JPWO2018131531A1 - Optical member forming laminate, optical member sheet and method of manufacturing the same, three-dimensional structure and method of manufacturing the same - Google Patents

Abstract

The laminate for forming an optical member has a thermoplastic base material containing an ultraviolet absorber, and an optical member forming layer disposed on the surface of the thermoplastic base material, and the optical member forming layer includes the thermoplastic group. A photopolymerization initiator having a maximum absorption wavelength on the shorter wavelength side than the wavelength at which the light transmittance of the material is 50%, and a maximum on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate is 50%. And a photopolymerization initiator having an absorption wavelength. Moreover, the optical member sheet | seat using the said laminated body for optical member formation, its manufacturing method, a three-dimensional structure, and its manufacturing method are provided.

Description

  The present disclosure relates to an optical member forming laminate, an optical member sheet and a method of manufacturing the same, and a three-dimensional structure and a method of manufacturing the same.

Optical member sheets provided with various optical lenses on the substrate surface are used in various applications.
As an optical member sheet provided with an optical lens, for example, it has a hemispherical optical lens on a base material, and has an optical member which can be enlarged when the article is visually observed, an optical lens having a sawtooth cross section A prism sheet capable of displaying various optical designs, a lenticular sheet having an optical lens in which convex lenses having semi-cylindrical surfaces are aligned in one direction and displaying different images depending on viewing angles, or A microlens array having a plurality of hemispherical microlenses on a substrate, and the like can be mentioned.

Among optical member sheets, lenticular sheets are used in various fields as a medium for displaying an image different depending on a viewing angle.
In the lenticular sheet, generally, an image row group (lenticular image) in which a plurality of interlaced images are combined is arranged on the side opposite to the side having the lenticular lens, and the image row group is observed through the lenticular lens. Depending on the angle to be observed, one or more images of the image sequence group can be displayed.
As described above, the lenticular sheet, the prism sheet, the microlens array and the like described above are provided on the surface of the substrate opposite to the side having the optical lens layer (hereinafter referred to as the substrate) for the purpose of taking advantage of design characteristics. It may be generally used by forming a printing layer on the back side of

Moreover, as a conventional photocurable resin composition for optical members or optical members, what was described in Unexamined-Japanese-Patent 2004-258071 or Unexamined-Japanese-Patent 2013-228729 is known.
In JP-A-2004-258071, in an optical article in which an optically useful fine concavo-convex pattern is formed on a translucent base material, the fine concavo-convex patterns are ultraviolet curable resin on both sides of the translucent base material. There is proposed an optical article which is formed, and the ultraviolet curable resin is different on both sides.
Further, in JP 2013-228729 A, the glass transition temperature of the homopolymer thereof is 80 to 200 ° C., and the glass transition temperature of the homopolymer thereof is -40 to 40 ° C. A glass transition temperature of the cured product of the active energy ray irradiation is 40 to 50, comprising, as essential components, a polyfunctional (meth) acrylate (B), a polydialkylsiloxane (C) which may be modified, and a photopolymerization initiator (D) An active energy ray curable composition for optical parts characterized in that the temperature is 80 ° C. has been proposed.

Problem to be solved by one embodiment of the present invention is to provide a layered product for optical member formation which can obtain an optical member sheet which is excellent in fabrication nature, abrasion resistance, and light resistance.
The problem to be solved by the other embodiments of the present invention is to provide an optical member sheet excellent in moldability, abrasion resistance and light resistance, a method of manufacturing the same, a three-dimensional structure and a method of manufacturing the same. .

Means for solving the above problems include the following aspects.
<1> Thermoplastic base material containing a UV absorber, and
An optical member forming layer disposed on the surface of the thermoplastic substrate,
The optical member forming layer has a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light transmittance of the thermoplastic substrate is 50 A laminate for forming an optical member, comprising: a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the% wavelength.
<2> Thermoplastic base material containing a UV absorber, and
An optical member forming layer disposed on the surface of the thermoplastic substrate,
The optical member forming layer has a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light transmittance of the thermoplastic substrate is 50 A laminate for forming an optical member, comprising: a polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the% wavelength wavelength.
<3> In the optical member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% in the optical member forming layer is 0.1% by mass to 1.0% by mass with respect to the total mass,
In the optical member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is the total mass of the optical member forming layer. On the other hand, the laminate for forming an optical member as described in <1>, which is 0.1 mass% to 1.0 mass%.
<4> In the optical member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% in the optical member forming layer is 0.1% by mass to 1.0% by mass with respect to the total mass,
In the optical member forming layer, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material becomes 50% is the optical member The laminated body for optical member formation as described in said <2> which is 0.025 mass%-0.25 mass% with respect to the total mass of.
<5> The wavelength at which the light transmittance of the ultraviolet absorber is 50% is more than 380 nm and less than 405 nm,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50% is 380 nm or less,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is 405 nm or more. Any of the above <1> to <4> The laminated body for optical member formation as described in any one.

<6> Thermoplastic base material containing UV absorber, and
And an optical member disposed on the surface of the thermoplastic substrate,
A polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light of the thermoplastic substrate An optical member sheet comprising: a polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than a wavelength at which the transmittance is 50%.
<7> In the optical member, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% is optical 0.025 mass% to 0.25 mass% with respect to the total mass of the member forming layer,
In the optical member, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is the entire optical member The optical member sheet as described in said <6> which is 0.025 mass%-0.25 mass% with respect to mass.
<8> The wavelength at which the light transmittance of the ultraviolet absorber is 50% is more than 380 nm and less than 405 nm,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50% is 380 nm or less,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is 405 nm or more, described in the above <6> or <7> Optical member sheet.

<9> A thermoplastic base material containing a UV absorber, and an optical member forming layer disposed on the surface of the thermoplastic base material, wherein the optical member forming layer is the light transmittance of the thermoplastic base material And a photopolymerization initiator having a maximum absorption wavelength on the shorter wavelength side than a wavelength of 50%, and a light having a maximum absorption wavelength on a longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate is 50%. Preparing an optical member-forming laminate including a polymerization initiator, and
A method of manufacturing an optical member sheet, comprising the step of forming an optical member by exposing the optical member forming layer twice or more.
<10> The wavelength at which the light transmittance of the ultraviolet absorber is 50% is more than 380 nm and less than 405 nm,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50% is 380 nm or less,
The optical member sheet according to the above <9>, wherein the maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate is 50% is 405 nm or more Manufacturing method.
<11> In the step of forming the optical member, the above <9> or <10>, wherein one or more exposures are performed from the thermoplastic substrate side, and then one or more exposures are performed from the optical member forming layer side The manufacturing method of the optical member sheet as described in-.
<12> Between the first exposure and the last exposure in the process of forming the optical member,
Forming a printing layer on the side of the thermoplastic substrate opposite to the side on which the optical member forming layer is disposed;
A step of cutting the optical member forming laminate into a desired shape;
The manufacturing method of the optical member sheet as described in any one of said <9>-<11> which performs at least 1 process chosen from the group which consists of the process of shaping the said optical member formation layer in the shape of an optical member. .
<13> A laminate for forming an optical member according to <2> or <5>, or a three-dimensional molding of the optical member sheet according to any one of <6> to <8> Dimensional structure.
<14> A step of three-dimensionally molding the optical member sheet as described in <2> or <5>, or the optical member sheet according to any one of <6> to <8>. Method of manufacturing three-dimensional structure.
The manufacturing method of the three-dimensional structure as described in said <14> which further includes the process of inject-molding resin in the three-dimensional molded object obtained by the process of <15> said three-dimensional molding.

According to one embodiment of the present invention, it is possible to provide an optical member forming laminate from which an optical member sheet excellent in moldability, abrasion resistance and light resistance can be obtained.
Furthermore, according to another embodiment of the present invention, it is possible to provide an optical member sheet excellent in moldability, abrasion resistance and light resistance, a method of manufacturing the same, a three-dimensional structure and a method of manufacturing the same.

It is a schematic diagram showing an example of a lenticular sheet in the present disclosure.

Hereinafter, the present disclosure will be described in detail.
In addition, in this specification, the description of "xx-yy" represents the numerical range containing xx and yy.
The upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit in the numerical range other stepwise described in the numerical range described stepwise in the present specification. . In addition, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the example.
In the present specification, "(meth) acrylic" is a term used in a concept including both acrylic and methacrylic, and "(meth) acryloyl" is a term used as a concept including both acryloyl and methacryloyl. It is.
In addition, the term "step" in the present specification is not limited to an independent step, and may be referred to as the term if the intended purpose of the step is achieved, even if it can not be clearly distinguished from other steps. included.
A hydrocarbon group such as an alkyl group, an aryl group, an alkylene group and an arylene group in the present disclosure may have a branch or a ring structure unless otherwise specified.
Furthermore, in the present disclosure, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
Also, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Moreover, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all are trade names manufactured by Tosoh Corp.) unless otherwise noted. It is a molecular weight which is detected using a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and a polystyrene as a standard substance.

(Laminated body for optical member formation)
A first embodiment of the laminate for forming an optical member according to the present disclosure (also referred to as “the first laminate according to the present disclosure”) is a thermoplastic substrate containing a UV absorber, and the above-mentioned thermoplastic group Photopolymer having an optical member forming layer disposed on the surface of the material, wherein the optical member forming layer has a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50% An initiator (also referred to as a “short wavelength type photopolymerization initiator”) and a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% (“ Also referred to as “long-wavelength photopolymerization initiator”.
A second embodiment (also referred to as a “second laminate according to the present disclosure”) of a laminate for forming an optical member according to the present disclosure is a thermoplastic base material containing an ultraviolet absorber, and the above-mentioned thermoplastic group Photopolymer having an optical member forming layer disposed on the surface of the material, wherein the optical member forming layer has a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50% It includes an initiator and a polymerization-type decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate is 50%.
The second embodiment of the optical member forming laminate according to the present disclosure is the optical member forming layer in the first embodiment of the optical member forming laminate according to the present disclosure from the thermoplastic base material side. It is a laminated body for optical member formation exposed through the plastic base material.
Moreover, the 1st embodiment and 2nd embodiment of the laminated body for optical member formation which concern on this indication can be used suitably for manufacture of the optical member sheet which concerns on this indication.

