JP2014156067A - Method of producing resin lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a resin lens by forming a functional resin layer by cast molding and providing a resin lens which shows excellent adhesion not only in an adhesion test during mechanical processing but also in a test of warm water resistance and hot water resistance and expectantly improved use durability under high-temperature, high-humidity conditions.SOLUTION: A method of producing a resin lens is based on cast molding. With a substrate lens 11 as a first mold 11', a second mold 17 is arranged on one side of the first mold 11' at a nearly specified interval. The peripheral surface clearance between the first mold 11' and the second mold 17 is sealed with a taping 19 to form a cavity 21. A liquid resin raw material is injected into the cavity 21 to form a functional resin layer by cast molding so as to integrate the substrate lens 11 and the functional resin layer 15 together. The first mold 11' consists of the substrate lens 11 in which an adhesive layer of a thermoplastic elastomer is formed on the surface to be formed with the functional resin layer 15.

Description

  The present invention relates to a method for manufacturing a resin lens provided with a functional resin layer.

  Conventionally, functional lenses such as photochromic lenses, anti-glare lenses, and infrared absorption lenses are manufactured by molding (usually cast molding) a lens (semi-finished product) and then cutting and polishing the product to the prescription frequency of the customer.

  In this manufacturing method, a considerable part of the molded lens is discarded at the time of cutting, and at the same time, the expensive photochromic agent, the specific wavelength absorber and the infrared absorber added are discarded, which is uneconomical.

  Furthermore, when these functional lenses are lenses with a degree of medium or higher, there is a problem in terms of fashionability because a difference in color tone occurs due to a difference in thickness between the inner and outer circumferences.

  That is, there is a demand for a method of manufacturing a lens with a degree that is as thin as possible, has a small thickness difference, and hardly causes a difference in color tone.

  Therefore, it is conceivable to apply the following production method described in Patent Document 1 (see paragraph 0005).

  “A method of manufacturing a resin lens having a refractive index of 1.45 or more using at least two types of resin materials, wherein at least one type of resin material is formed as a non-flowable molded body, and a cavity is formed on the adhesion surface of the molded body. Resin molding in which at least two types of resin materials having different properties are closely attached to each other by injecting another material material having different properties from the resin material into the cavity and polymerizing and curing in the cavity A lens in which at least one of surface reflection characteristics, physical properties, dyeability, and processability is improved by obtaining a product and complementing the properties of the resin material having at least two different properties from the resin molding. It is characterized by manufacturing. "

  However, in Patent Document 1, as shown in Table 3 “Polymerization adhesion test” of the same document, the base lens: thiourethane resin (MR system) (ne = 1.60) and the functional resin layer: methyl methacrylate resin With the combination of (PMMA) (ne = 1.55), it is difficult to obtain adhesion.

  Furthermore, even in the case of a combination of sulfur-containing resins of a base lens; episulfide resin (ne = 1.74) and a functional resin layer: thiourethane resin (ne = 1.60), the present inventors It was also found that it was difficult to obtain sufficient adhesion irrespective of the adhesion pretreatment (see Comparative Examples 2-1 and 2-2 and Reference Example 2 in Table 2).

  In such a case, it is conceivable to interpose the adhesive layer on the functional resin layer forming surface side of the base lens, but the functional resin lens interposing such an adhesive layer, the present inventors, I don't know it by hearing.

  The reason is considered as follows.

  If the thiourethane resin itself is a thermosetting resin, and the base lens is a similar sulfur-containing resin, it is considered that cross-linking adhesion occurs at the time of curing after injection, and it is difficult to expect further improvement in adhesion, Conversely, the adhesion may be reduced due to the presence of the heterogeneous layer.

  In addition, when an adhesive layer is interposed between the functional resin layer and the base lens, there is a risk that refraction abnormality or color unevenness may occur.

  In addition, although it does not affect the patentability of the present invention, in Patent Document 2, when a transparent synthetic resin layer is cast and molded by polymerizing and curing a polymerizable liquid material on one side or both sides of a polarizing film, a polarizing film ( A manufacturing method of a polarizing resin lens (polarizing element) in which an adhesive layer having rubber-like elasticity is interposed on at least one surface of a polarizing sheet has been proposed (claim 1 and the like).

  However, the polarizing film (polarizing sheet) corresponding to the base lens (for example, center thickness) formed of a thermosetting resin such as (thio) urethane resin is usually thin (film: 50 μm, sheet: 700 μm) and the material is also It is heterogeneous with polyvinyl alcohol (PVAL).

