Method for molding transparent resin laminate

Abstract

To provide a molding method of a transparent resin laminate in which adhesive tapes and gaskets are not required to form cavities in a functional resin layer so as to expect the reduction in man-hours, the by-production of waste can be suppressed, and good adhesion of the functional resin layer to a transparent resin base can be ensured.SOLUTION: A molding method of a transparent resin laminate having a functional resin layer on at least one side of a transparent resin base, including the following processes: (1) a first process of dropping a monomer M of a thermosetting molding material on a concave surface 13b of a seat mold 13 in an amount exceeding the amount capable of forming a functional resin layer 12; (2) a second process of exposing an assembly with a transparent resin base 11 placed on the dripped monomer M to an atmosphere at a temperature at which the molding material can gelate for a predetermined time to allow air to escape between the seat mold 13 and the transparent resin base 11 while allowing the monomer M to diffuse and further gelate on the underside of the transparent resin base 11 to form the mold; and (3) a third process of hardening and mold-releasing the gelatinized installations on the assembly after the second process.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for molding a transparent resin laminate having an optically functional layer on at least one surface of a transparent resin substrate made of resin, and to an optically functional resin layer composition suitable for the method. [Background technology]

[0002] Here, we will mainly use eyeglass lenses, especially polarized lenses, as examples, but the present invention is expected to be applicable to sunglasses, telescope lenses, mobile phones, TVs, and even vehicle and architectural window glass. In this specification and claims, composition units and temperatures refer to mass units and ambient temperature, respectively, unless otherwise specified. Furthermore, the numerical values ​​preceding the resin names refer to the refractive index (nD).

[0003] In the present invention, the NCO component means a polyisocyanate component, the SH component means a polythiol component, and the OH component means a polyol component, and the abbreviations for each component are as follows: HDI: Hexamethylene diisocyanate NBDI: 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane GST: 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol PEMP: Pentaerythritol tetrakis(mercaptopropionate) PAO: Polyalkylene oxide EOPO: Ethylene oxide propylene oxide copolymer EOPO(B): EOPO block copolymer EOPO(R): EOPO random copolymer BPA derivative: EOPO adduct of bisphenol A

[0004] Recently, spectacle lenses made of a transparent resin substrate with an optically functional resin layer having various functions (performances), such as photochromic properties and specific wavelength absorption properties (UV / blue light blocking, etc.), have been well known (Patent Document 1 [Abstract], [Claim 1], [Claim 3], [Fig. 1], [Fig. 4], etc.; Patent Document 2 [Abstract], [Claim 1], [Fig. 1], etc.). To impart these functions to the entire lens requires the incorporation of large amounts of expensive photochromic agents and UV absorbers, and in the case of prescription lenses, color unevenness due to thickness changes is likely to occur (Patent Document 2

[0002] to

[0005] etc.).

[0005] In addition, polarized eyeglass lenses and sunglasses with embedded polarizing films to impart polarization, etc., are known in the literature (Patent Document 1 [Claim 4], [Figure 4], etc., Patent Document 3 [Claim 1], [Figure 2], [Figure 3], etc.).

[0006] However, when embedding a polarizing film in an injection molding process, adhesive tape (taping) or a gasket is required to form a molded cavity when injecting the functional resin layer. Taping increases the number of steps, and the adhesive tape or gasket is discarded after each molding. Furthermore, to accommodate the post-injection cure shrinkage, a gasket is typically made of a resilient olefin-based TPE (heat resistance of 90°C or less, Patent Document 3

[0028] ), which partially melts during curing after injection and cannot be reused. Furthermore, with these molding methods, the adhesion between the functional resin layer or polarizing functional layer and the lens substrate is sometimes insufficient without an adhesive layer (Patent Document 2

[0008] to

[0009] , Patent Document 3

[0011] to

[0015] ).

[0007] Furthermore, when molding polarized lenses, the extruded polarizing film is usually cut into a circle to hold it in the mold, but this requires the removal of cutting powder that adheres to the film, washing with water, and drying, which increases the number of steps required before injection molding, and also makes it difficult to position and set the polarizing film inside the injection mold. This problem is particularly pronounced when molding sunglasses with a small curve (large radius of curvature), as the film tends to curl easily.

[0008] Furthermore, resin lens substrates (semi-finished products) are usually subjected to hard coating treatments or the like to produce finished products. The polarized film in finished lenses has had problems with adhesion to the lens substrate (Patent Document 3

[0013] to

[0014] ). This is thought to be because, since it is a stretched film, the lens substrate thermally expands during the hard coating curing heating process, which is usually carried out in an atmosphere of 110°C, while the polarized film (made of polyvinyl alcohol (PVAL)) has a thermal shrinkage rate. Adhesion problems are particularly pronounced in the case of episulfide resins, which have a high thermal expansion rate (see Patent Document 3

[0015] ).

[0009] For the lens substrate (outer diameter 80 mm) molded from various molding materials, the temperature was raised from 25°C to 100°C, and the outer diameter was measured at 25°C intervals to determine the linear expansion coefficient. -3 / K) was 12.1 for allyl diglycol carbonate resin (ADC), 5.1 for 1.60 thiourethane resin, 4.4 for 1.67 thiourethane resin, 6.1 for episulfide resin, and 4.9 for polycarbonate (PC). From these results, it is predicted that it is more difficult to obtain adhesion with eposulfide resin than with thiourethane resin, and even more difficult to obtain adhesion with ADC.