Conventional optical member sheets are insufficient in light resistance, and none of them can achieve both the contradictory performance of moldability (moldability) and hardness (scratch resistance) that are hard to be scratched. The
As a result of conducting detailed studies by the present inventors, it has been found that an optical member sheet excellent in moldability, abrasion resistance and light resistance can be obtained by the above constitution.
Although the detailed mechanism is unknown, by being a thermoplastic base material containing an ultraviolet absorber, it is excellent in light resistance, and the optical member forming layer is a short wavelength type photopolymerization initiator and a long wavelength type photopolymerization. By including an initiator, it is possible to perform curing by two or more times of exposure, and it is estimated that not only excellent in light resistance but also compatibility of moldability and abrasion resistance can be achieved.

  First, a first embodiment of a laminate for forming an optical member according to the present disclosure will be described.

First Embodiment of Laminate for Forming an Optical Member According to the Present Disclosure
A first laminate according to the present disclosure has a thermoplastic base material containing an ultraviolet absorber, and an optical member forming layer disposed on the surface of the thermoplastic base material, and the optical member forming layer has a short length. It contains a wavelength type photopolymerization initiator and a long wavelength type photopolymerization initiator.

<Thermoplastic substrate>
The thermoplastic substrate (also simply referred to as “substrate”) used in the first laminate according to the present disclosure contains an ultraviolet absorber.
The thermoplastic substrate used in the present disclosure is a substrate as a support material, and a sheet-like or film-like thermoplastic substrate can be suitably used.
It is preferable that the said thermoplastic base material contains a thermoplastic resin.
The thermoplastic resin is not particularly limited, but thermoplastic resins low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, cycloolefin polymer, ethylene-vinyl acetate copolymer, ionomer Resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene acrylic acid, Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc., polyvinyl acetate resins, polyester resins, polystyrene resins, etc .; acrylic Fat, polyester resins, polycarbonate resins preferably.
Among them, an acrylic resin base material is preferable from the viewpoint of moldability and light resistance.

The ultraviolet absorber used in the present disclosure is not particularly limited, and conventionally known ones can be used. For example, triazine based ultraviolet absorbers, benzophenone based ultraviolet absorbers, salicylate based ultraviolet absorbers, acrylonitrile based ultraviolet absorbers and the like can be mentioned.
Among them, triazine-based ultraviolet absorbers are preferred. The triazine-based ultraviolet absorber has a high ultraviolet absorbing ability and is excellent in light resistance.

Specifically, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5- is used as the triazine-based UV absorber. Tris [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione etc. are mentioned. Be
Specifically as a benzotriazole type ultraviolet absorber, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, polyethylene Examples thereof include 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of glycol and the like.

  Commercially available UV absorbers include TINUVIN 234, TINUVIN 329, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVI 900, TINUVIN 928, TINUVIN 1130, TINUVIN P (all manufactured by BASF), JF-77 (JSF-77) Johoku Chemical Industry Co., Ltd., Sea Soap 701 (Shiroishi Calcium Co., Ltd.), Sumi Soap 200 (Sumitomo Chemical Co., Ltd.), Bio Soap 520 (Kyoyaku Co., Ltd.), Adekastab LA-32 ((share And the like) and the like.

The ultraviolet absorber may be contained singly or in combination of two or more.
The content of the UV absorber is arbitrarily set according to the UV absorbing ability of the UV absorber, but from the viewpoint of light resistance, 0.001% by mass or more and 10% by mass with respect to the total mass of the thermoplastic substrate It is preferable that it is% or less, It is more preferable that it is 0.01 to 5 mass%, It is still more preferable that it is 0.1 to 2 mass%.

  A commercially available product of a thermoplastic substrate containing a UV absorber may be used as the thermoplastic substrate and the UV absorber. Specifically, Technoloy S001 (manufactured by ESCABO SHEET Co., Ltd.), ACRIPRENE HBS010P (manufactured by Mitsubishi Rayon Co., Ltd.), Sundurene 009 HCN (manufactured by Kaneka Co., Ltd.) and the like can be mentioned.

  The wavelength at which the light transmittance of the ultraviolet absorber is 50% is preferably more than 380 nm and less than 405 nm from the viewpoint of moldability and light resistance of the obtained optical member sheet, and is 382 nm or more and 400 nm or less More preferably, 385 nm or more and 395 nm or less.

In addition, the light transmittance of the ultraviolet absorber in this indication is the light transmittance in 25 degreeC, and shall measure the transmittance | permeability of the light of the range of 360 nm or more and 420 nm or less.
As a measurement method, specifically, the transmittance of the base material was measured by an ultraviolet visible infrared spectrophotometer V660 (manufactured by JASCO Corporation) using an integrating sphere ISV 722 as a detector.

  The thickness of the thermoplastic substrate is not particularly limited, and is preferably in the range of 50 μm to 300 μm, more preferably in the range of 50 μm to 250 μm, and still more preferably in the range of 50 μm to 200 μm. It is excellent in the thermoforming property of an optical member sheet as it is the said range, a crack does not generate | occur | produce easily during handling (for example, during conveyance) at the time of shaping processing, it is hard to break also at the time of three dimensional shaping | molding, and it is excellent by moldability.

<Optical member forming layer>
A first laminate according to the present disclosure has an optical member forming layer disposed on the surface of the thermoplastic substrate, and the optical member forming layer is a short wavelength type photopolymerization initiator, and a long wavelength type light. And a polymerization initiator.
It is preferable that the said optical member formation layer in the 1st laminated body which concerns on this indication is a layer which consists of a curable composition shown below.
The thickness of the optical member forming layer is not particularly limited and may be selected according to the desired optical member, but is preferably 1 μm or more and 500 μm or less, more preferably 5 μm or more and 400 μm or less, and 10 μm or more More preferably, it is 300 μm or less.

In the first laminate according to the present disclosure, the wavelength at which the light transmittance of the ultraviolet absorber is 50% is 380 nm from the viewpoint of the moldability of the optical member sheet to be obtained, the abrasion resistance and the light resistance. The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the shorter wavelength side than the wavelength at which the light transmittance of the above-mentioned thermoplastic substrate is 50% or more, which is more than 405 nm, is 380 nm or less The maximum absorption wavelength of the photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the base material is 50% is preferably 405 nm or more.
Furthermore, in the first laminate according to the present disclosure, the light transmittance of the thermoplastic base material in the optical member forming layer is 50 in terms of the moldability of the obtained optical member sheet, the abrasion resistance and the light resistance. The content of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the% wavelength wavelength is 0.1 mass% to 1.0 mass% with respect to the total mass of the optical member forming layer, and the above optical In the member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is 0. 0 based on the total mass of the optical member. It is preferable that it is 1 mass%-1.0 mass%.

Further, the optical member forming layer preferably contains a polymerizable compound, and more preferably contains an ethylenically unsaturated compound.
As a polymeric compound, polymeric compounds, such as a (meth) acrylate compound contained in the curable composition mentioned later, are mentioned suitably.

[Curable composition]
Below, although an example of the curable composition which can be used suitably for formation of the said optical member formation layer is mentioned concretely, an example of the curable composition which can be used for this indication is limited to the following examples. I will not.
Moreover, the preferable aspect and content of each component in the said optical member formation layer are the same as the preferable aspect and content of each component in the curable composition mentioned later.
Hereinafter, each component used for the curable composition which can be used suitably for this indication is explained in full detail.

<< Short wavelength type photopolymerization initiator >>
The curable composition used in the present disclosure is a photopolymerization initiator (short wavelength type photopolymerization initiator) having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%. including.
The short wavelength type photopolymerization initiator is preferably a photo radical polymerization initiator from the viewpoint of moldability of the obtained optical member sheet, abrasion resistance and light resistance, and an α-hydroxyacetophenone compound and an α-aminoacetophenone More preferably, it is at least one compound selected from the group consisting of compounds, and more preferably an α-hydroxyacetophenone compound.

  The maximum absorption wavelength of the short wavelength photopolymerization initiator is preferably 390 nm or less, more preferably 380 nm or less, and more preferably 200 nm or more and 380 nm or less from the viewpoint of the abrasion resistance of the obtained optical member sheet Is more preferable, and is particularly preferably 220 nm or more and 380 nm or less.

The maximum absorption wavelength of the short wavelength photopolymerization initiator and the long wavelength photopolymerization initiator in the present disclosure is to measure absorption of light in the range of 300 nm to 420 nm at 25 ° C. to determine the maximum absorption wavelength. Do.
As a measurement method, specifically, a solution prepared by dissolving a photopolymerization initiator in the same amount as the amount to be actually added in 1-vinyl-2-pyrrolidone is put into a quartz cell with an optical path length of 1 mm. The transmittance is measured using an infrared spectrophotometer V660 (manufactured by JASCO Corporation).

  As a short wavelength type photopolymerization initiator, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2) -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  The short wavelength type photopolymerization initiator may be a commercially available product, and specific examples of the commercially available product include IRGACURE series (eg, IRGACURE 184, IRGACURE 1173, etc.) manufactured by BASF.

The curable composition used in the present disclosure may contain one type of short wavelength photopolymerization initiator alone or may contain two or more types.
The content of the short wavelength photopolymerization initiator in the curable composition used in the present disclosure is a curable composition from the viewpoints of the curability, the moldability of the obtained optical member sheet, the abrasion resistance and the light resistance. 0.01 mass% or more and 5 mass% or less are preferable with respect to the total mass of the thing, 0.02 mass% or more and 2 mass% or less are more preferable, 0.05 mass% or more and 1.5 mass% or less are more preferable 0.1 mass% or more and 1.0 mass% or less are especially preferable.

<< Long wavelength type photopolymerization initiator >>
The curable composition used in the present disclosure is a photopolymerization initiator (long wavelength type photopolymerization initiator) having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate is 50%. including.
The long wavelength photopolymerization initiator is preferably a photo radical polymerization initiator from the viewpoint of moldability of the obtained optical member sheet, abrasion resistance and light resistance, and is more preferably an acyl phosphine oxide compound And monoacyl phosphine oxide compounds are more preferable.

  The maximum absorption wavelength of the long wavelength photopolymerization initiator is preferably 400 nm or more, more preferably 405 nm or more, and more preferably 410 nm or more and 500 nm or less from the viewpoint of the moldability of the obtained optical member sheet More preferably, it is particularly preferably 415 nm or more and 460 nm or less.

  Examples of long wavelength photopolymerization initiators include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide.

  The long wavelength type photopolymerization initiator may use a commercially available product, and specific examples of the commercially available product include IRGACURE series (eg, IRGACURE TPO, IRGACURE 819, etc.) manufactured by BASF.