  Also, during machining, peeling occurs between the polarizing film or polarizing sheet and the transparent synthetic resin layer adjacent to the thin polarizing film layer (usually around 50 μm) or the polarizing sheet (usually around 700 μm). This is due to the occurrence of wrinkles based on the difference in thickness from the transparent synthetic resin layer to be formed, and is different from the peeling when the thin resin layer is formed with respect to the thick resin layer assumed in the present invention. (See cited reference 2, paragraph 0021).

Japanese Patent No. 4087335 JP 2011-145513 A

  In view of the above, the present invention is a method for producing a resin lens by casting a functional resin layer, and the produced resin lens is not only at the time of machining, but also has an adhesion property in a hot water resistance and hot water resistance test. Another object of the present invention is to provide a method for producing a resin lens that is also excellent and that can be expected to improve the durability of use under high temperature and high humidity conditions.

  In order to solve the above-mentioned problems, the present inventors have made extensive efforts to develop an adhesive made of a specific thermoplastic elastomer or the like for a high refractive index base lens made of a thermosetting resin. It was found that by interposing the layer, not only the mechanical adhesion between the base lens and the functional resin layer is improved, but also the durability under high temperature and high humidity conditions is effective. And based on this knowledge, it came up with the manufacturing method of the resin lens of the following structure.

The base lens is the first mold, and the second mold is arranged on one side or both sides of the first mold so as to have a substantially constant predetermined gap, and the circumferential gap between the first and second molds is provided. Seal with taping or gasket to form the cavity,
In the method for producing a resin lens, injecting a liquid resin raw material containing a functionality-imparting agent into the cavity and casting the functional resin layer, the base lens and the functional resin layer are integrated.
A base lens in which an adhesive layer of a thermoplastic elastomer is formed on the side surface on which the functional resin layer is formed is the first mold.
It is characterized by that.

It is a flowchart which shows an example of the manufacturing method of the resin lens of this invention. It is a graph which shows the spectral characteristics in Examples 4-6 which formed the functional resin layer containing a specific wavelength absorber.

  Hereinafter, the manufacturing method of the resin lens of this invention is demonstrated in detail.

(1) Molding of base lens The base lens 11 is molded from a thermosetting resin material having a high refractive index (ne = 1.58 or more, preferably 1.65 or more). This is because the lens with a degree is easily thinned. When the molding material for the base lens is a thermosetting resin material, the molding method is usually cast molding. When the molding material of the base lens is a thermoplastic resin material, it may be injection molding.

  In molding by the taping method, unevenness is generated on the peripheral surface (edge surface) of the base lens 11 due to polymerization shrinkage. If this peripheral surface is uneven, when the functional resin layer 15 to be implemented later is molded by the taping method, the cavity 21 cannot be sufficiently sealed by the taping 19, and the liquid resin raw material of the functional resin layer 15 becomes the cavity. There is a possibility that a leakage void is formed from 21. For this reason, the minimum necessary peripheral surface cutting is performed on the base lens 11 after the cast molding. In addition, the outer diameter of the base lens 11 is set to be the same as the outer diameter of the second mold 17 to be used later in the molding of the functional resin layer 15.

  As the high refractive index thermosetting resin material, sulfur-containing thermosetting resins such as the following thiourethane resins (a) and episulfide resins (b) can be preferably used.

  (a) A thiourethane resin is a polymer (resin) having a bond (-NHCOS-, -NHCSO-, -NHCSS-) in which at least one oxygen atom of a polyurethane bond (-NHCOO-) is replaced with a sulfur atom. One or two or more polyisocyanates selected from polyisocyanate, polyisothiocyanato, polyisocyanatothioisocyanate, and one or more known polyisocyanates selected from polythiols and appropriate polyols. An active hydrogen compound can be preferably used (see JP-A-8-208792 etc.).

  Here, polyisocyanates include aliphatic, alicyclic, aromatic, and derivatives thereof, and sulfide, polysulfide, and thiocarbonyl (thioketone) derivatives in which sulfur is introduced into part of their carbon chains. The compound can be mentioned. Of these, aliphatic or alicyclic polyisocyanates are desirable from the standpoint of yellowing resistance.

  Similarly, polythiols include aliphatic, alicyclic, aromatic, and derivatives thereof, and sulfides, polysulfides, and polythioethers in which sulfur is introduced into a part of their carbon chains as a base compound. Can be mentioned. Of these, aliphatic or alicyclic polyols are desirable from the standpoint of yellowing resistance.

