WO2021172570A1

WO2021172570A1 - Method for manufacturing light-transmitting laminated body, light-transmitting member modifying liquid, light-transmitting laminated body and lens

Info

Publication number: WO2021172570A1
Application number: PCT/JP2021/007560
Authority: WO
Inventors: 勝之高口; 河戸　伸雄
Original assignee: 三井化学株式会社
Priority date: 2020-02-27
Filing date: 2021-02-26
Publication date: 2021-09-02

Abstract

A method for manufacturing a light-transmitting laminated body, having, in the following order: a first step for preparing a laminated body in which a dyeable hard coat layer, a primer layer that contains a visible light absorbing agent, and a light-transmitting substrate are laminated in this order; and a second step for bringing a liquid comprising an ultraviolet absorbing agent into contact with the dyeable hard coat layer of the laminated body.

Description

Manufacturing method of light-transmitting laminate, light-transmitting member modification liquid, light-transmitting laminate and lens

The present disclosure relates to a method for manufacturing a light-transmitting laminate, a light-transmitting member modifying liquid, a light-transmitting laminate, and a lens.

As a method of imparting desired characteristics to a plastic eyeglass lens, a method of adding a functionalizing agent such as an organic dye compound, a photochromic compound, or an ultraviolet absorber to a lens base material (so-called immas method) or a method of imparting functionality is performed. Examples thereof include a method of adding the agent into the component layer laminated on the lens base material.

For example, Patent Document 1 describes a step of preparing a hard coat liquid containing a specific organic dye compound, a specific solvent, and a hard coat material, and the primer of a lens substrate having a primer layer on at least one surface. A method for producing a laminate including a step of coating the hard coat liquid on the layer and a step of curing the hard coat liquid coated on the primer layer to form a hard coat layer is disclosed. There is.

Patent Document 2 discloses a method for producing a hard coat layer containing an organic dye compound, in which a hard coat composition containing an organic dye compound, a resin, and a leveling agent is coated on a functional layer and then dried or the like. Has been done.

Patent Document 3 discloses a plastic spectacle lens including a specific plastic lens wafer and one or more component layers.

[Patent Document 1] International Publication No. 2018/181375 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-134618 [Patent Document 3] US Pat. No. 7,506,977

Patent Documents 1 to 3 describe a laminate in which a primer layer and a hard coat layer are provided on a base material. In Patent Documents 1 to 3, it is assumed that a visible light absorber, an infrared absorber, or an organic dye is added to the primer layer, the hard coat layer, etc., but there is room for improvement in the weather resistance of the visible light absorber, etc. ..

Further, in Patent Documents 1 to 3, a configuration in which an ultraviolet absorber is added to a hard coat layer or the like is not examined. According to the study by the present inventors, when a liquid containing an ultraviolet absorber is impregnated into a light transmitting member such as a laminate to include the ultraviolet absorber in the light transmitting member, the haze of the light transmitting member is large. It was found that the appearance may deteriorate.

An object of the present disclosure is to provide at least one light-transmitting laminate having excellent weather resistance selected from the group consisting of a visible light absorber, an infrared absorber and an organic dye, and a method for producing the same.
Another object of the present disclosure is to provide a light transmitting member modifying liquid capable of maintaining a good appearance of the applied light transmitting member.

The means for solving the above problems include the following aspects.
<1> A dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting base material were laminated in this order. The first step of preparing the laminate and
The second step of bringing the liquid containing the ultraviolet absorber into contact with the dyeable hard coat layer of the laminate, and
A method for producing a light-transmitting laminate having the above in this order.
<2> The method for producing a light-transmitting laminate according to <1>, wherein the liquid containing the ultraviolet absorber further contains a surfactant and a solvent having a hydrophilic group and an aromatic ring.
<3> Production of the light-transmitting laminate according to <1> or <2>, wherein the ultraviolet absorber contains at least one selected from the group consisting of a benzophenone-based compound, a benzotriazole-based compound, and a triazine-based compound. Method.
<4> UV absorbers containing benzophenone compounds and
Surfactant and
Solvents with hydrophilic groups and aromatic rings,
A light-transmitting member modifying liquid containing.
<5> The light-transmitting member modifying liquid according to <4>, wherein the surfactant contains an anionic surfactant.
<6> The light-transmitting member modifying liquid according to <4> or <5>, wherein the surfactant is a salt of an alkyl sulfate ester.
<7> The light-transmitting member modifying liquid according to any one of <4> to <6>, wherein the solvent contains an aromatic alcohol.
<8> The light transmissive member modifying liquid according to any one of <4> to <7>, which satisfies the conditions of the formula (1) or the formula (2) on a mass basis.
Content of benzophenone compound ≥ Content of solvent having hydrophilic group and aromatic ring> Surfactant ... Formula (1)
Content of solvent having hydrophilic group and aromatic ring ≥ Content of benzophenone compound> Content of surfactant ... Formula (2)
<9> In the production of a light transmissive laminate comprising a dyeable hard coat layer and a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber and an organic dye. The light-transmitting member modifying solution according to any one of <4> to <8>, which is used to allow the ultraviolet absorber contained in the member modifying solution to permeate the dyeable hard coat layer and absorb it into the primer layer. ..
<10> A laminate of a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting base material. A light-transmitting laminate in which the primer layer has a higher concentration of an ultraviolet absorber than the dyeable hard coat layer.
<11> A laminate of a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting base material. A light-transmitting laminate in which the concentration of the ultraviolet absorber is higher in the primer layer than in the substrate.
<12> A light-transmitting laminate of <10> or <11> in which the concentration of the ultraviolet absorber is a primer layer> a base material> a dyeable hard coat layer.
<13> The light transmission according to any one of <10> to <12>, wherein the ultraviolet absorber contains at least one selected from the group consisting of a benzophenone compound, a benzotriazole compound and a triazine compound. Sex laminate.
<14> The light transmissive laminate according to any one of <10> to <13>, wherein the visible light absorber has at least one absorption peak in the wavelength range of 400 nm to 650 nm.
<15> A lens comprising the light-transmitting laminate according to any one of <10> to <14>.

The present disclosure can provide at least one light-transmitting laminate having excellent weather resistance selected from the group consisting of a visible light absorber, an infrared absorber and an organic dye, and a method for producing the same.
Further, the present disclosure can provide a light transmitting member modifying liquid capable of maintaining a good appearance of the applied light transmitting member.

_{6 is a graph showing the intensities of C 13} H ₁₁ O ₅ ⁺ ions derived from 2,2', 4,4'-tetrahydroxybenzophenone in a dyeable hard coat layer, a primer layer and a lens substrate. _{_{2,2 ', 4,4'- C 13 H 9}} O 5 derived from tetrahydroxybenzophenone ^- is a graph showing dyeable hard coat layer of ions, the strength of the primer layer and the lens substrate.

In the present disclosure, "-" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the present disclosure, when the amount of each component in the composition or each layer is referred to, when a plurality of substances corresponding to each component are present in the composition or each layer, unless otherwise specified, the composition or each layer It means the total amount of multiple substances present in each layer.
In the present disclosure, the "dyeable hard coat layer" means that when the layer is formed on the surface of a transparent material, it has scratch resistance and is brought into contact with a liquid containing a dye, an ultraviolet absorber, or the like. , A dye, an ultraviolet absorber or the like permeates the layer, and the dye, the ultraviolet absorber or the like means a primer layer having an interface with the layer or a layer capable of contacting, permeating and diffusing with a transparent material.

