WO2018070537A1 - Hardening composition, hardened substance and method for manufacturing same, layered sheet, optical member, lenticular sheet, and three-dimensional structure - Google Patents

Abstract

Provided is a hardening composition that has a rupture elongation of an obtained hardened substance at 100°C of 6–80%, a molecular weight at cross-linking points of the obtained hardened substance of 20–2,000 g/mol, and a rupture elongation at 100°C of 6–80%. Moreover, the hardened substance has a molecular weight at cross-linking points of 20–2,000 g/mol. Furthermore, provided are a method for manufacturing the hardened substance, and a laminated sheet, an optical member, a lenticular sheet, and a three-dimensional structure that include the hardened substance of the hardening composition.

Description

Curable composition, cured product and method for producing the same, laminated sheet, optical member, lenticular sheet, and three-dimensional structure

The present disclosure relates to a curable composition, a cured product and a manufacturing method thereof, a laminated sheet, an optical member, a lenticular sheet, and a three-dimensional structure.

Conventionally, a curable composition contains a polymerizable resin and an initiator, is cured by causing a polymerization reaction by heat or light, and is widely used in various applications.
Moreover, the laminated sheet which laminated | stacked the hardened | cured material obtained by hardening | curing a curable composition is utilized widely, such as an optical member, a gas barrier film, a protective film, an optical filter, an antireflection film.
Furthermore, the cured product obtained by curing the curable composition is used for various members such as an antireflection film, a transparent pixel, a transparent insulating film, and a planarization film.
In recent years, there are a wide variety of optical members, and the optical structure of the optical member is not limited to a flat surface shape, for example, and is used for a brightness enhancement lens and a diffusion lens of a backlight for liquid crystal, and a screen of a video projection television. Examples include Fresnel lenses and micro lenses. In such a device, a desired geometrical optical performance is obtained mainly by forming a fine structure with a resin material.
Further, as the optical structure, a lenticular sheet using a lenticular lens in which convex lenses having a semi-cylindrical surface are arranged in parallel is known as a medium for displaying different images depending on viewing angles.
In a lenticular sheet, generally, an image sequence group (lenticular image) in which a plurality of interlaced images are combined is arranged on the back side of the lenticular lens (the surface opposite to the semi-cylindrical surface of the convex lens). When the row group is observed through a lenticular lens, one or more images in the image row group can be displayed depending on the viewing angle.
Therefore, it is expected to be used in various commercial applications including optical materials and optical screens. However, the applications proposed heretofore are mostly used in a two-dimensional form such as a sheet or a film, and are not often applied to a three-dimensional form formed into a three-dimensional shape.
Examples of conventional curable compositions include the compositions described in Patent Documents 1 to 6.

Japanese Patent Laying-Open No. 2015-182912 JP 2005-82639 A JP 2006-249220 A JP 2005-281406 A JP 2004-333902 A JP 2009-37204 A

However, when a cured product or a laminated sheet having the cured product is prepared using a conventionally proposed curable composition and further three-dimensionally molded by vacuum molding or the like, the three-dimensional formability of the cured product is reduced. It is not sufficient, and the cured product may be cracked or three-dimensionally molded or the cured product itself may be damaged.

The problem to be solved by one embodiment of the present invention is to provide a curable composition that is excellent in the three-dimensional moldability and wear resistance of the resulting cured product.
The problem to be solved by another embodiment of the present invention is to provide a cured product excellent in three-dimensional formability and wear resistance and a method for producing the same.
Still another embodiment of the present invention is to provide a laminated sheet, an optical member, a lenticular sheet, and a three-dimensional structure having a cured product of the curable composition.

Means for solving the above problems include the following aspects.
<1> Curing elongation at 100 ° C. of the obtained cured product is 6% or more and 80% or less, and a molecular weight between crosslinking points of the obtained cured product is 20 g / mol or more and 2,000 g / mol or less. Composition.
<2> The curable composition according to the above <1>, wherein the obtained cured product has a molecular weight distribution between crosslinking points of 1% or more and 30% or less.
<3> The curable composition according to the above <1> or <2>, comprising a polyfunctional (meth) acrylate compound having a ring structure and an N-vinyl compound.
<4> Curable composition as described in said <3> whose content of the polyfunctional (meth) acrylate compound which has the said ring structure is 1 mass% or more and 75 mass% or more with respect to the total mass of a curable composition. object.
<5> The curable composition according to the above <3> or <4>, wherein the content of the N-vinyl compound is 8% by mass to 60% by mass with respect to the total mass of the curable composition.
<6> The method according to any one of <3> to <5>, wherein the N-vinyl compound is at least one compound selected from the group consisting of N-vinylpyrrolidone and N-vinylcaprolactam. Curable composition.
<7> The curable composition according to any one of <1> to <6>, which contains a monofunctional (meth) acrylate compound.
<8> The curable composition according to <7>, wherein the content of the monofunctional (meth) acrylate compound is 1% by mass to 80% by mass with respect to the total mass of the curable composition.
<9> The curable composition according to any one of the above <1> to <8>, comprising a photopolymerization initiator.
<10> The above, wherein the urethane (meth) acrylate compound is not contained or the content of the urethane (meth) acrylate compound is more than 0% by mass and less than 4% by mass with respect to the total mass of the curable composition < The curable composition according to any one of 1> to <9>.
<11> A step of preparing the curable composition according to any one of <1> to <10> above, and a temperature unevenness in the range of 0.5 ° C. or more and 10 ° C. or less of the curable composition. The manufacturing method of hardened | cured material including the process hardened | cured in the state which has.
<12> A laminated sheet having a cured product of the curable composition according to any one of <1> to <10>.
<13> An optical member having a cured product of the curable composition according to any one of <1> to <10>.
<14> A lenticular sheet having a cured product of the curable composition according to any one of the above items <1> to <10>.
<15> A three-dimensional structure which is a three-dimensional molded product of the laminated sheet according to <12>.
<16> A cured product having a breaking elongation at 100 ° C. of 6% or more and 80% or less and a molecular weight between crosslinking points of 20 g / mol or more and 2,000 g / mol or less.
<17> The cured product according to <16>, wherein the molecular weight distribution between cross-linking points is 1% or more and 30% or less.

According to one embodiment of the present invention, it is possible to provide a curable composition excellent in the three-dimensional moldability and wear resistance of the obtained cured product.
Moreover, according to other embodiment of this invention, the hardened | cured material excellent in three-dimensional moldability and abrasion resistance, and its manufacturing method can be provided.
Furthermore, according to other embodiment of this invention, the laminated sheet, optical member, lenticular sheet, and three-dimensional structure which have the hardened | cured material of the said curable composition can be provided.

It is the schematic which shows an example of the lenticular sheet in this indication.

Hereinafter, the present disclosure will be described in detail.
In the present specification, the description “xx to yy” represents a numerical range including xx and yy.
In this specification, “(meth) acryl” is a term used in a concept including both acryl and methacryl, and “(meth) acryloyl” is a term used as a concept including both acryloyl and methacryloyl. It is.
In addition, the term “process” in this specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended purpose of the process is achieved. included.
Unless otherwise specified, hydrocarbon groups 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.
In the present disclosure, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) unless otherwise specified. The molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.

(Curable composition)
In the curable composition according to the present disclosure, the obtained cured product has a breaking elongation at 100 ° C. of 6% or more and 80% or less, and the obtained cured product has a molecular weight between crosslinking points of 20 g / mol or more and 2,000 g. / Mol or less.
The curable composition concerning this indication is used suitably as a curable composition for optical member formation, and is more suitably used as a curable composition for lenticular sheet (especially lenticular lens in a lenticular sheet) formation.