The curable composition used in the present disclosure may contain the long wavelength photopolymerization initiator singly or in combination of two or more.
The content of the long-wavelength photopolymerization initiator in the curable composition used in the present disclosure is a curable composition from the viewpoints of the curability, the moldability of the obtained optical member sheet, the abrasion resistance and the light resistance. 0.01 mass% or more and 5 mass% or less are preferable with respect to the total mass of the thing, 0.02 mass% or more and 2 mass% or less are more preferable, 0.05 mass% or more and 1.5 mass% or less are more preferable 0.1 mass% or more and 1.0 mass% or less are especially preferable.

<< Monofunctional (Meth) Acrylate Compound >>
The curable composition used in the present disclosure preferably contains a monofunctional (meth) acrylate compound from the viewpoint of the moldability and the abrasion resistance of the obtained optical member sheet.
As a monofunctional (meth) acrylate compound, a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure and a (meth) acryloyl group at the end, from the viewpoint of moldability and abrasion resistance of an optical member sheet to be obtained Preferred are resins having a group.

-Monofunctional (meth) acrylate compound having aliphatic hydrocarbon ring structure-
The curable composition used in the present disclosure preferably contains a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure from the viewpoint of the moldability and the abrasion resistance of the obtained optical member.
The aliphatic hydrocarbon ring structure is selected from the group consisting of a tricyclodecane ring structure, a cyclohexane ring structure, a norbornene ring structure, and an adamantane ring structure from the viewpoint of moldability and abrasion resistance of an optical member to be obtained At least one ring structure is preferable, and a tricyclodecane ring structure is more preferable.

Specifically, as a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure, it has a tricyclodecane ring structure such as dicyclopentanyl (meth) acrylate and dicyclopentanyl oxy (meth) acrylate (Meth) acrylate compounds, (meth) acrylate compounds having a cyclohexane ring structure such as cyclohexyl (meth) acrylate, (meth) acrylate compounds having a norbornene ring structure such as isoboronyl (meth) acrylate, 1-adamantyl (meth) acrylate, etc. And (meth) acrylate compounds having an adamantane ring structure of
Among them, a (meth) acrylate compound having a tricyclodecane ring structure is preferable, and dicyclopentanyl (meth) acrylate is more preferable, from the viewpoint of moldability and abrasion resistance of an optical member sheet to be obtained.

The curable composition used in the present disclosure may contain one kind of monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure alone, or may contain two or more kinds.
The content of the monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure in the curable composition used in the present disclosure is the curable composition from the viewpoint of the moldability and the abrasion resistance of the obtained optical member sheet 0.5 mass% or more and 50 mass% or less are preferable with respect to the total mass of a thing, 10 mass% or more and 45 mass% or less are more preferable, and 20 mass% or more and 40 mass% or less are especially preferable.

-Resin having (meth) acryloyl group at the end-
The curable composition used in the present disclosure preferably contains a resin having a (meth) acryloyl group at an end. Since the above-mentioned resin has a (meth) acryloyl group at the end of the molecular chain, the crosslink density in the entire curable composition can be obtained by using it in combination with another polymerizable compound, particularly a polyfunctional (meth) acrylate compound. It is excellent in moldability and abrasion resistance of an optical member sheet which is controlled and obtained.

The resin may be a polymer having a (meth) acryloyl group at an end, and examples thereof include (meth) acrylic resin, polystyrene, polystyrene-methacrylate (MS resin), polystyrene-acrylonitrile (AS resin), polypropylene, polyethylene, Polymers having at least one (meth) acryloyl group at the end of the main chain structure, such as polyethylene terephthalate, glycol-modified polyethylene terephthalate, polyvinyl chloride (PVC), thermoplastic elastomers, or copolymers thereof, cycloolefin polymers, etc. Can be mentioned. Among them, a (meth) acrylic resin having a (meth) acryloyl group at an end or a polystyrene having a (meth) acryloyl group at an end is preferable from the viewpoint of three-dimensional moldability and abrasion resistance of a cured product obtained. (Meth) acrylic resin having a (meth) acryloyl group is more preferable.
Further, as the (meth) acrylic resin having a (meth) acryloyl group at an end, polymethyl methacrylate having a (meth) acryloyl group at an end is preferable from the viewpoint of abrasion resistance.
Furthermore, it is preferable that the resin which has a (meth) acryloyl group at the terminal has a methacryloyl group at the terminal.

  Examples of the resin having a (meth) acryloyl group at an end include macromonomer series (eg, macromonomer AA-6 (polymethyl methacrylate having a methacryloyl group) manufactured by Toagosei Co., Ltd., macromonomer AS-6 or AS) 6S (polystyrene having a methacryloyl group), macromonomer AN-6S (polystyrene / acrylonitrile having a methacryloyl group), macromonomer AB-6 (polybutyl methacrylate having a methacryloyl group), and the like can be used.

  From the viewpoint of moldability, the number average molecular weight of the resin having a (meth) acryloyl group at the end is preferably 1,000 or more and 10,000 or less, more preferably 3,000 or more and 10,000 or less, and 5,000 or more 10,000 or less is more preferable.

  The glass transition temperature (Tg) of the resin having a (meth) acryloyl group at the end is preferably 50 ° C. or more, more preferably 80 ° C. or more, from the viewpoint of the abrasion resistance of the obtained optical member sheet. Further, from the viewpoint of moldability, Tg is preferably less than 250 ° C., and more preferably 200 ° C. or less.

The curable composition used in the present disclosure may contain a single type of resin having a (meth) acryloyl group at an end, or may contain two or more types.
The content of the resin having a (meth) acryloyl group at the end of the curable composition used in the present disclosure is the total mass of the curable composition from the viewpoint of the moldability and the abrasion resistance of the resulting optical member sheet. On the other hand, 0.5 mass% or more and 50 mass% or less are preferable, 10 mass% or more and 45 mass% or less are more preferable, and 20 mass% or more and 40 mass% or less are particularly preferable.

-Other monofunctional (meth) acrylate compounds-
The curable composition used in the present disclosure may contain monofunctional (meth) acrylate compounds (other monofunctional (meth) acrylate compounds) other than those described above.
Specific examples of other monofunctional (meth) acrylate compounds include 2-ethyl-2-butylpropanediol (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl ( Ta) Acrylate, ethylene oxide (hereinafter referred to as "EO") modified cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate , Isobutyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate G, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumyl phenoxy ethylene glycol (meth) acrylate, epichlorohydrin (hereinafter also referred to as "ECH"). Modified phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, stearyl (meth) acrylate, EO modified succinic acid ( Meta) acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribro Mophenyl (meth) acrylate, dodecyl (meth) acrylate, etc. are mentioned.

The curable composition used in the present disclosure may contain other monofunctional (meth) acrylate compounds singly or in combinations of two or more.
The curable composition used in the present disclosure does not contain other monofunctional (meth) acrylate compounds from the viewpoint of the abrasion resistance of the resulting optical member sheet, or the content of the curable composition is a curable composition. The content is preferably not more than 20% by mass, or more preferably 10% by mass or less, based on the total mass of the curable composition. It is more preferable that the content not be contained or the content be 5% by mass or less with respect to the total mass of the curable composition, or the content not be contained or the content be the entire content of the curable composition. It is particularly preferable that the content is 1% by mass or less with respect to the mass.

The curable composition used for this indication may contain a monofunctional (meth) acrylate compound individually by 1 type, and may contain 2 or more types.
The content of the monofunctional (meth) acrylate compound in the curable composition used in the present disclosure is, based on the total mass of the curable composition, from the viewpoint of the moldability and the abrasion resistance of the obtained optical member sheet 1 mass% or more and 80 mass% or less are preferable, 15 mass% or more and 75 mass% or less are more preferable, and 30 mass% or more and 70 mass% or less are particularly preferable.

<< Multifunctional (Meth) Acrylate Compound >>
It is preferable that the curable composition used for this indication contains a polyfunctional (meth) acrylate compound from a heat resistant viewpoint of the optical member sheet | seat obtained.

  Specific examples of the polyfunctional (meth) acrylate compound include diethylene glycol monoethyl ether di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene oxide modified 1,6-Hexanediol di (meth) acrylate, ECH modified 1,6-Hexanediol di (meth) acrylate, allyloxy polyethylene glycol (meth) acrylate, 1,9-nonanediol di (meth) acrylate, ethylene oxide modified Bisphenol A di (meth) acrylate, propylene oxide (hereinafter, also referred to as “PO”) modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) Acrylate, ECH modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, PO modified neopentyl Glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di ( Meta) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol Lu di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) Acrylate, PO modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO modified phosphate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO Modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, diglycerin ethylene oxide (EO) modified (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, di (meth) acryloxy Examples thereof include alkylated isocyanurate, ethylene oxide modified with isocyanurate ethylene oxide tri (meth) acrylate, ethylene oxide modified with isocyanurate ethylene oxide, and the like.

  Among these, the above-mentioned curable composition preferably contains a polyfunctional (meth) acrylate compound having a cyclic structure from the viewpoint of the moldability of the obtained optical member sheet, and tricyclodecane dimethanol di (meth) acrylate More preferably,

The said curable composition may contain a polyfunctional (meth) acrylate compound individually by 1 type, and may contain 2 or more types.
The content of the polyfunctional (meth) acrylate compound in the curable composition used in the present disclosure is relative to the total mass of the curable composition from the viewpoint of the moldability and the abrasion resistance of the obtained optical member sheet. 1 mass% or more and 90 mass% or less are preferable, 10 mass% or more and 85 mass% or less are more preferable, 15 mass% or more and 80 mass% or less are more preferable, and 20 mass% or more and 60 mass% or less are particularly preferable.

<< N-vinyl compound >>
The curable composition used in the present disclosure preferably contains an N-vinyl compound from the viewpoint of the moldability of the resulting optical member sheet.
The N-vinyl compound is preferably a monofunctional N-vinyl compound, and preferably has a ring structure.
Among them, the N-vinyl compound is at least one compound selected from the group consisting of N-vinylpyrrolidone and N-vinylcaprolactam from the viewpoint of the abrasion resistance and high-temperature stretchability of the obtained cured product. Is preferred, and N-vinyl pyrrolidone is more preferred.
Among the N-vinyl compounds, examples of N-vinylpyrrolidone include N-vinyl-2-pyrrolidone and the like. In addition, examples of N-vinylcaprolactam include N-vinyl-ε-caprolactam and the like.