  Specifically, it is desirable that the polythioether represented by the following chemical formula is composed of or is mainly composed of a base compound.

  As other polythiols, a fully substituted ester of a ω-mercapto aliphatic carboxylic acid of a branched hydrocarbon polyhydric alcohol can be suitably used.

  Specifically, trimethylolpropane tris (2-mercaptoglycolate), pentaerythritol tetrakis (2-mercaptoglycolate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropioate) Nate) and the like.

  (B) Episulfide-based resin means a polymer (resin) obtained by reacting a dithioepoxy compound, a curing agent, and another polymerizable compound. For example, a linear alkyl represented by the following chemical formula Known compounds obtained by curing a sulfide-type dithioepoxy compound can be used (Japanese Patent Application Laid-Open Nos. 9-1101979 and 10-114764, etc.).

  As the curing agent, amines, organic acids, or inorganic acids, which are ordinary epoxy resin curing agents, can be used.

(2) Application of adhesive:
An adhesive layer 13 made of a thermoplastic elastomer (TPE) is formed on the side surface of the base lens 11 on which the functional resin layer 15 is formed (on the convex side in the example). When the functional resin layer 15 is formed on both surfaces, the adhesive layer 13 is formed on both surfaces of the base lens 11.

  An adhesive is applied to the base lens 11 by a known method such as dipping (dip coating), spin coating, and the like, and solidified by normal temperature and heat drying to prepare a first mold 11 ′ having an adhesive layer 13.

  At this time, the thickness of the adhesive layer 13 varies slightly depending on the material of the adhesive and the type of the base lens 11, but is 300 nm (preferably 650 nm) or more from the viewpoint of adhesion, and from the viewpoint of optical characteristics. It is appropriately selected from the range as 1200 nm (preferably 1000 nm) or less.

  Moreover, the conditions of normal temperature and heat drying are suitably selected from the range of 20 to 120 ° C. × 5 minutes to 10 hours depending on the material of the adhesive and the type of the base lens.

  Specifically, the following (a) ester-based TPE and (b) urethane-based TPE can be suitably used as the TPE.

(a) Ester TPE:
As the ester-based TPE (TPEE), both a polyester / polyether type and a polyester / polyester type can be used.

  The TPEE is a multi-block copolymer using polyester as a hard segment and polyether or polyester as a soft segment.

  The molar ratio of the hard segment and the soft segment of the TPEE is the former / the latter = about 30/70 to 90/10, preferably about 40/60 to 80/20. When the ratio of the hard segment is too small, the hardness, modulus, mechanical strength and heat resistance are lowered, and when it is excessive, the rubbery elasticity and the low temperature characteristics are lowered.

  As TPEE in this invention, what shows surface hardness (Shore D): about 35-75 and a bending elastic modulus: about 4-800 MPa is desirable.

  Specific examples of TPEE hard and soft segments are given below.

・ Hard segment polyester:
Specifically, it consists of a dicarboxylic acid and a low molecular glycol.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid, carbon numbers such as succinic acid, adipic acid, azelaic acid, decamethylene dicarboxylic acid, and octadecanedicarboxylic acid. 4-20 linear saturated aliphatic dicarboxylic acids, aliphatic oxocarboxylic acids such as ε-oxycaproic acid (see the following general formula), dimer acids (aliphatic monocarboxylic acids having a double bond were dimerized. Dibasic acid) and the like, and ester-forming derivatives thereof. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are desirable.

General formula: R ¹ CO (CH ₂ ) _n COOH
Note) R ¹ : alkyl group or H, n = 0-19.

  Examples of the low molecular weight glycol include ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,6-cyclohexanedimethanol, and the like. These ester-forming derivatives are mentioned. Among these, ethylene glycol and 1,4-butanediol are desirable.

・ Polyester composing soft segment:
It consists of a dicarboxylic acid and a long chain glycol, and examples of the dicarboxylic acid include those described above.

  Examples of the long chain glycol include poly (1,2-butadiene glycol), poly (1,4-butadiene glycol), and hydrogenated products thereof.

  Also, ε-caprolactone (C6), enanthlactone (C7), caprylolactone (C8), and the like are useful as soft segment polyesters.

  Of these, ε-caprolactone is desirable.

・ Polyether constituting soft segment:
And poly (alkylene oxide) glycols such as poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (tetramethylene oxide) glycol. Of these, poly (tetramethylene oxide) glycol is desirable for use.

