use of these solvents is a particularly effective method for uniformly dispersing the photochromic compound in the urethane resin.

  The photochromic compound, which is a photochromic dye used in the present invention, is not particularly limited as long as the compatibility with the polyurethane prepolymer is good, and a commercially available organic photochromic compound can be used. As the organic photochromic compound, spirobenzopyran derivatives, naphthopyran derivatives, and spirooxazine derivatives are preferable from the viewpoint of photochromic performance.

  Specific examples of the spirobenzopyran derivatives include, for example, 1,3,3-trimethylspiro (indoline-2,2 ′-[2H] -1′-benzopyran), 1,3,3-trimethylspiro (indoline- 8'-nitro-2,2 '-[2H] -1'-benzopyran), 1,3,3-trimethylspiro (indoline-6'-hydroxy-2,2'-[2H] -1'-benzopyran) 1,3,3-trimethylspiro (indoline-8′-methoxy-2,2 ′-[2H] -1′-benzopyran), 5-chloro-1,3,3-trimethylspiro (indoline-2,2) '-[2H] -1'-benzopyran), 1,3,3-trimethylspiro (indoline-6', 8'-dibromo-2,2 '-[2H] -1'-benzopyran), 1,3,3 , 4,7-Penta Chirpspiro (indoline-8′-ethoxy-2,2 ′-[2H] -1′-benzopyran), 5-chloro-1,3,3-trimethylspiro (indoline-6′-nitro-2,2 ′-[ 2H] -1′-benzopyran) and 5-chloro-1,3,3-trimethylspiro (indoline-6 ′, 8′-dinitro-2,2 ′-[2H] -1′-benzopyran) Can do.

  Specific examples of the naphthopyran derivative include 1,3,3-triphenylspiro (indoline-2,3 ′-[3H] -naphtho- (2,1-b) -pyran), 1- (2, 3,4,5,6-pentamethylbenzyl) -3,3-dimethylspiro (indoline-2,3 ′-[3H] -naphtho- (2,1-b) -pyran), 1- (2-methoxy) -5-nitrobenzyl) -3,3-dimethylspiro (indoline-2,3 '-[3H] -naphtho- (2,1-b) -pyran), 1- (2-nitrobenzyl) -3,3 -Dimethylspiro (indoline-2,3 '-[3H] -naphtho- (2,1-b) -pyran) and 1- (2-naphthylmethyl) -3,3-dimethylspiro (indoline-2,3' -Naphth (2,1-b) -pyran

Specific examples of the spirooxazine compound include, for example, 1,3,3,4,5-pentamethylspiro (indoline-2,3 ′-[3H] -naphtho (2,1-b)-( 1,4) -oxazine), 1,3,3,4,6-pentamethylspiro (indoline-2,3 ′-[3H] -naphtho- (2,1-b)-(1,4) -oxazine ), 1,3,3-trimethylspiro (indoline-2,3 ′-[3H] -naphth-2,1-b)-(1,4) -oxazine, 5-methoxy-1,3,3-trimethyl Spiro (indoline-2,3 ′-[3H] -naphth-2,1-b)-(1,4) -oxazine, 1,3,3-trimethylspiro (indoline-6- (1-piperidyl) -2 , 3 ′-[3H] -naphth-2,1-b)-(1,4) -oxazine, 1,3,3 Trimethylspiro (indoline-6 ′-(1-morpholyl) -2,3 ′-[3H] -naphtho- (2,1-b)-(1,4) -oxazine), 1,3,3,4, 5-pentamethylspiro (indoline-6 ′-(1-piperidyl) -2,3 ′-[3H] -naphtho- (2,1-b)-(1,4) -oxazine), 1,3,3 , 5,6-pentamethylspiro (indoline-6 ′-(1-piperidyl) -2,3 ′-[3H] -naphtho- (2,1-b)-(1,4) -oxazine), 1, 3,3-trimethylspiro (indoline-6 ′-(1-piperidyl) -9 ′-(methoxy) -2,3- [3H] -naphth- (2,1-b)-(1,4) -oxazine ), 5-chloro-1,3,3-trimethylspiro (indoline-2,3 ′-[3H] -naphth-2,1-b)-(1 , 4) -oxazine, 4,7-diethoxy-1,3,3-trimethylspiro (indoline-2,3 ′-[3H] -naphth-2,1-b)-(1,4) -oxazine, 1 , 3,3,5-tetramethylspiro (indoline-9 ′-(methoxy) -2,3 ′-[3H] -naphth-2,1-b)-(1,4) -oxazine, 1-isopropyl- 3,3,5-trimethylspiro (indoline-2,3 ′-[3H] -naphth-2,1-b)-(1,4) -oxazine, 1- (p-chlorobenzyl) -3,3 ′ -Dimethylspiro (indoline-2,3 '-[3H] -naphth-2,1-b)-(1,4) -oxazine and 1,3,3-trimethylspiro (indoline-2,2'-[2H ] -Phenanthro-9,10-b)-(1,4) -oxazine and the like. it can.
Among these organic photochromic compounds, a spirooxazine derivative is particularly preferable from the viewpoint of light resistance.

