JP5065511B2 - Polarizing molded body and method for producing the same - Google Patents

Description

  The present invention relates to a technique for providing a polarizing base material incorporating a polarizer and having a high impact strength, for example, a lens base material used for impact-resistant goggles, sunglasses, and prescription sunglasses.

  Goggles and glasses used in sports fields such as skiing, snowboarding, ice skating, yachting, boating, motorcycles, motorcycles, and general industrial fields such as construction and civil engineering are used to prevent glare from direct light, reflected light, wind Used for the purpose of protecting eyes from snow, rain, seawater, water, sand, chemicals and foreign substances. Further, general-purpose sunglasses and sunglasses with prescription are used for the purpose of preventing glare caused by light rays and reflected light.

  Conventionally, there has been a polarizing glass lens in which both surfaces of a polarizer sheet are covered with glass, and a polarizing plastic lens, for example, a polarizing CR-39 lens, which is cast by inserting the polarizer sheet into a mold.

  Also known is an optical composite molded article in which a polarizing plate having a laminated structure in which a polarizer sheet is sandwiched between two polycarbonate sheets is inserted into a mold, and further, injection-molded so that the polycarbonate resin layer is thermally bonded to the polycarbonate sheet. (JP-A-8-52817).

The polarizing glass lens sheet in which both surfaces of the above-described polarizer sheet are covered with glass has a tendency to break due to being a glass substrate, and lack of workability due to the substrate being difficult to deform.

  In addition, a polarizing plastic lens cast by inserting a polarizer sheet into a mold requires technology to incorporate the polarizer sheet into the mold, and the polarizer sheet shrinks due to long-term heat received during casting. In addition, there was a problem that the polarization performance deteriorated due to thermal decomposition.

  Further, as shown in JP-A-8-52817, an optical composite molded product obtained by insert injection molding so that the polycarbonate resin layer is thermally bonded to the outermost polycarbonate sheet of the polarizing plate includes a polarizing plate and a resin layer. Since the heat at the time of molding is transmitted straight to the polarizing plate, the polarization performance is degraded due to the shrinkage and thermal decomposition of the polarizer sheet, as in the case of cast molding.

  The technical means of the present invention for solving the above technical problem is a polarizing molded article having a laminated structure including a polarizing plate in which a polarizer sheet layer is sandwiched between two protective sheet layers, the protective sheet layer having one layer. And the polyurethane sheet layer or the polyamide sheet layer are bonded with an adhesive or a pressure-sensitive adhesive, and the polyurethane sheet layer or the polyamide sheet layer and the thermoforming resin layer are thermally bonded.

  Another technical means of the present invention is that the polyurethane sheet layer is a polyether polyurethane sheet or a polyester polyurethane sheet.

  Another technical means of the present invention is that the polyamide sheet layer is a transparent polyamide sheet.

  Another technical means of the present invention is that the thermoforming resin layer is a resin that can be thermally bonded to a polyurethane sheet layer or a polyamide sheet layer selected from the group consisting of polyamide, thermoplastic polyurethane, and polycarbonate.

  Another technical means of the present invention is that the polyamide is a transparent polyamide.

  According to another technical means of the present invention, at least one of the surfaces of the polarizing molded body is at least one of a functional surface-treated film selected from the group consisting of a hard coat, antireflection, antifogging, antifouling, and mirror. It is in being covered with.

  Another technical means of the present invention is that the polarizing molded article is an optical lens.

  According to another technical means of the present invention, a polarizing plate having a structure in which a polarizer sheet layer is sandwiched between two protective sheet layers is prepared in the first stage, and a protective sheet layer 1 for polarizing plate is prepared in the second stage. Preparing a polarizing composite in which a polyurethane sheet layer or a polyamide sheet layer is bonded to the layer with an adhesive or a pressure-sensitive adhesive, and in the third stage, the polarizing composite is hot press-molded into a spherical shape, and in the fourth stage, The thermoforming resin layer is formed by thermoforming the polyurethane sheet layer or the polyamide sheet layer having a spherical shape.

  According to another technical means of the present invention, there is provided a hot press molding machine for hot press molding a polarizing composite body into a spherical shape body, a planar cradle having a hole having a size in the plane direction of the spherical shape body, A structure that consists of a clamp that fixes the polarizing composite around the hole in the base, and a heatable anvil that has a shape equivalent to the size and curvature of a spherical body, and the anvil can be inserted into the cradle. In the third stage, when the spherical shaped body is hot-press molded from the polarizing composite, [Install the polarizing composite on the cradle-Fix the polarizing composite cradle by clamp-Insert the anvil And hot press molding-returning the anvil and clamp to their original positions-taking out the spherical shape body] is one cycle.

  According to another technical means of the present invention, when the polarizing composite is installed on the cradle, the polyurethane sheet layer or the polyamide sheet layer is disposed on the lower surface, and the polyurethane sheet layer or the polyamide sheet layer side is a spherical shaped body. Heat press molding is performed so as to be on the convex surface side, the resulting spherical shape body is inverted, and the spherical shape body is arranged so that the polyurethane sheet layer or the polyamide sheet layer is on the concave surface side.

  According to another technical means of the present invention, the insert injection molding machine has a curvature of the same degree as that of the spherical shape body, and is composed of a fixed side mold for fixing the spherical shape body and a movable side mold having an arbitrary curvature. In insert injection molding of the polarizing molded body in the fourth stage, the spherical shape body is placed and fixed on the fixed side mold so that the polyurethane sheet layer or polyamide sheet layer is inside the mold. The tightening of the moving side mold, the injection molding of the thermoforming resin layer, and the removal of the polarizing molded body are set to one cycle.

  According to the present invention, there are provided a polarizing molded article having a high degree of polarization and strong against impact, and a method for producing the same.

The polarizing plate used in the present invention will be described. The polarizing plate of the present invention has a laminated structure in which one polarizer sheet layer is sandwiched between two protective sheet layers.

  The polarizer sheet layer is a uniaxially stretched sheet that is stabilized, such as a uniaxially stretched sheet of a resin sheet such as polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, etc., having a regular sheet thickness of 0.1 mm or less, or a formalized product thereof. It is. Practically, the degree of polarization is 80% or more, preferably 95% or more.