  The TPEE can be produced by a conventional method. Specifically, a lower alkyl ester of a dicarboxylic acid is mixed with an aliphatic long-chain glycol and a low-molecular glycol and heated at a temperature of about 150 to 200 ° C. in the presence of a catalyst such as tetrabutyl titanate to perform transesterification. A low polymer is synthesized by the reaction. And this low polymer is heat-stirred at about 220-280 degreeC under high vacuum, polycondensation is performed, and it is set as TPEE. The low polymer can also be obtained by a direct esterification reaction of a dicarboxylic acid with a long chain glycol and a low molecular glycol.

  In the above, the polymer that can be combined when TPEE is not the entirety of the coating film-forming polymer but is mainly used is not particularly limited as long as it is a polymer miscible with TPEE. For example, ordinary ester resins (PBT, PET, etc.), amide resins, and further amide TPE are arbitrary. The ratio of these polymers to the total polymer should be less than about 50%, desirably less than about 30%.

  Such TPEE may be added in the form of a solution type, but is preferably added in the form of an aqueous emulsion from the viewpoint of processability and environmental protection.

  This aqueous emulsification can be performed by a conventional method. Specifically, a forced emulsification method in which the polymer is forcibly emulsified by performing high mechanical shearing in the presence of a surfactant (external emulsifier) is desirable.

As surfactants usually used,
-Anionic surfactants: alkylbenzene sulfonates such as sodium lauryl benzene sulfonate, sodium dioctyl sulfosuccinate, etc.
・ Cationic surfactant: quaternary ammonium salt, etc.
Nonionic surfactant: polyethylene glycol, ethylene oxide adduct of long chain alcohol, ethylene oxide adduct of alkylphenol, etc.
Is mentioned. Of these, sodium laurylbenzene sulfonate is desirable.

  Alternatively, an ionic hydrophilic group may be introduced into the polymer, and dispersion may be stabilized in water without the aid of an emulsifier, or the polymer may be used in combination.

  In the above, when the solution type is used, various solvents such as hydrocarbons, halogenated compounds, alcohols, ketones, esters, and ethers are used alone or in combination to form a solution type.

(b) Urethane TPE
The urethane-based TPE may be added in the form of a solution type, but is preferably added in the form of an aqueous emulsion from the viewpoint of processability and environmental protection.

  The urethane-based TPE is usually composed of a soft segment composed of a long-chain polyol and polyisocyanate, and a hard segment composed of a short-chain polyol and polyisocyanate. Furthermore, it is desirable to add a reactive component such as polyamine so that it can be partially crosslinked after coating and curing on a base lens.

  The long-chain polyol constituting the soft segment may be any polyether such as polyalkylene glycol (PTMG, etc.) polyether, polyalkylene adipate, polycaprolactone, polycarbonate, or other polyester polyester. It is. Of these, polyester and polyether polyester are preferable from the viewpoint of impact resistance.

  The short-chain polyol constituting the hard segment includes ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol. Etc. can be illustrated.

  Examples of the polyisocyanate include aromatic groups such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthalenediisocyanate, 1,6-hexamethylene diisocyanate. And aliphatic and alicyclic compounds such as isophorone diisocyanate and hydrogenated MDI. From the viewpoint of light resistance and the like, a non-yellowing type aliphatic / alicyclic type is desirable.

  Such urethane-based TPE may be added in the form of a solution type as in the case of TPEE, but it is desirable to add it in the form of an aqueous emulsion from the viewpoint of processability and environmental protection. These aqueous emulsions and solution types can also be formed by the same method as in the TPEE.

(3) Cavity preparation:
In the mold 21 of the functional resin layer 15 of the present embodiment, the base lens 11 is the first mold 11 ′, and a substantially constant predetermined gap is formed on one side of the first mold 11 ′. The second mold 17 is disposed, and the peripheral gaps of the first and second molds 11 ′ and 17 are sealed with a taping 19. In the illustrated example, the taping method is used, but a gasket seal method may be used.

  And 1st mold 11 'shall have formed the adhesive bond layer 13 with the thermoplastic elastomer in the formation side surface of the functional resin layer 15 of the base lens 11. FIG. In addition, when forming a functional resin layer on both sides of the base lens, the second mold 17 is arranged on both sides of the first mold 13 so as to have a substantially constant spacing, and the adhesive layer 13 is provided on both sides. The base lens 11 on which is formed is defined as a first mold 11 ′.

  The second mold 17 is usually made of glass, but is not limited to glass, and may be made of resin, ceramic, or the like.