As a result of detailed studies by the present inventors, it has been found that by using the curable composition, the resulting cured product is excellent in three-dimensional formability and wear resistance.
Although the detailed mechanism is unknown, the strength at 100 ° C. of the obtained cured product is 6% or more and 80% or less, so that the strength of the cured product is increased even when the surface temperature of the cured product is increased by friction. And since it has moderate deformability, it is estimated that the three-dimensional moldability and wear resistance of the obtained cured product can be compatible.
Moreover, although a measuring method etc. are explained in full detail later, molecular weight between bridge | crosslinking points shows the magnitude | size of the network of a crosslinked structure.
When the molecular weight between cross-linking points of the obtained cured product is 20 g / mol or more and 2,000 g / mol or less, non-crosslinking molecules (for example, monofunctional (meth) acrylate compounds) can pass through the network appropriately. By curing, it is presumed that deformation in the obtained cured product is promoted and three-dimensional moldability is improved.
Furthermore, when the molecular weight between cross-linking points of the obtained cured product is 20 g / mol or more and 2,000 g / mol or less, the crosslinking density in the cured product is appropriate, and the balance between flexibility and strength is excellent and obtained. It is estimated that the three-dimensional formability and wear resistance of the cured product can be compatible.

In the curable composition according to the present disclosure, the elongation at break of the obtained cured product at 100 ° C. is 6% or more and 80% or less, and 15% from the viewpoint of the three-dimensional moldability and wear resistance of the obtained cured product. It is preferably 70% or less and more preferably 20% or more and 60% or less.

The elongation at break in the present disclosure is measured by the following method.
When the curable composition is available, the curable composition is sandwiched between two glass plates that have been subjected to a hydrophobic treatment, and heated under the following conditions until ultraviolet (UV) irradiation or thermosetting, The resin cured film (single film) having a film thickness of 50 μm is prepared by peeling from the plate.
The UV irradiation is performed using an ultraviolet (UV) irradiation apparatus (EXECURE 3000, manufactured by HOYA CANDEO OPTRONICS Co., Ltd.) until it is cured under the condition of a UV irradiation amount of 1.0 J / cm ² .
A cured resin film (single film) is punched into a size of 50 mm length x 10 mm width to prepare a sample piece, and a tensile test is performed using TENSILON RTC-1225A (manufactured by A & D) under the following conditions. To measure the elongation at break represented by the following formula. The elongation at break is measured three times, and the average value thereof is taken as the elongation at break.
Elongation at break (%) = 100 × (length broken by stretching−distance between chucks) / (distance between chucks)
-conditions-
・ Distance between chucks: 30mm
-Sample piece temperature: 100 ° C
・ Tensile speed: 1 mm / sec

When measuring the breaking elongation from the cured product, the cured product is processed to a size of 50 mm length × 10 mm width, a sample piece is produced, and the breaking elongation at 100 ° C. is measured by the same method as described above. To do. In this measurement, there is no influence on the elongation at break within the preferable thickness range of the cured film in the present disclosure described below.
In addition, the thickness of the cured film obtained by curing the curable composition according to the present disclosure into a film shape is preferably 10 μm to 100 μm, more preferably 15 μm to 80 μm, and still more preferably 20 μm to 60 μm. Within the above range, the handleability is excellent and the moldability is excellent.

The curable composition in the present disclosure has a molecular weight between cross-linking points of the obtained cured product of 20 g / mol or more and 2,000 g / mol or less. From the viewpoint of the three-dimensional moldability and wear resistance of the obtained cured product, 50 g / Mol to 1,500 g / mol, more preferably 100 g / mol to 1,200 g / mol.

The molecular weight between crosslinking points in the present disclosure is measured by the following method.
The same sample piece used for the measurement of the elongation at break is prepared, the temperature is raised to the temperature of the rubber region (250 ° C.), and DMA (Dynamic Mechanical Analyzer: Rheogel-E4000HP manufactured by UBM) is used. The storage elastic modulus (E ′) is determined by applying a strain of 0.01% at 10 Hz.
Subsequently, the molecular weight (Mc) between crosslinking points is determined using the following formula.
Mc = 3 × ρ × R × T / E ′
Mc = g / mol, ρ (density) = g / cm ³ , R (gas constant) = J / (mol · K), T (measured temperature) = K, E ′ = Pa

In the curable composition of the present disclosure, the distribution of molecular weight between crosslink points of the cured product obtained is preferably 1% or more and 30% or less, more preferably 2% or more and 25% or less. % To 20% is more preferable. When the distribution is 1% or more, the three-dimensional moldability of the resulting cured product is excellent, and when the distribution is 30% or less, the wear resistance of the resulting cured product is excellent.

In the present disclosure, the distribution of molecular weight between cross-linking points is measured by the following method.
The molecular weight between the crosslinking points is measured for 10 sample pieces used for the measurement of the molecular weight between the crosslinking points, and the difference between the maximum value and the minimum value in each value of the molecular weight between the crosslinking points measured with 10 sample pieces. Is divided by the average value, and the value expressed as a percentage is defined as the distribution of molecular weight between cross-linking points.

Further, the curable composition in the present disclosure preferably has a glass transition temperature (Tg) of the obtained cured product exceeding 90 ° C. from the viewpoint of the three-dimensional moldability and wear resistance of the obtained cured product, and 95 ° C. The temperature is more preferably 200 ° C. or lower and even more preferably 100 ° C. or higher and 180 ° C. or lower.
The glass transition temperature (Tg) of the cured product or resin in the present disclosure is obtained from the measured main maximum peak using a differential scanning calorimeter (Perkin Elmer, Inc .: DSC-7) according to ASTM D3418-8. be able to. The temperature correction of the detection part of this device (DSC-7) uses the melting point of indium and zinc, and the correction of heat uses the heat of fusion of indium. For the sample, an aluminum pan is used, and an empty pan is set as a control. The temperature is raised at a rate of 10 ° C./min, held at 200 ° C. for 5 minutes, cooled from 200 ° C. to 20 ° C. at −10 ° C./min using liquid nitrogen, held at 20 ° C. for 5 minutes, and again 20 The onset temperature analyzed from the endothermic curve during the second temperature increase obtained by increasing the temperature from 10 ° C. to 200 ° C./min was defined as Tg.

Such a cured film (cured resin layer) is preferably formed and used on a base material. For example, when a flat film is formed on the base material without molding, it can be used as a hard coat film. In addition, since the cured product according to the present disclosure obtained by curing the curable composition according to the present disclosure is excellent in extensibility, it is also preferable that the flat film is three-dimensionally molded.
Furthermore, after applying the curable composition which concerns on this indication on a base material, it is also preferable to provide shapes, such as an unevenness | corrugation. For example, when molded into a semi-cylindrical shape, it can be used as a lenticular lens, when shaped into a triangular prism, it can be used as a prism sheet or a brightness enhancement film, and when molded into a hemispherical shape, it can be used as a microlens sheet. When the saw blade shape as shown in FIG. 4A of 2015/102100 is formed concentrically, it can be used as a prism sheet.

Hereinafter, each component used in the curable composition according to the present disclosure will be described in detail. By containing these components as appropriate, a curable composition satisfying the breaking elongation and the molecular weight between crosslinking points in the cured product can be obtained.

<Polymerizable compound>
The curable composition according to the present disclosure preferably contains a polymerizable compound.
As the polymerizable compound, an ethylenically unsaturated compound is preferable.
Preferred examples of the ethylenically unsaturated compound include polyfunctional (meth) acrylate compounds having a ring structure and N-vinyl compounds.
Further, the curable composition according to the present disclosure may contain a polyfunctional (meth) acrylate compound having a ring structure and an N-vinyl compound from the viewpoint of the three-dimensional moldability and wear resistance of the resulting cured product. preferable.