[Manufacturing method of light-transmitting laminate]
The method for producing a light-transmitting laminate of the present disclosure includes a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting layer. The first step of preparing a laminate in which the base materials of the above are laminated in this order, and the second step of bringing a liquid containing an ultraviolet absorber into contact with the dyeable hard coat layer of the laminate, in this order. Have in.

In the method for producing a light-transmitting laminate of the present disclosure, the weather resistance of at least one selected from the group consisting of visible light absorbers, infrared absorbers and organic dyes (hereinafter, also referred to as "visible light absorbers and the like"). A light-transmitting laminate having excellent properties can be produced. The reason for this is presumed as follows. By bringing the liquid containing the ultraviolet absorber into contact with the dyeable hard coat layer of the laminate, the ultraviolet absorber permeates the dyeable hard coat layer and is absorbed by the primer layer. As a result, the weather resistance of the visible light absorber and the like contained in the primer layer is improved. Therefore, in the method for producing the light transmissive laminate of the present disclosure, a light transmissive laminate having excellent weather resistance of the visible light absorber and the like is used. Can be manufactured.

Further, even when a lens or the like having no ultraviolet ray blocking function is used as a light transmitting base material, visible light having a specific wavelength can be obtained by adopting the method for producing a light transmitting laminated body of the present disclosure. And a light-transmitting laminate that absorbs and cuts ultraviolet rays can be obtained. For example, even when a light-transmitting base material that does not contain an ultraviolet absorber, such as a lens composed of ADC (allyl diglycol carbonate) to which an ultraviolet absorber cannot be added, is used, the light-transmitting laminate of the present disclosure is used. By adopting the manufacturing method of, a sufficient ultraviolet absorber is supplied to the primer layer in order to exhibit the ultraviolet blocking function. Therefore, in the method for producing a light-transmitting laminate of the present disclosure, it is possible to obtain a light-transmitting laminate that maintains the weather resistance of a visible light absorber or the like and further exhibits a sufficient ultraviolet ray blocking function.

(First step)
The method for producing a light-transmitting laminate of the present disclosure includes a first step of preparing a laminate in which a dyeable hard coat layer, a primer layer, and a light-transmitting base material are laminated in this order. The above-mentioned laminate may be obtained from the outside to prepare the laminate, or the laminate may be prepared by producing the laminate by the method described later.

The laminate may be one in which a primer layer and a dyeable hard coat layer are laminated on at least a part of a light-transmitting base material. When the light-transmitting base material is plate-shaped, columnar, or the like, the laminated body may be one in which a primer layer and a dyeable hard coat layer are laminated on at least one surface of the light-transmitting base material. , The primer layer and the dyeable hard coat layer may be laminated on the entire surface of the light-transmitting base material.

The first step is a step of preparing a light-transmitting base material on which a primer layer is formed (preparation step) and a step of forming a dyeable hard coat layer on the light-transmitting base material on which a primer layer is formed. (Dyedable hard coat layer forming step) and may be provided in this order. Further, the above-mentioned preparation step may be a step of forming a primer layer on a light-transmitting substrate (primer layer forming step).

The primer layer forming step may be, for example, a step of forming a primer layer on a light transmitting base material by applying a primer composition to the light transmitting base material.

<Light-transparent base material>
The light-transmitting base material is not particularly limited as long as it is a base material capable of transmitting visible light. Examples of the light-transmitting base material include a glass base material and a plastic lens base material.

The plastic lens base material is poly (thio) urethane, poly (thio) urethane urea, polysulfide, epoxy, polycarbonate, poly (meth) acrylate, ADC (allyl diglycol carbonate), polyolefin, cyclic polyolefin, polyene-polythiol polymer, It may be a base material containing at least one selected from a ring-opened metathesis polymer, polyester, poly (thio) ether, polyamide and polyimide.

The shape of the light-transmitting base material is not particularly limited, and examples thereof include a plate shape and a columnar shape, and a plate shape is preferable.
The plate shape includes a flat plate shape, a shape in which at least one of the two opposing main surfaces in the plate shape is distorted outward, a shape in which at least one of the two opposing main surfaces in the plate shape is distorted inward, and the like.

Light-transmitting base materials include lens base materials such as eyeglass lenses, sunglasses, and single-lens safety glasses, parallel plates for optical equipment, building materials such as window glass, goggles, helmet shields, automobiles, windows used in construction machinery, etc. Examples include glass and front screens.

<Primer composition>
The primer composition is not particularly limited as long as it contains a primer agent and can form a primer layer on a light-transmitting substrate. Hereinafter, the components that can be contained in the primer composition will be described.

The primer composition contains a primer agent. The primer agent preferably contains a resin.
The resin preferably contains at least one selected from urethane-based resin, thiourethane resin, epoxy-based resin, polyester-based resin, melamine-based resin, polyvinyl acetal, and acrylic resin.

The primer composition may contain at least one selected from the group consisting of visible light absorbers, infrared absorbers and organic dyes. The visible light absorber preferably has at least one absorption peak in the wavelength range of 400 nm to 650 nm. The infrared absorber preferably has at least one absorption peak in the wavelength range of 650 nm to 1000 μm.
The visible light absorber, the infrared absorber, and the organic dye may be used independently or in combination of two or more.

As the visible light absorber, a porphyrin-based compound, a squarylium-based compound, a phthalocyanine-based compound and the like are preferable.
Among the above, the visible light absorber is preferably at least one selected from the group consisting of porphyrin compounds, squarylium compounds and phthalocyanine compounds from the viewpoint of light absorption at a wavelength of 585 nm, and is preferably a porphyrin compound. Is more preferable.

When the primer composition contains a visible light absorber, the content of the visible light absorber may be 10 ppm to 1000 ppm or 50 ppm to 300 ppm with respect to the total mass of the primer composition.

As the visible light absorber, a commercially available product may be used, and an organic dye compound is preferable. Specific examples thereof include porphyrin compounds and tetraazaporphyrin compounds. More specifically, PD-311S (manufactured by Yamamoto Kasei Co., Ltd.), UVY-0026 (manufactured by Yamamoto Kasei Co., Ltd.) and UVY-1023 (manufactured by Yamamoto Kasei Co., Ltd.) can be mentioned.

As the infrared absorber, for example, a material that strongly absorbs light in the range from the visible light long wavelength region to the far infrared region having a wavelength of 650 nm to 1000 μm is preferable, and the range from the visible light long wavelength region to the near infrared region having a wavelength of 650 nm to 1000 nm is preferable. A material that strongly absorbs infrared light is more preferable.
More specific examples of the infrared absorber include a composite tungsten oxide and a complex cyclic porphyrazine metal complex. Composite tungsten oxide microparticles have the general formula _M y WO _z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, Fe, 1 kind selected Sn, Al, a Cu It is preferable that the above elements are represented by 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and have a hexagonal crystal structure, and YMDS-manufactured by Sumitomo Metal Mining Co., Ltd. 874 and the like can be mentioned. Examples of the complex cyclic porphyrazine metal complex include YKR-5010 manufactured by Yamamoto Chemicals, Inc. Among these, the infrared absorber tends to preferably contain a complex cyclic porphyrazine metal complex.

Other infrared absorbers and organic dyes include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds, azomethine compounds, squarylium compounds, etc. Examples thereof include organic compounds such as organic metal complexes and cyanine compounds.

When the primer composition contains an infrared absorber or an organic dye, the content of the infrared absorber or the organic dye (or the total content of the UV absorber and the organic dye) is independently determined with respect to the total mass of the primer composition. It may be 10 ppm to 1000 ppm, or 50 ppm to 300 ppm.