  The predetermined gap, which is the gap between the cavities 21 at this time, varies depending on the flow characteristics of the liquid resin raw material and the functionality imparted to the functional resin layer 15, but is usually from the viewpoint of castability and functionality. It is 0.2 mm or more, preferably 0.3 mm or more, more preferably 0.5 mm or more, and 3 mm or less, preferably 1.5 mm or less, more preferably 1 mm or less from the viewpoint of fashionability and weight reduction.

(4) Casting molding of functional resin layer Next, the liquid resin raw material of the functional resin layer 15 is injected into the cavity 21 and polymerized or crosslinked and cured by means such as thermosetting polymerization or ultraviolet curing polymerization. .

  The liquid resin raw material used here has a refractive index lower than that of the base lens forming resin. By setting it as the said composition, the reflectance by the side of a functional resin layer falls, and the transmittance | permeability increases as a result (patent document 1 paragraph 0014 * 0015).

  For example, low to medium refractive index to low refractive index (ne = 1.58) thermoplastic resin such as methacrylate or polycarbonate, urethane resin, diallyl carbonate (CR-39), thermosetting such as diallyl phthalate (DAP) Resin can be used. Furthermore, even when the base lens is a thiourethane resin, a thiourethane resin having a lower refractive index than that used for the base lens may be used.

  As the liquid resin material, a material containing at least one of a photochromic agent, a specific wavelength absorber and an infrared absorber is used. These chemicals are appropriately diffused in a solvent and mixed with the liquid resin raw material.

  As the photochromic agent, spiropyran compounds, spirooxazine compounds, chromene compounds, fulgide compounds, and the like can be suitably used.

  As the specific wavelength absorber, squarylium compounds, tetraazaporphyrin compounds, neodymium compounds, and the like can be suitably used.

  As the infrared absorber, phthalocyanine compounds, inorganic sols, and the like can be suitably used.

  In the production of the functional resin layer by casting, various additives such as dyes, bluing agents, internal mold release agents, deodorants, You may add antioxidant, a stabilizer, a polymerization initiator, etc. as needed. The resin curing (polymerization) is performed by thermosetting polymerization, ultraviolet curing polymerization, or the like.

(5) Resin lens release and post-treatment:
The liquid resin material becomes a molded product (resin lens) in which the functional resin layer 15 and the base lens 11 (first mold 11 ′) are integrated by polymerization and curing. The resin lens is taken out by releasing the molded product from the second mold 17. It is desirable that the surface of the resin lens provided with the functional resin layer 15 manufactured in this way is subjected to a modification treatment such as hardness by applying a generally applied reinforced coating (hard coat).

  Furthermore, general-purpose surface treatments such as antifogging treatment, antireflection treatment, water repellent treatment, and antistatic treatment are appropriately applied.

  Hereinafter, the present invention will be described in more detail based on examples. In the following description, “part” indicating “composition composition” is a mass unit unless otherwise specified. In addition, what is shown in brackets along with the company name is a registered trademark unless otherwise specified.

  As the adhesive tape forming the cavity, an adhesive tape No. “6263-71” manufactured by Sliontec Co., Ltd. in which a silicone adhesive was applied on a 38 μm thick PET film was used.

<Example 1 group>
It is a group of combinations in which the base lens 11 is formed with a thiourethane resin (thermosetting) and the functional resin layer 15 is formed with a methacrylate resin (thermoplastic) containing a photochromic agent.

(1) Preparation of molding die for base lens A mold cavity was prepared by taping two pairs of a convex mold and a concave mold having the following specifications with an adhesive tape so that the center distance was 5.0 mm.
・ Convex side mold: Glass, φ80mm, R = 66.16mm, CT = 4.0mm
・ Concave side mold: Glass, φ80mm, R = 66.16mm, CT = 4.0mm

1) Preparation of liquid resin raw material for base lens
2,5-bicyclo [2,2,1] heptanebis (methylisocyanato): 100 parts dibutyltin dichloride as a curing agent: 0.1 part, 2 parts alkyl phosphate as an internal mold release agent, and 3- Monoester of 5-[(2-benzotriazole) -3-t-butyl-4-hydroxyphenyl] propionic acid and polyethylene glycol: 2.0 parts were sufficiently stirred for 1 hour in a nitrogen gas atmosphere at a liquid temperature of 15 ° C. Thereafter, 50 parts of pentaerythritol tetrakis (3-mercaptopropionate): 50 parts and 4,7-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol: 50 parts were further added. The mixture was stirred for 1 hour while adjusting the temperature to 15 ° C. in a nitrogen gas atmosphere. Subsequently, the mixture was degassed for 1 hour while stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, and then filtered through a 1 μm filter to prepare a liquid resin raw material for a thiourethane lens having a refractive index (ne) of 1.60.