  In order to obtain a high degree of polarization, the uniaxially stretched sheet is doped with iodine or a dichroic dye. As the polarizer sheet layer in the present invention, those prepared by any method of iodine doping method and dye doping method can be used.

  The iodine doping method using iodine is less likely to give a unique color to the polarizer sheet than the dye doping method using a dye and has a characteristic that a high degree of polarization is easily obtained, but has a disadvantage of poor heat resistance. is there. On the other hand, the dye doping method has higher heat resistance, but has a problem that a hue unique to the doping dye appears in the polarizer sheet.

  The protective sheet layer in the present invention is generally an extruded or cast sheet.

  The extruded protective sheet layer is preferably a highly transparent resin sheet, especially a thermoplastic resin sheet.

  The following are typical examples. Polycarbonate, polyamide, polyester, polyurethane, polystyrene, homopolymers such as methyl methacrylate and cyclohexyl methacrylate, acrylics including copolymers, vinyl chloride, polystyrene / methyl methacrylate, acrylonitrile / styrene, Examples include poly-4-methylpentene-1, a main chain hydrocarbon type having a main chain of an adamantane ring and a cyclopentane ring, and a cellulose type.

  As a protective sheet for the polarizer sheet layer, it is desirable that the optical anisotropy is as small as possible. For the purpose of reducing the formation of optical anisotropy, a resin having a low photoelastic coefficient, such as triacetyl cellulose, diacetyl cellulose, etc. JSR's "Arton", Zeon's "Zeonex", Mitsui Chemicals, which has propylcellulose such as acetylcellulose, tripropylcellulose and dipropylcellulose, polymethylmethacrylate, adamantane ring and cyclopentane ring as the main chain The main chain of “Apel” is a hydrocarbon-based resin, and polyamide is called transparent nylon or amorphous nylon, for example, “Grillamide TR-55”, “Grillamide TR-90”, manufactured by MMS, Polyus such as “Trogamide CX-7323” from Huls As Tan, highly transparent, such as Takeda birdies Chez Urethane Co. "ELASTOLLAN" 11 belonging to the type are preferably used. Among these, acyl cellulose resins such as acetyl cellulose and propyl cellulose are preferably used in the present invention because they are inexpensive.

  One way of extrusion is described. In the case of a polymer having a large photoelastic coefficient, the polymer melted and extruded from the horizontally long die is received by a gripping device or a traveling belt, or stretched in the longitudinal or lateral direction. There are a method of solidifying into a sheet form without stretching (T-die method) and a method of extruding resin in a balloon ball shape and solidifying (tubular method). The extrusion method has an advantage that a sheet can be prepared at low cost, but tends to be inferior to the cast method in terms of optical or appearance uniformity of the sheet.

  As a method for forming the protective sheet, it is preferable to adopt a casting method for the purpose of obtaining a uniform sheet with as little optical anisotropy as possible. Since the protective sheet of the cast molding method has no orientation, it is also preferable that it has no heat shrinkability. The reason is that, when forming the thermoforming resin layer of the polarizing molded body, the protective sheet does not shrink by heat, so that the polarizer sheet does not shrink and can maintain a high degree of polarization.

  In cast molding methods in which crosslinkable monomers such as diethylene glycol diallyl ether, diallyl phthalate and acrylic monomers are the main components, or polyurethane raw materials are cast between sheets or in sheet form, the hardness and barrier properties of the molded protective sheet Therefore, it can be used appropriately for the present invention. However, excessive cross-linking may reduce thermoformability.

  A solvent method casting method in which a preformed polymer is dissolved in a solvent, a plasticizer is added as necessary, cast into a sheet, and then the solvent is removed can form a protective sheet relatively inexpensively. For this purpose, it is preferable that the above-described resins have a property of being dissolved at a high concentration in a low boiling point solvent that can be easily removed.

  Resins suitable for the solvent casting method include acyl celluloses such as triacetyl cellulose, diacetyl cellulose, tripropyl cellulose, and dipropyl cellulose, “Arton” from JSR, which has an adamantane ring and a cyclopentane ring in the main chain, Japan The main chain hydrocarbons such as “Zeonex” from Zeon and “Apel” from Mitsui Chemicals, polycarbonate resins such as polybisphenol A carbonate, and polymethyl methacrylate resins are recommended. Of these, acetyl cellulose and propyl cellulose are preferable from the viewpoint of high transparency, easy coloring, and ease of sheet production.

  Regarding the solvent method cast molding method, one of the production methods is described. The polymer solution cast on a belt or a flat plate is subjected to dry desolvation by heating or decompression treatment, and is subjected to wet desolvation in a coagulation bath. Although it is made by a method, a dry desolvation method is preferable from the viewpoint of transparency and ease of production.

  A protective sheet formed by an extrusion molding method or a cast molding method is particularly preferably used having a thickness of about 0.01 to 1.5 mm, preferably about 0.02 to 1.2 mm. If the thickness is less than 0.01 mm, it is difficult to prepare the protective sheet itself. On the other hand, if the thickness exceeds 1.5 mm, the total thickness of the polarizing plate increases too much, and the thickness of the polarizing molded body increases. Furthermore, in the case of preparing by a solvent cast molding method, uniform desolvation becomes difficult, leading to a tendency to increase the manufacturing cost.

  The polarizing plate in the present invention is recommended to have a protective sheet layer attached to both surfaces of the polarizer sheet with an adhesive or a pressure-sensitive adhesive in such a manner as to sandwich the polarizer sheet layer. Both adhesives and pressure-sensitive adhesives require long-term durability against water, heat, light and the like, and are not particularly limited as long as they basically pass them.

  Examples of the adhesive include isocyanate, polyurethane, polythiourethane, epoxy, vinyl acetate, acrylic, and wax. Examples of the adhesive include vinyl acetate and acrylic.