<< Polyfunctional (meth) acrylate compound having a ring structure >>
It is preferable that the curable composition which concerns on this indication contains the polyfunctional (meth) acrylate compound which has a ring structure from a viewpoint of the three-dimensional moldability and abrasion resistance of the hardened | cured material obtained.
The ring structure is not particularly limited, but may be an aliphatic hydrocarbon ring structure that may have some heteroatoms as ring members, and an aliphatic that may have some heteroatoms as ring members. A condensed ring structure in which two or more aromatic hydrocarbon rings are condensed is preferred. The aliphatic hydrocarbon ring is preferably a 5-membered ring or a 6-membered ring.
Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is particularly preferable.
Among them, the ring structure is at least selected from the group consisting of an isocyanuric ring structure, a tricyclodecane ring structure, a triazine ring, and a cyclohexane ring structure from the viewpoint of the three-dimensional moldability and wear resistance of the resulting cured product. One ring structure is preferable, an isocyanuric ring structure or a tricyclodecane ring structure is more preferable, and an isocyanuric ring structure is particularly preferable.
Moreover, it is preferable that the polyfunctional (meth) acrylate compound which has a ring structure in this indication does not contain urethane bonds other than an isocyanuric ring structure.

The polyfunctional (meth) acrylate compound having the ring structure is not particularly limited as long as it is bifunctional or higher, but is trifunctional to hexafunctional from the viewpoint of three-dimensional moldability and wear resistance of the obtained cured product. Is preferable, trifunctional or tetrafunctional is more preferable, and trifunctional is particularly preferable.

Specific examples of the polyfunctional (meth) acrylate compound having the ring structure include tricyclodecane dimethanol di (meth) acrylate, di (meth) acryloxyalkylated isocyanurate, isocyanuric acid ethylene oxide (hereinafter referred to as ethylene oxide). Also referred to as “EO”.) Modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, and the like.
Among these, isocyanuric acid ethylene oxide-modified tri (meth) acrylate is particularly preferable.

The molecular weight of the polyfunctional (meth) acrylate compound having the ring structure is preferably 200 or more and 1,500 or less.
The curable composition concerning this indication may contain the polyfunctional (meth) acrylate compound which has a ring structure individually by 1 type, or may contain 2 or more types.
The content of the polyfunctional (meth) acrylate compound having a ring structure in the curable composition according to the present disclosure is the total mass of the curable composition from the viewpoint of the three-dimensional moldability and wear resistance of the obtained cured product. On the other hand, 1 mass% or more and 75 mass% or less are preferable, 10 mass% or more and 70 mass% or less are more preferable, and 20 mass% or more and 60 mass% or less are still more preferable.

<< N-vinyl compound >>
The curable composition according to the present disclosure preferably contains an N-vinyl compound. The N-vinyl compound contributes to the improvement of the adhesion to the base material and improves the stretchability at the time of molding the cured product.
Thereby, the cylindrical lens which is a cured product is less likely to be peeled off from the resin base material, and generation of cracks or the like that easily occur during molding is suppressed, and the three-dimensional moldability is excellent.
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 three-dimensional moldability and wear resistance of the resulting cured product. N-vinylpyrrolidone is more preferable.
Among N-vinyl compounds, examples of N-vinylpyrrolidone include N-vinyl-2-pyrrolidone. Examples of N-vinylcaprolactam include N-vinyl-ε-caprolactam.

The curable composition according to the present disclosure may contain one N-vinyl compound alone or two or more kinds.
The content of the N-vinyl compound in the curable composition according to the present disclosure includes all of the curable composition from the viewpoint of the three-dimensional moldability and wear resistance of the resulting cured product and the shape retention of the cylindrical lens. 8 mass% or more and 60 mass% or less are preferable with respect to mass, 15 mass% or more and 50 mass% or less are more preferable, 20 mass% or more and 40 mass% or less are still more preferable, and 25 mass% or more and 35 mass% or less are especially preferable. preferable.

<< Monofunctional (meth) acrylate compound >>
It is preferable that the curable composition which concerns on this indication contains a monofunctional (meth) acrylate compound from the viewpoint of the three-dimensional moldability and abrasion resistance of the hardened | cured material obtained.
The monofunctional (meth) acrylate compound is a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure and a (meth) acryloyl at the terminal from the viewpoint of the three-dimensional moldability and wear resistance of the resulting cured product. Preferred is a resin having a group.

-Monofunctional (meth) acrylate compounds having an aliphatic hydrocarbon ring structure-
It is preferable that the curable composition which concerns on this indication contains the monofunctional (meth) acrylate compound which has an aliphatic hydrocarbon ring structure from a viewpoint of the three-dimensional moldability and abrasion resistance of the hardened | cured material obtained.
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 the three-dimensional formability and wear resistance of the resulting cured product. At least one kind of ring structure is preferable, and a tricyclodecane ring structure is more preferable.

As a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure, specifically, it has a tricyclodecane ring structure such as dicyclopentanyl (meth) acrylate and dicyclopentanyloxyethyl (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 isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, etc. And (meth) acrylate compounds having an adamantane ring structure.
Among these, from the viewpoint of three-dimensional moldability and wear resistance of the obtained cured product, a (meth) acrylate compound having a tricyclodecane ring structure is preferable, and dicyclopentanyl (meth) acrylate is more preferable.

The curable composition concerning this indication may contain the monofunctional (meth) acrylate compound which has an aliphatic hydrocarbon ring structure individually by 1 type, or may contain 2 or more types.
As content of the monofunctional (meth) acrylate compound which has an aliphatic hydrocarbon ring structure in the curable composition which concerns on this indication, it is a curable composition from a viewpoint of the three-dimensional moldability and abrasion resistance of the hardened | cured material obtained. Is preferably 0.5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and particularly preferably 20% by mass or more and 40% by mass or less.

-Resin with (meth) acryloyl group at the end-
The curable composition according to the present disclosure preferably includes a resin having a (meth) acryloyl group at the terminal. Since the resin has a (meth) acryloyl group at the end of the molecular chain, the crosslink density in the entire curable composition can be increased by using it in combination with other polymerizable compounds, particularly polyfunctional (meth) acrylate compounds. Controlled and excellent in three-dimensional moldability and wear resistance of the resulting cured product.

The resin may be a polymer having a (meth) acryloyl group at the terminal, for example, (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, copolymers thereof, and cycloolefin polymers Can be mentioned. Among these, from the viewpoint of the three-dimensional moldability and wear resistance of the resulting cured product, a (meth) acrylic resin having a (meth) acryloyl group at the terminal or a polystyrene having a (meth) acryloyl group at the terminal is preferable. A (meth) acrylic resin having a (meth) acryloyl group is more preferable.
The (meth) acrylic resin having a (meth) acryloyl group at the terminal is preferably polymethyl methacrylate having a (meth) acryloyl group at the terminal from the viewpoint of wear resistance.
Furthermore, the resin having a (meth) acryloyl group at the terminal preferably has a methacryloyl group at the terminal.
The resin having a (meth) acryloyl group at the end is preferably a resin having a (meth) acryloyl group at the end of the main chain, and a resin having a (meth) acryloyl group at one end of the main chain. Is more preferable.
In the present disclosure, “main chain” represents a relatively long bond chain in the molecule of the polymer compound constituting the resin, and “side chain” represents a carbon chain branched from the main chain. .

Examples of the resin having a (meth) acryloyl group at the terminal include a macromonomer series manufactured by Toagosei Co., Ltd. (eg, macromonomer AA-6 (polymethyl methacrylate having a methacryloyl group), 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.