2) The liquid resin raw material prepared in 1) above is poured into a mold, molded under the following heating conditions, and after the resin raw material is heat polymerized, it is physically (mechanically) released with a wedge-shaped tool. And then removed from the mold.
20 ° C → 8 hours → 20 ° C → 4 hours → 60 ° C → 2 hours → 100 ° C → 1 hour → 120 ° C → 2 hours → 120 ° C → 4 hours → 40 ° C

(2) Application of adhesive Aqueous emulsion ester TPE adhesive “A-01” prepared by stirring until uniform in the following formulation is applied to both surfaces (one side in the example) of the base lens 11 under the following conditions. Was applied to prepare a first mold (concave-side mold in the illustrated example) 11 '. Although an unnecessary adhesive layer remains on the surface that is not on the functional resin layer forming side, the surface is cut according to the required frequency of the consumer, and therefore a step of removing the adhesive layer is unnecessary.

・ “Pesresin A-160P” (manufactured by Takamatsu Yushi Co., Ltd., water-dispersed emulsion, solid content 27%): 100 parts ・ Methyl alcohol: 900 parts ・ Silicone surfactant “SILWET L-77” (Momentive Performance Material) 2 parts Application method: Dipping (15 ° C, 30 seconds, Example 1-1: 45 mm / min, Example 1-2: 200 mm / min, Example 1-3: 300 mm / min) )
Drying conditions: 50 ° C x 30 minutes

(3) Preparation of cavity Cavity 21 (molding die) was prepared by taping 19 with an adhesive tape using a first mold 11 'and a second mold 17 having the following specifications so as to have a center interval of 1.0 mm.

・ First mold 11 ′: Base lens, φ80mm, R (adhesion surface) = 66.16mm, CT = 5.0mm
・ Second mold 17: glass, φ80mm, R = 66.16mm, CT = 4.0mm

(4) Molding of functional resin layer:
1) Preparation of functional resin material:
Photochromic functional lens material “Transhade 500PRE” manufactured by Tokuyama Corporation: 100 parts, AKZO Nobel's “Trigonox23-C7” as a curing catalyst: 1.3 parts, “Trigonox21S”: 0.1 part at 20 ° C. in a nitrogen gas atmosphere The mixture was stirred for 30 minutes while adjusting.

  Methacrylate system containing a photochromic agent with a refractive index (ne) of 1.55 by degassing for 1 hour with stirring under the set conditions of liquid temperature: 15 ° C and absolute pressure: 133Pa using a vacuum pump. A liquid resin raw material for the resin was prepared.

2) The liquid resin raw material was poured into the cavity prepared in (3) and molded under the following heating conditions.
35 ° C → 8 hours → 35 ° C → 4 hours → 50 ° C → 2 hours → 70 ° C → 1 hour → 90 ° C → 2 hours → 90 ° C → 2 hours → 60 ° C

(5) Mold release:
The resin lens (molded product) in which the base lens 11 (first mold 11 ') and the functional resin layer 15 are integrated by heat polymerization of the liquid resin material in the cavity is removed from the second mold 17 with a wedge-shaped tool. Each sample (resin lens) was released physically (mechanically).

<Comparative example 1 group>
In the above Example 1 group, instead of applying an adhesive, plasma etching treatment (Comparative Example 1-1) or alkali etching treatment (Comparative Example 1-2) was performed on the base lens under the following conditions. A sample (resin lens) was prepared under the same conditions.
Comparative Example 1-1: Performed under the conditions of oxygen gas (flow rate 40 cc / min), plasma output 100 W × treatment time 40 seconds, using “Plasma Reactor PR501A” manufactured by Yamato Scientific Co., Ltd.
Comparative Example 1-2: It was immersed for 5 minutes in 30 degreeC NaOH aqueous solution (10 wt%).

<Reference Example 1>
In the above Example 1 group, a sample (resin lens) was prepared under the same conditions with the base lens being untreated.

<Example 2 group>
This is a group of combinations in which the base lens 11 is formed of an episulfide resin (thermosetting resin) and the functional resin layer 15 is formed of a thiourethane system (thermosetting resin) blended with a specific wavelength absorber.