[0010] Furthermore, the PVA polarized film after shaping, which had an approximately octagonal outer shape (length and width at 25°C: 96.65 mm), was heated from 25°C to 100°C in the same manner as in the case of the lens substrate, and the length and width were measured at each temperature in 25°C intervals to determine the shrinkage rate. It was found that the shrinkage rate at 100°C compared to 25°C was approximately 2.25%.

[0011] Materials similar to the molding material for the functional resin layer used in the present invention, namely, technologies relating to thiourethane resins blended with PAO as an adhesive or photochromic modifier, are publicly known in the literature (Patent Document 4 [Claim 1], [Abstract], etc., Patent Document 5 [Claim 1], [Abstract], etc.). Similarly, thiourethane resins that actively use alicyclic diisocyanates are also known in the literature (Patent Document 6 [Claim 1, 2, 3], etc.). [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. 2003 / 008171 [Patent Document 2] Patent No. 2014-156067 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-145513 [Patent Document 4] International Publication No. 2018 / 124063 [Patent Document 5] International Publication No. 2015 / 115648 [Patent Document 6] International Publication No. 2005 / 087829 Summary of the Invention [Problem to be solved by the invention]

[0013] In view of the above, one object (object) of the present invention is to provide a method for molding a transparent resin laminate, which, when producing a transparent resin laminate having a functional resin layer on at least one side of a transparent resin substrate, does not require adhesive tape or gaskets for forming cavities in the functional resin layer, which is expected to reduce the number of steps, can suppress the production of by-products of waste, and has the effect of improving the adhesion of the functional resin layer to the transparent resin substrate.

[0014] Another object (object) of the present invention is to provide a molding method for a transparent resin laminate that, in addition to the above-mentioned effects, can significantly reduce the number of steps required to set the functional film in the mold and also achieve good adhesion between the functional film and the substrate when producing a transparent resin laminate having a functional resin layer in which a functional film (e.g., a polarizing film) is embedded on at least one side of the transparent resin laminate substrate. [Means for solving the problem]

[0015] One of the present inventions (first invention) solves the above-mentioned problems by a method for molding a transparent resin laminate having the following configuration: A method for molding a transparent resin laminate having a functional resin layer on at least one surface of a transparent resin substrate, comprising: (1) A seat mold having a concave surface corresponding to the underside of the transparent resin substrate is prepared, and the concave surface Growth a first step of dropping a monomer (including a prepolymer) of a thermosetting molding material in an amount greater than the volume of the functional resin layer after molding; (2) The assembly in which the transparent resin substrate is placed on the dropped monomer is exposed to an atmosphere at a temperature at which the molding material can gel for a predetermined period of time, thereby diffusing the monomer on the underside of the transparent resin substrate. together The functional resin layer is leaked out of the molding portion, and the backflow to the molding portion is accompanied. Gel formation a second step of shaping the mixture; (3) A third step of hardening the gelled shaped material in the assembly after the second step and releasing it from the mold.

[0016] In the case of the molding method according to the first invention, there is no by-production of waste materials (adhesive tape and gaskets) that occur with conventional molding. By maintaining the mixture in a gelling temperature atmosphere for a predetermined time, Monomer As gelation progresses, The transparent resin laminate is shaped while being subjected to the weight (compressive force). Associated with gelation Absorbs polymerization shrinkage (especially in the vertical direction) At the same time, the monomer flows back into the voids formed on the inner periphery of the molded part. Therefore, the functional resin layer Transparent resin base The adhesion to the substrate is improved.

[0017] In the first invention, it is also possible to "further prepare a spacer mold having an upper cylindrical portion into which the transparent resin substrate can be loosely fitted above and below the spacer portion, and a lower cylindrical portion into which the seat mold can be tightly fitted, and then assemble the seat mold to the lower cylindrical portion of the spacer mold to perform the first drip of the monomer of the molding material in the first step." In this molding method, in addition to the above effects, it is necessary to prepare a spacer mold, but even if the transparent resin substrate has a higher specific gravity than the cured molding material, there is no risk of compressing the shaped gelled product and not being able to ensure the required thickness of the functional resin layer, and since the spacer mold can be reused, almost no waste is produced as a by-product.

[0018] Another aspect of the present invention (second invention) solves the above-mentioned problems by a method for molding a transparent resin laminate having the following configuration.

[0019] On one or both sides of a transparent resin base (semi-finished product) A functional film or functional sheet (hereinafter simply referred to as "functional film") is embedded in upper and lower transparent resin layers. A method for molding a transparent resin laminate, comprising: (1) A seat mold having a concave surface corresponding to the underside of the transparent resin substrate is prepared, and the concave surface a volume greater than the volume of the lower transparent resin layer after molding; A monomer of a thermosetting molding material is first dropped, and then the functional film is placed on the dropped monomer; more than the upper transparent resin layer after molding on the functional film, a first step of adding a second drop of a monomer of a thermosetting molding material; (2) exposing the assembly in which the transparent resin substrate is placed on the second dropped monomer to an atmosphere at a temperature at which the monomer can gel for a predetermined period of time; The monomers are allowed to leak from the molding portions of the upper and lower transparent resin layers, With backflow to each molding section, (2) a second step of gelling and shaping the gelled shaped material; and (3) a third step of hardening the gelled shaped material in the assembly after the second step and releasing it from the mold.