The curable composition used for this indication may contain N-vinyl compound individually by 1 type, or may contain 2 or more types.
The content of the N-vinyl compound in the curable composition used in the present disclosure is the curable composition from the viewpoint of the moldability and the abrasion resistance of the optical member sheet obtained and the shape retention of the optical member. 3 mass% or more and 60 mass% or less is preferable with respect to the total mass, 5 mass% or more and 50 mass% or less is more preferable, 5 mass% or more and 40 mass% or less is more preferable, 8 mass% or more and 35 mass% or less Particularly preferred.

<< Other Ethylenically Unsaturated Compounds >>
In addition, the curable composition used in the present disclosure may contain other ethylenically unsaturated compounds other than those described above.
As other ethylenically unsaturated compounds, known polymerizable compounds, particularly known ethylenically unsaturated compounds can be used.

The curable composition used in the present disclosure may contain other ethylenically unsaturated compounds singly or in combination of two or more.
The curable composition used in the present disclosure does not contain other ethylenically unsaturated compounds, or the content of the curable composition is a curable composition from the viewpoint of the heat resistance and the thermoforming property of the resulting optical member sheet. It is preferable that it is 20 mass% or less with respect to the total mass of a thing, or it is not contained, or it is more preferable that the content is 10 mass% or less with respect to the total mass of curable composition. More preferably, the content is 5% by mass or less based on the total mass of the curable composition, or the content is not contained or the content of the curable composition is It is particularly preferable that the content is 1% by mass or less with respect to the total mass.

<< Multifunctional Mercapto Compound >>
The curable composition used in the present disclosure may contain a polyfunctional mercapto compound as the polymerizable compound.
The polyfunctional mercapto compound in the present disclosure means a compound having two or more mercapto groups (thiol groups) in the molecule. As a polyfunctional mercapto compound, a low molecular weight compound having a molecular weight of 100 or more is preferable, and specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 is more preferable.

  Specific examples of polyfunctional mercapto compounds include ethylene glycol bisthiopropionate, butanediol bisthiopropionate, trimethylolpropane tris (3-mercaptopropionate), and tris [(3-mercaptopropionyloxy) ethyl]. Isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl) Rate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H). , 3H, 5H -Trione, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2 '-(ethylenedithio) diethane Thiol, meso-2,3-dimercaptosuccinic acid, p-xylenedithiol, m-xylenedithiol, di (mercaptoethyl) ether and the like can be exemplified.

  The polyfunctional mercapto compound is preferably a compound having 2 to 8 mercapto groups, more preferably a compound having 2 to 6 mercapto groups, and 3 or more mercapto groups. More preferably, it is a compound having 8 or less.

In the present disclosure, the polyfunctional mercapto compounds may be used alone or in combination of two or more.
The content of the polyfunctional mercapto compound is preferably 0.1% by mass to 40% by mass, and more preferably 1% by mass to 35% by mass, with respect to the total mass of the curable composition.

-Other ingredients-
The curable composition used for this indication may contain other components, such as an organic solvent and an inorganic particle, as needed other than the above-mentioned component.
Examples of the organic solvent include toluene and methyl ethyl ketone. Since the curable composition used in the present disclosure contains a polymerizable compound such as the (meth) acrylic compound described above, the polymerizable compound may also function as a solvent and may not contain an organic solvent separately. .
Examples of the inorganic particles include particles called so-called fillers such as silicon dioxide (silica). As an example of an inorganic particle, organosilica sol MEK-ST series (example: MEK-ST-40, MEK-ST-L etc.) of Nissan Chemical Industries, Ltd. are mentioned as a commercial item marketed.

The curable composition used in the present disclosure is preferably a composition curable by actinic radiation. The “actinic radiation” in the present disclosure is a radiation capable of giving energy to generate a polymerization initiation species in the curable composition by the irradiation, such as α rays, γ rays, X rays, ultraviolet rays, visible rays, electron rays, etc. Includes Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable, from the viewpoint of curing sensitivity and availability of the apparatus.
The curable composition used in the present disclosure is preferably an active radiation curable type curable composition, more preferably an active radiation curable type oil curable composition. The curable composition used in the present disclosure preferably contains as little water and volatile solvent as possible, and even if contained, it is preferably 5% by mass or less based on the total mass of the curable composition. The content is more preferably 1% by mass or less and still more preferably 0.5% by mass or less.

  There is no restriction | limiting in particular as a formation method of the said optical member formation layer in this indication, ie, the provision method of the said curable composition, A curable composition is provided on a thermoplastic substrate by a well-known application method, The said optical A member forming layer can be formed.

  The first laminate according to the present disclosure may further have a protective layer on the optical member forming layer. There is no restriction | limiting in particular as a protective layer, A well-known protective film and protective sheet can be used.

[Second embodiment of laminate for forming optical member according to the present disclosure]
A second embodiment of a laminate for forming an optical member according to the present disclosure (a second laminate according to the present disclosure) is disposed on the surface of a thermoplastic substrate containing a UV absorber, and the above-mentioned thermoplastic substrate A photopolymerization initiator having a maximum absorption wavelength on the shorter wavelength side than the wavelength at which the light transmittance of the thermoplastic base material becomes 50%, It contains a polymerization-type decomposition product (also referred to as a “long-wavelength decomposition product”) of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the plastic substrate becomes 50%. .

The second laminate according to the present disclosure can be easily produced by irradiating the first laminate according to the present disclosure with actinic radiation from the thermoplastic substrate side.
More specifically, by irradiating the actinic radiation from the thermoplastic substrate side, the light transmittance of the thermoplastic substrate in the first laminate according to the present disclosure becomes 50% of the longer wavelength than the wavelength at which the light transmittance becomes 50%. A photopolymerization initiator having a maximum absorption wavelength generates a polymerization initiation species by irradiation with actinic radiation, and a polymerizable compound or the like partially reacts. Further, the decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate becomes 50% reacts with the polymerizable compound etc., and the thermoplastic substrate (4) to form a polymerized decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of 50% is 50%.
The “polymerized decomposition product of the photopolymerization initiator” in the present disclosure is a product generated by reacting the decomposition product of the photopolymerization initiator with one or more molecules of the polymerizable compound.

Polymerized decomposition of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate of the optical member forming layer in the second laminate according to the present disclosure is 50% The content of the product is preferably 0.01% by mass to 0.5% by mass, more preferably 0.025% by mass to 0.25% by mass, with respect to the total mass of the optical member forming layer. % By mass to 0.2% by mass is more preferable, and 0.07% by mass to 0.18% by mass is particularly preferable. Within the above range, the crosslink density and the function as a lubricant are sufficient, and the scratch resistance is more excellent.
Further, the second laminate according to the present disclosure is characterized in that the light transmittance of the thermoplastic base material in the optical member forming layer is 50 in terms of the moldability of the obtained optical member sheet, the scratch resistance and the light resistance. The content of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the% wavelength wavelength is 0.1 mass% to 1.0 mass% with respect to the total mass of the optical member forming layer, and the above optical In the member forming layer, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material becomes 50% is the optical member forming layer It is preferable that it is 0.025 mass%-0.25 mass% with respect to the total mass of these.

  The method for specifying the structure of the polymerization-type decomposition product of the photopolymerization initiator in the present disclosure and the method for quantifying the same are carried out by the methods described below.

-Structure identification method-
1. Method for specifying structure of polymerization decomposition product A photopolymerization initiator and a material used for the curable composition are mixed and irradiated with ultraviolet light to obtain a reactant. When the composition is a powder, it is dissolved in pyrrolidone, irradiated with ultraviolet light for reaction, and then evaporated to dryness to obtain a reaction product.
The obtained reaction product is analyzed by TOF-SIMS PHI nanoTOF (manufactured by ULVAC-PHI, Inc.), and the structure of the polymerizable decomposition product is identified from the obtained spectrum, and the spectrum is related to the polymerizable decomposition product.
Next, after cutting the cross section of the curable composition with a microtome, the cross section was measured with TOF-SIMS PHI nanoTOF (manufactured by ULVAC-PHI, Inc.) and newly appeared by comparison with the SIMS spectrum of the base material alone. Detect the signal. The newly detected signal is compared with the spectrum obtained from the standard to identify the polymerizable degradation product in the curable composition.

2. Method of determining the amount of degradation of the polymerization A curable composition was prepared by changing the addition amount of the photopolymerization initiator, analyzed by TOF-SIMS PHI nanoTOF (manufactured by ULVAC-PHI, Inc.), and polymerization relative to the addition amount of the photoinitiator Prepare a calibration curve of the spectral intensities of sexual decomposition products.
Next, the polymerizable decomposition product in the curable composition is calculated from the TOF-SIMS spectrum intensity of the curable composition and the calibration curve.

  As a polymerization type decomposition product (long wavelength type decomposition product) of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the above-mentioned thermoplastic substrate becomes 50%, the following formula L1 Preferred is a compound represented by any one of the formulas L4.

In formulas L1 to L4, Poly ^{A to} Poly ^E each independently represent a polymerization chain of one or more molecules of a polymerizable compound, and R ^{L1 to} R ^L8 each independently represent an alkyl group or an aryl group, R ^re represents an acyl group or a group (for example, a hydrogen atom, a hydroxyl group, etc.) formed by deactivating the polymerization initiating species generated in a part of the decomposition product of the long wavelength photopolymerization initiator.

Preferably, Poly ^{A to} Poly ^E are each independently a polymer chain of a polymerizable compound having 1 to 20 molecules in average, and a polymer chain of a polymer compound having 1 to 12 molecules on average It is more preferable that it is a polymerization chain of a polymerizable compound having 2 or more and 10 or less molecules on average.
In the present disclosure, when a macromonomer such as a resin having a (meth) acryloyl group at the above-described terminal is used as the polymerizable compound, in the polymer chain, a polymer chain formed from the macromonomer is It shall be counted as one molecule.

Each of R ^{L1 to} R ^L8 is preferably independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 5 to 12 carbon atoms from the viewpoint of scratch resistance and light resistance, and preferably 5 to 12 carbon atoms. The aryl group is more preferably an aryl group, and particularly preferably a phenyl group.
The alkyl group and the aryl group may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a hydroxy group, a halogen atom and the like.
R ^re is preferably an acyl group, a hydrogen atom or a hydroxy group, more preferably a hydrogen atom or a hydroxy group.