(1) Preparation of mold for base lens A mold was prepared by taping with an adhesive tape so that the center distance between the convex mold and concave mold of the following specifications was 5.0 mm.
・ Convex side mold: Glass, φ80mm, R = 66.16mm, CT = 4.0mm
-Concave side mold: Glass, φ80mm, R (adhesion surface) = 66.16mm, CT = 4.0mm

1) Preparation of polymerizable liquid material for base lens Bis (2,3-epithiopropyl) disulfide: 90 parts, 4,7-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecane Dithiol: 10 parts mixed and stirred for 30 minutes while adjusting the temperature to 15 ° C. under nitrogen gas atmosphere, N, N-dimethylcyclohexylamine as a curing agent: 0.3 part, isopulegol as a fragrance imparting agent: 0.3 part, further UV absorption 3-5 [-(2-benzotriazole) -3-t-butyl-4-hydroxyphenyl] propionic acid and polyethylene glycol monoester: 1.5 parts of each were added as agents, and 15 ° C. in a nitrogen gas atmosphere. The mixture was stirred for 30 minutes while adjusting the temperature. Subsequently, the mixture was deaerated for 1 hour with stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, and then filtered through a 1 μm filter to prepare a liquid resin raw material of an episulfide resin having a refractive index (ne) of 1.74.

2) The liquid resin raw material prepared in 1) above is injected into the mold for the base lens, molded under the following heating conditions, and after heat polymerization, is physically (mechanically) released with a wedge-shaped tool. did.
20 ° C → 8 hours → 20 ° C → 4 hours → 60 ° C → 2 hours → 100 ° C → 1 hour → 120 ° C → 2 hours → 120 ° C → 4 hours → 40 ° C

(2) Application of adhesive Aqueous emulsion ester TPE-based adhesive “A-02” prepared by stirring until the following formulation is uniformed is applied to both sides (one side in the example) of the base lens 11 as follows. It apply | coated on conditions and it was set as 1st mold (concave surface mold) 11 '.

・ Aqueous emulsion polyurethane “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd., solid concentration: 30%, non-yellowing type, ester / ether type): 100 parts ・ Methyl alcohol: 600 parts ・ Silicon-based surfactant as leveling agent Agent: 1 part Application method: Dipping (20 ° C., 60 seconds, Example 2-1: 45 mm / min, Example 2-2: 200 mm / min, Example 2-3: 300 mm / min)
Drying conditions: 70 ° C x 60 minutes

(3) Configuration of cavity Using a first mold (concave surface mold) 11 ′ and a second mold (convex surface mold) 17 having the following specifications, taping 19 with an adhesive tape so that the center distance is 1.0 mm, and cavity 21 A (mold) was prepared.

・ First mold 11 ': Base lens, φ80mm, R (adhesion surface) = 66.16mm, CT = 5.0mm
・ Second mold 17: glass, φ80mm, R = 66.16mm, CT = 4.0mm

(4) Molding of functional resin layer
1) Preparation of functional resin material:
2,5-bicyclo [2,2,1] heptanebis (methylisocyanato): 100 parts dibutyltin dichloride as a curing agent: 0.1 part, 2 parts alkyl phosphate as an internal mold release agent, and 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol: 4.8 parts, tetraazaporphyrin-based metal complex compound (absorption peak wavelength 480 nm) as a specific wavelength absorber: 3 × 10 ⁻³ parts and tetraazaporphyrin-based metal complex compound (absorption peak wavelength 595 nm): 1 × 10 ⁻³ parts and phthalocyanine-based metal complex compound (absorption peak wavelength 760 nm) as an infrared absorber: 1 × 10 ⁻³ parts The mixture was sufficiently stirred for 1 hour in a nitrogen gas atmosphere at a liquid temperature of 15 ° C. Thereafter, 50 parts of pentaerythritol tetrakis (3-mercaptopropionate): 50 parts and 4,7-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol: 50 parts were added, and nitrogen was further added. The mixture was stirred for 1 hour while adjusting the temperature to 15 ° C. in a gas atmosphere.

  The mixture was degassed for 1 hour with stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, and then filtered through a 1 μm filter to prepare a liquid resin raw material for a thiourethane lens having a refractive index (ne) of 1.60.

2) The liquid resin raw material was poured into the cavity prepared in (3) and molded under the following heating conditions.
20 ° C → 8 hours → 20 ° C → 4 hours → 60 ° C → 2 hours → 100 ° C → 1 hour → 120 ° C → 2 hours → 120 ° C → 4 hours → 40 ° C

(5) Mold release:
The resin lens (molded product) in which the base lens 11 (first mold 11 ') and the functional resin layer 15 are integrated by heat polymerization of the liquid resin material in the cavity is removed from the second mold 17 with a wedge-shaped tool. Each sample (resin lens) was released physically (mechanically).