  In order to ensure the lifetime, various stabilizers are preferably added to the thermosetting polyurethane resin layer containing the photochromic compound of the present invention. Examples of the stabilizer include hindered amine light stabilizers and antioxidants such as hindered phenols.

  Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1-methyl -8- (1,2,2,6,6-pentamethyl-4-piperidyl) -sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2, 6,6-tetramethylpiperidine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, triethylenediamine, 8-acetyl-3- And dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione. Other nickel-based UV stabilizers include [2,2′-thiobis (4-tert-octylphenolate)]-2-ethylhexylamine nickel, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl, Phosphoric acid monoethylate, nickel dibutyl-dithiocarbamate, etc. can also be used. In particular, the hindered amine light stabilizer is preferably a hindered amine light stabilizer containing only a tertiary amine, specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl). -Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, or A condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.

  Antioxidants such as various hindered phenols can be used as the antioxidant, and among them, phenolic antioxidants, thiol antioxidants, and phosphite antioxidants can be used. preferable.

  Examples of the phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-tert). -Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, 2,6-di-tert-butyl-p-cresol, 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,3,5-tris (3 ′, 5′-di-) tert-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl-β- (3,5-di tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-di-methyl -2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxoxaspiro [5,5] undecane, 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

  Examples of the thiol-based antioxidant include distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), and the like.

  Examples of the phosphite antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, and di (2,6-di-tert-butylphenyl) penta. Erythritol diphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene- Examples include diphosphonite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

A light control laminate comprising at least one polycarbonate transparent sheet and a thermosetting polyurethane resin layer containing a photochromic compound in which the sheets are laminated is produced by the following method.
A photochromic compound is added to a solution obtained by diluting a polyurethane prepolymer with a specific organic solvent at a ratio of 0.2 to 5% by weight based on the resin solid content, and further 0.1 to 5% by weight of a hindered amine based on the resin solid content. Add additives such as system light stabilizers and / or antioxidants, and stir and mix uniformly. Thereafter, the curing agent is further added with a ratio I / H of the isocyanate group (I) and the hydroxyl group (H) of the curing agent of 0.9 to 20, preferably 1 to 10, and further stirred to form a solution. The polymer concentration in the solution is generally 40 to 90% by weight. The solution is applied to one side of a transparent polycarbonate sheet using a doctor blade having a coating thickness of 50 to 1000 microns. After coating, the coated surface is dried by heating until it is substantially free of solvent, and another transparent polycarbonate sheet is bonded to the coated surface of the synthetic resin sheet to form a sandwich. The above heat drying is usually performed at 20 to 50 ° C. for 30 to 120 minutes. The laminated sheet was heated to cure the urethane prepolymer containing a curing agent, thereby obtaining a transparent synthetic resin laminate. The curing conditions of the polyurethane prepolymer are usually 60 to 140 ° C. and 2 hours to 1 week.

  Examples of the dilution solvent used in the production of the light control laminate include hydrocarbons such as hexane, heptane, octane, cyclohexane, toluene, xylene, and ethylbenzene, ethyl acetate, methyl acetate, isopropyl acetate, n-propyl acetate, and acetic acid. Esters such as isobutyl, n-butyl acetate, isoamyl acetate, methyl propionate and isobutyl propionate, ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexyl ketone, cellosolve acetate, diethylene glycol diacetate, ethylene glycol Ether esters such as mono n-butyl ether acetate and propylene glycol monomethyl ether acetate, diacetone alcohol, tert-amyl alcohol and the like It may be mentioned alcohols and tetrahydrofuran. Among these, ethyl acetate, tetrahydrofuran and toluene are particularly preferable.