Moreover, it is preferable that the said optical member formation layer in the 2nd laminated body which concerns on this indication has a crosslinked structure from a heat resistant viewpoint.
The crosslinked structure can be easily introduced into the optical member forming layer by copolymerizing a polyfunctional polymerizable compound such as a polyfunctional (meth) acrylate compound described later.

Like the first laminate according to the present disclosure, the optical member forming layer in the second laminate according to the present disclosure may be a flat layer, and can be suitably used as an optical member. It may have a desired shape.
Since the said optical member formation layer is not completely hardened as it is the state of the 2nd laminated body which concerns on this indication which a short wavelength type photoinitiator is contained in the said optical member formation layer still, shape maintenance property And it is excellent in the balance of deformation ease, and the said optical member formation layer can be easily formed in the shape of an optical member.

Examples of the optical member include, as convex lenses, cylindrical lenses, prism lenses, hemispherical microlenses, Fresnel lenses, and lenticular lenses in which a plurality of convex lenses (cylindrical lenses) are arranged in one direction.
The optical member may be in the form of dots (dots) or columns (lines), but is preferably columns having a large contact area with the thermoplastic substrate.
The cross section of the column in the columnar shape is not particularly limited, such as polygonal and semicircular, but it is more preferable to be semicircular, which easily disperses residual stress generated in the optical member.
Among them, the optical member is preferably a lens, and more preferably a cylindrical lens.

When the optical member is a lenticular lens, the size of the lenticular lens is preferably 50 μm to 1,000 μm, more preferably 80 μm to 600 μm, and still more preferably 100 μm to 300 μm.
The height of the lenticular lens is preferably 10 μm to 500 μm, more preferably 15 μm to 400 μm, and still more preferably 20 μm to 300 μm.
When the height and the pitch of the lenticular lens are within the above-mentioned range, the size of the lenticular lens becomes appropriate, and when winding in a roll shape or cutting out an optical member sheet and stacking it as a sheet, the lenticular The damage of the below-mentioned printing layer resulting from contacting with a lens, and the fall of the adhesiveness of a printing layer are controlled. Furthermore, when the sheet is rolled up or the optical member sheet is cut out and stacked as a single sheet, the slidability of the lenticular lens and the print layer becomes good, and the handleability becomes good.

<Printing layer>
The second laminate according to the present disclosure may have a print layer on the side of the thermoplastic base opposite to the side on which the optical member forming layer is disposed, from the viewpoint of design.
Although formation of a printing layer is performed by a conventional method according to the intended purpose of the optical member sheet | seat obtained, it is preferable after irradiating the actinic radiation to the said optical member forming layer from the said thermoplastic base material side.
Examples of the printing method for forming the printing layer include offset printing, screen printing, inkjet printing, lithographic printing, flexographic printing, gravure printing, and printing using a printing roll. Among them, the offset printing method, the gravure printing method, the inkjet printing method and the like are preferable from the viewpoint of the printing accuracy.

Various printing methods can be selected.
The printing can be performed, for example, by applying an ultraviolet curable ink (UV ink) onto the surface of the substrate using a screen printer, an inkjet recording device, or the like. As the ultraviolet curable ink, for example, UV resin of acrylate resin type can be used.
Moreover, for example, it can carry out using an offset printing apparatus. In offset printing, a multicolor image is formed by using a plurality of devices. When applying an offset printing method, oil-based offset ink or ultraviolet curing offset ink can be used as printing ink, for example.

When printing on a thermoplastic substrate, printing can be performed using a synthetic rubber printing roll equipped with a metal doctor blade. In this case, the ink applied to the surface of the thermoplastic substrate is filled between the printing roll and the doctor blade, and the uncured ink adheres to the surface of the substrate in contact with the printing roll by rotating the printing roll. Do. According to this method, when the thermoplastic substrate has irregularities, printing can also be performed on the convex portion of the thermoplastic substrate.
In the printing method using a printing roll, printing can be performed by moving the optical member sheet in the same direction as the rotation direction of the printing roll by a conveying device of the optical member sheet at a specific speed such as 5 m / min.

As the printing ink, an ink suitable for the printing method may be selected and used.
The standard viscosity of the ink used for printing is 15 Pa · s to 30 Pa · s for lithographic printing ink, 1 Pa · s to 5 Pa · s for flexographic printing ink, and 2 Pa for screen printing ink In the case of s ̃5 Pa · s, and an ink for gravure printing, the range of 1 Pa · s ̃5 Pa · s can be adopted. The viscosity of the ink is not limited to these ranges.

A known ink receiving layer may be provided on the surface of the thermoplastic substrate on which the printing layer is to be formed in order to improve the receptivity of the printing ink. The ink receiving layer may be formed according to the characteristics of the printing ink used for forming the printing layer.
From the viewpoint of enhancing the adhesion between the substrate and the printing layer, the printing surface side of the substrate may be subjected to surface treatment (for example, corona discharge treatment).
The ink receiving layer may be provided, for example, by applying a preparation liquid for forming the ink receiving layer to a substrate.

The application of the preparation liquid can be performed, for example, by application.
The preparation liquid preferably contains a solid component and a solvent for forming the ink receiving layer. The ink receiving layer preferably contains a resin, and at least a part of the resin is preferably crosslinked by a crosslinking agent. Therefore, the aspect containing resin and a crosslinking agent as a solid component contained in preparation liquid is preferable.
The resin used to form the ink receiving layer is preferably at least one resin selected from the group consisting of polyester, acrylic resin and urethane resin, and is particularly advantageous when forming a parallax image by offset printing .

<Thermoplastic resin layer (backing layer)>
The second laminate according to the present disclosure has a thermoplastic resin layer (also referred to as a “backing layer”) on the print layer from the viewpoint of thermoforming and protection of the print layer during injection molding described later. Furthermore, it is preferable to have.
Examples of thermoplastic resins used for the thermoplastic resin layer include olefin-based thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); vinyl chloride, chlorinated vinyl resin, etc. Halogen-containing thermoplastic resins; acrylic thermoplastic resins such as polymethyl methacrylate; polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer etc. Plastic resins; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyamides such as nylon 6, nylon 66 and nylon 610; Polyacetal; Polycarbonate resin; Polyphenylene oxide; Nsurufido; polyetheretherketone; polysulfone; polyether sulfone; polyoxyethylene benzylidene alkylene; polyamideimide, acrylic resins.
Among these, styrene-based thermoplastic resins are preferable, and an acrylonitrile-butadiene-styrene copolymer (ABS resin) is particularly preferable, from the viewpoints of thermoforming and printing layer protection at the time of injection molding.

  The thickness of the thermoplastic resin layer is preferably 0.10 mm to 0.50 mm, and is 0.15 mm to 0.45 mm, from the viewpoint of followability at the time of heat molding and protection of the printing layer at the time of injection molding. More preferably, it is 0.18 mm to 0.45 mm.

Although the formation method of a thermoplastic resin layer does not have a restriction | limiting in particular, The method of affixing the thermoplastic resin sheet to the said printing layer by heat sealing | fusion or an adhesive agent is mentioned suitably.
Among them, a method of attaching a thermoplastic resin sheet to the print layer with a hot melt adhesive is preferable. That is, it is preferable that the optical member sheet which concerns on this indication has a hot-melt layer which consists of a hot-melt-adhesive agent between the said printing layer and the said thermoplastic resin layer.
The adhesive used in the present disclosure, in particular a hot melt adhesive, is not particularly limited, and any known adhesive can be used. However, the heat resistance of the printing layer or the thermoplastic resin sheet used for forming the thermoplastic resin layer can be used. Depending on the situation, it may be selected appropriately.
The thickness of the hot melt layer is not particularly limited as long as sufficient adhesion can be obtained.

<Optical member protective layer>
The second laminate according to the present disclosure may further include an optical member protective layer on the optical member forming layer in order to protect the optical member forming layer from scratches and the like.
As a material of an optical member protective layer, thermoplastic resins, such as polyethylene, a polypropylene, and a polyethylene terephthalate (PET), are mentioned suitably.
For forming the optical member protective layer, the sheet or film of the thermoplastic resin used for the above-mentioned thermoplastic substrate can be suitably used, and the sheet or film may be attached.
The thickness of the optical member protective layer is preferably in the range of 10 μm to 100 μm from the viewpoint of handleability, even if a scratch occurs, it is difficult to reach the product.
Further, the shape of the optical member protective layer may or may not follow the shape of the optical member. For example, a sheet-like optical member protective layer may be provided on the optical member without following the shape of the optical member.

The optical member protective layer may be in close contact with at least a part of the optical member forming layer.
The formation of the optical member protective layer may be before or after the formation of the printing layer.

In addition, the second laminate according to the present disclosure may be three-dimensionally molded.
There is no restriction | limiting in particular as three-dimensional shaping | molding, What is necessary is just to be three-dimensionally formed in a desired shape by the well-known three-dimensional shaping | molding method which is mentioned later.

The optical member forming layer in the second laminate according to the present disclosure is partially polymerized by decomposition of the long wavelength photopolymerization initiator, so the content of the polymerizable compound is higher than that of the first laminate according to the present disclosure There is also less.
Further, the configuration and components other than those described above in the second laminate according to the present disclosure are the same as the configuration and components in the first laminate according to the present disclosure, and preferred aspects and contents thereof are also the same. .

(Optical member sheet)
An optical member sheet according to the present disclosure includes a thermoplastic base material including an ultraviolet light absorber, and an optical member disposed on the surface of the thermoplastic base material, and the optical member is a light of the thermoplastic base material. A polymerized decomposition product (also referred to as a “short wavelength decomposition product”) of a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of a wavelength at which the transmittance is 50%, and the thermoplastic substrate And a polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance is 50%.
In addition, configurations and components other than those described later in the optical member sheet according to the present disclosure are the same as the configurations and components in the second laminate according to the present disclosure, and preferable aspects and contents are also the same. In addition, the optical member formation layer in the 2nd laminated body which concerns on this indication shall be read as an optical member.

The optical member sheet according to the present disclosure can be suitably produced using the first laminate according to the present disclosure or the second laminate according to the present disclosure, and the second laminate according to the present disclosure is used. Can be produced more suitably.
The optical member sheet according to the present disclosure can be easily manufactured by irradiating the second laminate according to the present disclosure with actinic radiation from the side of the optical member forming layer. The said optical member formation layer in the 2nd laminated body which concerns on this indication is hardened | cured by irradiation of the said actinic radiation, and forms an optical member.