The primer composition may contain a solvent. When the primer composition contains a solvent, the viscosity of the primer composition can be adjusted, and the solubility and storage stability of visible light absorbers and the like that can be contained in the primer composition can be improved.

Solvents that can be contained in the primer composition include 1-methoxy-2-propanol, butanol, ethylene glycol monobutyl ether (butyl cellosolve), water, methanol, ethanol, isopropyl alcohol, diacetone alcohol, ethylene glycol monomethyl ether, and ethylene glycol mono. Ethyl ether, ethylene glycol monopropyl ether, n-methylpyrrolidone (NMP) and the like can be mentioned. As the solvent, 1-methoxy-2-propanol, butanol, and ethylene glycol monobutyl ether are preferable.

In addition, the primer composition may contain other function-imparting agents. Other function-imparting agents include anti-fog material, anti-staining material, water-repellent material, ultraviolet absorber, hindered amine-based light stabilizer, leveling agent for making the coating film uniform, and color adjustment. Examples thereof include dyes for this purpose, coating film strength, particles of metal oxide for adjusting the refractive index, and the like.
Examples of the metal oxide particles include silicon oxide; titanium oxide; zirconium oxide; tin oxide; aluminum oxide; tungsten oxide; and antimony oxide particles.
In addition, the primer composition may contain a curing agent for the purpose of accelerating curing. Specific examples of the curing agent include inorganic acids, organic acids, amines, metal complexes, organic acid metal salts, metal chlorides and the like.

Examples of the method of applying the primer composition to the light-transmitting base material include a method of applying the primer composition to the light-transmitting base material, a method of immersing the light-transmitting base material in the primer composition, and the like. .. In the above-mentioned coating method, the primer composition may be applied to a light-transmitting substrate by a known coating method such as spin coating, dip coating, spray coating, or flow coating.

In the method of immersing in the primer composition described above, the immersing time may be 3 seconds to 60 seconds or 10 seconds to 30 seconds.

In the method of immersing the light-transmitting base material in the primer composition described above, the pulling speed at which the light-transmitting base material is pulled up after a lapse of a predetermined time after immersing the light-transmitting base material in the primer composition is 0.1 mm / s. It may be up to 5.0 mm / s, or 0.5 mm / s to 2.5 mm / s.

By curing the primer composition applied on the light-transmitting base material, a primer layer can be formed on the light-transmitting base material.
Examples of the curing method include drying curing, thermosetting, and curing method by irradiation with a single line of energy such as ultraviolet rays and visible light. For example, the primer composition may be heat-cured at 15 ° C. to 130 ° C. under the conditions of 3 minutes to 2 hours.

A step of forming a dyeable hard coat layer on a light-transmitting base material on which a primer layer is formed (a step of forming a dyeable hard coat layer) may be provided in this order. Further, the above-mentioned preparation step may be a step of forming a primer layer on a light-transmitting substrate (primer layer forming step).

The dyeable hard coat layer forming step is, for example, a step of forming a dyeable hard coat layer on the primer layer by applying the hard coat composition to the light transmissive base material on which the primer layer is formed.

<Hard coat composition>
The hard coat composition is not particularly limited as long as it contains a hard coat agent and can form a dyeable hard coat layer on the primer layer. Hereinafter, the components that can be contained in the hard coat composition will be described.

The hard coat composition contains a hard coat agent.
Examples of the hard coat agent include metal oxide particles such as silicon oxide; titanium oxide; zirconium oxide; tin oxide; aluminum oxide; tungsten oxide; particles such as antimony oxide; alkyl group, allyl group, alkoxy group, methacryloxy group, etc. Examples thereof include a silane compound having at least one functional group selected from an acrylicoxy group, an epoxy group, an amino group, an isocyanato group, and a mercapto group; and at least one compound selected from the hydrolyzate of the silane compound. ..

Commercially available hard coat agents may be used, for example, SDC Technologies Inc., which contains a hydrolyzate of a metal oxide and a silane compound. Examples thereof include a hard coat material-containing liquid TC-3000 manufactured by the company.

The hard coat composition may contain a resin.
Examples of the resin include resins such as urethane-based resin, thiourethane resin, epoxy-based resin, polyester-based resin, melamine-based resin, polyvinyl acetal, and acrylic resin.

The hard coat composition may contain at least one selected from the group consisting of visible light absorbers, infrared absorbers and organic dyes (visible light absorbers and the like).
The preferred embodiment of the visible light absorber or the like is the same as the preferred embodiment of the visible light absorber or the like that can be contained in the primer composition.

The hard coat composition may contain a solvent.
Preferred embodiments of the solvent are the same as preferred embodiments of the solvent that can be contained in the primer composition.

The hard coat composition may contain other function-imparting agents, curing agents, etc. that may be contained in the primer composition.

As a method of applying the hard coat composition to the light transmissive base material on which the primer layer is formed, a method of applying the hard coat composition on the primer layer and a light transmissive base material on which the primer layer is formed are used. Examples thereof include a method of immersing in a hard coat composition. In the above-mentioned coating method, the hard coat composition may be applied to a light-transmitting substrate by a known coating method such as spin coating, dip coating, spray coating, or flow coating.

When a hard coat composition containing at least one selected from the group consisting of a visible light absorber, an infrared absorber and an organic dye is applied to a light transmissive substrate on which a primer layer is formed, the hard coat composition is coated. The included visible light absorber or the like is impregnated into the primer layer, and a region containing the visible light absorber or the like is formed in the thickness direction of the primer layer from the surface in contact with the hard coat composition. As a result, even when the primer layer before forming the hard coat layer does not contain a visible light absorber or the like, a laminate having a primer layer containing a visible light absorber or the like can be obtained.

When forming a primer layer containing a visible light absorber or the like using a hard coat composition, it is preferable that the hard coat composition contains a visible light absorber or the like and a solvent. As a result, the impregnation property of the visible light absorber or the like into the primer layer is improved, and the primer layer containing the visible light absorber or the like can be suitably formed. Further, from the viewpoint of efficiently forming a primer layer containing a visible light absorber or the like, the light-transmitting base material on which the primer layer is formed is immersed in a hard coat composition containing a visible light absorber or the like and a solvent. Is preferable.

In the method of immersing in the hard coat composition described above, the immersing time may be 1 second to 300 seconds or 10 seconds to 200 seconds.

In the above-mentioned method of immersing in the hard coat composition, a light-transmitting base having a primer layer formed is formed after a lapse of a predetermined time after being immersed in the hard coat composition. The pulling speed at the time of pulling up the material may be 0.1 mm / s to 10.0 mm / s, or 0.5 mm / s to 5.0 mm / s.

By curing the hard coat composition applied on the primer layer, a dyeable hard coat layer can be formed on the primer layer.
Examples of the curing method include drying curing, thermosetting, and curing method by irradiation with a single line of energy such as ultraviolet rays and visible light. For example, the hard coat composition may be heat-cured at 15 ° C. to 150 ° C. under the conditions of 30 minutes to 5 hours.

From the above, it is possible to manufacture a laminate in which a dyeable hard coat layer, a primer layer, and a light-transmitting base material are laminated in this order.

(Second step)
The method for producing a light-transmitting laminate of the present disclosure includes a second step of bringing a liquid containing an ultraviolet absorber into contact with a dyeable hard coat layer of the laminate.