The coating of the (meth) acrylate polymerizable composition on the transparent sheet can be performed after the light control laminate is formed, or the (meth) acrylate polymerizable composition is previously coated with a transparent film. The sheet (the coated sheet of the present invention) can be used to bond to a sheet-shaped light adjuster to form the coated sheet-shaped light adjuster of the present invention. This coating sheet-like light control body also includes a coated light control 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.
Thus, the (meth) acrylate polymerizable composition film laminated on the transparent sheet is cured by an active energy ray such as ultraviolet rays to form a (meth) acrylate polymerizable resin layer.

  In the method for producing a plastics light control lens body according to the present invention, a coating sheet-like light control body in which at least one surface is coated with a (meth) acrylate polymerizable composition is a very wide range of polymerizability for lens substrates. It is possible to mold a lens in combination with the composition. 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 CR39 but also a wide range of polymerizable compositions can be used. As such a polymerizable composition, a polymerizable composition containing a sulfur-containing polymerizable compound is preferable, and in particular, for a high refractive index lens body such as a thiourethane-based polymerizable composition and an episulfide-based polymerizable composition. The polymerizable composition is more preferable.

The thiourethane-based polymerizable composition (including a copolymer and a polymer mixture) is 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 tetra Kiss (2-mercaptoacetate), 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercapto) Methyl) 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-thiane, 1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4 -Mercaptophenyl) ether, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4- Lucaptophenyl) 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, glycerylthio Glycolate, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, etc. Polythiols, and their dimers to 2 It may be mentioned oligomers such as dimers. 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 Mention may be made of (β-epithiopropylthio) pentane, 1,6-bis (β-epithiopropylthio) hexane, bis (β-epithiopropylthioethyl) sulfide.

  As the monomer used in 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), tri Ethylene glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), propylene glycol bis (2-ethylallyl carbonate), 1,3-butenediol bis (allyl carbonate), 1,4-bute Diol 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 for a lens body and the sheet-shaped light-regulating body having at least one surface coated with a (meth) acrylate-based polymerizable composition can be performed by a very general casting polymerization method.
That is, it is used by using a glass mold having such a structure that the polymerizable composition for a lens body can be injected from at least one of the upper and lower sides of the sheet-like light-regulating body on which the (meth) acrylate-based polymerizable resin layer is laminated. The polymerization may be performed under conditions suitable for the polymerizable composition.
Therefore, in the case of a sheet-shaped light control body in which a (meth) acrylate-based polymerizable resin layer is laminated on one side, only the coated surface of the sheet-shaped light control body may be integrated with the lens body polymerizable composition. Even if both sides of the surface laminated with the (meth) acrylate polymerizable resin layer of the sheet-like light control body and the surface on which the sheet-like light control body is exposed are integrated with the polymerizable composition for a lens body Good. In addition, in the case of a sheet-shaped light control body in which a (meth) acrylate-based polymerizable resin layer is laminated on both sides, the both surfaces are usually integrated with the polymerizable composition for a lens body, but only one side is integrated. May be used.

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

  Specific examples of the plastics light control lens body of the present invention include, for example, plastics light control lenses, plastics light control lens windows for automobiles and houses, light control lens windows, sun visors, ski goggles, airplanes and motorcycles. Windshield etc. can be mentioned. Among these, it is preferable to use as a plastics light control lens.

The significance of the “sheet-shaped light control body having at least a light control sheet” in the plastic light control lens body of the present invention is “at least the light control sheet in the method of manufacturing a plastics light control lens body according to the first aspect of the present invention. This is the same as the significance of the “sheet-shaped light control body having a”.
Further, the meaning of “lamination of (meth) acrylate resin layer on at least one surface” is “(meth) acrylate polymerizable composition on at least one surface” in the method for producing a plastics light control lens body according to the first invention of the present invention. This is the same as the meaning of the “coating film depending on the object” 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.
In addition, “(meth) acrylate-based” and “sheet-shaped dimmer” also have the same significance as in the first invention.