Containing of a polymeric decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate of the optical member in the optical member sheet according to the present disclosure is 50% 0.01 mass%-0.5 mass% are preferable with respect to the total mass of the said optical member, as for quantity, 0.025 mass%-0.25 mass% are more preferable, 0.05 mass%-0.2 % By mass is more preferable, and 0.07% by mass to 0.18% by mass is particularly preferable. A crosslinking density is enough as it is the said range, it is excellent in distortion suppression property of a molding, and it is excellent by moldability.
Moreover, the optical member sheet according to the present disclosure has a shorter wavelength than the wavelength at which the light transmittance of the thermoplastic base material of the optical member is 50% from the viewpoint of moldability, scratch resistance and light resistance. The content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength is 0.025% by mass to 0.25% by mass with respect to the total mass of the optical member, and the heat in the optical member The content of the polymerized decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the plastic substrate becomes 50% is 0.025 with respect to the total mass of the optical member It is preferable that it is mass%-0.25 mass%.

  As a polymerization type decomposition product (short wavelength type decomposition product) of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side from the wavelength at which the light transmittance of the thermoplastic substrate becomes 50%, the following formula S1 Or the compound represented by Formula S2 is mentioned preferably.

In formulas S1 and S2, Poly ^F and Poly ^G each independently represent a polymerization chain of one or more molecules of a polymerizable compound, and R ^{S1 to} R ^S3 each independently represent an alkyl group or an aryl group.

Preferably, Poly ^F and Poly ^F are each independently a polymer chain of a polymerizing compound of 1 to 20 molecules on average, and a polymer chain of a polymer compound of 1 to 12 molecules on average It is more preferable that it is a polymerization chain of a polymerizable compound having 2 or more and 10 or less molecules on average.

Each of R ^{S1 to} R ^S3 independently is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 5 to 12 carbon atoms, from the viewpoint of moldability and light resistance, and has 5 to 12 carbon atoms. An aryl group is more preferable, and a phenyl group is particularly preferable.
The alkyl group and the aryl group may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a hydroxy group, a halogen atom and the like.

  The optical member of the optical member sheet according to the present disclosure is, as described above in the second laminate according to the present disclosure, a cylindrical lens as a convex lens, a prism lens, a hemispherical microlens, a Fresnel lens, and a plurality of convex A lenticular lens etc. which the lens (cylindrical lens) was paralleled in one direction are mentioned. Among them, the optical member is preferably a lens, and more preferably a cylindrical lens.

In addition, the optical member sheet according to the present disclosure may have at least one layer from the group consisting of a printing layer, a thermoplastic resin layer (backing layer), and an optical member protective layer.
As the printing layer, the thermoplastic resin layer (backing layer), and the optical member protective layer, the layers described above in the second laminate according to the present disclosure are preferably mentioned.
Furthermore, the optical member sheet according to the present disclosure may be three-dimensionally molded.
Furthermore, the optical member sheet according to the present disclosure may be an injection-molded body which is three-dimensionally molded and further injection-molded.

  Moreover, the optical member sheet | seat which concerns on this indication may have another well-known structure besides the structure mentioned above.

<Structure of Lenticular Sheet>
The configuration of a lenticular sheet will be described as an example of the optical member sheet according to the present disclosure.
For example, as shown in FIG. 1, the lenticular sheet may be a lenticular decorative sheet having an ink receiving layer and a lenticular image. A lenticular sheet is a display medium that displays an image different according to the viewing angle by having a lenticular lens in which convex cylindrical lenses having semi-cylindrical surfaces are arranged in one direction on an image suitable for lenticular display Display body). FIG. 1 is a schematic view showing an example of a lenticular sheet.

The lenticular sheet 10 shown in FIG. 1 is a semicylindrical shape of a lenticular lens 12 in which a plurality of convex lenses (cylindrical lenses) 12A having a semicylindrical surface are arranged in one direction and a convex lens 12A of the lenticular lens 12. And a lenticular image 14 disposed on the side opposite to the front surface.
The x direction indicates the width direction of the lens, and the y direction indicates the longitudinal direction of the lens.

The lenticular sheet preferably has a lenticular lens layer in which a plurality of cylindrical lenses having a semi-cylindrical surface are arranged in parallel. The width per cylindrical lens is not particularly limited, and the pitch width of the lens may be selected depending on the purpose.
The width per cylindrical lens is usually represented by LPI (Line Per Inch), which represents the number of lenses per inch (2.54 cm). For example, 100 LPI indicates that 100 cylindrical lenses (100 rows) are arranged in parallel, and the lens pitch is 254 μm. As the number of lines per inch (the number of arranged lenses) increases, the lens pitch decreases and the definition improves.
A low definition lenticular sheet (for example, 60 LPI etc.) is suitable for use as a poster or the like displaying a pattern with a relatively distant viewing position, but for the purpose of reading small text information such as a business card, It is preferable that the lenses constituting the lenticular lens layer are arranged in parallel at least 100 rows per one inch. On the other hand, from the viewpoint of the resolution of the lenticular image, it is more preferable that the number of arrangement of the convex lenses constituting the lenticular lens layer is 200 or less (200 LPI) per 2.54 cm.

In FIG. 1, the lenticular image 14 is a display image sequence 14A, 14B for displaying two display images separately, and an interpolation image sequence 14C inserted between adjacent display image sequences 14A, 14B. And image sequence groups including.
Specifically, the display image sequences 14A and 14B extracted in stripes from each display image are arranged adjacent to each other for each convex lens 12A at the corresponding position, and the adjacent display image sequences 14A, The color (interpolated color) between the color of one of the adjacent display image sequences 14A and 14B and the other color at the position where the colors of the adjacent display image sequences 14A and 14B are different from each other between 14B. An interpolated image sequence 14C is inserted.

(Method of manufacturing optical member sheet)
Although the manufacturing method of the optical member sheet which concerns on this indication does not have a restriction | limiting in particular, It has an optical member forming layer arrange | positioned on the surface of the thermoplastic base material containing an ultraviolet absorber and the said thermoplastic base material, The optical member forming layer has a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light transmittance of the thermoplastic substrate is 50% Preparing a laminate for forming an optical member comprising a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the above-mentioned wavelength, and exposing the above-mentioned optical member formation layer twice or more It is preferable to include the forming step.
As the thermoplastic base material, the optical member forming layer and the optical member in the method of manufacturing an optical member sheet according to the present disclosure, those described above can be suitably used.

It is preferable that the first exposure in the method of manufacturing an optical member sheet according to the present disclosure is performed from the side of the thermoplastic substrate.
By performing the exposure from the thermoplastic substrate side, only the long wavelength photopolymerization initiator can be decomposed to generate a polymerization initiation species, and the optical member forming layer is not completely cured, It is possible to easily form an optical member forming layer in which the short wavelength photopolymerization initiator, the polymerizable compound and the like remain.
Moreover, it is preferable that the exposure after the 2nd time in the manufacturing method of the optical member sheet which concerns on this indication performs exposure from the said optical member formation layer side.
By performing exposure from the side of the optical member forming layer, a short wavelength type photopolymerization initiator can be decomposed to generate a polymerization initiation species, and the optical member forming layer is completely cured to form an optical member. Can.
Further, in the method of manufacturing an optical member sheet according to the present disclosure, from the viewpoint of moldability, abrasion resistance and light resistance, in the step of forming the optical member, one or more exposures are performed from the thermoplastic substrate side. It is preferable to perform it and to perform one or more exposure after that from the said optical member formation layer side.

A mercury lamp, a metal halide lamp, a UV fluorescent lamp, a gas laser, a solid laser and the like are widely known as a light source for generating actinic radiation used for the exposure. In addition, a semiconductor ultraviolet light emitting device may be applied as a light source, and in terms of small size, high life, high efficiency, and low cost, LEDs (Light Emitting Diodes) and LDs (Laser Diodes) are also suitable.
As a light source, a metal halide lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an LED or a blue-violet laser is preferable.

The dose of actinic radiation may be appropriately selected depending on the composition or the like of the optical member forming layer, it is preferable that the 0.3 J / cm ² or more 5 J / cm ² or less.

  The irradiation with actinic radiation can be performed by selecting a known device provided with a light source capable of emitting actinic radiation described above. For example, an ultraviolet (UV) irradiation apparatus such as EXECURE 3000 manufactured by HOYA CANDEO OPTRONICS may be used.

  Moreover, the manufacturing method of the optical member sheet according to the present disclosure is characterized by the above-mentioned process between the first exposure and the last exposure in the process of forming the optical member, from the viewpoint of process simplicity, moldability and abrasion resistance. Forming a printed layer on the opposite side of the thermoplastic substrate on the side where the optical member forming layer is disposed, cutting the optical member forming laminate into a desired shape, and forming the optical member It is preferred to carry out at least one step selected from the group consisting of shaping the layer into the shape of the optical member.

In the method of manufacturing an optical member sheet according to the present disclosure, between the first exposure and the last exposure in the step of forming the optical member, the side of the thermoplastic base on which the optical member forming layer is disposed is It is preferable to include the process of forming a printing layer on the opposite side.
There is no restriction | limiting in particular as a formation method of a printing layer, The method mentioned above is mentioned preferably. Moreover, the ink mentioned above is used suitably as an ink used for printing.
Moreover, the manufacturing method of the optical member sheet | seat which concerns on this indication is a process of cutting the said optical member formation laminated body into a desired shape between the first exposure in the process of forming the said optical member, and the last exposure. It is preferable to include.
There is no restriction | limiting in particular as a cutting method of the said optical member forming laminated body, It can cut | judge by a well-known method. For example, it can be suitably cut into a sheet shape.