[0020] In the case of the second invention, in addition to the effects of the first invention, the following effects are achieved. In conventional methods, mold-formed polarizing film material requires water washing and drying processes. Furthermore, after circular cutting, any adhering cutting powder must be removed before the circularly cut polarizing film can be set into the injection mold using tweezers on a gasket or film holding member. In contrast, the method of the present invention simply involves placing the film on the seat mold after the first drip. Although deburring is required in a later process, this method is expected to significantly reduce the number of steps required to set the functional film into the injection mold.

[0021] Furthermore, in the above configuration, as in the first invention described above, "a spacer mold can be further prepared, which includes an upper cylindrical portion into which the transparent resin substrate can be loosely fitted and a lower cylindrical portion into which the seat mold can be tightly fitted, and the seat mold can be assembled to the lower cylindrical portion of the spacer mold, and the first drip of the molding material monomer can be performed in the first step." This method, in addition to the effect of providing the spacer mold in the first invention, makes it easier to hold the functional film in a set position. In particular, holding the functional film in a set position is even easier when the peripheral edge of the functional film contacts or engages with the inner surface of the upper cylindrical portion of the spacer mold.

[0022] In the molding method of forming functional resin layers on both sides of a functional film in the second invention group, if the first and second dropped functional resin molding materials are used as the upper and lower layers of the resin substrate, and the seat mold is replaced with the lower mold and the transparent resin substrate is replaced with the upper mold, it can also be applied to molding polarized lenses as shown in Cited Document 3 [Figure 3]. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 2 is an explanatory cross-sectional view showing an example of a molding method (step) when the lens body of the present invention has a specific gravity equal to or greater than that of the molding material of the functional resin layer (with prescription). [Figure 2] FIG. 10 is an explanatory cross-sectional view showing an example of a molding method when the functional resin layer is a polarizing resin layer. [Figure 3] FIG. 2 is an explanatory cross-sectional view showing an example of a method (step) for molding a transparent resin laminate in the case where the lens base of the present invention has a specific gravity lower than that of the molding material of the functional resin layer (no prescription). DETAILED DESCRIPTION OF THE INVENTION

[0024] The molding method for the transparent resin laminate of the present invention will be explained below using "prescription lenses," "polarized lenses," and "non-prescription lenses" as examples.

[0025] The molding method of the present invention is an alternative to the conventional injection molding method of functional resin layers, and does not require the formation of a molding cavity using a gasket or taping.

[0026] The functional resin layer 12 is typically thinner than the lens substrate (transparent resin substrate, organic glass substrate) 11 and has a substantially uniform thickness. Furthermore, its application is not limited to the front (convex) surface of the lens substrate 11, but can also be applied to the rear (concave) surface or both surfaces (convex and concave surfaces) of the lens substrate 11. Since the maximum thickness of the lens substrate 11 is typically 2 to 10 mm and the center thickness is 0.3 to 8 mm, the thickness of the functional resin layer is 1 to 2 mm, e.g., 0.05 to 2.5 mm, and preferably 1 mm or less from the viewpoint of preventing distortion without adhesion. Here, the functional resin layer 12 is exemplified as an optical layer, but is not limited to optical layers and includes layers with chemical or electrical functions such as antibacterial or antiviral agents and antistatic agents.

[0027] Examples of the lens substrate (organic glass substrate) 11 used in the molding method of the present invention include the following transparent organic glass materials for semi-finished, prescription, and non-prescription lenses (specific gravities are given in parentheses). These materials are commercially available from various companies in various grades.

[0028] Semi-finished products and prescription lenses: Episulfide (1.45-1.48), thiourethane (1.2-1.37), polyurethane (1.2-1.3), ADC (1.32), aromatic allyl carbonate (1.25) For non-prescription lenses: PC (1.2), methacrylate (1.2), amorphous polyamide (1.01)

[0029] (1) First, we will explain the molding method for forming a prescription lens (high refractive index lens) into a lens body (semi-finished product; resin body) 11 (see FIG. 1). Here, the lens body 11 is molded from a highly refractive material, and typically has a specific gravity equal to or greater than that of a functional resin molding material.

[0030] In this case, a glass seat mold 13 for shaping the surface side of the functional resin layer 12 and a spacer mold 15 for regulating the thickness of the functional resin layer 12 are prepared.

[0031] Here, the glass seat mold 13 has an outer diameter that can fit (it may be tight or loose) on the lower cylindrical portion 15a of the spacer portion 15a, and the upper surface of the outer periphery is formed as a raised seat surface 13a, with the inside being provided with a curved concave surface 13b that corresponds to the convex surface of the lens body 11. When the spacer mold 15 is assembled to the glass seat mold 13, a seal is formed between the lower surface of the spacer portion 15a and the raised seat surface 13a of the glass seat mold 13. Note that the glass seat mold 13 is usually made of glass from the viewpoints of heat resistance, demoldability, and durability, but the glass seat mold may also be made of other inorganic materials as long as they have similar properties.

[0032] The spacer mold 15 also has lower and upper cylindrical portions 15b, 15c above and below the annular spacer portion 15a, which has a set thickness for the functional resin layer 12. The upper cylindrical portion 15c has an inner diameter that provides a gap around the outer periphery of the lens substrate 11 when the lens substrate 11 is placed on the spacer portion 15a, and serves to prevent leakage of monomer to the outside of the spacer mold 15. The spacer mold 15 is usually made of polypropylene (PP) (e.g., softening temperature: 130°C) from the viewpoints of ease of assembly (adequate flexibility), heat resistance, solvent resistance, and mold releasability, but may also be made of other thermoplastic resins (e.g., polyoxymethylene (POM), polytetrafluoroethylene (PTFE), etc.) that have similar properties.