The preferred embodiment of the liquid containing the ultraviolet absorber is the same as the preferred embodiment of the light transmitting member modifying liquid described later. The UV absorber preferably has at least one absorption peak in the wavelength range of 260 nm to 380 nm.
Specific examples of the ultraviolet absorber include benzophenone-based compounds, benzotriazole-based compounds, triazine-based compounds, and the like, and benzophenone-based compounds are preferable from the viewpoint of being superior in weather resistance of the light-transmitting laminate due to ultraviolet rays, high temperature, and the like.

Examples of the benzophenone compound include 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-. Examples thereof include dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.
Examples of the benzotriazole-based compound include 2- (2H-benzotriazole-2-yl) -4-methylphenol, 2- (2H-benzotriazole-2-yl) -4-tert-octylphenol, and 2- (2H). -Benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-di-tert-pentylphenol, 2- (5-Chloro-2H-benzotriazole-2-yl) -4-methyl-6-tert-butylphenol, 2- (5-chloro-2H-benzotriazole-2-yl) -2,4-tert- Butylphenol, 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and the like can be mentioned.
Examples of the triazine-based compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] 4,6-bis (2,4-dimethylphenyl) -1,3. , 5-Triazine, 2- [4- (2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 dimethylphenyl) -1,3,5- Triazine, 2- [4-[(2-Hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- Examples thereof include 4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine.

Examples of the method of bringing the liquid containing the ultraviolet absorber into contact with the dyeable hard coat layer of the laminate include a method of applying the above-mentioned liquid to the dyeable hard coat layer, a method of immersing the laminate in the above-mentioned liquid, and the like. .. In the above-mentioned coating method, the above-mentioned liquid may be applied to the dyeable hard coat layer by a known coating method such as spin coating or dip coating.

In the method of immersing the laminate in the liquid described above, the immersion time may be 1 minute to 1 hour or 5 minutes to 30 minutes.

In the method of immersing the laminate in the above-mentioned liquid, the temperature of the above-mentioned liquid at the time of immersing the laminate is 50 ° C. to 150 ° C. from the viewpoint of suitably permeating the ultraviolet absorber into the dyeable hard coat layer. It may be 70 ° C. to 120 ° C., or 90 ° C. to 100 ° C.

The liquid containing the ultraviolet absorber may contain a surfactant, a solvent having a hydrophilic group and an aromatic ring, other components and the like. Preferred forms of the surfactant, the solvent having a hydrophilic group and an aromatic ring and other components are the solvent having a surfactant, a hydrophilic group and an aromatic ring described later in the section of the light transmitting member modifying liquid of the present disclosure. And the preferred form of the other ingredients.

As described above, the dyeable hard coat layer, the primer layer, and the light-transmitting base material are laminated in this order, and at least one of the dyeable hard coat layer and the primer layer is a light-transmitting laminate containing an ultraviolet absorber. , Preferably, the dyeable hard coat layer, the primer layer, and the light-transmitting base material are laminated in this order, and the light-transmitting laminate in which the concentration of the ultraviolet absorber is higher in the primer layer than in the dyeable hard coat layer. The body is obtained.

[Light-transmitting laminate]
(First Embodiment)
The light-transmitting laminate of the first embodiment of the present disclosure includes a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and light. It is a laminate with a transparent base material, and the concentration of the ultraviolet absorber is higher in the primer layer than in the dyeable hard coat layer. Since this configuration improves the weather resistance of the visible light absorber and the like contained in the primer layer, it is presumed that the light transmissive laminate of the first embodiment has excellent weather resistance of the visible light absorber and the like.

The method for producing the light-transmitting laminate of the first embodiment is not particularly limited, and for example, it may be produced by the above-described method for producing the light-transmitting laminate of the present disclosure.

In the light-transmitting laminate of the first embodiment, the concentration of the ultraviolet absorber gradually increases from the surface of the dyeable hard coat layer on the primer layer side to the surface of the dyeable hard coat layer opposite to the primer layer side. It may have a reduced configuration.
In the present disclosure, the "plane of the dyeable hard coat layer on the primer layer side" may be the interface between the dyeable hard coat layer and the primer layer.

Further, the concentration of the ultraviolet absorber on the surface of the dyeable hard coat layer on the primer layer side may be higher than the concentration of the ultraviolet absorber other than the surface of the dyeable hard coat layer on the primer layer side.

In the light transmissive laminate of the first embodiment, even if both the primer layer and the dyeable hard coat layer contain at least one selected from the group consisting of visible light absorbers, infrared absorbers and organic dyes. good. As a configuration in which both the primer layer and the dyeable hard coat layer contain a visible light absorber or the like, for example, a hard coat composition containing a visible light absorber or the like is used as a light transmissive base material on which the primer layer is formed. It is obtained by applying and forming a hard coat layer.

Examples of the ultraviolet absorber contained in at least one of the dyeable hard coat layer and the primer layer include benzophenone compounds, benzotriazole compounds, triazine compounds and the like.

(Second Embodiment)
The light-transmitting laminate of the second embodiment of the present disclosure includes a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and light. It is a laminate with a transparent base material, and the concentration of the ultraviolet absorber is higher in the primer layer than in the base material. Since this configuration improves the weather resistance of the visible light absorber and the like contained in the primer layer, it is presumed that the light transmissive laminate of the second embodiment has excellent weather resistance of the visible light absorber and the like.

Even if the light-transmitting laminate of the second embodiment has a structure in which the concentration of the ultraviolet absorber gradually decreases from the surface of the light-transmitting base material on the primer layer side to the opposite surface. good.
In the present disclosure, the "plane on the primer layer side of the light-transmitting base material" may be the interface between the light-transmitting base material and the primer layer.

The possible forms of the light-transmitting laminate of the first embodiment and the possible forms of the light-transmitting laminate of the second embodiment may be appropriately combined.
In the light-transmitting laminate, the concentration of the ultraviolet absorber is preferably primer layer> base material> dyeable hard coat layer.
The concentration of the ultraviolet absorber in the base material may be read as the concentration of the ultraviolet absorber in the region containing the ultraviolet absorber in the base material. The region containing the above-mentioned ultraviolet absorber may be a region up to 20 μm or a region up to 15 μm in the thickness direction of the base material from the surface of the base material on the primer layer side. good.

The content of the ultraviolet absorber contained in the primer layer is preferably 40% by mass or more, preferably 50% by mass or more, assuming that all the ultraviolet absorbers contained in the light-transmitting laminate are 100% by mass. Is more preferable, and 60% by mass or more is further preferable. The upper limit of the content of the ultraviolet absorber contained in the primer layer is not particularly limited, and may be 90% by mass or less, or 80% by mass or less.

The content of the ultraviolet absorber contained in the base material may be 10% by mass or more, or 20% by mass or more, assuming that all the ultraviolet absorbers contained in the light-transmitting laminate are 100% by mass. May be good. The upper limit of the content of the ultraviolet absorber contained in the base material is not particularly limited, and may be 60% by mass or less, or 50% by mass or less.

The content of the ultraviolet absorber contained in the dyeable hard coat layer may be 10% by mass or less, assuming that all the ultraviolet absorbers contained in the light-transmitting laminate are 100% by mass. The lower limit of the content of the ultraviolet absorber contained in the dyeable hard coat layer is not particularly limited, and may be 0% by mass or more.

[lens]
The lens of the present disclosure comprises the light transmissive laminate of the present disclosure.
The type of the above-mentioned lens is not particularly limited, and examples thereof include plastic spectacle lenses, goggles, spectacle lenses for vision correction, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, wrenchular lenses, various plastic lenses such as contact lenses, and the like. ..