  These adhesives or pressure-sensitive adhesives can be uniformly applied to a protective sheet or a polarizer sheet by a commonly used application method such as a gravure coating method or an offset coating method. The thickness of the adhesive layer or the pressure-sensitive adhesive layer is usually 0.1 to 100 μm, preferably 0.5 to 80 μm. When the thickness of the adhesive layer or the pressure-sensitive adhesive layer is less than 0.1 μm, the bonding force is low, and when it exceeds 100 μm, the adhesive or the pressure-sensitive adhesive may ooze out from the end face of the polarizing molded article.

  Each of the above sheets may be bonded by a method in which an adhesive or a pressure-sensitive adhesive is applied in advance or just before application, and then superimposed on each other directly from a roll or in a cut state, and a curing treatment is performed as necessary. Is possible.

  For the purpose of improving the bonding strength between the sheet layers by the adhesive layer or pressure-sensitive adhesive layer, the surface of the protective sheet or polarizer sheet is subjected to chemical chemical treatment with acid, alkali, etc., ultraviolet treatment, plasma or corona discharge treatment in advance. There is.

  The polarizing plate is usually a flat sheet.

  Next, a polyurethane sheet layer or a polyamide sheet layer for thermally bonding to the thermoformed resin layer will be described. In consideration of the thermal adhesiveness with the thermoformed resin layer, polyurethane and polyamide were optimal as the resin. In the present invention, the sheet layer used for this purpose is hereinafter simply referred to as a polyurethane sheet layer or a polyamide sheet layer.

  The polyurethane used for the polyurethane sheet layer is thermosetting or thermoplastic.

  In the case of thermosetting, a trifunctional or higher isocyanate compound or a compound having three or more hydroxyl groups in the molecule is partially used. In this case, the resulting sheet is excellent in hardness, barrier properties, and the like, but excessive crosslinking may cause a decrease in thermoformability and thermal adhesiveness with the thermoformable resin layer.

  Therefore, in this invention, it is preferable that it is a thermoplastic polyurethane polymerized mainly by the diisocyanate compound and the compound having two hydroxyl groups in the molecule.

  Diisocyanate compounds include tolylene diisocyanate (TDI), metaxylylene diisocyanate (MDI), diphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate, 1,5- Aromatic diisocyanates such as naphthalene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated TDI, and hydrogenated MDI. In the present invention, non-yellowing aliphatic diisocyanates are particularly preferably used.

  Examples of compounds having two hydroxyl groups in the molecule include polyether glycols such as polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, and ester glycols such as caprolactone, adipate, and copolyester. , Carbonate glycols, ethylene glycol, 1,3-propane glycol, 1,4-butane glycol, aliphatic glycols such as 1,6-hexane glycol, bisphenol A, ethylene oxide adduct of bisphenol A, bisphenol A And aromatic ring-containing glycols such as propylene oxide adducts.

  In the present invention, in particular, polyether glycols or polyester glycols are used because of non-yellowing, meltability, hydrolysis resistance, thermal adhesiveness with thermoforming resin layer, and amorphous (transparency). Is suitable.

  In addition, the polyurethane is particularly suitable for the present invention when the hardness measured by the JIS A method is 75 or more, preferably 80 or more. When the hardness is less than 75, the sheet is too soft and difficult to form.

  Examples of the polyurethane suitable for the present invention include 1180A, 1190ATR, 1195ATR, 1154D, 1164D, and 1174D belonging to “Elastolan” 11 type, which is a polyether-based polyurethane of Takeda Burdishurethane, and the polyester-based polyurethane of the company “ Examples include S80A, S85A, S90A, S95A, etc. belonging to Elastolan S type.

  The polyurethane sheet can be prepared by a cast molding method or an extrusion molding method. In the case of a cast molding method, a mixture of a compound having an isocyanate and a hydroxyl group is injected between the plates and polymerized, or cast into a sheet and polymerized. In the latter method, a solvent can be used, and the solvent is removed after casting into a sheet.

  Further, a solvent method cast molding method in which a preformed polymer dissolved in a solvent is cast into a sheet and desolvated can be used. In the case of a solvent having a relatively high boiling point such as dimethylformamide, a wet method is often applied. The cast molding method is suitable for obtaining a uniform sheet.

  The extrusion method is applied to thermoplastic polyurethane. Although a sheet can be obtained at a low cost, the optical anisotropy may increase or the appearance uniformity may be inferior.

  Polyamide used for the polyamide sheet layer includes diamine components such as hexamethylenediamine, m-xylyleneamine, bis (p-aminocyclohexyl) methane, 3,3-dimethyl-4,4-diaminodicyclohexylmethane, and trimethylhexamethylenediamine. There are polycondensates of dicarboxylic acid components such as adipic acid, dodecanedioic acid, isophthalic acid and terephthalic acid, and polycondensates of lactams such as caprolactam. Among these, transparent nylon or amorphous nylon, for example, “Grillamide TR-55”, “Grillamide TR-90” by Emus and “Trogamide CX-7323” by Huls have transparency. Since it is high and has little optical distortion, it is preferably used in the present invention.

  In general, a solvent casting method or an extrusion molding method is used for forming a polyamide sheet.

  The polyurethane sheet and the polyamide sheet thus formed are particularly preferably those having a thickness of about 0.01 to 1.5 mm, preferably about 0.02 to 1.2 mm. If the thickness is less than 0.01 mm, preparation of the sheet itself becomes difficult. On the other hand, when the thickness exceeds 1.5 mm, the thickness of the polarizing molded body increases. Furthermore, in the case of preparing by the solvent cast molding method, since uniform desolvation becomes difficult, the manufacturing cost tends to increase.

  In order to join one layer of the protective sheet of the polarizing plate and the polyurethane sheet or the polyamide sheet, a method of sticking the polyurethane sheet or the polyamide sheet to one side of the polarizing plate with an adhesive or an adhesive is recommended. Both adhesives and pressure-sensitive adhesives require long-term durability against water, heat, light and the like, and are not particularly limited as long as they basically pass them.

  Examples of the adhesive include isocyanate, polyurethane, polythiourethane, epoxy, vinyl acetate, acrylic, and wax. Examples of the adhesive include vinyl acetate and acrylic.