The number average molecular weight of the resin having a (meth) acryloyl group at the terminal is preferably 1,000 or more and 10,000 or less, more preferably 3,000 or more and 10,000 or less, from the viewpoint of the three-dimensional moldability of the resulting cured product. Preferably, 5,000 or more and 10,000 or less are more preferable.
The resin in the present disclosure preferably has a number average molecular weight of 1,000 or more.

The glass transition temperature (Tg) of the resin having a (meth) acryloyl group at the terminal is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of wear resistance of the obtained cured product. In addition, from the viewpoints of adhesion of the obtained cured product to the resin base material and three-dimensional moldability, Tg is preferably less than 250 ° C, and more preferably 200 ° C or less.

The curable composition according to the present disclosure may contain one kind of resin having a (meth) acryloyl group at the terminal alone or two or more kinds.
The content of the resin having a (meth) acryloyl group at the terminal in the curable composition according to the present disclosure is from the viewpoint of the three-dimensional moldability and wear resistance of the resulting cured product, with respect to the total mass of the curable composition. 0.5 mass% or more and 50 mass% or less is preferable, 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.

-Other monofunctional (meth) acrylate compounds-
The curable composition according to the present disclosure may include a monofunctional (meth) acrylate compound (other monofunctional (meth) acrylate compounds) other than the urethane (meth) acrylate described later and 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 ( Acrylate), 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, nonylphenoxypolyethyleneglycol (Meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene 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 (meth) acrylate, tert- Butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, dodecyl ( And (meth) acrylate.

The curable composition concerning this indication may contain other monofunctional (meth) acrylate compounds individually by 1 type, or may contain 2 or more types.
The curable composition according to the present disclosure does not contain other monofunctional (meth) acrylate compounds from the viewpoint of wear resistance of the obtained cured product, or the content thereof is the total of the curable composition. It is preferable that it is 20 mass% or less with respect to mass, and it is not contained, or it is more preferable that the content is 10 mass% or less with respect to the total mass of the curable composition, and it does not contain. Or the content thereof is more preferably 5% by mass or less with respect to the total mass of the curable composition, and it is not contained or the content thereof is in the total mass of the curable composition. On the other hand, it is particularly preferably 1% by mass or less.

The curable composition concerning this indication may contain the monofunctional (meth) acrylate compound individually by 1 type, or may contain 2 or more types.
As content of the monofunctional (meth) acrylate compound in the curable composition which concerns on this indication, it is 1 with respect to the total mass of a curable composition from a viewpoint of the three-dimensional moldability and abrasion resistance of the hardened | cured material obtained. The mass% is preferably 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, and particularly preferably 30% by mass or more and 70% by mass or less.

<< Urethane (meth) acrylate compound >>
The curable composition according to the present disclosure may include a urethane (meth) acrylate compound.
The urethane (meth) acrylate compound in the present disclosure is a compound having one or more urethane bonds and one or more (meth) acryloyl groups. However, the urethane bond of the urethane (meth) acrylate compound in the present disclosure does not include an isocyanuric ring structure.
The urethane (meth) acrylate compound may be monofunctional or polyfunctional, but a bifunctional to 15 functional compound is preferable.
Moreover, it is preferable that the weight average molecular weights of a urethane (meth) acrylate compound are 1,000 or more and 100,000 or less.

Examples of urethane (meth) acrylate compounds include polyether polyols such as polyethylene glycol and polytetramethyl glycol; succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) Reaction of dibasic acids such as phthalic acid with diols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol Polyester polyol obtained by: Poly ε-caprolactone modified polyol; Polymethylvalerolactone modified polyol; Ethylene glycol, propylene glycol, 1,4-butanedi 1, polyols such as 1,6-hexanediol and neopentyl glycol; bisphenol A skeleton alkylene oxide-modified polyols such as ethylene oxide-added bisphenol A and propylene oxide-added bisphenol A; ethylene oxide-added bisphenol F and propylene oxide-added bisphenol F Bisphenol F skeleton alkylene oxide modified polyol, or a mixture thereof and organic polyisocyanates such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Hydroxy group-containing (meth) acrylate such as (meth) acrylate 1,5,5-trimethyl-1-[(1-methacryloyloxypropan-2-yl) carbamoylmethyl] -3- (1-methacryloyloxypropan-2-yl) And carbamoylcyclohexane, 1,5,5-trimethyl-1-[(2-methacryloyloxyethyl) carbamoylmethyl] -3- (2-methacryloyloxyethyl) carbamoylcyclohexane, and the like.

In addition, commercially available urethane (meth) acrylate compounds include the Shigemitsu series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., U-2PPA, U-4HA, U-6HA, U-6LPA manufactured by Shin-Nakamura Chemical Co., Ltd. , U-15HA, U-324A, UA-122P, UA5201, UA-512, etc .; CN964A85, CN964, CN959, CN962, CN963J85, CN965, CN982B88, CN981, CN983, CN996, 9006C, manufactured by Sartomer Japan CN9007, CN9009, CN9010, CN9011, CN9178, CN9788, CN9873, EB204, EB230, EB244, EB245, EB270, EB284, EB285, EB810, EB483 manufactured by Daicel Cytec Co., Ltd. , EB4835, EB4858, EB1290, EB210, EB215, EB4827, EB4830, EB4849, EB6700, EB204, EB8402, EB8804, it includes EB8800-20R like.

The curable composition concerning this indication may contain the urethane (meth) acrylate compound individually by 1 type, or may contain 2 or more types.
From the viewpoint of the three-dimensional moldability of the resulting cured product, the curable composition according to the present disclosure does not contain a urethane (meth) acrylate compound, or the content thereof is based on the total mass of the curable composition. The content is preferably less than 4% by mass, not contained, or the content thereof is more preferably 2% by mass or less with respect to the total mass of the curable composition. The content is more preferably 1% by mass or less, particularly preferably not contained, with respect to the total mass of the curable composition.
When a urethane (meth) acrylate compound is contained, the molecular weight between crosslinking points tends to increase.

<< Other polyfunctional (meth) acrylate compounds >>
The curable composition according to the present disclosure includes a polyfunctional (meth) acrylate compound (another polyfunctional (meth) acrylate compound) other than a polyfunctional (meth) acrylate compound having a ring structure and a urethane (meth) acrylate compound. You may go out.

Specific examples of other polyfunctional (meth) acrylate compounds 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, ECH Modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, pro Ren oxide (hereinafter also referred to as “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 (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol 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 tri (meth) acrylate phosphate, 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, ethoxy Pentaerythritol tetra (meth) acrylate, diglycerin ethylene oxide (EO) modified (meth) acrylate, and the like.

The curable composition concerning this indication may contain other polyfunctional (meth) acrylate compounds individually by 1 type, or may contain 2 or more types.
The curable composition according to the present disclosure does not contain other polyfunctional (meth) acrylate compounds from the viewpoint of the three-dimensional moldability of the obtained cured product, or the content thereof is the total of the curable composition. It is preferable that it is 20 mass% or less with respect to mass, and it is not contained, or it is more preferable that the content is 10 mass% or less with respect to the total mass of the curable composition, and it does not contain. Or the content thereof is more preferably 5% by mass or less with respect to the total mass of the curable composition, and it is not contained or the content thereof is in the total mass of the curable composition. On the other hand, it is particularly preferably 1% by mass or less.

Moreover, the curable composition which concerns on this indication may contain other ethylenically unsaturated compounds other than having mentioned above.
As other ethylenically unsaturated compounds, known polymerizable compounds, particularly known ethylenically unsaturated compounds can be used.

<Polymerization initiator>
The curable composition according to the present disclosure preferably includes a polymerization initiator from the viewpoint of curability.
As the polymerization initiator, a known photopolymerization initiator and a known thermal polymerization initiator can be used.
Among these, from the viewpoint of three-dimensional moldability and wear resistance of the obtained cured product, a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.