FIG. 1 schematically shows an example of a plastics light control lens body when the sheet light control body in the plastic light control lens body of the present invention is a light control laminate.
In FIG. 1, the transparent sheet 2 adhere | attaches on both surfaces of the light control sheet 1, and the sheet-like light control body which is a light control laminated body is formed. The (meth) acrylate resin layer 3 is coated on both surfaces of the sheet-like light control body. Furthermore, a plastics light control lens body is formed by laminating a polymerizable resin layer 4 for a lens body on these (meth) acrylate resin layers.

The coated sheet-shaped light control body according to the third aspect of the present invention is a coated sheet-shaped light control body suitable for manufacturing a plastics light control lens body including a sheet-shaped light control body having at least a light control sheet. The (meth) acrylate-based polymerizable composition film is formed on at least one surface of the sheet-like light control body.
The coated sheet-like light control body of the present invention is manufactured by coating a surface of a very general light control laminate or by pasting a transparent film whose surface has been previously coated to the light control laminate. It is possible to manufacture very easily. Since the plastics light control lens body of the present invention can be obtained by performing cast polymerization using the coated sheet-like light control body as it is, it is useful as an intermediate product of the plastics light control lens body of the present invention. is there.
It is preferable that the sheet-like light control body in the coated sheet-shaped light control body of the present invention is a light control laminate comprising a light control sheet and a transparent sheet that covers at least one surface of the light control sheet.

The significance of the “sheet-shaped light control body having at least a light control sheet” in the coated sheet-shaped light control body of the present invention is “at least light control in the manufacturing method of the plastics light control lens body according to the first aspect of the present invention. This is the same as the meaning of the “sheet-shaped light control body having a sheet”.
In addition, the meaning of “lamination of (meth) acrylate-based polymerizable composition film on at least one surface” means “(meth) acrylate-based on at least one surface” in the method for producing a plastics light control lens body according to the first invention of the present invention. The meaning is the same as that of the “coating film by the polymerizable composition”.
In addition, “(meth) acrylate-based” and “sheet-shaped dimmer” also have the same significance as in the first invention.

As a specific example of the light control laminate in the coated sheet-like light control body of the present invention, for example, a general light control laminate such as a light control film sandwiched on both sides with triacetyl cellulose is exemplified. be able to.
In addition, as described above, after the light control sheet is prepared by a normal method, both sides are laminated in a sandwich shape with an optical transparent resin typified by an alicyclic polyolefin-based resin film such as ARTON, ZEONOR, and APEL. You can also.

  When one example of the light control laminated body of this invention is typically shown in a figure, the light control sheet 1 except the polymeric resin layer 4 for lenses and the (meth) acrylate type resin layer 3 in FIG. 1, transparent The laminated body which consists of a sheet | seat 2 is mentioned.

The present invention also provides a coated sheet-shaped light control in which a (meth) acrylate-based polymerizable composition film is formed on at least one surface of the sheet-shaped light control body and is coated with the (meth) acrylate-based polymerizable composition. It is a covering sheet used for manufacturing a body, and is a covering sheet formed by coating a (meth) acrylate polymerizable composition on one side of a transparent sheet.
The coated sheet of the present invention is very useful because the coated sheet-shaped light control body can be obtained simply by adhering the cover sheet to a sheet-shaped light control body such as an existing light control sheet.
Specifically, as mentioned above, a so-called polyurethane light control sheet used for injection molding is used as a light control sheet, and a coated sheet whose surface is coated with a (meth) acrylate polymerizable composition is mentioned. Can do. In the case of a polyurethane light control sheet, heat resistance is high and 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 the appearance of the plastic light control lenses manufactured in the following Examples and Comparative Examples, and to measure and calculate the transmittance, the color development speed, and the decoloration speed.
(A) External appearance observation The external appearance of the plastics light control lens was observed by visual judgment.
(B) Transmittance In a constant temperature layer adjusted so that the sample becomes 23 ° C., the irradiance of a xenon lamp (SUPERCURE-203S, manufactured by SAN-EI ELECTRIC) is 25 W / m ² (315 mm to 400 nm) on the sample surface. (Integrated value at wavelength) is irradiated, and the visible light average transmittance (T2) 7 minutes after the start of irradiation and the visible light average transmittance (T1) without irradiation are measured with a spectrophotometer V It measured using -550 (made by JASCO Corporation).
(C) Color development speed and decoloration speed The transmittance of the wavelength that exhibits the minimum transmittance in the visible light region at the time of light irradiation is t2, the wavelength at the time of non-irradiation of the wavelength is t1, Asked.
Color development speed: time for the transmittance to change from t1 to (t1 + t2) / 2 Decoloring speed: time for the transmittance to change from t2 to (t1 + t2) / 2