The method for producing an optical member sheet according to the present disclosure preferably includes the step of shaping the optical member forming layer into the shape of the optical member, and the first exposure and the last exposure in the step of forming the optical member More preferably, the step of shaping the optical member forming layer into the shape of the optical member is included in between. The step of shaping the optical member forming layer into the shape of the optical member may be performed simultaneously with the first exposure. In addition, between the first exposure and the last exposure, the first exposure or the same as the last exposure is also included.
At the process of shape | molding the said optical member formation layer in the shape of an optical member, a curable composition is shape | molded in the shape of the optical member made into the objective. The molding is not particularly limited as long as a desired shape can be obtained, but in terms of molding efficiency and molding accuracy, molding using a mold such as a mold or a wood mold is preferable.
Specifically, for example, a roll-shaped mold in which a desired lens shape is processed on the circumference of a roll is prepared, and pressed against a curable product formed on the base, and then the base Light from the side and shape.
In addition, after the curable composition is poured into a mold and dried if necessary, the curable composition may be cured. Thus, a molded product molded into a target shape can be stably obtained.
Furthermore, as another shaping | molding method using a metal mold | die, the method of forming a curable composition layer on a base material, pressing the heated metal mold, and shape | molding etc. is mentioned. It is preferable to heat the mold at 100 ° C to 150 ° C.

Moreover, in addition to said each process, the manufacturing method of the optical member sheet which concerns on this indication can include arbitrary other processes.
For example, the manufacturing method of the optical member sheet concerning this indication includes the process of forming a thermoplastic resin layer on the above-mentioned printing layer, the process of providing an optical member protection layer on the above-mentioned optical member, etc.
The formation method of the thermoplastic resin layer mentioned above as a formation method of the thermoplastic resin layer in the process of forming the above-mentioned thermoplastic resin layer is mentioned suitably. Moreover, the manufacturing method of the optical member sheet | seat which concerns on this indication may further include the process of providing a hot-melt-adhesive on the said printing layer.
The formation method of the optical member protection layer mentioned above as a formation method of the optical member protection layer in the process of providing the said optical member protection layer is mentioned suitably.
The step of providing an optical member protective layer on the optical member is not particularly limited, and may be between the first exposure and the last exposure in the step of forming the optical member, or even after the last exposure. Good. In addition, the method of manufacturing an optical member sheet according to the present disclosure includes the step of removing the optical member protective layer between the first exposure and the last exposure in the step of forming the optical member or after the last exposure. It may be

(Three-dimensional structure and its manufacturing method)
The three-dimensional structure according to the present disclosure is a two-dimensional laminate according to the present disclosure or a three-dimensional molded product (preferably by a method such as thermoforming or vacuum forming) of the optical member sheet according to the present disclosure.
Moreover, the manufacturing method of the three-dimensional structure which concerns on this indication does not have a restriction | limiting in particular, It is preferable to include the process of carrying out the three-dimensional shaping | molding of the optical member sheet which concerns on this indication.
In the step of three-dimensionally molding, the second laminate according to the present disclosure or the optical member sheet according to the present disclosure is molded. In this process, the optical member sheet according to the present disclosure may be formed, and may be subjected to a forming process using a mold such as a mold.
When three-dimensionally molding the second laminate according to the present disclosure, it is preferable to perform exposure from the side of the optical member forming layer after three-dimensional molding.

The three-dimensional molding in the above-described three-dimensional molding process can be performed using a known molding method, but from the viewpoint of moldability, it is performed by at least one molding method selected from the group consisting of thermal molding and vacuum molding. Is preferred.
The method of vacuum forming or pressure forming is not particularly limited, but a method of forming in a heated state under vacuum or under pressure is preferable.
The vacuum refers to a state in which the interior is evacuated to a vacuum degree of 100 Pa or less. The pressure air is preferably 0.1 MPa or more and 5 MPa or less.
The temperature at the time of molding is preferably a temperature range of 60 ° C. or more for both compressed air and vacuum, a temperature range of 80 ° C. or more is more preferable, and a temperature range of 100 ° C. or more is even more preferable. In general, the upper limit of the molding temperature is preferably 200 ° C.
The temperature at the time of molding refers to the temperature of the lenticular sheet to be molded, and is measured by attaching a thermocouple to the surface of the lenticular sheet.

  The vacuum forming can be performed using a vacuum forming technique widely known in the forming field, and for example, it may be formed by vacuum using Formech 508 FS manufactured by Japan-made Kikusui Kogyo Co., Ltd. As pressure forming, for example, SDF600 type manufactured by Sodick can be used for pressure forming. In addition, a polymer dictionary (Maruzen Co., Ltd.) p. Reference can be made to the item of "heat molding" described in 766 to 768 and the documents cited in the item. It is also preferable to use both vacuum forming and pressure forming.

The three-dimensional structure according to the present disclosure may be an injection-molded body obtained by further injection molding a second laminate according to the present disclosure or a three-dimensional molded article of the optical member sheet according to the present disclosure.
Moreover, the manufacturing method of the three-dimensional structure which concerns on this indication may further include the process of inject-molding resin in the three-dimensional structure obtained by the process of carrying out the said three-dimensional shaping | molding.
The injection molding is preferably performed by an injection molding machine. The mold used for producing the injection-molded body is preferably formed by a fixed mold and a moving mold disposed opposite to each other, and a cavity sandwiched by both molds is formed. In addition, as an example of injection molding by an injection molding machine, a molding resin material which is filled in a hollow portion of a mold through a sprue, a runner, and a gate is molded, cooled and solidified, and then the mold is prepared. There is an aspect in which the injection molded body is opened and taken out.
Mold cavities are also referred to as cavities. The mold is previously manufactured so as to form a cavity adapted to the shape of the resin molding to be manufactured, and the resin filled in the cavity is the optical member sheet according to the present disclosure disposed in the mold. It is integrated with a three-dimensional molded product to obtain an injection molded product.
In the injection molding step, the optical member side of the three-dimensional molding of the optical member sheet according to the present disclosure is disposed so as to be the mold side.
When the injection molding is performed, the three-dimensional molding may be performed using a mold for performing the injection molding.
The optical member sheet according to the present disclosure or the three-dimensional molded product of the optical member sheet according to the present disclosure is disposed in the mold, preferably on the side of the fixed mold.

As the thermoplastic resin injected into the cavity in the above-mentioned injection molding, resins known to those skilled in the art can be used. The resin includes acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate (PC) resin, polypropylene (PP) resin, polyethylene (PE) resin, and polyethylene terephthalate (PET) resin. Moreover, you may use the mixed resin containing these at least 1 sort (s).
The conditions for injection molding are appropriately determined depending on the type of the thermoplastic resin to be injected, the shape of the molded product, and the like. Taking the case of ABS resin as an example, a cylinder temperature of 180 ° C. to 260 ° C., mold temperature of 40 ° C. to 80 ° C., it is preferred that the injection pressure 500kg weight ^/ cm 2 ^~1,800kg heavy / cm ^2.

Hereinafter, the embodiment of the present invention will be more specifically described by way of examples, but the present disclosure is not limited to the following examples as long as the gist thereof is not exceeded. In addition, unless otherwise indicated, "part" is a mass reference | standard.
In addition, the measuring method of the wavelength from which the light transmittance of the thermoplastic substrate in Example is 50%, the measuring method of the maximum absorption wavelength of each photopolymerization initiator, the specifying method of the structure of the decomposition product, and The method of quantifying the amount was measured by the method described above.

  The compounds etc. which were used by the present Example are shown below.

<Thermoplastic substrate>
Technoloy S 001 G (acrylic resin base material containing an ultraviolet light absorber, wavelength at which light transmittance is 50%: 392 nm, manufactured by ESCABO SHEET, thickness 139 μm)
Technoloy S000 (acrylic resin base material not containing an ultraviolet light absorber, wavelength at which the light transmittance is 50%: none, manufactured by Escarbo Sheet Inc., thickness 139 μm)
An acrylic resin substrate containing TINUVIN 400 (polymethyl methacrylate substrate containing UV absorber, TINUVIN 400 (UV absorber, manufactured by BASF)) containing 0.25% by mass, the wavelength at which the light transmittance is 50%: 365 nm, thickness 139 μm)
An acrylic resin substrate containing TINUVIN P (a polymethyl methacrylate substrate containing an ultraviolet light absorber, TINUVIN P (ultraviolet light absorber, manufactured by BASF)) containing 0.25% by mass, the wavelength at which the light transmittance is 50%: 390 nm, thickness 139 μm)

<Polymerizable compound>
・ AA 6 (AA-6 manufactured by Toagosei Co., Ltd., methacrylic resin having a methacryloyl group at the end (polymethyl methacrylate))
・ FA 513 AS (funcryl FA 513 AS, manufactured by Hitachi Chemical Co., Ltd., dicyclopentanyl acrylate)
-M 315 (Toon Gosei Co., Ltd. Alonics M-315, tris (2-acryloxyethyl) isocyanurate)
N-vinyl pyrrolidone (NVP, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Triallyl isocyanurate (made by Nippon Kasei Co., Ltd.)
-Allyl cyclohexane propionate (Allyl 3-cyclohexyl propionate, manufactured by Tokyo Chemical Industry Co., Ltd.)
Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate), manufactured by Showa Denko KK)

<Photoinitiator>
-IRGACURE 184 (manufactured by BASF, 1-hydroxycyclohexyl phenyl ketone)
-IRGACURE TPO (manufactured by BASF, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide)
・ IRGACURE 819 (manufactured by BASF, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide)
-IRGACURE 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenylpropan-1-one)

(Examples 1 to 17 and Comparative Examples 1 to 3)
1. Preparation of Curable Composition The components shown in Table 1 were mixed to prepare each curable composition.

2. Preparation of Lenticular Sheet The above curable composition was coated on the thermoplastic substrate described in Table 1 so as to have the following lens height, and then a plurality of convex lenses having a semi-cylindrical surface as shown in FIG. Shape of a lenticular lens (lens height 60 μm, length y in the longitudinal direction y 80 mm, lens width (lens pitch) 200 LPI (Line Per Inch)) in which cylindrical lenses 12 having the portion 12A are arranged in parallel in one direction The molded mold (width 100 mm × depth 100 mm) is pressed by evacuating to form the above curable composition on the thermoplastic substrate into the shape of a lenticular lens, and then ultraviolet light (UV) is transmitted through the thermoplastic substrate , UV irradiation equipment (EXECURE 3000, HOYA CANDEO OPTRONICS Ltd.) using, irradiation dose It irradiated at 0.3 J / cm < ² >. After the irradiation, the mold was removed, and ultraviolet rays were irradiated from the above-mentioned optical member forming layer side (lens surface side) at an irradiation amount of 1.0 J / cm ² to produce a lenticular sheet.
In Example 8, the irradiation of ultraviolet light from the side of the optical member forming layer was performed twice at 0.5 J / cm ² .
In Example 17, the second exposure was performed on the thermoplastic substrate side (substrate side).