The radical photopolymerization initiator is not particularly limited in structure. For example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 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, etc. Kill.

Commercially available products that are commercially available may be used as the photoradical polymerization initiator. As specific examples of commercially available products, IRGACURE series (example: IRGACURE TPO, IRGACURE 819, IRGACURE 651, IRGACURE 184, IRGACURE 1173 manufactured by BASF) may be used. IRGACURE 2959, IRGACURE 127, IRGACURE 907, etc.).

Examples of the thermal polymerization initiator include known azo compounds and known peroxide compounds. Examples of the azo compound include azobis compounds. Examples of the peroxide compound include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate.

The curable composition concerning this indication may contain the polymerization initiator individually by 1 type, or may contain 2 or more types.
As content of the polymerization initiator in the curable composition which concerns on this indication, it is 0.05 mass% with respect to the total mass of a curable composition from the viewpoint of the three-dimensional moldability and abrasion resistance of the hardened | cured material obtained. It is preferably 10% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less.

-Other ingredients-
In addition to the above components, the curable composition according to the present disclosure may contain other components such as an organic solvent and inorganic particles as necessary.
Examples of the organic solvent include toluene and methyl ethyl ketone. Since the curable composition concerning this indication contains polymerizable compounds, such as the above-mentioned (meth) acrylic compound, a polymerizable compound serves as a solvent and does not need to contain an organic solvent separately.
Examples of the inorganic particles include so-called filler particles such as silicon dioxide (silica). Examples of the inorganic particles include commercially available organosilica sol MEK-ST series (eg, MEK-ST-40, MEK-ST-L, etc.) manufactured by Nissan Chemical Industries.

The curable composition according to the present disclosure is preferably a composition that can be cured by active energy rays. “Active energy rays” are radiation that can give energy to generate polymerization initiation species in the curable composition by irradiation, and include α rays, γ rays, X rays, ultraviolet rays, visible rays, electron rays, etc. To do. Among these, from the viewpoint of curing sensitivity and device availability, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable.
The curable composition according to the present disclosure is preferably an active energy ray-curable curable composition, and more preferably an oil-based curable composition. The curable composition according to the present disclosure preferably contains as little water and volatile solvent as possible, and even if it contains, it is more preferably 5% by mass or less with respect to the total mass of the curable composition. The content is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

(Cured product and optical member)
The cured product according to the present disclosure has a breaking elongation at 100 ° C. of 6% or more and 80% or less, and a molecular weight between crosslinking points of 20 g / mol or more and 2,000 g / mol or less.
In addition, the cured product according to the present disclosure preferably has a molecular weight distribution between cross-linking points of 1% or more and 30% or less from the viewpoint of the three-dimensional moldability and wear resistance of the obtained cured product.
Furthermore, the cured product according to the present disclosure is preferably a cured product obtained by curing the curable composition according to the present disclosure (cured product of the curable composition according to the present disclosure).
Preferred ranges and preferred embodiments of the cured product according to the present disclosure at 100 ° C. in breaking elongation, molecular weight between crosslinking points, and distribution thereof are the same as the preferred ranges and preferred embodiments of the curable composition according to the present disclosure described above. .
The cured product according to the present disclosure can be suitably used as an optical member, and a cylindrical lens, a prism, a hemispherical microlens, a Fresnel lens, or the like can be more suitably used as a convex lens, and a plurality of convex lenses It can be particularly suitably used as a lenticular lens in which (cylindrical lenses) are arranged in parallel.
Moreover, the optical member according to the present disclosure includes the cured product according to the present disclosure, and preferably includes the cured product of the curable composition according to the present disclosure.

(Method for producing cured product)
Although the manufacturing method of the hardened | cured material which concerns on this indication does not have a restriction | limiting in particular, The process of preparing the curable composition which concerns on this indication, and the temperature of the range of 0.5 degreeC or more and 10 degrees C or less of the said curable composition It is preferable that it is a manufacturing method including the process hardened | cured in the state which has nonuniformity.
By curing in a state having temperature unevenness in the above range, the molecular weight distribution between cross-linking points can be easily set to 1% or more and 30% or less in the cured product.
The step of preparing the curable composition according to the present disclosure is not particularly limited except for preparing the curable composition according to the present disclosure.
The temperature range of the temperature unevenness in the step of curing in the state having the temperature unevenness is 0.7 from the viewpoint of easily adjusting the three-dimensional moldability and wear resistance of the obtained cured product, and the molecular weight distribution between the crosslinking points. The temperature is preferably from 8 ° C to 8 ° C, and more preferably from 1 ° C to 6 ° C.
When curing the curable composition, the temperature range of the above temperature unevenness is to divide the substrate surface of the portion to which the curable composition is applied into 3 × 3 equal parts, measure the temperature of each central part, and measure the maximum temperature. And the difference between the minimum temperature.
Examples of the method for forming temperature unevenness include, for example, a method of changing the amount of hot air blown to the curable composition on the substrate surface in the width direction, and a base capable of adjusting the temperature by dividing the surface into a plurality of temperature sections. Examples thereof include a method of imparting a temperature distribution using a material and a method of using a plurality of radiant heat sources having different temperatures.
1: The method of changing the air volume in the width direction can be achieved by, for example, dividing the blowing nozzle and blowing air from a hot air generator set to a plurality of temperatures.
2: As a method of changing the temperature of the substrate, it can be achieved by preparing a plurality of panel heaters and changing these set temperatures. Moreover, a temperature distribution can also be provided by passing a heat medium through the base material and providing a baffle plate in this flow path.
3: The plurality of radiant heat sources can be achieved by changing the temperature of a plurality of radiant heat sources (for example, halogen lamp, IR heater, nichrome wire, etc.) provided above and below the sample.
Further, the curing in the step of curing in a state having temperature unevenness may be photocuring (curing by irradiation with active energy rays) or thermal curing, but is preferably photocuring.

(Laminated sheet and lenticular sheet)
The laminated sheet according to the present disclosure may be a laminated sheet having a cured product of the curable composition according to the present disclosure. Specifically, the cured curable composition according to the present disclosure is cured on the base material and the base material. It is preferable to have at least a product.
Moreover, the laminated sheet which concerns on this indication is a laminated sheet which has the hardened | cured material which concerns on this indication.
Especially, it is preferable that the laminated sheet which concerns on this indication has a resin base material and the hardened | cured material of the curable composition which concerns on this indication provided in the at least one surface of the said resin base material.
There is no restriction | limiting in particular in the shape of the hardened | cured material of the curable composition which concerns on this indication which the lamination sheet which concerns on this indication has, Even if it is a desired shape, it is like a cylindrical lens mentioned later. It may be a shape in which semi-cylindrical objects are arranged, or a shape in which hemispherical objects are arranged like a microlens.
The laminated sheet according to the present disclosure is suitable as a laminated sheet having a hard coat film, a three-dimensionally laminated sheet, a laminated sheet having a brightness enhancement film, a lenticular sheet, a prism sheet, a microlens sheet, a Fresnel lens sheet, a fly eye lens, and the like. Can be used.

The lenticular sheet according to the present disclosure has a cured product of the curable composition according to the present disclosure.
Moreover, the lenticular sheet which concerns on this indication has the hardened | cured material which concerns on this indication.
The cured product in the lenticular sheet according to the present disclosure is preferably a lenticular lens.
In addition, the lenticular sheet according to the present disclosure preferably includes a resin base material and a cylindrical lens disposed on at least one surface of the resin base material, on the opposite side of the resin base material from the side having the cylindrical lens. It is more preferable to have a recording layer. In addition, an embodiment in which an image (hereinafter also referred to as a decorative image) can be imparted to the recording layer by a known recording method such as an inkjet method is preferable.