  These adhesives or pressure-sensitive adhesives are uniformly applied to the bonding surface of the polarizing plate, the polyurethane sheet or the polyamide sheet by a commonly used application method such as a gravure coating method or an offset coating method. The thickness of the adhesive layer or the pressure-sensitive adhesive layer is usually 0.1 to 100 μm, preferably 0.5 to 80 μm. When the thickness of the adhesive layer or the pressure-sensitive adhesive layer is less than 0.1 μm, the bonding force is low, and when it exceeds 100 μm, the adhesive or the pressure-sensitive adhesive may ooze out from the end face of the polarizing molded article.

  A method in which a polarizing plate and a polyurethane sheet or polyamide sheet are coated with an adhesive or a pressure sensitive adhesive in advance or just before being applied, and then overlap each other directly from a roll or in a cut state, and a curing treatment is performed if necessary. Can be joined.

  The surface of the polarizing plate, polyurethane sheet, and polyamide sheet is preliminarily subjected to chemical chemical treatment with acids, alkalis, ultraviolet treatment, plasma or corona discharge treatment for the purpose of improving the bonding strength between the layers by the adhesive layer or the adhesive layer. Sometimes.

  The joined body of the polarizing plate and the polyurethane sheet or polyamide sheet used in the present invention is hereinafter referred to as a polarizing composite. The polarizing composite is usually in the form of a flat sheet.

  The polarizing molded body in the present invention is often used in a lens shape. For such a purpose, either side of the light-polarizing shaped product is made to have a convex shape. In order to thermally bond the thermoforming resin layer to the polyurethane sheet layer or the polyamide sheet layer of the polarizing composite, the surface of the polarizing molded body of the present invention has a protective sheet layer with a polarizing plate on one side and a thermoforming resin layer on the other side. become.

  In the case of molding into a lens shape, it is easy in terms of molding technology to perform thermoforming so that the protective sheet layer side is convex and the thermoforming resin layer side is concave, flat, or convex.

  To form a convex shape on the protective sheet layer side inevitably means to form a spherical shape in which the protective sheet layer side of the polarizing composite has a convex shape and the polyurethane sheet layer or polyamide sheet layer side has a concave shape. In general, it is recommended that such a shaped body is heat-shaped into a spherical shape in advance before the thermoforming resin layer is thermally bonded.

  A case where a hot press molding apparatus is used will be described below as a method for thermally shaping the polarizing composite as described above.

  A hot press molding apparatus is generally composed of a movable mold and a fixed mold. If one of the movable mold and the fixed mold is male, the other has a female shape, and a polarizing composite is sandwiched between the two shapes, and the two shapes are combined. Perform hot pressing and shaping.

Regarding the hot press method, there are the following combinations depending on the mold shape and the presence or absence of heating.
Case 1 When a male mold is pressed against a polarizing composite to form a spherical shape. The male tip has a spherical shape for which shaping is desired, and that portion is heated. A spherical female die is not necessarily required as the fixed die.
Case 2 When forming a spherical body with a female type. The female concave surface has a spherical shape desired to be shaped, and the portion is heated. Although a male type is necessary, the shape of the tip may be a rubber-like deformable one. Male heating is not always necessary.
Case 3 When molding a spherical body with both male and female molds. The male tip and the female concave surface have a spherical shape for which shaping is desired, and at least one of them is heated.

  The present invention can be applied to any of the above methods, but the case 1 is particularly preferably used because of the appearance and reproducibility of the molded body. Among them, the hot press molding machine includes a planar cradle having holes about the size of the spherical body in the plane direction, a clamp for fixing the polarizing composite around the hole on the cradle, and a spherical shape. It is composed of a heatable anvil having a tip shape corresponding to the size and curvature of the body in the plane direction, and has a structure in which the anvil can be fitted into the cradle.

  In order to obtain a uniform spherical body, the holes in the hot press are generally circular. The clamp is generally ring-shaped and fixes the polarizing complex concentrically in the hole.

  Here, the cradle and the anvil correspond to molds, one of which is a movable mold and the other is a fixed mold. However, in the present invention, when the anvil is a movable mold, the mechanical structure is further simplified. This is preferable because it is possible.

  The anvil corresponds to a male type, and its tip is manufactured so as to have a curvature of a spherical shape desired to be shaped. In addition, a mechanism that can be heated to a certain temperature by a heater or a heating medium is incorporated.

  In this case, there is nothing equivalent to a female type, and a polarizing composite is formed by a flat cradle having a hole about the size of a spherical shape body and a ring-shaped clamp fixed concentrically around the hole. Then, the anvil is pressed against the polarizing composite, and then hot press-molded into a desired spherical shape by a method of fitting into the hole of the cradle.

  The temperature of the anvil is preferably higher than the glass transition temperature of the sheet layer that plays the role of imparting formability in the sheet layer constituting the polarizing composite. Generally, it is about 90-200 degreeC. After the hot press molding, for example, a cooling operation such as blowing air on the spherical shape body may be performed.

  When performing hot press molding, the operation procedure is as follows: [Polarizing composite is placed on cradle-Fixing the polarizing composite cradle by clamp-Anvil insertion and hot press molding-Anvil and clamp in their original positions] "Return-taking out spherical shape body" is one cycle.

  The polarizing composite before hot press molding is usually prepared with a large sheet having the direction of polarized light aligned in a certain direction. In that state, since it is too large to be easily placed on the cradle and is not suitable for economic efficiency, it is generally performed in advance by a punching device. In that case, in order to know the direction of the polarized light after the cut, it is convenient to perform the subsequent operations if the cut polarizing composite is provided with a protrusion or notch mark indicating the direction of the polarized light. Is good.

Further, it may be arranged in the hot press apparatus so that either surface of the polarizing composite is on the concave shape side. For example, if the polyurethane sheet layer or the polyamide sheet layer is disposed on the concave shape side, the completed spherical shape body is used as it is. If it arrange | positions so that the protection sheet layer side may come to the concave shape side, the spherical-shaped body completed will be reversed and it will be used so that a polyurethane sheet layer or a polyamide sheet layer may come to the concave shape side.