<Example 1 to Example 3>
(A) Production of polymerizable composition containing photochromic compound (1) (light control sheet raw material in the present invention) NCO group equivalent weight (here, “equivalent weight” means an average molecular weight per functional group) 15 g of polyurethane prepolymer (obtained by reacting diphenylmethane-4,4′-diisocyanate and polypropylene glycol having an average polymerization degree of 15) with 15 g of organic solvent (4.636 g of toluene, methyl ethyl ketone 1). 4- [4- [6- (4-morpholinyl) -3-phenyl-3H-naphtho (2,1-b)] as a photochromic compound in a solution diluted with 13.58 g of .745 g and ethyl acetate 7.2 g). [Pyran-3-yl] phenyl] -morphine (trade name Reversol Flame, James Robin) on LTD) (0.075 g) and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 0.453 g and 3,9-bis [1,1-di-methyl as additives -2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxoxaspiro [5,5] undecane After stirring until uniform, a curing agent having a hydroxyl equivalent weight of 630 (obtained by reacting tolylene diisocyanate and polypropylene glycol. Trade name: BHS6020C: manufactured by Toyo Morton Co., Ltd.) 6 g was added and further stirred.

(B) Transparent film (2) (transparent sheet in the present invention)
A polycarbonate sheet (trade name: Iupilon, manufactured by Mitsubishi Gas Chemical Co., Inc.) having a thickness of 300 μm was used as the transparent film (2).

(C) (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.

(D) Transparent sheet (2) showing the polymerizable composition (1) containing the photochromic compound obtained in the production (a) of the light control laminate coated with the (meth) acrylate-based composition (2) ) Using a doctor blade (manufactured by Yoshimitsu Seiki Co., Ltd.) having a clearance of 200 μm. Thereafter, the mixture was placed in a 60 ° C. hot air dryer for 10 minutes to volatilize the solvent. After laminating another transparent sheet (2) similar to the above on the coating film, it was heat-cured at 70 ° C. for 2 days. Thus, the laminated body which consists of a thermosetting polyurethane resin layer containing the photochromic compound interposed between two transparent sheets and this sheet | seat was obtained.
A (meth) acrylate composition (3) is applied to the outermost layer on one side of this laminate using a bar coater # 24, and a polyethylene film (50 μm, manufactured by Toray Synthetic Film Co., Ltd.) is applied thereon, and the polyethylene Ultraviolet rays were irradiated from above the film under the condition of 2200 mJ / cm ² .
The same treatment was performed on the other surface. It was confirmed that the thickness of both coating surfaces after curing was 6 to 8 μm.

(E) Manufacture of a plastics light control lens by cast polymerization (e-1) Bending of a coated light control laminate (e-1) Bending of a photochromic laminate (d) The laminate obtained in (d) Was punched out into a circle and vacuum-molded in an atmosphere of 140 ° C. and 3 mmHg over 5 minutes to obtain a lens-shaped bent product having a radius of curvature R = 87.2 mm.

(E-2) Cast polymerization (e-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 polymerizable composition for a lens body comprising 39.55 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), 30.45 parts by weight of metaxylylene diisocyanate and 0.035 parts by weight of dibutyltin dilaurate is formed on the top and bottom of the processed product. After injection, the temperature was raised from 30 ° C. to 100 ° C. at a rate of 3.5 ° C./hour, further raised from 100 ° C. to 120 ° C. at a rate of 20 ° C./hour, and then kept at 120 ° C. for 3 hours. Polymerization was carried out under the following conditions.
A lens with good transparency in which the light control laminate and the lens base material were firmly integrated was obtained. The color tone of the obtained lens is not significantly changed visually even when compared with the sheet before polymerization, and the photochromic characteristics (appearance, transmittance, contrast, response speed) are also evaluated in the spectrophotometer. As shown in Table 1, it was confirmed that the properties of the laminate were retained and good.