The lenticular sheet according to the present disclosure may be a lenticular decorative sheet having a configuration in which a recording layer is attached and a lenticular image is attached as shown in FIG. The lenticular decorative sheet has a lenticular lens in which convex cylindrical lenses having a semicylindrical surface are arranged on an image suitable for lenticular display, thereby displaying a different image depending on the viewing angle (lenticular display). Body). FIG. 1 is a schematic diagram illustrating an example of a lenticular decorative sheet (lenticular sheet).

A lenticular decorative sheet 10 shown in FIG. 1 includes a lenticular lens 12 in which a plurality of convex lenses (cylindrical lenses) 12A having a semicylindrical surface are arranged in parallel, and a semicylindrical surface of a convex lens 12A of the lenticular lens 12. And a lenticular image 14 disposed on the opposite side (also referred to as the back side).
The x direction indicates the width direction of the lens, and the y direction indicates the longitudinal direction of the lens.

The lenticular sheet according to the present disclosure preferably includes a lenticular lens layer in which a plurality of convex lenses (cylindrical lenses) having a semicylindrical surface are arranged in parallel. The width per cylindrical lens is not particularly limited, and the pitch width of the lenses may be selected depending on the purpose. The width per cylindrical lens is usually often expressed by LPI (Line Per Inch) representing the number of lenses per inch (2.54 cm). For example, 100 LPI indicates that 100 cylindrical lenses (100 rows) per inch are arranged in parallel, and the pitch of the lenses is 254 μm. The larger the value of the number of lines per inch (number of lenses arranged), the smaller the lens pitch, and the higher the definition.
A low-definition lenticular sheet (for example, 60 LPI) is suitable for use in a poster or the like that displays a pattern whose observation position is relatively far. 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 100 rows or more per 2.54 cm (1 inch). On the other hand, from the viewpoint of the resolution of the lenticular image, the number of convex lenses constituting the lenticular lens layer is more preferably 200 rows (2.5 LPI) or less per 2.54 cm.

Conventionally, lenticular materials are often used in the form of sheets or films, and there are few attempts to use them in a three-dimensional shape. However, in conventional lenticular sheets, for example, the resin component used for the lens portion is generally a thermoplastic resin, and is easily deformed by heat when molded into a three-dimensional shape, and has heat resistance that can maintain the shape. Easy to run out. On the other hand, although a technique using a thermosetting resin as a resin component has been proposed, the thermosetting resin generally has a cross-linked structure and thus tends to have poor stretchability when deformed. For this reason, thermal deformation is hardly caused when exposed to a high temperature during three-dimensional molding, but there is a concern that cracks or the like are likely to occur when the three-dimensional molding is extended.
The lenticular sheet according to the present disclosure is excellent in three-dimensional moldability by having a lenticular lens formed by curing the curable composition according to the present disclosure.

<Resin substrate>
The resin base material used in the present disclosure is a base material as a support material, and any resin can be selected depending on the purpose and the like. As the resin substrate, a sheet-like or film-like substrate can be suitably used.
As an example of a resin base material, sheets or films, such as an acrylic resin and a polyester resin, are mentioned.
There is no restriction | limiting in particular in the thickness of a resin base material, The range of 50 micrometers or more and 300 micrometers or less is preferable, and the range of 50 micrometers or more and 200 micrometers or less is more preferable from a viewpoint of shape | molding (shaping) uniformly at high temperature. When it is in the above range, the resin base material is not easily torn, and cracks are hardly generated during handling (for example, during transportation) during molding processing, and are also difficult to crack during three-dimensional molding.

Commercially available products may be used as the resin base material. For example, acrylic resin film (Acryprene HBS010P, thickness: 125 μm) manufactured by Mitsubishi Rayon Co., Ltd., polyethylene terephthalate resin film (Lumirror, manufactured by Toray Industries, Inc.) S10, thickness: 100 μm), polycarbonate resin film (Iupilon H-3000, thickness 125 μm) manufactured by Teijin Chemicals Ltd. can be used.

<Recording layer>
In the lenticular sheet according to the present disclosure, a recording layer for recording an image (lenticular image) displayed in a lenticular manner may be provided on the opposite side of the resin base having the cylindrical lens.
The surface on which the recording layer of the resin substrate is provided may be subjected to a surface treatment (for example, corona discharge treatment) from the viewpoint of increasing the adhesive force between the resin substrate and the recording layer. The recording layer may be provided, for example, by applying a preparation liquid for forming the recording layer to the resin substrate.
The preparation liquid can be applied, for example, by coating.
The preparation liquid preferably contains a solid component and a solvent for forming the recording layer. The recording layer preferably contains a resin, and at least a part of the resin is preferably crosslinked with a crosslinking agent. Therefore, the aspect containing resin and a crosslinking agent as a solid component contained in a preparation liquid is preferable.
The resin is preferably at least one resin selected from the group consisting of polyester, acrylic resin and urethane resin, and is particularly advantageous when a parallax image is formed by offset printing.

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

(3D structure)
The three-dimensional structure according to the present disclosure is a three-dimensional molded product (preferably three-dimensionally molded by a technique such as thermoforming or vacuum molding) of the laminated sheet according to the present disclosure.
The three-dimensional structure according to the present disclosure is preferably a three-dimensional molded product of the lenticular sheet according to the present disclosure.
The three-dimensional structure according to the present disclosure is not particularly limited by the molding method as long as it is manufactured using the laminated sheet according to the present disclosure.
As a method for producing a three-dimensional structure using the lenticular sheet according to the present disclosure, for example, a curable composition according to the present disclosure is molded, cured by irradiating active energy rays, and a cylindrical lens is formed on a resin substrate. A process for producing the lenticular sheet (hereinafter also referred to as “lenticular sheet production process”) and three-dimensional molding (preferably vacuum molding or pressure molding) of the produced lenticular sheet to obtain a three-dimensional molded article of lenticular A method including a step (hereinafter, also referred to as “three-dimensional molding step”) is preferable.
Moreover, it is preferable that the said lenticular sheet preparation process includes the process hardened | cured in the state which has the temperature nonuniformity mentioned above.

Since the lenticular sheet according to the present disclosure that is excellent in three-dimensional moldability is used at the time of molding exposed to a relatively high temperature, it is difficult to cause shape deformation by being melted by heat at the time of molding, and extended during molding Occurrence of cracks or the like that tend to occur at the time is also suppressed.

-Lenticular sheet manufacturing process-
In the lenticular sheet production step, the curable composition according to the present disclosure is molded and cured by irradiation with active energy rays to produce a lenticular sheet having a cylindrical lens on a resin substrate.
The details of the curable composition according to the present disclosure are as described above, and the preferred embodiments are also the same.

Moreover, it is preferable that the curable composition which concerns on this indication contains radical photopolymerization initiator. Radiation is generated by irradiating active energy rays, and curing occurs by the polymerization reaction of the polymerizable compound. Thereby, a cylindrical lens that is a cured product of the curable composition according to the present disclosure is formed.
In molding the cylindrical lens, the curable composition may be cured after the resin substrate is brought into contact with the curable composition in advance before the curable composition is cured. By curing in a state where the resin base material and the curable composition are in contact with each other, an improvement in adhesion due to curing shrinkage can be expected, and in addition to the adhesion effect derived from the composition, the improvement in the adhesion to the resin base material is achieved. More effective.
From the viewpoint of adhesion of the cylindrical lens to the resin base material, a lenticular sheet having a cylindrical lens having superior adhesion can be obtained by curing the curable composition in contact with the resin base material.