<Comparative example 2 group>
In the above Example 2 group, instead of applying the adhesive, plasma etching treatment similar to Comparative Example 1-1 (Comparative Example 2-1) or alkali etching treatment of Comparative Example 1-2 (Comparative Example 2-2) Each sample was prepared under the same conditions except that was applied to the base lens.

<Reference Example 2>
In the group of Example 2 described above, a sample (resin lens) was created under the same conditions with the base lens being untreated.

<Consideration of results>
The results of the evaluation test are shown in Tables 2 and 3.

1) Evaluation of optical characteristics The difference in transmittance before and after UV irradiation in Example 1 group, Comparative Example 1 group and Reference Example 1 and the spectral characteristics of Example 2 group, Comparative Example 2 group and Reference Example 2 are all desired. The optical characteristics of were obtained.

2) Evaluation of adhesion
2-1) Example 1 group, Comparative example 1 group and Reference example 1:
When the lens material shown in Table 1 is a methacrylic functional resin (photochromic) layer and a thiourethane base lens, the comparison between plasma and alkali etching treatments as well as the untreated reference example 1 in the interlayer adhesion It was also found that there was a problem in the Example 1 group. Also in Example 1 group in which the film thickness of A-01 was changed, when the film thickness of A-01 was thinner than 650 nm (Example 1-1), there was a problem in adhesion, and the film thickness of A-01 When the thickness was larger than 1000 nm (Example 1-3), it was found that the adhesive layer was clouded white and there was a problem in appearance.

2-2) Example 2 group, Comparative example 2 group and Reference example 2:
When the lens material shown in Table 1 is a thiourethane-based functional resin layer and an episulfide-based base lens, the reference example 2 in which the interlayer adhesion is not treated, as well as in the comparative example 2 group of plasma / alkali etching treatment, is used. Also found that there was a problem. Further, in Example 2 group in which the film thickness of A-02 was changed, when the film thickness of A-02 was thinner than 650 nm (Example 2-1), there was a problem in adhesion, and the film thickness of A-02 When the thickness was larger than 1000 nm (Example 2-3), it was found that the adhesive layer was clouded white and there was a problem in appearance.

  Compared to these comparative and reference examples, Examples 1-2 and 2-2 of the present invention are not only in terms of lens appearance and optical characteristics, but also in the adhesion between the functional resin layer and the base lens. Confirmed that there is no.

11 Base lens 11 ′ First mold (concave surface mold)
13 Adhesive Layer 15 Functional Resin Layer 17 Second Mold (Convex Side Mold)
19 Taping 21 Cavity

Claims (7)

The base lens is the first mold, and the second mold is arranged on one side or both sides of the first mold so as to have a substantially constant predetermined gap, and the circumferential gap between the first and second molds is provided. Seal with taping or gasket to form the cavity,
In the method for producing a resin lens, injecting a liquid resin raw material containing a functionality-imparting agent into the cavity and casting the functional resin layer, the base lens and the functional resin layer are integrated.
A base lens in which an adhesive layer of a thermoplastic elastomer is formed on the side surface on which the functional resin layer is formed is the first mold.
A method for producing a resin lens.   The method for producing a resin lens according to claim 1, wherein the adhesive layer has a thickness of 300 to 1200 nm.   The method for producing a resin lens according to claim 1 or 2, wherein the adhesive layer is formed by dipping using an aqueous emulsion type of an ester-based thermoplastic elastomer or a urethane-based thermoplastic elastomer.   4. The method for producing a resin lens according to claim 1, wherein the base lens used as the first mold is cast-molded and circumferentially cut.   The method for producing a resin lens according to claim 1, wherein the predetermined gap in the cavity is 0.2 to 3 mm.   The refractive index of the raw material resin that forms the functional resin layer is lower than the refractive index of the resin forming the base lens, and the raw material resin is selected from a methacrylate resin, a urethane resin, and a thiourethane resin, The method for producing a resin lens according to claim 1, wherein the base lens forming resin is formed of a thiourethane resin or an episulfide resin.   The method for producing a resin lens according to claim 1, wherein at least one kind is selected from the group of a photochromic agent, a specific wavelength absorber, and an infrared absorber as the functionality-imparting agent.

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