(E-2-2) Cast Polymerization Using Episulfide Polymerizable Composition As a polymerizable composition for a lens body, 95 parts by weight of bis (β-epithiopropyl) sulfide, bis (2-mercaptoethyl) sulfide 5 Part by weight and 0.05 part by weight of tetra-n-butylphosphonium bromide were mixed and prepared.
As polymerization conditions, the temperature was increased from 20 ° C. to 100 ° C. at a rate of 4 ° C./hour, and further from 100 ° C. to 120 ° C. at a rate of 20 ° C./hour, and then maintained at 120 ° C. for 3 hours. Except for this, the same operation as in (e-2-1) was performed.
Also in this case, a good lens was obtained, and it was confirmed that the photochromic characteristics were good as shown in Table 1.

(E-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 prepared.
As the polymerization conditions, (e-2-2) 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 1) was performed.
Also in this case, a good lens was obtained, and it was confirmed that the photochromic characteristics were good as shown in Table 1.

<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, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (polymerization initiator, product name: Darocur 1173, manufactured by Ciba Specialty Chemicals) (meth) acrylate using 3 parts by weight A system polymerizable composition was prepared (urethane acrylate system 2).
Otherwise, the same operations as in Examples 1 to 3 were performed, and cast polymerization was performed using a thiourethane-based polymerizable composition, an episulfide-based polymerizable composition, and CR-39 (Examples 4 to 5). Example 6). The coating thickness of the outermost layer of the obtained light control laminate was 5 to 8 μm.
A good lens was obtained in any combination with the polymerizable composition for a lens body, and the optical characteristics of each lens were good as shown in Table 1.

<Example 7 to Example 9>
48 parts by weight of PO-modified neopentyl glycol diacrylate (manufactured by Sannopco, trade name: Photomer 4127-SN), 49 parts by weight of trifunctional urethane acrylate oligomer (manufactured by Daicel UCB, trade name: Ebecryl 264), benzophenone (polymerization initiator, A (meth) acrylate polymerizable composition composed of 3 parts by weight (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared (urethane acrylate 3).
As a photochromic compound, Reversesol Midnight Gray (trade name, manufactured by James Robinson LTD) was used.
The other operations were performed in exactly the same manner as in Examples 3 to 3, and cast polymerization was performed using a thiourethane-based polymerizable composition, an episulfide-based polymerizable composition, and CR-39 (Examples 7 to Examples). 9). The coating thickness of the outermost layer of the obtained light control laminate was 5 to 8 μm.
A good lens was obtained in any combination with the polymerizable composition for a lens body, and the optical characteristics of each lens were good as shown in Table 1.

<Example 10 to Example 12>
Using urethane acrylate paint UT-001 (manufactured by Nippon B Chemical Co., Ltd.) as a (meth) acrylate composition (urethane acrylate system 4), as a photochromic compound, Reversesol Midnight Gray (trade name, manufactured by James Robinson LTD) Except for use, the same operation as in Example 3 was performed. The coating thickness of the outermost layer of the obtained light control laminate was 7 to 9 μm.
A good lens was obtained in any combination with the polymerizable composition for a lens body, and the optical characteristics of each lens were good as shown in Table 1.

<Example 13 to Example 15>
PO modified neopentyl glycol diacrylate (manufactured by Sannopco, trade name: Photomer 4127-SN) 45 parts by weight, tetrafunctional polyester acrylate oligomer Ebecryl 80 (manufactured by Daicel UCB) 30 parts by weight, trifunctional urethane acrylate oligomer Ebecryl 264 (manufactured by Daicel UCB) A (meth) acrylate polymerizable composition comprising 20 parts by weight and 5 parts by weight of benzophenone (polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) was prepared (polyester acrylate type).
As a photochromic compound, 6 ′-(2,3-dihydro-1H-indol-1-yl) -1,3-dihydro-3,3-dimethyl-1-propyl-spiro (2H-indole-2,3′- [3H] -naphtho- (2,1-b)-(1,4) oxazine) (trade name: Reversesol Storm Purple, manufactured by James Robinson LTD) was used.
The other operations were the same as those in Examples 3 to 3. The coating thickness of the outermost layer of the obtained light control laminate was 7 to 9 μm.
A good lens was obtained in any combination with the polymerizable composition for a lens body, and the optical characteristics of each lens were good as shown in Table 1.