In this step, first, the curable composition is molded into the shape of the target cylindrical lens before curing. The molding is not particularly limited as long as the target shape can be obtained, but from the viewpoint of molding efficiency and molding accuracy, molding using a mold such as a mold or a wooden mold is preferable.
Specifically, for example, a mold processed into a desired lens shape is prepared, the curable composition is poured into the mold, dried as necessary, and then the curable composition is cured. Good. Thereby, the molded object shape | molded by the target shape is obtained stably.

As light sources for generating active energy rays, mercury lamps, metal halide lamps, UV fluorescent lamps, gas lasers, solid lasers, and the like are widely known. Further, a semiconductor ultraviolet light emitting device may be applied as a light source, and an LED (Light Emitting Diode) and an LD (Laser Diode) are also suitable in terms of small size, long life, high efficiency, and low cost.
As the 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. Among them, an ultra-high pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm, a high-pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm, or light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm Is more preferable, and an LED capable of irradiating light with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is particularly preferable.

The dose of the active energy ray may be appropriately selected depending on the composition and amount of the lenticular lens curable composition, it is preferable to 0.3 J / cm ² or more 5 J / cm ² or less.

The irradiation with the active energy ray can be performed by selecting a known device including a light source capable of irradiating the active energy ray. For example, an ultraviolet (UV) irradiation device such as EXECULE 3000 manufactured by HOYA CANDEO OPTRONICS may be used.

-Solid molding process-
In the three-dimensional molding step, the lenticular sheet produced in the lenticular sheet production step is three-dimensionally molded. In this step, it is sufficient that the lenticular sheet can be molded, and the lenticular sheet may be subjected to a molding process using a mold such as a mold.

Suitable examples of the three-dimensional molding include thermal molding and vacuum molding.
The method of vacuum forming is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferable.
The vacuum refers to a state in which the room is evacuated to a degree of vacuum of 100 Pa or less.
The temperature at the time of three-dimensional molding is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher. The upper limit of the temperature for three-dimensional molding is preferably 200 ° C.
The temperature at the time of three-dimensional molding refers to the temperature of the lenticular sheet subjected to three-dimensional molding, and is measured by attaching a thermocouple to the surface of the lenticular sheet.

The above-described vacuum molding can be performed using a vacuum molding technique widely known in the molding field. For example, the vacuum molding may be performed using Formech 508FS manufactured by Nippon Shikki Kogyo Co., Ltd.

Hereinafter, the embodiments of the present invention will be described more specifically by way of examples. However, the present disclosure is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

The compounds used in this example are shown below.

(1) Polyfunctional (meth) acrylate compound having a ring structure A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd .: tricyclodecane dimethanol diacrylate M-315 (manufactured by Toagosei Co., Ltd .: isocyanuric acid EO) Modified triacrylate (trifunctional acrylate compound having isocyanuric ring structure)
・ KUA-4I (manufactured by KS Corporation: tetrafunctional urethane (meth) acrylate (tetrafunctional urethane acrylate having a cyclohexyl ring)
・ KUA-6I (manufactured by KS Corporation: 6-functional urethane acrylate containing a cyclohexyl ring)

(2) Monofunctional (meth) acrylate compound AA6 (AA-6 manufactured by Toagosei Co., Ltd .: Methacryloyl group-containing methacrylic resin (polymethyl methacrylate))
・ Fancryl FA513AS (FA513AS, manufactured by Hitachi Chemical Co., Ltd .: dicyclopentanyl acrylate)
MMm (Mitsui Chemicals Co., Ltd. MMA: methyl methacrylate)
・ PO (Kyoeisha Chemical Co., Ltd. light ester PO, phenoxyethyl methacrylate)
BR-31 (Daiichi Pharmaceutical Industry Co., Ltd. New Frontier BR-31, EO-modified tribromophenyl acrylate)
・ PHE (Daiichi Kogyo Seiyaku Co., Ltd. New Frontier PHE, phenoxyethyl acrylate)
・ BnA (Biscoat # 160, benzyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ PO-A (Kyoeisha Chemical Co., Ltd. light acrylate PO-A, phenoxyethyl acrylate)

(3) N-vinyl compound / N-vinylpyrrolidone (NVP, manufactured by Wako Pure Chemical Industries, Ltd.)
・ N-vinyl-ε-caprolactam (NVC, manufactured by Tokyo Chemical Industry Co., Ltd.)

(4) Polymerization initiator <photopolymerization initiator>
・ Irgacure 184 (manufactured by BASF: 1-hydroxycyclohexyl phenyl ketone)
・ Irgacure TPO (BASF: 2,4,6-trimethylbenzoyldiphenylphosphine oxide)
<Thermal polymerization initiator>
AIBN (manufactured by Wako Pure Chemical Industries, Ltd .: 2,2′-Azobis (isobutyronitrile, decomposition start temperature: 70 ° C.)

(5) Polyfunctional (meth) acrylate compound having no ring structure A-TMPT (Tokyo Chemical Industry Co., Ltd .: trimethylolpropane triacrylate / 3-functional acrylate compound / not including cyclic structure)

(6) Other components IPPM (1,5,5-trimethyl-1-[(1-methacryloyloxypropan-2-yl) carbamoylmethyl] -3- (1-methacryloyloxypropan-2-yl) carbamoylcyclohexane And a urethane (meth) acrylate compound, synthesized by the method described in paragraph 0120 of JP-A-2006-249220, which also applies to a polyfunctional (meth) acrylate compound having a ring structure.
UA1 (urethane acrylate compound, synthesized by the following method. Note that this also applies to a polyfunctional (meth) acrylate compound having a ring structure.)
・ VR-90 (Lipoxy VR-90 manufactured by Showa Denko KK, bisphenol A epoxy acrylate)
・ ACMO (KJ Chemicals Co., Ltd .: acryloylmorpholine)
UA2 (urethane acrylate compound, synthesized by the following method. Note that this also applies to a polyfunctional (meth) acrylate compound having a ring structure.)
IK-2 (Art resin IK-2 manufactured by Negami Kogyo Co., Ltd., urethane acrylate compound, and also a polyfunctional (meth) acrylate compound having a ring structure)
3000A (Kyoeisha Chemical Co., Ltd. Epoxy ester 3000A, acrylic acid adduct of bisphenol A diglycidyl ether, and also a polyfunctional (meth) acrylate compound having a ring structure)

<Synthesis of UA1>
In a reaction vessel equipped with a stirrer, 35.47% by mass of 2,4-tolylene diisocyanate, 0.08% by mass of di-n-butyltin dilaurate, 2,6-di-t-butyl-p-cresol 02% by mass was charged. While stirring, 23.65% by mass of 2-hydroxyethyl acrylate was added dropwise so that the temperature was kept at 30 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 30 ° C. for 1 hour. Next, 40.77% by mass of bisphenol A ethylene oxide addition diol (number of ethylene oxide structural units = 4; average molecular weight = 400) was added, and the reaction was continued at 50 ° C. to 70 ° C. for 2 hours. The reaction was terminated when the residual isocyanate was 0.1% by mass or less.

<Synthesis of UA2>
In a reaction vessel equipped with a stirrer, 20.14% by mass of 2,4-tolylene diisocyanate, 0.08% by mass of di-n-butyltin dilaurate, 2,6-di-t-butyl-p-cresol 02% by mass was charged. While stirring, 12.85% by mass of 2-hydroxy-3-phenyloxypropyl acrylate was added dropwise so that the temperature was maintained at 30 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 30 ° C. for 1 hour. Next, 66.90 mass% of bisphenol A poly (degree of polymerization: n = 10 as an average value) propoxyglycol was added, and the reaction was continued at 50 ° C. to 70 ° C. for 2 hours. The reaction was terminated when the residual isocyanate was 0.1% by mass or less.