[Light-transmitting member modifying liquid]
The light-transmitting member modification liquid of the present disclosure contains an ultraviolet absorber containing a benzophenone-based compound, a surfactant, and a solvent having a hydrophilic group and an aromatic ring. The light-transmitting member modifying liquid of the present disclosure can maintain a good appearance of the imparted light-transmitting member by containing each of the above-mentioned components. The reason for this is presumed as follows. Since the light-transmitting member modifying liquid contains a solvent having a hydrophilic group and an aromatic ring, it has a high affinity with a benzophenone compound also containing an aromatic ring. Therefore, when the light-transmitting member modifying liquid is brought into contact with the light-transmitting member, the benzophenone-based compound easily permeates the light-transmitting member together with the solvent that permeates the light-transmitting member. As a result, since the benzophenone-based compound preferably permeates the inside of the light-transmitting member, deterioration of the appearance due to the occurrence of whitening, cracks, etc. is suppressed, and the appearance of the light-transmitting member can be kept good.

Examples of the light-transmitting member include the above-mentioned laminate and a light-transmitting base material.

The light transmissive member modifying liquid is used in the production of a light transmissive laminate including a dyeable hard coat layer and a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber and an organic dye. In addition, the ultraviolet absorber contained in the light-transmitting member modifying liquid may be used to permeate the dyeable hard coat layer and absorb it into the primer layer. The UV absorber penetrates into the dyeable hard coat layer and is absorbed by the primer layer, which improves the weather resistance of the visible light absorber contained in the primer layer, and thus has excellent weather resistance of the visible light absorber and the like. A light-transmitting laminate can be produced.
The light-transmitting member modifying liquid may be used to allow the ultraviolet absorber to permeate the dyeable hard coat layer and the primer layer and to be absorbed by the primer layer and the substrate.

A preferred form of the dyeable hard coat layer, the visible light absorber, etc. contained in the light-transmitting laminate produced by using the light-transmitting member modifying liquid is the method for producing the light-transmitting laminate of the present disclosure described above. It is the same as the preferred form of at least one selected from the group consisting of the dyeable hard coat layer and the visible light absorber, the infrared absorber and the organic dye described in the item. The light-transmitting laminate produced by using the light-transmitting member modifying liquid is formed by laminating a dyeable hard coat layer, a primer layer containing a visible light absorber, and a light-transmitting base material in this order. It may be the light-transmitting laminate described in the first embodiment and the second embodiment described above.

In the light-transmitting laminate produced by using the light-transmitting member modifying liquid, the concentration of the ultraviolet absorber derived from the light-transmitting member modifying liquid is preferably higher in the primer layer than in the dyeable hard coat layer. It is preferable that the concentration of the ultraviolet absorber derived from the light-transmitting member modifying liquid is higher in the primer layer than in the base material.
The "ultraviolet absorber derived from the light transmitting member modifying liquid" refers to the ultraviolet absorbing agent contained in the light transmitting member modifying liquid, and does not include the ultraviolet absorber previously contained in the base material or the like.
In the light-transmitting laminate produced by using the light-transmitting member modifying liquid, the concentration of the ultraviolet absorber derived from the light-transmitting member modifying liquid may be primer layer> base material> dyeable hard coat layer. preferable.

When the light-transmitting laminate according to the first embodiment and the second embodiment described above is a light-transmitting laminate produced by using a light-transmitting member modifying liquid, preferable conditions for an ultraviolet absorber (for example, for example). The content of the ultraviolet absorber, the concentration of the ultraviolet absorber, etc.) are preferable conditions for the ultraviolet absorber derived from the light-transmitting member modifying liquid (content of the ultraviolet absorber derived from the light-transmitting member modifying liquid, light transmission). It may be read as (concentration of ultraviolet absorber derived from the sex member modifying liquid, etc.).

The light transmitting member modifying liquid contains a benzophenone compound. Specific examples of the benzophenone-based compound include the benzophenone-based compound exemplified in the liquid containing the above-mentioned ultraviolet absorber.

The content of the benzophenone-based compound contained in the light-transmitting member modifying solution is 10 with respect to the total of the benzophenone-based compound, the surfactant, and the solvent having a hydrophilic group and an aromatic ring (hereinafter, also referred to as "specific component"). It is preferably from mass% to 90% by mass, more preferably from 25% by mass to 75% by mass.

The light transmitting member modifying liquid contains a surfactant. As the surfactant, an anionic surfactant is preferable. The anionic surfactant is not particularly limited, and salts of alkyl sulfates such as sodium dodecyl sulfate, sodium alkylbenzene sulfonate, and the like are preferable.

The content of the surfactant contained in the light-transmitting member modifying liquid is preferably 0.1% by mass to 80% by mass, more preferably 1% by mass to 60% by mass, based on the benzophenone compound. preferable.

The light-transmitting member modifying liquid contains a solvent having a hydrophilic group and an aromatic ring. The above-mentioned solvent is not particularly limited as long as it has a hydrophilic group and an aromatic ring. The above-mentioned solvent is preferably a solvent having a hydroxy group and an aromatic ring, and such a solvent is preferably an aromatic alcohol. Specific examples of the aromatic alcohol include benzyl alcohol and phenethyl alcohol, and benzyl alcohol is preferable from the viewpoint that cracks and the like are less likely to occur on the surface of the obtained light-transmitting laminate and the appearance is improved.

The content of the solvent having a hydrophilic group and an aromatic ring contained in the light-transmitting member modifying liquid is preferably 15% by mass to 65% by mass, and 20% by mass to 50% by mass with respect to a specific component. Is more preferable.

The light-transmitting member modifying liquid may satisfy the conditions of the formula (1) or the formula (2) on the basis of mass.
Content of benzophenone compound ≥ Content of solvent having hydrophilic group and aromatic ring> Content of surfactant ... Formula (1)
Content of solvent having hydrophilic group and aromatic ring ≥ Content of benzophenone compound> Content of surfactant ... Formula (2)

From the viewpoint that the benzophenone compound as well as the solvent that permeates the light transmissive member can be more preferably permeated by the light transmissive member, the light transmissive member modifying liquid satisfies the above formula (1) or formula (2) and further has a mass. By the standard, the content of the benzophenone compound: the content of the solvent having a hydrophilic group and the aromatic ring: the content of the surfactant = 1: 0.2 to 2.5: 0.01 to 0.75 is satisfied. Is preferable, and it is more preferable to satisfy 1: 0.2 to 1.9: 0.01 to 0.5.

The light-transmitting member modification liquid may contain a benzophenone-based compound, a surfactant, or other components other than a solvent having a hydrophilic group and an aromatic ring. Examples of other components include ultraviolet absorbers other than benzophenone compounds, solvents other than solvents having a hydrophilic group and an aromatic ring, and the like.

The light transmitting member modifying liquid does not contain other components, or the content of other components is preferably 10% by mass or less based on the total amount of the light transmitting member modifying liquid, and contains other components. It is more preferably absent or 5% by mass or less.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "parts" are based on mass.

(Example 1)
[Preparation of substrate and primer composition]
A lens base material (RAV7 AX, manufactured by Shanghai Conant Optics, 70 mm in diameter, Plano lens) was prepared as a base material, and a primer composition composed of a primer agent (PR-1135, manufactured by SDC Technologies Inc) was prepared.

[Formation of primer layer]
The above-mentioned primer composition was placed in a container, and the above-mentioned lens base material was immersed in the container. The immersion time of the lens substrate in the primer composition was 15 seconds, and the pulling speed of the lens substrate after immersion was 1.3 mm / sec. As described above, the primer composition was applied to the lens base material. Subsequently, the lens substrate was allowed to stand in an oven at 80 ° C. for 5 minutes to dry, and then left to stand at room temperature for 5 minutes or more to cool to obtain a lens having a primer layer.