  When using acylcelluloses such as triacetylcellulose, diacetylcellulose, tripropylcellulose, and dipropylcellulose as the protective sheet, the protective sheet layer side should be the heating surface for smooth thermoforming into a spherical shape. It is recommended that the polarizing composite be placed in a hot press. For example, when the case 1 is employed, the protective sheet layer side made of acylcellulose is arranged so as to be on the concave shape side, the resulting spherical shape body is inverted, and the polyurethane sheet layer or the polyamide sheet layer is on the concave shape side. Arrange the spherical shape body.

  In addition, after hot press molding, it is common practice to cut and remove unnecessary portions on the periphery of the spherical shaped body with a punching device. Also in this case, in order to understand the direction of the polarized light after the cut, it is convenient for performing the subsequent operations if the cut spherical shape body is provided with a projection or a notch mark indicating the direction of the polarized light. Is good.

  Next, the thermoformed resin layer in the present invention will be described. What is suitably used as the thermoforming resin layer is polyamide-based, polyurethane-based, polyester-based, polycarbonate-based, polystyrene-based, homopolymers such as methyl methacrylate and cyclohexyl methacrylate, acrylic-based including copolymers, vinyl chloride-based, Thermoplastics such as polystyrene / methyl methacrylate, acrylonitrile / styrene, poly-4-methylpentene-1, main chain hydrocarbons having an adamantane ring or cyclopentane ring as the main chain, and celluloses typified by triacetyl cellulose Resin.

In the present invention, any thermoplastic resin that can be thermally bonded to the polyurethane sheet layer or the polyamide sheet layer of the polarizing composite is not particularly limited.
Particularly preferred thermoforming resins for the thermoforming resin layer are polyamide, thermoplastic polyurethane, and polycarbonate because of their thermal adhesiveness, optical homogeneity, transparency, impact resistance, thermoformability, and the like.

  Polyamides include diamine components such as hexamethylenediamine, m-xylyleneamine, bis (p-aminocyclohexyl) methane, 3,3-dimethyl-4,4-diaminodicyclohexylmethane, trimethylhexamethylenediamine, adipic acid, dodecane There are polycondensates of dicarboxylic acid components such as acids, isophthalic acid and terephthalic acid, and polycondensates of lactams such as caprolactam. Among these, transparent nylon or amorphous nylon, for example, “Grillamide TR-55”, “Grillamide TR-90” by Emus and “Trogamide CX-7323” by Huls have transparency. It is suitable for the present invention because of its high optical distortion.

  The thermoplastic polyurethane is preferably a thermoplastic polyurethane polymerized mainly with a diisocyanate compound and a compound having two hydroxyl groups in the molecule.

  Diisocyanate compounds include tolylene diisocyanate (TDI), metaxylylene diisocyanate (MDI), diphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate, 1,5- Aromatic diisocyanates such as naphthalene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated TDI, and hydrogenated MDI. In the present invention, non-yellowing aliphatic diisocyanates are particularly preferably used.

  Examples of compounds having two hydroxyl groups in the molecule include polyether glycols such as polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, and ester glycols such as caprolactone, adipate, and copolyester. , Carbonate glycols, ethylene glycol, 1,3-propane glycol, 1,4-butane glycol, aliphatic glycols such as 1,6-hexane glycol, bisphenol A, ethylene oxide adduct of bisphenol A, bisphenol A And aromatic ring-containing glycols such as propylene oxide adducts.

  In the present invention, those using polyether glycols are particularly suitable from the viewpoint of non-yellowing, meltability, hydrolysis resistance, thermal adhesiveness with a thermoformed resin layer, and amorphous (transparency).

  Polycarbonate includes polybisphenol A carbonate. In addition, 1,1′-dihydroxydiphenyl-phenylmethylmethane, 1,1′-dihydroxydiphenyl-diphenylmethane, 1,1′-dihydroxy-3,3′-dimethyldiphenyl-2,2-propane homopolymerized polycarbonate, These copolycarbonates are copolycarbonates with bisphenol A.

  In general, polycarbonate has a drawback that birefringence tends to increase. That is, optical anisotropy due to molding distortion and local orientation tends to occur inside the molded body. Therefore, when using polycarbonate in the present invention, it is important to prevent the formation of optical anisotropy as much as possible. As a countermeasure, the fluidity is high and it is difficult to receive excessive shearing force during molding, that is, residual strain. It is preferable to use a resin having a relatively low degree of polymerization, in which local orientation is difficult to occur. In the present invention, it is recommended to use a polycarbonate having a polymerization degree of 120 or less, more preferably a polymerization degree of 100 or less.

  The polyurethane sheet layer or polyamide sheet layer of the polarizing composite and the thermoforming resin layer need to be thermally bonded with a practical level of adhesive strength. Generally, when the molding temperature of the thermoforming resin layer is higher than the softening temperature of the polyurethane sheet layer or the polyamide sheet layer, the thermal adhesiveness of both tends to increase.

  The polarizing molded body of the present invention is particularly preferably a combination of a polyurethane sheet layer and a polyamide thermoforming resin layer, and a polyamide sheet layer and a polyamide thermoforming resin layer in view of transparency, solvent crack resistance, resin hardness, and adhesiveness. .

  Next, a method for thermally bonding the thermoformed resin layer to the polyurethane sheet layer or the polyamide sheet layer will be described by taking a thermoforming method as an example.

  Thermoforming refers to molding by pressing a hot-melted resin into a mold, such as compression molding, transfer molding, or injection molding. From the viewpoint of productivity and precision, the insert injection molding method as shown in Japanese Patent Application No. 10-49707 is basically preferable. That is, this is a method in which a polarizing composite having a surface to be thermally bonded facing inward is disposed on one surface of a mold, and a resin layer is injection-molded on that surface.

  In this case, since the polarizing molded body is often in the form of a lens, a spherical mold is used, and as described above, the polarizing composite has a convex surface with a spherical surface having substantially the same curvature as this mold. Often, the shape is hot press molded.

  In insert injection molding, in general, if the direction of the resin flowing from the gate is matched with the polarization main axis (polarizer orientation direction) of the spherical shaped body, a highly polarizable molded product can be obtained. Cheap. In particular, it is a preferable method in the case of a resin having high optical anisotropy. As a guide, projections and notch marks indicating the direction of polarized light provided on the spherical shape pair are utilized.