3. Evaluation method <Moldability>
The laminate obtained after the first exposure in the preparation of the lenticular sheet is punched into a size of 50 mm in length × 10 mm in width to prepare a sample piece, and manufactured by TENSILON RTC-1225A (manufactured by A & D Co., Ltd.) The tensile elongation was measured by conducting a tensile test under the following conditions, and the evaluation was made according to the following evaluation criteria. Two or more are the range without a problem in practical use.
-Condition-
-Distance between chucks: 30 mm
・ Temperature of sample piece: 100 ° C
· Tensile speed: 1 mm / sec 5: Elongation at break 20% or more 4: Elongation at break 15% or more and less than 20% 3: Elongation at break 10% or more and less than 15% 2: Elongation at break Degree is 5% or more and less than 10% 1: Elongation at break is 0% or more and less than 5%

<Abrasion resistance>
Tests were conducted using Technoloy S000 (thickness = 0.3 mm) under the following conditions, and the scratched surface after the test was visually observed.
The lenticular sheet 1 cm ² was prepared under a load of 200 g at HEIDON Co. surface property measuring instrument Tribogear contacting a Tekunoroi S000 (thickness = 0.3 mm) with respect to the optical member side of the lenticular sheet at 100 mm / min The sliding test was performed for 100 reciprocal sliding tests. Evaluation criteria are shown below. Two or more are the range without a problem in practical use.
5: No flaws are visible even when observed with a magnifying glass (magnification: 200 times) 4: no flaws are visible when visually observed through fixation 3: no flaws are visible even when observed visually 2: visual observation The wound is visible when observed with the eye, but it is inconspicuous level 1: The wound is clearly visible when observed visually

<Light resistance>
Using a metallizing weather meter MV3000 (manufactured by Suga Test Instruments Co., Ltd.) and a metal halide lamp M3.0 (manufactured by Suga Test Instruments Co., Ltd.), the prepared lenticular sheet was used at an irradiation amount of 0.46 J / cm ² . Irradiated for 60 hours. The reduction rate ((Transmittance after irradiation for 400 hours / initial transmission) × 100) of light having a wavelength of 450 nm before and after irradiation for 60 hours was calculated and evaluated according to the following evaluation criteria. Two or more are the range without a problem in practical use.
5: The reduction rate is 0% or more and less than 5% 4: The reduction rate is 5% or more and less than 10% 3: The reduction rate is 10% or more and less than 15% 2: The reduction rate is 15% or more and less than 20% Is 1: The reduction rate is 20% or more

  The long wavelength type-I, the long wavelength type-II, and the short wavelength type-I, which are decomposition products of the long wavelength type or the short wavelength type photopolymerization initiator described in Table 2, respectively, a compound having a structure shown below It is.

In the chemical formulae, Poly ^{A to} Poly ^G each independently represent a copolymer of a polymerizable compound contained in the curable composition used, R ^re represents an unreacted 2,4,6-trimethyl benzoyl group, Alternatively, it represents a group formed by the deactivation of a generated radical such as a hydrogen atom or a hydroxy group.
Further, the copolymerization ratio of the polymerizable compound in the Poly ^A ~Poly ^G was similar to the content mass ratio of the polymerizable compound in the curable composition used.
The average repetition number (n) of the decomposition product of the long wavelength photopolymerization initiator described in Table 2 is, in the case of long wavelength type-I, a monomer unit which each of Poly ^A and Poly ^B has (provided that it is from the above AA6) The average number of monomer units counted is one monomer unit, which is the same as in the following), and in the case of long wavelength type-II, the monomer units possessed by Poly ^C , Poly ^D and Poly ^E respectively In the case of short wavelength type-I, it is the average number of the monomer units which Poly ^F and Poly ^G have, respectively.

As apparent from the results of Tables 1 and 2, it can be seen that the optical member forming laminate according to the present disclosure can provide an optical member sheet that is excellent in moldability, abrasion resistance, and light resistance.
Moreover, as is clear from the results of Tables 1 and 2, it can be seen that the optical member sheet according to the present disclosure is excellent in moldability, abrasion resistance and light resistance.
In addition, as shown in Examples 1 to 12, the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material in the optical member forming layer is 50%. When the content is 0.025% by mass to 0.25% by mass with respect to the total mass of the optical member forming layer, the formability is excellent.
As shown in Examples 1 to 10, 13 and 14, the maximum absorption wavelength is on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material in the optical member forming layer is 50%. It is excellent by abrasion resistance that content of the photoinitiator which it has is 0.025 mass%-0.25 mass% with respect to the total mass of an optical member.
As shown in Examples 1 to 10, 15 and 16, when the polymerizable compound is a compound selected from the group consisting of (meth) acrylate compounds and N-vinyl compounds, scratch resistance and Excellent by light resistance.
As shown in Examples 1 to 10 and 17, if one or more exposures are performed from the thermoplastic substrate side and then one or more exposures are performed from the optical member forming layer side, the scratch resistance and Excellent by light resistance.

(Example 11)
An ink layer was formed on the thermoplastic base material side of the lenticular sheet of Example 2 by offset printing.
About 10 μm of hot melt ADHM-6 (made by Jujo Chemical Co., Ltd.) is formed by screen printing on the ink layer side of the lenticular sheet on which the ink layer is formed, and after drying, a 430 μm ABS sheet is heated to 120 ° C. Lamination was performed under the condition of 1 MPa to obtain a laminate of a lenticular sheet.
The laminate of the obtained lenticular sheet was measured by a vacuum pressure air forming machine FI (manufactured by Asano Research Institute) at a temperature of 140 ° C., a pressure of 0.4 MPa, a pressure of 0.1 MPa, and a side of 5 cm. As a result of molding with a regular tetrahedral mold, it was possible to mold without breaking.

The disclosure of Japanese Patent Application No. 2017-3726, filed January 12, 2017, is incorporated herein by reference in its entirety.
All documents, patent applications and technical standards described herein are the same as if each individual document, patent application and technical standard was specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

10: optical member sheet (lenticular sheet), 12: lenticular lens, 12A: convex lens, 14: lenticular image, 14A, 14B: display image row, 14C: interpolation image row, x: lens width direction, y: Longitudinal direction of lens

Claims (15)

A thermoplastic substrate comprising a UV absorber, and
It has an optical member forming layer disposed on the surface of the thermoplastic substrate,
The optical member forming layer has a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light transmittance of the thermoplastic substrate is 50 A laminate for forming an optical member, comprising: a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the% wavelength. A thermoplastic substrate comprising a UV absorber, and
It has an optical member forming layer disposed on the surface of the thermoplastic substrate,
The optical member forming layer has a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light transmittance of the thermoplastic substrate is 50 A laminate for forming an optical member, comprising: a polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the% wavelength wavelength. In the optical member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% is the total mass of the optical member forming layer And 0.1 mass% to 1.0 mass%,
In the optical member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is the total mass of the optical member forming layer It is 0.1 mass%-1.0 mass% with respect to the laminated body for optical member formation of Claim 1. In the optical member forming layer, the content of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% is the total mass of the optical member forming layer And 0.1 mass% to 1.0 mass%,
In the optical member forming layer, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material becomes 50% is the optical member It is 0.025 mass%-0.25 mass% with respect to the total mass of the formation layer. The laminated body for optical member formation of Claim 2. The wavelength at which the light transmittance of the ultraviolet absorber is 50% is more than 380 nm and less than 405 nm,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% is 380 nm or less,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is 405 nm or more. The laminated body for optical member formation of 1 item | term. A thermoplastic substrate comprising a UV absorber, and
It has an optical member disposed on the surface of the thermoplastic substrate,
A polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic substrate is 50%, and the light of the thermoplastic substrate An optical member sheet comprising: a polymerizable decomposition product of a photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than a wavelength at which the transmittance is 50%. In the optical member, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the shorter wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is the entire optical member. 0.025% by mass to 0.25% by mass with respect to the mass,
In the optical member, the content of the polymerization type decomposition product of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is the entire content of the optical member The optical member sheet according to claim 6, which is 0.025% by mass to 0.25% by mass with respect to the mass. The wavelength at which the light transmittance of the ultraviolet absorber is 50% is more than 380 nm and less than 405 nm,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% is 380 nm or less,
The maximum absorption wavelength of the photopolymerization initiator having a maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic base material is 50% is 405 nm or more. Optical member sheet. It has a thermoplastic base material containing a ultraviolet absorber, and an optical member formation layer arranged on the surface of the thermoplastic base material, and the optical member formation layer has a light transmittance of 50% of the thermoplastic base material. And a photopolymerization initiator having a maximum absorption wavelength at a longer wavelength side than a wavelength at which the light transmittance of the thermoplastic base material is 50%. Providing a laminate for forming an optical member, comprising:
A method of manufacturing an optical member sheet, comprising the step of exposing the optical member forming layer twice or more to form an optical member. The wavelength at which the light transmittance of the ultraviolet absorber is 50% is more than 380 nm and less than 405 nm,
The maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the short wavelength side of the wavelength at which the light transmittance of the thermoplastic base material is 50% is 380 nm or less,
10. The optical member sheet according to claim 9, wherein the maximum absorption wavelength of the photopolymerization initiator having the maximum absorption wavelength on the longer wavelength side than the wavelength at which the light transmittance of the thermoplastic substrate is 50% is 405 nm or more. Production method.   The optical according to claim 9 or 10, wherein, in the step of forming the optical member, one or more exposures are performed from the thermoplastic substrate side, and then one or more exposures are performed from the optical member forming layer side. Method of manufacturing member sheet. Between the first exposure and the last exposure in the process of forming the optical member,
Forming a printing layer on the side of the thermoplastic substrate opposite to the side on which the optical member forming layer is disposed;
Cutting the optical member forming laminate into a desired shape;
The method for producing an optical member sheet according to any one of claims 9 to 11, wherein at least one step selected from the group consisting of a step of shaping the optical member forming layer into a shape of an optical member is performed.   The three-dimensional structure which is a three-dimensional molded object of the laminated body for optical member formation of Claim 2 or Claim 5, or the optical member sheet | seat of any one of Claims 6-8.   A laminate for forming an optical member according to claim 2 or claim 5, or a three-dimensional structure comprising a step of three-dimensionally molding an optical member sheet according to any one of claims 6 to 8 Method.   The method for producing a three-dimensional structure according to claim 14, further comprising the step of injection-molding a resin on the three-dimensional molded product obtained by the three-dimensional molding process.