[Formation of dyeable hard coat layer]
The lens having a primer layer was hard-coated by the following method.
A masterbatch solution having a concentration of 1% by mass in which the visible light absorber shown in Table 1 was dissolved in butyl cellosolve was prepared, and this solution was added to the hard coat agent shown in Table 1 to prepare a hard coat composition. Table 1 shows the amounts of each component of the hard coat agent, the visible light absorber, and the butyl cellosolve in the hard coat composition.
The above-mentioned hard coat composition was placed in a container, and a lens having a primer layer was immersed in the container. The immersion time of the lens in the hard coat composition was 120 seconds, and the pulling speed of the lens after immersion was 1.5 mm / sec. As described above, the hard coat composition was applied to the lens having the primer layer. Subsequently, the obtained lens was allowed to stand in an oven at 110 ° C. for 3 hours to be heat-cured, and then left to cool at room temperature for 5 minutes or more. As a result, a laminate in which the dyeable hard coat layer, the primer layer, and the lens were laminated in this order was obtained.

[Manufacturing of light-transmitting laminate]
As described below, a liquid containing an ultraviolet absorber (ultraviolet absorber-containing composition) was brought into contact with the dyeable hard coat layer of the above-mentioned laminate to produce a light-transmitting laminate.
First, the ultraviolet absorber, the surfactant, and the solvent benzyl alcohol shown in Table 1 are prepared, and each component in the blending amount shown in Table 1 is mixed with water to bring the total amount to 100 parts by mass (shown in Table 1). An ultraviolet absorber-containing composition having a total content of each component and water (100 parts by mass) was prepared.
The above-mentioned UV absorber-containing composition was placed in a container, and the laminate was immersed in the container. The immersion time of the laminate in the ultraviolet absorber-containing composition was 10 minutes, and the temperature of the ultraviolet absorber-containing composition at the time of immersion was 95 ° C. to 98 ° C. Ten minutes after immersing the laminate in the UV absorber-containing composition, the laminate was pulled up, the surface was rinsed with water, and then the laminate was dried. As a result, a light-transmitting laminate in which a dyeable hard coat layer, a primer layer containing a visible light absorber, and a lens were laminated in this order was obtained. Furthermore, when the ultraviolet absorber contained in the light-transmitting laminate was analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the concentration of the ultraviolet absorber was higher in the primer layer than in the dyeable hard coat layer. I confirmed that it was expensive.

[Appearance evaluation of light-transmitting laminate]
The appearance of the light-transmitting laminate obtained by immersing the laminate in the ultraviolet absorber-containing composition as described above was evaluated according to the following evaluation criteria. The results are shown in Table 1.
-Evaluation criteria-
No change: No change in appearance before and after immersion in the UV absorber-containing composition (no haze occurs).
Vanishing haze ... Haze occurred after immersion, but the haze of the light-transmitting laminate disappeared after being left at room temperature for several minutes.
Slight haze ... A slight haze was observed in the light-transmitting laminate.
Slight haze in spots ... Slight spot-like haze was observed in the light-transmitting laminate.
Haze: Haze was observed in the light-transmitting laminate.

(Examples 2 to 12 and Comparative Examples 1 to 8)
In Example 1, the type and amount of a visible light absorber in the hard coat composition, the type of ultraviolet absorber in the composition containing an ultraviolet absorber, the type and amount of a surfactant, the type of solvent, and the like. A light-transmitting laminate was obtained in the same manner as in Example 1 except that the blending amount was changed as shown in Tables 1 to 3.
The appearance of the light-transmitting laminates obtained in Examples 2 to 12 and Comparative Examples 1 to 8 was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

The components of Tables 1 to 3 and Tables 4 and 5 described later are as follows. The blanks in Tables 1 to 3 mean that they have not been mixed.
<Hard coating agent>
TC-3000, SDC Technologies Inc. Made,
MP-1179, SDC Technologies Inc. Made <Visible light absorber>
・ PD-311S, manufactured by Yamamoto Chemicals, Inc. <UV absorber>
・

Seeserb

106, 2,2', 4,4'-tetrahydroxybenzophenone, manufactured by Cipro Kasei Co., Ltd. ・ Seeserb 107, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, manufactured by Cipro Kasei Co., Ltd. ・ Seeserb 101 , 2-Hydroxy-4-methoxybenzophenone,

Seisorb

100, 2,4-dihydroxybenzophenone, Cipro Kasei Co., Ltd., Tinuvin PS, 2- (2-hydroxy-5-tert-butylphenyl) 2H -Benzophenone, manufactured by BASF Japan Co., Ltd. Tinuvin 405, 2- [4-[(2-Hydroxy-3- (2'-ethyl) hydroxy) oxy] -2-hydroxyphenyl] -4,6-bis (2) , 4-Dimethylphenyl) -1,3,5-triazole, manufactured by BASF Japan Co., Ltd. <Facial active agent>
・ SDS, sodium dodecyl sulfate ・ Nikkasan Salt # 7000, manufactured by NICCA CHEMICAL CO., LTD.

As shown in Tables 1 and 2, in Examples 1 to 12, the appearance of the light-transmitting laminate was good by using the specific ultraviolet absorber-containing composition.
On the other hand, as shown in Table 3, in Comparative Examples 1 and 2 using the ultraviolet absorber-containing composition containing no surfactant and a solvent having a hydrophilic group and an aromatic ring, haze was observed in the light-transmitting laminate. The appearance was poor.
Further, as shown in Table 3, in Comparative Examples 3 to 6 in which the UV absorber-containing composition containing no solvent having a hydrophilic group and an aromatic ring was used, haze was observed in the light-transmitting laminate, and the appearance was poor. Met.
Further, as shown in Table 3, in Comparative Examples 7 and 8 in which the ultraviolet absorber-containing composition containing no benzophenone compound was used, spot-like haze was observed in the light-transmitting laminate, and the appearance was poor. rice field.

(Examples 13 to 21)
By changing the content of each component of the ultraviolet absorber-containing composition in Example 1 as shown in Tables 4 and 5, the ultraviolet absorber-containing compositions used in Examples 13 to 21 were prepared.
Regarding the production conditions of the light-transmitting laminate (immersion conditions in Table 4 and Table 5), the immersion time was changed as shown in Tables 4 and 5, but the same as in Example 1 from Example 13 to Example 1. Twenty-one light-transmitting laminates were produced.

[Measurement of transmittance before and after immersion]
Transmittance of the laminate (transmittance before immersion in the UV absorber-containing composition) and transmittance of the light-transmitting laminate of Examples 13 to 21 (transmittance after immersion in the UV absorber-containing composition) Was measured using a spectrophotometer (UV-1800, manufactured by Shimadzu Corporation). The results of transmittance at 380 nm, 400 nm and 585 nm are shown in Tables 4 and 5.

[Appearance evaluation of light-transmitting laminate]
The appearance of the light-transmitting laminates of Examples 13 to 21 obtained by immersing the laminate in the ultraviolet absorber-containing composition as described above was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
-Evaluation criteria-
No change: No change in appearance before and after immersion in the UV absorber-containing composition (no haze occurs).
Vanishing haze ... Haze occurred after immersion, but the haze of the light-transmitting laminate disappeared after being left at room temperature for several minutes.
Slight haze in spots ... Slight spot-like haze was observed in the light-transmitting laminate.
Cracks ... Some cracks were seen.