  In addition, if a mark indicating the direction of polarization (engraved, protruding, or retractable on the polarizing molded body) is also placed on the mold, the polarization direction of the polarizing molded body can be identified only from the appearance after molding. it can.

  Insert injection molding has the following operating procedure: [A spherical shape body is placed on the fixed side mold so that the polyurethane sheet layer or polyamide sheet layer is inside the mold, and fixed-clamping the moving side mold-thermoforming resin The cycle of injection molding of the layer-taking out the polarizing molded product] is defined as one cycle. When placing and fixing the spherical shape to the fixed mold, suction is performed through the suction hole provided in the fixed mold, and the spherical shape is sucked and fixed. In some cases, the molded body can be molded.

  An insert type injection compression molding method is preferred for applications that require particularly high precision, such as sunglasses, goggles, and correction lenses. In the injection compression molding method, after the resin is injected into the mold at a low pressure, the mold is closed at a high pressure and a compression force is applied to the resin. The resulting optical anisotropy is unlikely to occur. Further, by controlling the mold compression force uniformly applied to the resin, the resin can be cooled at a constant specific volume, so that a molded product with high dimensional accuracy can be obtained. This method is particularly preferably applied to a polycarbonate resin having a large birefringence.

  Assuming that the thickness of the polarizing composite in the present invention is A and the thickness of the thermoforming resin layer is B, A is a uniform thickness of about 0.03 mm to 3 mm in the entire region of the optical composite of the present invention. It is a thing of thickness. On the other hand, B may have a uniform thickness, or a lens with a degree of thickness that varies continuously from the center to the periphery, such as a minus power lens or a plus power lens. Usually, it is molded so that the thickness of B is at least about 1 mm, but this depends on the fluidity of the resin used for molding and the design of the polarizing molded body.

  The polarizing molded body in the present invention is preferably hard-coated on at least one of the surfaces. The hard coat may be any type of hard coat that is generally used, such as a thermosetting hard coat such as silane or epoxy, or an actinic ray curable hard coat such as acrylic or epoxy. Usually, it is applied with a film thickness of about 0.5 to 15 μm, but in some cases, for the purpose of improving adhesion, a hard coat process may be performed after coating a primer coat layer such as an acrylate type.

  Moreover, it is preferable that at least the surface of either side of the polarizing molded body in the present invention is antireflection processed. The antireflection processing is usually performed by depositing about 2 to 8 layers of inorganic films having different refractive indexes on adjacent hard layers on the hard coat by a vacuum deposition method or the like by a wet method. About three organic films are stacked with an optical film thickness.

  Moreover, it is preferable that at least the surface of either side of the polarizing molded body in the present invention is antifogged. In the antifogging process, a hydrophilic resin such as polyvinyl alcohol or polyvinylpyrrolidone is usually applied with a film thickness of about 1 to 50 μm. In the case of an acetyl cellulose resin, antifogging properties can be imparted by saponification of the surface.

  Moreover, it is preferable that at least the surface of either side of the polarizing molded body in the present invention is antifouling processed. The antifouling process is usually performed by vacuum deposition or wet method with several tens of nanometers of fluorine-based organic compounds for the purpose of preventing contamination by organic substances such as fingerprint stains on the antireflection film and facilitating wiping. To a thickness on the order of μm.

  Moreover, it is preferable that at least one of the surfaces of the polarizing molded body of the present invention is mirror processed. In mirror processing, a metal film such as aluminum, silver, gold, or platinum is usually applied on a hard coat by vacuum deposition or the like.

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[Example 1]
As a protective sheet layer, a TAC (triacetyl cellulose) sheet having a thickness of about 80 μm was used, and a polarizing plate (Sumitomo Chemical Co., Ltd.) was prepared in which a polarizer sheet having a thickness of about 40 μm was sandwiched between two TAC sheets. .
A polyether-based polyurethane “Elastolan 1195ATR” (Takeda Birdish Urethane Kogyo Co., Ltd.) (JIS A hardness 95) was used as the polyurethane sheet layer, and a sheet having a thickness of about 200 μm prepared by an extrusion molding method was prepared.
On one side, an acrylic adhesive “Cybinol AT-250” (Syden Chemical Co., Ltd.) was applied to a thickness of about 30 μm.
The polyurethane sheet was stuck on one side of the polarizing plate to prepare a polarizing composite.
Using this polarizing composite, a circular sheet having a diameter of 100 mm was punched with a punching device having a punching blade having a diameter of 100 mm. In this case, a small protrusion for indicating the direction of polarization is provided on a part of the punching blade, and the direction of polarization of the polarizing composite is set so as to coincide with this mark to obtain a circular sheet with small protrusions. Punched out. The sheet after punching was hot press-molded into a spherical shape body by the following method using the following hot press apparatus.
The hot press molding machine includes a flat cradle having a hole diameter of 84 mm, a ring-shaped clamp having an inner diameter of 88 mm for concentrically fixing the polarizing composite around the hole on the cradle, and a hole in the cradle. In addition, an apparatus composed of a heatable anvil having a diameter of 82 mm and a convex tip shape of 8C (curve) having a structure that can be fitted from the top was prepared.
Hot press molding was performed as follows. The polarizing composite was concentrically disposed on the hole of the hot press apparatus cradle so that the upper surface was a TAC protective sheet layer of a polarizing plate and the lower surface was a polyurethane sheet layer. The polarizing complex was fixed with a ring-shaped clamp. Subsequently, the anvil heated to 140 ° C. was inserted into the hole of the cradle from the top of the polarizing composite, and was hot press-molded so that the polarizing composite had an 8C spherical shape. The anvil was returned to its original position, the spherical shaped body was cooled, and then the ring-shaped clamp was returned to its original position. Thereafter, the spherical shape body of 8C was taken out from the cradle.
Unnecessary portions around the spherical shape body were cut and removed by a circular punching machine having a diameter of 77 mm. In this case as well, a small protrusion for indicating the direction of polarization is provided on a part of the punching blade, and the direction of polarization of the spherical shape body is set so as to coincide with this mark. It was punched out as a spherical body having a thickness of 77 mm, the convex side being a polyurethane sheet layer, and the concave side being a TAC protective sheet layer.
Thereafter, the resulting spherical shaped body was inverted so that the TAC protective sheet layer was on the convex side and the polyurethane sheet layer was on the concave side.
The polarizing molded body was prepared as follows.
The insert injection compression molding machine includes an 8C concave fixed side mold capable of fixing a spherical shape body and an 8C convex moving side mold.
Using this device, the obtained 8C spherical shaped body was set and fixed in a concave fixed mold. In this case, the spherical TAC protective sheet layer is in close contact with the stationary mold, and the polyurethane sheet layer is oriented toward the moving mold. Both the fixed side mold and the moving side mold were structured so that a small protrusion indicating the direction of polarized light was attached to a part of the periphery of the polarizing molded body.
The moving mold was fastened to the fixed mold, and a molding cavity was formed between the fixed mold and the moving mold.
As the thermoforming resin layer, transparent nylon “Grillamide TR-90” (MMS Co., Ltd.) in which a smoked dye was dissolved was used. The polarizing molded article was injection compression molded at a maximum temperature of 280 ° C., and the polyurethane sheet layer and the thermoformed resin layer were thermally bonded. Thereafter, the polarizing molded body was taken out from the insert injection compression molding machine.
The obtained polarizing molded body is an 8C plano lens having a thickness of 2.2 mm in which a TAC protective sheet is disposed on the convex side and a thermoformed resin layer of transparent nylon is integrally disposed on the concave side.
A silane hard coat film having a film thickness of about 2.5 μm was formed on both surfaces of the same product.
The resulting lens had a visible light transmittance of 20% measured at the center, and exhibited extremely tough mechanical properties. The degree of polarization was 98% or more.