<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-hydroxy-2-methyl-1-phenyl-propan-1-one (polymerization initiator manufactured by Ciba Specialty Chemicals, trade name: Darocur 1173) ) An acrylate polymerizable composition was prepared (epoxy acrylate).
As a photochromic compound, 6 ′-(2,3-dihydro-1H-indol-1-yl) -1,3-dihydro-3,3-dimethyl-1-propyl-spiro (2H-indole-2,3′- [3H] -naphtho- (2,1-b)-(1,4) oxazine) (trade name: Reversesol Storm Purple, manufactured by James Robinson LTD) was used.
The other operations were the same as those in Example and Example 3. The coating thickness of the outermost layer of the obtained light control laminate was 7 to 10 μm.
A good lens was obtained in any combination with the polymerizable composition for a lens body, and the optical characteristics of each lens were good as shown in Table 1.

<Example 18>
(E-) of Example 1 except that a fluorene polyester resin OKP4 film (manufactured by Osaka Gas Chemical Co., Ltd .: a resin was press-molded at 280 ° C. to prepare a sheet of about 200 μm) was used as the transparent sheet. A thiourethane resin lens was produced under the same conditions as in 2-1). It was confirmed that the photochromic characteristics of the obtained lens were good as shown in Table 1.

<Example 19>
As a transparent sheet, a TAC film (manufactured by Konica Minolta Opto Co., Ltd., thickness: 80 μm) was used under the same conditions as in (e-2-2) of Example 1 except that the bending temperature was 95 ° C. An episulfide resin lens was produced. It was confirmed that the photochromic characteristics of the obtained lens were good as shown in Table 1.

<Example 20>
Thiourethane under the same conditions as (e-2-1) of Example 1 except that APEL (APL6509T, manufactured by Mitsui Chemicals, Inc., thickness: 200 μm) was used as the transparent film and the bending temperature was 80 ° C. A resin lens was prepared. It was confirmed that the photochromic characteristics of the obtained lens were good as shown in Table 1.

<Comparative Example 1>
A light control laminate was produced in the same manner as in Example 1.
Bending was performed in the same manner as in (e-1) of Example 1 without treating the surface of this laminate, and an episulfide resin lens molding was attempted in the same manner as in (e-2-2) of Example 1. .
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 9 was performed, and an episulfide resin lens molding was attempted in the same manner as in Example 1 (e-2-2) without any treatment on the surface of the TAC.
The polymerizable resin as the lens substrate and the TAC film did not adhere.

<Comparative Example 3>
The same operation as in Example 10 was performed without any treatment on the surface of APEL. A thiourethane resin lens molding was attempted in the same manner as in Example 1 (e-2-1).
The polymerizable resin as the lens substrate and the apel did not adhere.

<Comparative example 4>
The same operation as in Example 8 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 manufacturing a plastics light control lens body according to the present invention is useful for manufacturing a plastics light control lens body using a very wide range of lens base materials, and is simple and has high productivity. . In the plastics light control lens body obtained by this manufacturing method, the optical characteristics of the light control sheet used are not impaired, and in particular, the photochromic characteristics are less dependent on the properties of the lens substrate, and are responsive to many lens materials. A plastics light control lens body having excellent properties and contrast can be provided.

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

Explanation of symbols

1 Light control sheet 1
2 Transparent sheet 2
3 (Meth) acrylate resin layer 3
4 Polymerizable resin layer 4 for lens body

Claims (7)

A method for producing a plastics light control lens body by a casting polymerization method using a sheet-shaped light control body having at least a light control sheet,
A lens-shaped polymerizable composition used for the casting polymerization is a thiourethane-based polymerizable compound and an episulfide-based polymerization, which uses a sheet-like light-regulating body coated with a (meth) acrylate-based polymerizable composition on at least one side. A method for producing a plastics light control lens body, comprising at least one selected from a functional compound.   The method for producing a plastics light control lens body according to claim 1, wherein the (meth) acrylate-based polymerizable composition has ultraviolet curability.   The (meth) acrylate-based polymerizable composition is at least one 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 light control lens body according to claim 1 or 2, which is a seed.   The method for producing a plastics light control lens body according to any one of claims 1 to 3, 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 light control lens body according to any one of claims 1 to 4, wherein the sheet-shaped light control body is a light control laminate.   6. The method of manufacturing a plastics light control lens body according to claim 5, wherein the light control laminate includes a light control sheet and a transparent sheet that covers at least one surface of the light control sheet.   The plastics light control lens body according to claim 6, wherein the transparent sheet is formed of at least one selected from polycarbonate resin, cellulose resin, alicyclic polyolefin resin, and polyester resin. Manufacturing method.

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