[Measurement of transmittance before and after accelerated weather resistance test]
The transmittance of the light-transmitting laminates of Examples 13 to 21 before the accelerated weather resistance test and the transmittance of the light-transmitting laminates of Examples 13 to 21 after the accelerated weather resistance test are measured by a spectrophotometer (UV-1800, stock. It was measured using the company Shimadzu Seisakusho). The measurement wavelengths are 380 nm, 400 nm and 585 nm. The results are shown in Tables 4 and 5.
The accelerated weather resistance test was carried out using an accelerated weather resistance tester (Model QUV / se) manufactured by Q-Lab under ^{the conditions of an irradiation amount of 0.50 W / m 2} , a temperature of 50 ° C., and a test time of 150 hours (rainfall /). No humidity control).

[Appearance evaluation of light-transmitting laminate after accelerated weather resistance test]
The appearance of the light-transmitting laminates of Examples 13 to 21 after the accelerated weather resistance test as described above was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
-Evaluation criteria-
No signicant change: No change in appearance (no haze occurs) before and after immersion in the composition containing an ultraviolet absorber.
Very slit color fading ... Slight fading was seen.
Color fading ... Fading was seen.
Cracks ... Some cracks were seen.
Some longer Cracks ... Some longer cracks were seen.

(Comparative Example 9)
A laminate not immersed in the UV absorber-containing composition of Example 1 was prepared. Using this laminate, the transmittance before and after the accelerated weather resistance test was measured in the same manner as in Example 13. The results are shown in Table 5.

As shown in Tables 4 and 5, the rate of change in transmittance (Delta) before and after the accelerated weathering test in Examples 13 to 21 is smaller than the rate of change in transmittance before and after the accelerated weathering test in Comparative Example 9. there were. As a result, it was found that the light-transmitting laminates obtained in Examples 13 to 21 were superior to the light-transmitting laminates obtained in Comparative Example 9 in the weather resistance of the visible light absorber. ..
Further, as shown in Tables 4 and 5, in Examples 13 to 21, the transmittance at 380 nm and 400 nm after immersion was lower than the transmittance at 380 nm and 400 nm before immersion. As a result, it was confirmed that the ultraviolet absorber contained in the ultraviolet absorber-containing liquid was supplied into the light-transmitting laminate.

(Examples 22 to 24)
In Example 1, the type and amount of a visible light absorber in the hard coat composition, the type of ultraviolet absorber in the composition containing an ultraviolet absorber, the type and amount of a surfactant, the type of solvent, and the like. A light-transmitting laminate was obtained in the same manner as in Example 1 except that the blending amount was changed as shown in Table 6.
The appearance of the light-transmitting laminates obtained in Examples 22 to 24 was evaluated in the same manner as in Example 1. The results are shown in Table 6. In Example 22, "Cracks" means that some cracks were found in the appearance of the light-transmitting laminate.

Each component of Table 6 and Table 7 described later is as follows. The blanks in Table 6 mean that they have not been mixed.
<Visible light absorber>
-UVY-1023, manufactured by Yamamoto Chemicals, Inc., maximum absorption wavelength 480 nm
-ABS 473, manufactured by Exciton, maximum absorption wavelength 473 nm
-ABS 594, manufactured by Exciton, maximum absorption wavelength 594 nm

(Examples 25 to 27)
An ultraviolet absorber-containing composition having the composition shown in Table 7 was prepared.
Regarding the production conditions of the light-transmitting laminate, the light-transmitting laminates of Examples 25 to 27 were produced in the same manner as in Example 1 as shown in Table 7.
Further, each physical property was measured in the same manner as in the light-transmitting laminates of Examples 13 to 21. The results are shown in Table 7.

(Comparative Examples 10 to 12)
Laminates not immersed in the UV absorber-containing compositions of Examples 25-27 were prepared. Using this laminate, the transmittance after the accelerated weathering test was measured in the same manner as in Example 13. The results are shown in Table 7.

As shown in Table 7, the volatility (Delta) of the transmittance after the accelerated weathering test in Examples 25 to 27 is smaller than the volatility of the transmittance after the accelerated weathering test in Comparative Examples 10 to 12. rice field. As a result, the light-transmitting laminates obtained in Examples 25 to 27 are superior to the light-transmitting laminates obtained in Comparative Examples 10 to 12 in the weather resistance of the visible light absorber. Do you get it.
Further, as shown in Table 7, in Examples 25 to 27, the transmittance at 380 nm and 400 nm after immersion was lower than the transmittance at 380 nm and 400 nm before immersion. As a result, it was confirmed that the ultraviolet absorber contained in the ultraviolet absorber-containing liquid was supplied into the light-transmitting laminate.

(Example 28)
[AFM-IR analysis]
An untreated lens substrate (RAV7 AX), a primer PR-1135 is applied, then a dried lens substrate (RAV7 AX), a hard coat agent TC-3000 is applied, and then thermosetting is performed. IR analysis was performed on the lens substrate (RAV7 AX), the ultraviolet absorber Seesorb 106, and the visible light absorber PD-311S. Was overwritten IR spectrum obtained, 1610 cm ^-1 and 1590 cm ^-1 in the peak derived from Seesorb 106 has confirmed that no overlap with peaks from other samples. Therefore, AFM-IR (Atomic Force Microscope based Infrared Spectroscopy) analysis was performed using these two peaks (1610 ^{cm -1} and 1590 cm ^{-1) as index peaks.}

A laminate in which a dyeable hard coat layer, a primer layer, and a lens base material are laminated in this order and the ultraviolet absorber-containing composition has not been immersed, and the laminate contains the ultraviolet absorber-containing composition of Example 1. A sample having a cross section in which a primer layer and a dyeable hard coat layer are laminated on a lens base material by processing a light-transmitting laminate obtained by immersing the object in an object at 95 ° C. to 98 ° C. for 5 minutes or 10 minutes, respectively. Was produced.

When the AMF image and IR intensity image of the sample derived from the laminate not subjected to the dipping treatment were confirmed, a dyeable hard coat layer and a primer layer were confirmed. Moreover, in the point analysis of the primer layer, only the peak of the primer component could be confirmed.

In the sample derived from the light-transmitting IR laminate obtained by immersing the composition in the UV absorber-containing composition for 5 minutes, the UV absorber was found from ^{the IR intensity image of the peak (1615 cm -1} ) derived from the UV absorber. Results presumed to be unevenly distributed in the primer layer were obtained. In the region including the primer layer, since the peak derived from an ultraviolet absorbent peak derived from the primer component (1530cm ^{^-1)} (1615cm ^-1) was confirmed in the same manner, the ultraviolet absorber is distributed throughout the primer layer It is presumed that it is.
When the peaks derived from the UV absorbers obtained on the dyeable hard coat layer side and the lens base material side of the primer layer were compared, no difference was observed in their strengths, and the UV absorbers were uniformly distributed in the primer layer. The analysis results are likely to exist.
Further, when the inside of the lens base material was analyzed, a peak derived from the ultraviolet absorber was observed inside about 2 μm from the surface, but at 5 μm inside, only the noise level could be confirmed as the above-mentioned peak. Therefore, it was confirmed that the ultraviolet absorber was impregnated up to about 2 μm inside the lens base material.