[0033] Here, the thickness of the spacer portion 15a corresponds approximately to the thickness of the functional resin layer 12. That is, the gap between the opposing surfaces of the lens body 11 and the glass mold 13 is usually preferably 0.05 to 2 mm, more preferably 0.3 to 1.5 mm, and even more preferably 0.4 to 1.0 mm. If the spacer portion 15a is too thin, when a highly viscous material is used, the initial diffusion of the molding material becomes difficult, resulting in molding defects, while if the spacer portion 15a is too thick, striae may occur due to uneven curing of the functional resin.

[0034] Next, the molding method of this embodiment will be specifically described. Note that the present invention is not limited to the following embodiment, but includes various embodiments within the technical scope described in the claims. First, with the spacer mold 15 assembled to the glass mold 13, a thiourethane resin monomer (hereinafter referred to as "monomer") M is dripped onto the concave surface 13a of the glass mold 13 (for example, when the resin layer thickness specification is 0.6 mm and the molding material is thiourethane, the dripping amount is 5 g) (Figure 1(I)).

[0035] The substrate 11 is placed on top of 15a (FIG. 1(II)), and the monomer M is then heat-cured. The heat-curing conditions are, for example, a starting temperature of about 60°C, a final temperature of about 100°C, and a total time of 6 to 10 hours.

[0036] During the initial heating period (initial temperature holding time) (temperature environment where the molding material can gel), the fluidity of the monomer M increases. After diffusing between the glass seat mold 13 and the lens substrate 11, the molding material (monomer) M gels and forms its shape. During this initial diffusion period, the monomer M's fluidity is so high that it leaks (overflows) from the linear annular contact area L between the convex surface 11a of the lens substrate 11 and the inner upper edge of the spacer portion 13a (Figure 1(II)). Then, due to the polymerization shrinkage (thermal curing) of the monomer in the horizontal (lateral) direction, the outer periphery of the filled monomer on the concave surface 11 becomes a reduced-pressure atmosphere, causing the leaked monomer to be sucked back, preventing damage to the outer periphery of the molded product due to polymerization shrinkage. This leakage and backflow of the monomer occurs smoothly because the lens substrate 11 is only lightly resting on the spacer portion 15. Furthermore, the vertical (longitudinal) polymerization shrinkage due to curing proceeds while bearing the weight of the lens substrate, thereby increasing vertical adhesion. In this way, a laminated lens is formed in which the functional resin layer 12 of a set thickness is hardened and adhered (polymerized and adhered) onto the base lens 11. (Figure 1(III)).

[0037] (2) Next, a molding method when the functional resin layer is a polarizing resin layer will be described (see FIG. 2).

[0038] The present invention is basically the same as above. The effect of the present invention is more pronounced when applied to a polarizing film that is prone to curling (especially when the curve is small, such as a 0.5 curve) and has large thermal shrinkage, so the polarizing film will be used as an example for explanation. Naturally, the present invention can also be applied to a polarizing sheet that has a protective layer on one or both sides of the polarizing film. Applicable Furthermore, it can also be applied to functional films such as wavelength cut filters and liquid crystal films. As the polarizing film or polarizing sheet, those exemplified in Patent Documents 3

[0032] and

[0033] can be used.

[0039] The difference is that the polarizing film 19 is embedded in the functional resin layer 12. First, a portion of the required amount of monomer M is dropped into the glass mold 13 (FIG. 2(I)). Next, the polarizing film 19 is placed on the spacer portion 15a, and then the remaining required amount of monomer M is dropped (FIG. 2(II)). Next, the lens body 11 is placed on the polarizing film 19 (FIG. 2(III)). Thereafter, the resin layer is heat-cured in the same manner as above to form a polarized lens (FIG. 2(IV)). Here, the thickness of the polarizing film 19 is preferably 10 to 50 μm. The polarizing film has polarization properties and is extensible enough to conform to the curved surface of the optical element.

[0040] Although the required amounts and compositions of the monomers used in the first and second droppings are the same in the above description, they may be different. That is, one may contain a photochromic agent and the other may contain a specific wavelength absorbing agent. Furthermore, this molding method is not limited to polarizing films, but can also be applied to functional resin layers in which specific wavelength cut films or liquid crystal films are embedded. As mentioned above in (1), this molding method is not limited to lenses with prescription, but can also be applied to lenses without prescription. Polarized lenses are often used in sunglasses without prescription.

[0041] Furthermore, the polarizing film can be made from the general-purpose compounds described in Patent Document 3

[0031] to

[0033] . Among these, the polarizing film uses polyvinyl alcohol (PVA), but from the standpoint of impact resistance, it is preferable to use one protected with polycarbonate. In this molding method, if the functional resin layer material is a thermosetting material such as a thiourethane-based material, the polarizing film after shaping does not require adhesive treatment as described in Patent Document 3

[0035] . This is because the polarizing film hardens and adheres to the resin layer as described above.

[0042] (3) Finally, we will explain the molding method when a non-prescription lens is used as the lens body (semi-finished product) 11 (see Figure 3). Non-prescription lenses 11 are usually injection molded from low specific gravity, impact resistant, low refractive index materials (nD: 1.50 or less), and many of them have a specific gravity lower than that of functional resin molding materials. In this molding method, unlike the above-mentioned molding methods, the functional resin layer 12 is formed using only the glass seat mold 13 and the lens body 11 .