[Example 2]
Except for using a sheet of about 200 μm thick prepared by an extrusion molding method of polyether polyurethane “Elastollan 1164D” (Takeda Burdish Urethane Kogyo Co., Ltd.) (JIS A hardness 95 or more) as a protective sheet layer. In the same manner as in Example 1, an 8C spherical body was prepared.
The spherical shaped body was fixed to the stationary mold of the insert injection compression molding machine in the same manner as in Example 1, and the moving mold was tightened in the same manner as in Example 1. As the thermoforming resin layer, uncolored transparent nylon “Trogamide CX-7323” (Daicel Huls) was used. The polarizing molded article was injection compression molded at a maximum temperature of 280 ° C., and the polyurethane sheet layer and the thermoformed resin layer were thermally bonded. Thereafter, the polarizing molded body was taken out from the insert injection compression molding machine.
Both the fixed side mold and the moving side mold were structured so that a small protrusion indicating the direction of polarized light was attached to a part of the periphery of the polarizing molded body.
The obtained polarizing molded body is an 8C semi-finished lens having a thickness of 13 mm in which a TAC protective sheet is disposed on the convex side and a thermoformed resin layer of transparent nylon is integrally disposed on the concave side.
The back surface of this lens was polished to produce a minus lens of −4.00 D (diopter) having a center thickness of about 2 mm.
After coating a silane hard coat with a film thickness of about 2.5μm on both sides of the same product, four layers of ZrO ₂ and SiO ₂ are alternately laminated with an optical film thickness by vacuum deposition on both sides. It was. Further, a fluorine-based antifouling film was applied on the antireflection film with a thickness of about 20 nm.
The resulting lens had a visible light transmittance of about 48% measured at the center, and exhibited extremely tough mechanical properties. The degree of polarization was 98% or more.

[Example 3]
The polarizing plate used in Example 1 was prepared.
As the polyamide sheet layer, a transparent nylon “grill amide TR-90” (EMS) sheet having a thickness of about 200 μm prepared by a solvent casting method was prepared.
On one side, the adhesive “Cybinol AT-250” used in Example 1 was applied to a thickness of about 30 μm. The transparent nylon sheet was attached to one side of the polarizing plate to prepare a polarizing composite.
Using this polarizing composite, a circular sheet having a diameter of 100 mm was punched with a punching device having a punching blade having a diameter of 100 mm. In this case, a small protrusion for indicating the direction of polarization is provided on a part of the punching blade, and the direction of polarization of the polarizing composite is set so as to coincide with this mark to obtain a circular sheet with small protrusions. Punched out.
The punched sheet was hot press-molded into an 8C spherical shape body by the following method using the same hot press apparatus as in Example 1.
The polarizing composite was concentrically disposed on the hole of the hot press apparatus cradle so that the upper surface was a TAC protective sheet layer of a polarizing plate and the lower surface was a transparent nylon sheet layer. The polarizing complex was fixed with a ring-shaped clamp. Subsequently, the anvil heated to 140 ° C. was inserted into the hole of the cradle from the top of the polarizing composite, and was hot press-molded so that the polarizing composite had an 8C spherical shape. The anvil was returned to its original position, the spherical shaped body was cooled, and then the ring-shaped clamp was returned to its original position. Thereafter, the spherical shape body of 8C was taken out from the cradle.
Unnecessary portions around the spherical shape body were cut and removed by a circular punching machine having a diameter of 77 mm. In this case as well, a small protrusion for indicating the direction of polarization is provided on a part of the punching blade, and the direction of polarization of the spherical shape body is set so as to coincide with this mark. It was punched out as a spherical body having a transparent nylon sheet layer on the convex surface side and a TAC protective sheet layer on the concave surface side at 77 mm.
Thereafter, the resulting spherical shaped body was inverted so that the TAC protective sheet layer was on the convex side and the transparent nylon sheet layer was on the concave side.
Using the same insert injection compression molding machine and mold as in Example 1, a polarizing molded body was prepared as follows.
The obtained 8C spherical shaped body was set and fixed in a concave fixed mold. In this case, the spherical TAC protective sheet layer is in close contact with the fixed mold, and the transparent nylon sheet layer is oriented toward the moving mold.
The moving mold was fastened to the fixed mold, and a molding cavity was formed between the fixed mold and the moving mold.
As the thermoforming resin layer, transparent nylon “Trogamide CX-7323” in which a smoked dye was dissolved was used. The polarizing molded article was injection compression molded at a maximum temperature of 280 ° C., and the transparent nylon sheet layer and the thermoformed resin layer were thermally bonded. Thereafter, the polarizing molded body was taken out from the insert injection compression molding machine.
The obtained polarizing molded body is an 8C plano lens having a thickness of 2.2 mm in which a TAC protective sheet is disposed on the convex side and a thermoformed resin layer of transparent nylon is integrally disposed on the concave side.
A silane hard coat film having a film thickness of about 2.5 μm was formed on both surfaces of the same product. Furthermore, a polyvinyl alcohol-based antifogging film was formed on the concave side.
The resulting lens had a visible light transmittance of 21% measured at the center, and exhibited extremely tough mechanical properties. The degree of polarization was 98% or more.