In the sample derived from the light-transmitting IR laminate obtained by immersing in the composition containing an ultraviolet absorber for 10 minutes, the ultraviolet absorber is unevenly distributed in the primer layer as in the sample obtained by immersing in the above-mentioned 5 minutes. The results presumed to be the case were obtained, and the analysis results were also obtained in which it is highly possible that the UV absorber was uniformly present in the primer layer.
Further, when the inside of the lens base material was analyzed, a peak derived from the ultraviolet absorber was observed inside 2 μm to 15 μm from the surface, but the above-mentioned peak was not confirmed inside 20 μm. Therefore, it was confirmed that the ultraviolet absorber was impregnated up to about 15 μm inside the lens base material.

(Example 29)
[TOF-SIMS analysis]
Sample 1 coated with only PR-1135 as a primer on glass, sample 2 coated with only TC-3000 as a hard coating agent on glass, and PR-1135 and TC-3000 coated on a lens substrate (RAV7 AX). Then, after curing, the sample 3 obtained by immersing the composition containing the ultraviolet absorber of Example 1 containing the ultraviolet absorber Seesorb 106 at 95 ° C. to 98 ° C. for 10 minutes, and the ultraviolet absorber. Sample 4 was prepared as a single Seesorb 106 (2,2', 4,4'-tetrahydroxybenzophenone). TOF-SIMS analysis (time-of-flight secondary ion mass spectrometry) was performed on Sample 3. As shown in FIGS. 1 and _{_{2 2,2 ', C 13 H 11}} O 5 + ions and _C 13 _H 9 _{O 5} from 4,4'-tetrahydroxy-benzophenone ^- slightly confirm ions lens surface It was confirmed that the primer layer was almost uniform on the lens cutting surface.
The analyzed sample 3 was cut at a low angle, and a primer layer having a film thickness of a little over 1 μm was observed at about 110 μm. Since the surface resolution of TOF-SIMS analysis is about 1 μm and the concentration gradient of the UV absorber is not confirmed in the primer layer, it is possible that the UV absorber is uniformly present in the primer layer for Sample 3. Can be judged to be high.
Further, as in the AFM-IR analysis, it was confirmed from the results of FIGS. 1 and 2 and the secondary ion image that the ultraviolet absorber may be present in the lens substrate.

(Examples 30 and 31 and Comparative Examples 13 and 14)
[Evaluation of transmittance before and after peeling of dyeable hard coat layer and primer layer]
The primer composition (PR-1135) was applied to the lens base material (RAV7 AX) in the same manner as in Example 1 to obtain a lens base material having a primer layer. Next, using the hard coat composition of Example 1, a dyeable hard coat layer, a primer layer, and a lens base material were laminated in this order in the same manner as in Example 1 to obtain a laminate.
Next, Seesorb 106, which is an ultraviolet absorber, SDS, which is a surfactant, and benzyl alcohol, which is a solvent, are dissolved in water to dissolve 1.75 parts by mass of the ultraviolet absorber and surface activity with respect to 100 parts by mass of the total amount. A UV absorber-containing liquid containing 0.1 parts by mass of the agent and 1.0 part by mass of benzyl alcohol was prepared.

The laminate obtained as described above was immersed in an ultraviolet absorber-containing liquid for 5 minutes or 10 minutes to obtain light-transmitting laminates of Examples 30 and 31, respectively. Further, only the lens base material on which the dyeable hard coat layer and the primer layer were not formed was designated as Comparative Example 13, and the laminate not subjected to the immersion treatment in the ultraviolet absorber-containing liquid was designated as Comparative Example 14.

The transmittances of the light-transmitting laminates of Examples 30 and 31 and the lens substrate of Comparative Example 13 and the laminate of Comparative Example 14 were measured using a spectrophotometer (UV-1800, manufactured by Shimadzu Corporation). bottom. The measurement wavelengths are 380 nm, 400 nm and 585 nm. These transmittances were measured before and after immersion in the ultraviolet absorber-containing liquid, and for Examples 30 and 31, and Comparative Example 14 on the light-transmitting laminate after the dyeable hard coat layer and the primer layer were peeled off. The results are shown in Table 8.

In Table 8, when the light-transmitting laminate after peeling off the dyeable hard coat layer and the primer layer of Comparative Example 14 and the lens base material of Comparative Example 13 were compared, the results of the transmittance were almost the same. ..
In the light-transmitting laminates of Examples 30 and 31, the transmittance at 380 nm was almost zero even after the dyeable hard coat layer and the primer layer were peeled off, and the transmittance at 400 nm was also higher than that before the peeling. However, the transmittance was lower than that of the lens base material of Comparative Example 13.
Therefore, from the results in Table 8, by immersing the laminate in the UV absorber-containing liquid for a relatively short time, the UV absorber diffuses into the primer layer, and the UV absorber in the primer layer comes into contact with the lens substrate. As a result, it is presumed that it diffuses into the lens substrate.

The disclosure of Japanese Patent Application No. 2020-032132 filed on February 27, 2020 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims

A laminate in which a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting base material are laminated in this order. The first step to prepare and
The second step of bringing the liquid containing the ultraviolet absorber into contact with the dyeable hard coat layer of the laminate, and
A method for producing a light-transmitting laminate having the above in this order.
The method for producing a light-transmitting laminate according to claim 1, wherein the liquid containing the ultraviolet absorber further contains a surfactant and a solvent having a hydrophilic group and an aromatic ring.
The method for producing a light-transmitting laminate according to claim 1 or 2, wherein the ultraviolet absorber contains at least one selected from the group consisting of a benzophenone compound, a benzotriazole compound and a triazine compound.
UV absorbers containing benzophenone compounds and
Surfactant and
Solvents with hydrophilic groups and aromatic rings,
A light-transmitting member modifying liquid containing.
The light-transmitting member modifying liquid according to claim 4, wherein the surfactant contains an anionic surfactant.
The light-transmitting member modifying liquid according to claim 4 or 5, wherein the surfactant is a salt of an alkyl sulfate ester.
The light-transmitting member modifying liquid according to any one of claims 4 to 6, wherein the solvent contains an aromatic alcohol.
The light-transmitting member modifying liquid according to any one of claims 4 to 7, which satisfies the conditions of the formula (1) or the formula (2) on a mass basis.
Content of benzophenone compound ≥ Content of solvent having hydrophilic group and aromatic ring> Surfactant ... Formula (1)
Content of solvent having hydrophilic group and aromatic ring ≥ Content of benzophenone compound> Content of surfactant ... Formula (2)
A light-transmitting member modifying liquid during the production of a light-transmitting laminate comprising a dyeable hard coat layer and a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber and an organic dye. The light-transmitting member modifying solution according to any one of claims 4 to 8, which is used to permeate the dyeable hard coat layer with the ultraviolet absorber contained in the above and absorb it into the primer layer.
It is a laminate of a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting base material, and is an ultraviolet absorber. A light-transmitting laminate having a higher concentration of the primer layer than the dyeable hard coat layer.
It is a laminate of a dyeable hard coat layer, a primer layer containing at least one selected from the group consisting of a visible light absorber, an infrared absorber, and an organic dye, and a light-transmitting base material, and is an ultraviolet absorber. A light-transmitting laminate having a higher concentration of the primer layer than that of the base material.
The light-transmitting laminate according to claim 10 or 11, wherein the concentration of the ultraviolet absorber is primer layer> base material> dyeable hard coat layer.
The light-transmitting laminate according to any one of claims 10 to 12, wherein the ultraviolet absorber contains at least one selected from the group consisting of a benzophenone compound, a benzotriazole compound and a triazine compound. ..
The light-transmitting laminate according to any one of claims 10 to 13, wherein the visible light absorber has at least one absorption peak in the wavelength range of 400 nm to 650 nm.
A lens comprising the light-transmitting laminate according to any one of claims 10 to 14.