[0043] Therefore, when the functional resin layer 12 made of a thiourethane resin is integrally molded onto the lens substrate 11 of a non-prescription lens, the specific gravity of the lens substrate 11 is smaller than that of the molding material forming the functional resin layer 12, as described above. Therefore, if the thickness of the substrate lens is approximately the same, there is no risk of the functional resin layer being compressed during curing and becoming thinner. Therefore, as shown in Figure 3, molding is possible without a spacer mold 15. Note that if the functional resin layer 12 is thin, such as 0.3 mm or less, this method can also be applied to prescription lenses by adjusting the lens substrate weight and monomer viscosity.

[0044] After dropping the required amount of monomer into the glass mold 13 (FIG. 3(I)), the lens body 11 is placed on the glass mold 13. In this state, the monomer is heated and cured under the same conditions as in (1) above. When the monomer is heated, the fluidity of the monomer increases at the beginning, and the weight of the lens body 11 causes the raised seating surface of the glass mold 13 to contact the lens body 11 and the glass mold 13. 13aThe resin diffuses to the vicinity of the lens body 11 (FIG. 3(II)). Then, as described above, once the heat curing has progressed to a certain extent and the rigidity has reached a level sufficient to hold the lens body 11, the lens body 11 will no longer be thinned. This is because the specific gravity of the lens body 11 is smaller than that of the molding material of the functional resin layer 12.

[0045] The molded article that has been heat-cured is then released from the glass mold 13 to obtain a non-prescription lens molded article in which the functional resin layer 12 has hardened and adhered to the lens body 11 (FIG. 3(III)). After release, the molded article is subjected to an annealing treatment (for example, at around 100°C for 2 to 3 hours when the molding material is a thiourethane resin) to post-cure it and remove internal strain.

[0046] As the raw material composition of the optical element, the functional agent is basically added to the functional resin layer 12, but the functional agent (photochromic agent, UV protection agent, anti-degradation agent, bluing agent, etc.) may also be added to the organic glass substrate 11 as appropriate.

[0047] The monomers (including prepolymers) of the molding compound composition of the functional resin layer used in each of the above embodiments will be specifically described below. Basically, the molding material is not particularly limited as long as it is a transparent thermosetting resin that can be hardened and bonded to the lens substrate (transparent resin substrate).

[0048] However, from the standpoints of transparency, curing adhesion, functional drug dispersibility, etc., thiourethane-based resins are desirable. Furthermore, thiourethane-based resins have a higher refractive index than other general-purpose transparent resins, such as urethane-based, methacrylic-based, polycarbonate-based, or polyamide-based resins, and thus easily resolve problems such as aberrations even when the lens substrate is a prescription lens (high refractive index lens). In particular, when undergoing a hard coating process, resins with heat resistance and a low coefficient of thermal expansion (e.g., Tg: 120°C or higher, see figure) are desirable from the standpoints of distortion and adhesion. Specifically, the thiourethane "MR20" (registered trademark) (catalog listing; Tg: 124°C) manufactured by Mitsui Chemicals, Inc., used in Example 1-1, is desirable, but MR8 (registered trademark) (Tg: 112°C) can also be used.

[0049] In the thiourethane system, desirable embodiments are described below.

[0050] The NCO component is composed mainly of or consists of an alicyclic diisocyanate, and the average functionality of the SH component (hereinafter referred to as "functionality") is preferably 3.0 or more, and more preferably 3.5 or more. The larger the average SH functionality, the smaller the distortion (Example 1-5 compared to Example 1-3, and Example 1-6 compared to Example 1-4). Here, the NCO / SH ratio may be 0.6 to 1.8, but is preferably in the range of 0.8 to 1.4, and more preferably 1.1 to 1.3. Outside these ranges, unreacted components are likely to remain, making it difficult to ensure sufficient heat resistance (softening temperature) (Examples 1-1, 1-3, and 1-4 compared to the remaining Example 1 group).

[0051] It is desirable to use EOPO or an EOPO chain-containing polyol as a modifying component, and adjust the static viscosity (25°C) to 0.2 to 10 Pa·s, preferably 0.5 to 6 Pa·s, and even more preferably 1.5 to 5.5. It has been confirmed that if the average number of functional groups is less than 3.0, it is difficult to ensure a practical surface hardness. If the static viscosity is too low or too high, it is difficult to obtain the appropriate moldability (shapeability) required in the present invention.

[0052] The reason why the NCO component is an alicyclic system is that it provides a resin lens that has relatively high reactivity, yellowing resistance, a high Abbe number, and an excellent balance of high heat resistance (Patent Document 6

[0003] ).

[0053] Among alicyclic NCO components, from the viewpoint of photochromic properties, dimethyl ethyl isocyanate of norbornane ring (bicyclo[2.2.1]heptane) or dimethyl isocyanate of cyclohexane ring is desirable, and bis(isocyanatomethyl)bicyclo[2.2.1]heptane (hereinafter referred to as NBDI) is even more desirable. However, from the viewpoint of lens distortion, hexamethylene diisocyanate (HDI) is more desirable than NBDI (Comparative Example 1-1 vs. Comparative Example 1-2).

[0054] It is sufficient that the alicyclic NCO is the main component, and other aliphatic or alicyclic NCOs can be used in combination. The other aliphatic or alicyclic NCOs can be appropriately selected from well-known NCOs exemplified in Patent Document 5

[0013] to

[0015] .

[0055] Here, the SH component is appropriately selected from various polythiols having functional groups of 2 to 4 listed in Patent Document 5

[0052] , and used alone or in combination after adjusting the average functionality to 3.0 or more as described above. Representative SH components include pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol (all with functional groups of 4), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (GST) (with functional groups of 3), and butanediol bis(thioglycolate) (BDTG) (with functional groups of 2).