[Example 4]
As the protective sheet, a polycarbonate sheet having a thickness of about 170 μm prepared from a bisphenol-based polycarbonate resin was used. A polarizing plate (Plastic Plastics Co., Ltd.) was prepared by attaching and sandwiching a polarizer sheet having a thickness of about 40 μm via an adhesive layer having a thickness of about 20 μm between the two sheets. On one side, the polyurethane sheet with the pressure-sensitive adhesive used in Example 1 was pasted to prepare a polarizing composite.
Using this polarizing composite, a circular sheet having a diameter of 100 mm was punched with a punching device having a punching blade having a diameter of 100 mm. In this case, a small protrusion for indicating the direction of polarization is provided on a part of the punching blade, and the direction of polarization of the polarizing composite is set so as to coincide with this mark to obtain a circular sheet with small protrusions. Punched out.
The punched sheet was hot press-molded into an 8C spherical shape body by the following method using the same hot press apparatus as in Example 1.
The polarizing composite was concentrically disposed on the hole of the hot press apparatus cradle so that the upper surface was a polyurethane sheet layer and the lower surface was a polycarbonate protective sheet layer of a polarizing plate. The polarizing complex was fixed with a ring-shaped clamp. Subsequently, the anvil heated to 140 ° C. was inserted into the hole of the cradle from the top of the polarizing composite, and was hot press-molded so that the polarizing composite had an 8C spherical shape. The anvil was returned to its original position, the spherical shaped body was cooled, and then the ring-shaped clamp was returned to its original position. Thereafter, the spherical shape body of 8C was taken out from the cradle.
Unnecessary portions around the spherical shape body were cut and removed by a circular punching machine having a diameter of 77 mm. In this case as well, a small protrusion for indicating the direction of polarization is provided on a part of the punching blade, and the direction of polarization of the spherical shape body is set so as to coincide with this mark. It was punched out as a spherical shaped body having a thickness of 77 mm, a polycarbonate protective sheet layer on the convex side, and a polyurethane sheet layer on the concave side.
Using the same insert injection compression molding machine as in Example 1, a polarizing molded body was prepared as follows.
The obtained 8C spherical shaped body was set and fixed in a concave fixed mold. In this case, the polycarbonate protective sheet layer having a spherical shape is in close contact with the fixed mold, and the polyurethane sheet layer faces the moving mold.
The moving mold was fastened to the fixed mold, and a molding cavity was formed between the fixed mold and the moving mold.
As the thermoforming resin layer, polyether-based thermoplastic polyurethane “Elastolan 1195ATR” (Takeda Birdish Urethane Kogyo Co., Ltd.) in which a smoked dye was dissolved was used. The polarizing molded article was injection compression molded at a maximum temperature of 205 ° C., and the polyurethane sheet layer and the thermoplastic polyurethane thermoformed resin layer were thermally bonded. Thereafter, the polarizing molded body was taken out from the insert injection compression molding machine.
The obtained polarizing molded body is an 8C plano lens having a thickness of 2.2 mm, in which a polycarbonate protective sheet is disposed on the convex side and a thermoplastic polyurethane thermoformed resin layer is integrally disposed on the concave side.
A silane hard coat film having a film thickness of about 2.5 μm was formed on both surfaces of the same product. Further, a mirror coat film was formed on the convex surface side by vacuum deposition.
The resulting lens had a visible light transmittance of 8% measured at the center, and exhibited extremely tough mechanical properties. The degree of polarization was 95% or more.

Claims (1)

In the first stage, a polarizing plate having a structure in which a polarizer sheet layer is sandwiched between two protective sheet layers is prepared. In the second stage, a polyurethane sheet layer or a polyamide is applied to one of the protective sheet layers of the polarizing plate. A polarizing composite in which a sheet layer is bonded with an adhesive or a pressure-sensitive adhesive is prepared, and in the third stage, the polarizing composite is hot press-molded into a spherical shape, and in the fourth stage, the spherical polyurethane sheet layer is formed. Alternatively, the method includes thermoforming polyurethane polyurethane, transparent nylon or polycarbonate on the polyamide sheet layer by an insert injection molding method, wherein each of the two protective sheet layers is polyamide-based, polyester-based, polyurethane-based, polystyrene system, acrylic, vinyl chloride, polystyrene methyl methacrylate, acrylonitrile-styrene, or poly-4 Chirupenten -1, characterized in that it consists of a main chain hydrocarbon-based resin having an adamantane ring and a cyclopentane ring in the main chain, comprising a polarizing plate which sandwiches polarizer sheet layer between the two protective sheet layer A polarizing molded article having a laminated structure, in which any one of the protective sheet layer and the polyurethane sheet layer or the polyamide sheet layer is bonded with an adhesive or a pressure-sensitive adhesive, and the polyurethane sheet layer or the polyamide sheet layer and the thermoplastic polyurethane or Transparent nylon or polycarbonate is thermally bonded, and each of the two protective sheet layers is polyamide, polyester, polyurethane, polystyrene, acrylic, vinyl chloride, polystyrene / methyl methacrylate, acrylonitrile / styrene. system or poly-4-methylpentene-1,, Ada Method for producing a polarizing molded article comprising a main chain hydrocarbon-based resin having a lanthanum ring or cyclopentane ring in the main chain.