[0056] As the OH component, those listed in Patent Document 5

[0016] to

[0043] can be used as appropriate. Among these, those described in Patent Document 4

[0042] to

[0043] , those represented by the following structural formulas (I) and (II), and those represented by the structural formulas in Patent Document 5

[0035] to

[0036] can be used alone or in combination. All of these have the effect of improving adhesion, but in particular, the one represented by structural formula (III) has a greater distortion improvement effect than structural formulas (I) and (II), despite having a small average molecular weight (Mn) of 750 (Table 1, Examples 1-6 and 1-7 versus Example 1-5). HO-(C2H4O) n1 -(C3H6O) m -(C2H4O) n2 -H···(I) HO-(C2H4O) n1 -ran-(C3H6O) n2 -H (II) (where n1, n2, and m are all integers, and Mn is in the range of 3,000 to 15,000)

[0057] [ka] (In formula (III), q and r may be the same or different, each representing a number of 1 or more, and the sum of q and r represents a number of 2 to 100. R 1 and R 2 may be the same or different and represent a hydrogen atom or a methyl group, and multiple R 1 or R 2 may be the same or different.)

[0058] The number average molecular weights (Mn) of the structural formulas (I) and (II) are (I): 2000 to 7000 (preferably 3000 to 5000) and (II): 400 to 2000 (preferably 500 to 1000) (Patent Document 5

[0038] ). They are used alone or in combination so as to achieve the static viscosity (25°C) of 0.2 to 10 Pa·s, preferably 0.5 to 8 Pa·s, and more preferably 1 to 6 Pa·s, which is suitable for the molding method of the present invention. In particular, the BPA derivative represented by structural formula (III) not only improves adhesion but also significantly suppresses the difference in lens substrate curve (center / edge) (see Table 1). The number-average molecular weight of the BPA derivative is not particularly limited as long as the above effects are achieved. In view of availability, it is 500 to 1500. The amount of the BPA derivative EOPO added is 1 to 50 parts, preferably 3 to 30 parts. If the amount added is too large, the viscosity increases, affecting moldability (Examples 1-1 to 1-4).

[0059] In particular, when the lens substrate is made of episulfide resin and a PVA polarized film is embedded, the episulfide resin has poor heat resistance (softening point (Tg) below 100°C). This also solves the problem of thermal deformation during hard coating thermal curing (usually at an ambient temperature of 110-120°C), making it difficult to maintain the set power. Furthermore, even when the lens substrate is made of ADC, which has a high thermal expansion coefficient, the molding method of the present invention allows the thiourethane resin (molding material) to cure while absorbing polymerization shrinkage in the horizontal and vertical directions before the ADC expands at the polymerization initiation temperature. Therefore, the functional resin layer is not molded under significant stress from the ADC lens substrate, making it easier to ensure polymerization adhesion between the functional resin layer and the lens substrate.

[0060] The OH components represented by formulas (I) and (II) can be used in combination with small amounts (0.3 times or less in molar ratio) of the BPA derivative represented by formula (III) above, those with an Mn of 10,000 or greater, as particularly preferred in Patent Document 4

[0044] , or the OH components listed in Patent Documents 5

[0016] to

[0043] , excluding these polyol components. For example, in the case of a BPA derivative, the amount of these components added is 3 parts or more, preferably 8 parts or more, to achieve distortion reduction. The upper limit of the amount of BPA derivative added is 30 parts, preferably 23 parts, and even more preferably 15 parts. Adding too much increases the viscosity, making it difficult to ensure a viscosity sufficient for the monomer of the molding material to diffuse (leak) to the outer periphery of the concave surface 13b of the glass seat mold 13 during the heat curing initiation process.

[0061] These monomer raw materials consisting of each NCO·SH·OH component are blended with functional chemicals such as photochromic agents, UV absorbers, specific wavelength absorbers, and blue-cutting agents as appropriate. The photochromic agent is usually added to a portion of the NCO component (e.g., half of the amount) in advance to pre-dissolve it, and then the remaining NCO·SH·OH components are added along with a catalyst, etc., and the mixture is stirred continuously until it becomes clear, and then filtered to prepare the product.

[0059] As the catalyst, dibutyltin dichloride (DBTC), dimethyltin dichloride (DMTC), etc. can be suitably used.

[0060] As the photochromic agent, one or a mixture of two or more compounds selected from various spiropyran-based, spirooxazine-based, fulgide-based, naphthopyran-based, and other compounds described in Patent Document 5

[0015] to

[0075] can be used as appropriate (ibid.

[0015] ).

[0061] Furthermore, the lens body 11 (optical element) on which the functional resin layer 15 is formed can be appropriately subjected to general-purpose surface treatments such as commonly performed hard coating, anti-fogging treatment, anti-reflection treatment, water-repellent treatment, and anti-static treatment. [Example]

[0062] The present invention will be described in more detail below with reference to examples. The glass seat mold used in the present invention has a concave surface (radius of curvature: 1046 mm), and the spacer mold has a spacer part with a spacer part thickness of 0.8 mm (however, in Examples 1-6, 0.1 mm). Example 1 and Comparative Example 1

[0063] (1) Forming of functional resin layer The compositions of the thiourethane resins forming the functional resin layer 15 are shown in Table 1.

[0064] The functional resin raw material was prepared according to the recipe shown, and 0.2 parts of a catalyst (dibutyltin dichloride) was added to 100 parts of the resin component (monomer), and specific wavelength absorbers (photochromic agent, specific wavelength absorber, and blue cut agent in the power change test in Table 3) were added and mixed. The mixture was then mixed and stirred for 1 hour under a nitrogen gas atmosphere while adjusting the temperature to 15°C.

[0065] Subsequently, the mixture was degassed for 1 hour while stirring and maintained at a liquid temperature of 15° C. and an absolute pressure of 150 Pa, and then filtered through a 1 μm filter to prepare each functional resin raw material for forming the functional resin layer 15.

[0066] The lens body has an outer diameter of 80.0 mm and a 0.5 curve (convex curvature radius: 1046 mm, but calculated with nD: 1.53) and a center thickness of 8.0 mm. A self-made injection molded product made of 1.74 episulfide resin was used.

[0067] In the molding method shown in FIG. 1, the set gap (functional resin layer thickness) was 0.8 mm (0.1 mm in Examples 1-5), and the curing conditions were a total heating time of 6 hours with one intermediate hold between 70 and 100°C.

[0068] In this way, the functional resin layer 12 was hardened and adhered to the organic glass substrate 11, and after demolding, an annealing treatment (110°C x 2 hours) was performed to prepare a laminated semi-finished lens. The outer periphery of the semi-finished product was then cut (deburred) and polished to obtain a laminated lens product (test piece) (untreated with hard coat) with a diameter of 70 mm.

[0069] <Edge distortion suppression effect verification test> For each test piece prepared above, the curve values ​​at the center and edge (10 mm inside the outer periphery) in the horizontal direction were measured using a Carton three-core curve meter, and the difference between these curves was calculated.

[0070] For reference, the initial viscosity and softening point of the molding material (monomer) were determined using the following methods. Initial viscosity: Measured using AS ONE's "Viscotester VT-06" when the raw materials were mixed (immediately before the dropping process). Softening point: A three-core dial gauge (Ozaki Seisakusho "DGN257") was placed on the lens surface, and the temperature was increased, and the temperature was measured when the depth value changed.

[0071] These test results are shown in Table 1-2. Among EOPOs, the BPA derivatives have a significant edge distortion suppression effect (Example 1-8 compared to Examples 1-9 and 1-10, which have the same basic composition). The larger the amount of BPA derivative added, the greater the edge distortion suppression effect, with 3 to 30 parts being preferable, and 8 parts or more being particularly effective (Examples 1-3 to 1-5). Furthermore, the thinner the resin layer thickness, the greater the distortion suppression effect (Example 1-3 with a layer thickness of 0.8 mm compared to Example 1-5 with a layer thickness of 0.1 mm). Furthermore, both Comparative Examples 1-1 and 1-2, which do not contain EOPO, have greater edge distortion than the Examples.

[0072] <Test to confirm change in power before and after hard coating treatment> In each basic formulation of Example 1-1 and Comparative Example 1-1, functional resin materials containing a photochromic agent (gray), a specific wavelength absorber, and a blue-cutting agent were used to prepare lenses in the same manner as the basic formulation. Then, functional lenses with an episulfide resin (nD: 1.74) lens substrate were multi-coated (hard coat treatment (110°C)). The dioptric powers in the horizontal (S) and vertical (C) directions before and after treatment were measured, and the change in dioptric power before and after treatment was determined. The results are shown in Table 2. Example 1-1, which contains a BPA derivative, showed almost no change in dioptric power, while Comparative Example 1-1, which does not contain a BPA derivative, showed a large change in dioptric power, especially in the horizontal direction. The addition of a BPA derivative suppresses the change in dioptric power in the horizontal direction. Example 2 and Comparative Example 2

[0073] <Forming of functional resin layer> The thiourethane resin forming the functional resin layer 15 had the following composition (the number of moles of functional groups in parentheses): NBDI: 46 parts (0.44), GST: 36 parts (0.41), EOPO(B): 18 parts (0.01). Here, NCO / SH: 1.07, NCO / (SH+OH)=1.07.

[0074] (i) Based on the above composition, a molding material was prepared in the same manner as in Example 1 and Comparative Example 1. The static viscosity (measured by the above method) was 0.03 Pa·s. (ii) The shaped polarizing film used was a PVAL polarizing film having a thickness of 33 μm, shaped into a 0.5 curve (radius of curvature 1046 mm) (approximately octagonal outer periphery). (iii) The lens substrates used were injection molded products (self-made) or injection molded products (commercially available) made of the organic glass materials shown in Table 2. In both cases, products with an outer diameter of 80 mm and a 0.5 curve were used. (iv) The spacer mold was assembled to the seat mold, and a polarized lens (test piece) was prepared using the molding method shown in FIG.

[0075] Specifically, it is as follows: (i) A glass seat mold is assembled to a spacer mold, and 5 g of each molding material is first dropped into the center of the depression in the seat mold. (ii) A shaped polarizing film having the same curve as the glass seat mold is placed on the spacer mold. (iii) A second drop of 2 g of thiourethane resin adhesive is applied onto the PVA polarizing film. (iv) Place each of the lens substrates shown.

[0076] The uncured assembly prepared above was placed in an oven and cured for 6 hours with the ambient temperature at 70°C starting and 100°C ending. Then, the glass seat mold and PP spacer mold were removed and the annealing Processing This process was carried out to prepare semi-finished lenses (semi-finished products). The outer periphery of the semi-finished products was cut (deburred) and polished to obtain finished lenses (test specimens) with a diameter of 70 mm that were not multi-coated. Then, conventional multi-coating processes were carried out to prepare each test specimen. Here, this multi-coating was formed by conventional undercoating, hard coating (110°C x 2 hours), and anti-reflection film treatment. Each test specimen was then subjected to evaluation tests for the following items.

[0077] <Film position deviation test> The test piece was cut, and the "displacement distance" of the polarizing film from the convex surface was measured using an AS ONE microscope "USB LDE-07W."

[0078] As can be seen from Table 3 showing the results, Comparative Example 2-1 using the taping method had almost the same positioning ability as the molding method of the present invention. However, in Comparative Example 2-1' using the molding method using a gasket, the film curled and could not be attached.

[0079] <Adhesion test> The following evaluation tests were carried out. (a) Vice breaking test: A non-prescription lens with a center thickness of 2 mm was made, and after processing into an edge shape, it was clamped in a vice and bent to 70% of its outer diameter. The presence or absence of peeling of the film was visually inspected. (b) Nylor processing test: After processing the 0.5mm deep nylon groove 1mm into the round shape, I pried it open with a flathead screwdriver. The presence or absence of film peeling was visually determined. (c) Drilling test A 1.5 mm hole was drilled and the presence or absence of film peeling was visually determined.

[0080] The test results are shown in Table 3. Each example showed good adhesion in all test items, whereas Comparative Example 2-1 using the taping method showed poor adhesion in all test items.

[0081] <Impact resistance test> Each of the above test pieces was processed to a center thickness of 1.2 mm, and after being subjected to a silicone hard coating (curing atmosphere: 110°C), an anti-reflection film was applied by vapor deposition to form the test piece. A steel ball was dropped onto the center of the lens of each test piece from a height of 127 cm in the following order of weight, and the weight of the ball that penetrated was determined. 16.2g → 32g → 50g → 75g → 100g → 200g → 300g → 400g → 500g

[0082] The test results are shown in Table 2, along with the penetration weight of each reference lens substrate. It can be seen that the laminated lenses of the present invention have good impact resistance. Furthermore, the episulfide resin and ADC, which have a penetration weight of 50 g, have significantly improved impact resistance.

[0083] [Table 1-1]

[0084] [Table 1-2]

[0085] [Table 2]

[0086] [Table 3] [Explanation of symbols]

[0087] 11. Lens substrate (transparent resin substrate) 12...Functional resin layer 13···Glass seat type (seat type) 13a... Seat part 13b...Concave 15 Spacer type 15a Spacer part 15b Upper cylindrical part 15c Lower cylindrical part M Functional resin monomer (molding material)

Claims

1. A method for molding a transparent resin laminate having upper and lower transparent resin layers in which a functional film or functional sheet (hereinafter simply referred to as "functional film") is embedded on one or both sides of a transparent resin substrate (semi-finished product), comprising: (1) A first step of preparing a seat mold having a concave surface corresponding to the lower surface of a transparent resin substrate, first dropping a monomer of a thermosetting molding material onto the concave surface in an amount greater than the volume of the lower transparent resin layer after molding, and then placing the functional film on the dropped monomer, and second dropping a monomer of a thermosetting molding material onto the functional film in an amount greater than the volume of the upper transparent resin layer after molding; (2) a second step of exposing the assembly in which the transparent resin substrate is placed on the second dropped monomer to an atmosphere at a temperature at which the monomer can gel for a predetermined time, thereby causing the monomers to leak from the respective molding portions of the upper and lower transparent resin layers and gel while flowing back into the respective molding portions, thereby forming a shape; (3) a third step of hardening the gelled shaped material in the assembly after the second step and releasing it from the mold; A method for molding a transparent resin laminate, comprising:

2. The method for molding a transparent resin laminate described in claim 1 further comprises preparing a spacer mold having an upper cylindrical portion into which the transparent resin substrate can be loosely fitted and a lower cylindrical portion into which the seat mold can be tightly fitted, assembling the seat mold to the lower cylindrical portion of the spacer mold, performing the first drip of the monomer of the molding material in the first step, and further placing the functional film on the spacer mold and performing the second drip.

3. A method for forming a transparent resin laminate in which a functional film has upper and lower thermosetting transparent resin layers on both sides, comprising: (1) A first step of preparing a spacer mold having a lower mold and an upper mold with a concave surface and a convex surface, an upper cylindrical portion into which the upper mold can be loosely fitted, and a lower cylindrical portion into which the lower mold can be tightly fitted, on the upper and lower sides of a spacer portion, and first dropping a monomer of a thermosetting molding material onto the concave surface of the lower mold in an amount greater than the volume of the lower transparent resin layer after molding, and second dropping a monomer of a thermosetting molding material onto the functional film in an amount greater than the volume of the upper transparent resin layer after molding; (2) a second step of exposing the assembly in which the upper mold is placed on the second dropped monomer to an atmosphere at a temperature at which the molding material can be gelled for a predetermined time, causing the monomers to leak from the molding parts of the upper and lower transparent resin layers and gel while flowing back into the molding parts, thereby forming a shape; (3) a third step of hardening and releasing the gelled shaped material in the assembly after the second step; A method for molding a transparent resin laminate, comprising:

4. 4. The method for molding a transparent resin laminate according to claim 3, wherein the second dropping is performed by bringing the peripheral edge of the functional film into contact with or engaging with the inner surface of the upper cylindrical portion of the spacer mold.

5. 5. The method for molding a resin laminate according to claim 1, wherein the functional film is a polarizing film.

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