(Examples 1 to 28 and Comparative Examples 1 to 8)
1. Preparation of Curable Composition Each component shown in Tables 1 to 3 was mixed to prepare each curable composition.

2. Preparation of cured film The above curable composition is sandwiched between two glass plates that have been subjected to a hydrophobic treatment, irradiated with ultraviolet rays (UV) or thermally cured under the following conditions, and peeled off from the glass plate to a film thickness of 50 μm. A cured resin film (single film) was produced.
UV irradiation is performed using an ultraviolet (UV) irradiation device (EXECURE 3000, manufactured by HOYA CANDEO OPTRONICS Co., Ltd.), blocking oxygen and curing at 25 ° C. under a UV irradiation amount of 1.0 J / cm ^2. Irradiated.
In thermosetting, oxygen was shut off and the mixture was heated to 70 ° C.
In addition, for the temperature unevenness during curing, the temperature difference (temperature unevenness) described in Tables 1 to 3 is achieved by using a 9-part hot plate as the base material on which the glass plate is placed and providing a temperature difference thereto. did.

<Measurement of elongation at break at 100 ° C.>
The obtained resin cured film (single film) was punched into a size of 50 mm length × 10 mm width to prepare a sample piece, and using TENSILON RTC-1225A (manufactured by A & D Co., Ltd.), the following A tensile test was performed under the conditions, and the elongation at break represented by the following formula was measured. The breaking elongation was measured three times, and the average value thereof was taken as the breaking elongation. The measurement results are shown in Table 1 or Table 2.
Elongation at break (%) = 100 × (length broken by stretching−distance between chucks) / (distance between chucks)
-conditions-
・ Distance between chucks: 30mm
-Sample piece temperature: 100 ° C
・ Tensile speed: 1 mm / sec

<Measurement of molecular weight between cross-linking points and measurement of molecular weight distribution between cross-linking points>
The temperature was raised to a temperature (250 ° C.) at which the curable composition became a rubber region, and measured by applying a strain of 0.01% at 10 Hz using DMA (Dynamic Mechanical Analyzer: Rheogel-E4000HP manufactured by UBM), and storage elasticity. The rate (E ′) was determined.
From the obtained storage elastic modulus (E ′), the molecular weight (Mc) between crosslinking points was obtained using the following formula.
Mc = 3 × ρ × R × T / E ′
Mc = g / mol, ρ (density) = g / cm ³ , R (gas constant) = J / (mol · K),
T (measured temperature) = K, E ′ = Pa
The above-mentioned measurement was performed on 10 samples, and the value obtained by dividing the difference between the maximum value and the minimum value by the average value of 10 points and expressed as a percentage was defined as the distribution of molecular weight between cross-linking points.
The calculated values are shown in Tables 1 to 3.

3. Production of laminated sheet (1) Production of lenticular sheet (molding of semi-cylinder, Examples 1 to 23 and 25 to 28, and Comparative Examples 1 to 8)
After applying the curable composition to the following lens height on an acrylic resin film (Acryprene HBS010P, film thickness 125 μm, manufactured by Mitsubishi Rayon Co., Ltd.) as a base material, a half cylinder as shown in FIG. Shape of a lenticular lens in which cylindrical lenses 12 having a plurality of convex lens portions 12A having a shape surface are arranged in parallel [height 33 .mu.m, length y in the longitudinal direction 80 mm, one lens width (lens pitch) 200 LPI (Line Per) Inch)] is pressed into a mold (width 100 mm × depth 100 mm), and while the applied curable composition is molded, ultraviolet rays (UV) are passed through the acrylic resin film, and UV irradiation apparatus (EXECURE 3000, HOYA). CANDEO OPTRONICS Co., Ltd.), UV irradiation amount 1 It was irradiated at 0J / cm ^2. After irradiation, the mold was removed to prepare a lenticular sheet.
In Example 18, the UV irradiation was not performed, and heating at 70 ° C. was performed.

(2) Production of flat laminated sheet (without shaping, Example 24)
In the above (1), a smooth roll was pressed against a lens processed into a lens width. Except this, it carried out similarly to said (1), and produced the flat laminated sheet.

<Evaluation of three-dimensional moldability>
A hemisphere having a diameter of 5 mm between 10 mm and 200 mm was prepared.
Using these, at the glass transition temperature of the cured product of the curable composition, the obtained lenticular sheet was vacuum-molded into the above hemispherical shape, and the minimum diameter at which cracks occurred on the surface was used as an index of three-dimensional moldability. Note that the three-dimensional formability is so high that cracking does not occur up to a small diameter.
The evaluation results are shown in Tables 1 to 3.

<Evaluation of wear resistance>
According to JIS K5600-5-10: 1999 (friction resistance), the surface of the obtained lenticular sheet was rubbed with silicon carbide abrasive paper and evaluated by the amount of wear (mg / DS) per round trip. However, silicon carbide abrasive paper # 1500 was used instead of p180.
The evaluation results are shown in Tables 1 to 3.

As is apparent from the results of Tables 1 to 3, it can be seen that when the curable composition according to the present disclosure is used, the resulting cured product is excellent in three-dimensional formability and wear resistance.
Further, as shown in Examples 1 to 4, when a polyfunctional (meth) acrylate compound having the above-mentioned ring structure having 3 to 6 functions is used, the wear resistance is more excellent.
As shown in Example 5 to Example 8, when the content of the polyfunctional (meth) acrylate compound having the ring structure is 10% by mass or more and 70% by mass or less with respect to the total mass of the curable composition Excellent in three-dimensional formability and wear resistance.
As shown in Examples 9 to 11, when the content of the N-vinyl compound is 8% by mass or more based on the total mass of the curable composition, the three-dimensional moldability is more excellent.
As shown in Examples 12 to 14, when the content of the polyfunctional (meth) acrylate compound having the ring structure is 1% by mass or more and 20% by mass or less with respect to the total mass of the curable composition Excellent in three-dimensional formability and wear resistance.
As shown in Examples 15 and 16, when N-vinylpyrrolidone is used as the N-vinyl compound, the three-dimensional moldability is excellent.
As shown in Example 17 and Example 18, when a photopolymerization initiator is used as the polymerization initiator, the three-dimensional moldability and wear resistance are superior.
As shown in Examples 19 to 23, when the distribution of molecular weight between cross-linking points is 0.5% or more and 10% or less, the three-dimensional moldability and the wear resistance are excellent.

The disclosures of Japanese Patent Application No. 2016-201891 filed on October 13, 2016 and Japanese Patent Application No. 2017-024371 filed on February 13, 2017 are hereby incorporated by reference in their entirety. Incorporated herein.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.

10 ... Lenticular decorative sheet (lenticular sheet)
12 ... Lenticular lens 12A ... Convex lens 14 ... Lenticular images 14A and 14B ... Display image row 14C ... Interpolated image row x ... Lens width direction y ... Lens of lens Longitudinal direction

Claims (17)

1. The breaking elongation at 100 ° C. of the obtained cured product is 6% or more and 80% or less,
   The curable composition whose molecular weight between crosslinking points of the hardened | cured material obtained is 20 g / mol or more and 2,000 g / mol or less.
2. The curable composition according to claim 1, wherein the molecular weight distribution between cross-linking points of the obtained cured product is 1% or more and 30% or less.
3. The curable composition according to claim 1 or 2, comprising a polyfunctional (meth) acrylate compound having a ring structure and an N-vinyl compound.
4. The curable composition according to claim 3, wherein the content of the polyfunctional (meth) acrylate compound having a ring structure is 1% by mass or more and 75% by mass or more with respect to the total mass of the curable composition.
5. The curable composition according to claim 3 or 4, wherein the content of the N-vinyl compound is 8% by mass or more and 60% by mass or less based on the total mass of the curable composition.
6. The curable composition according to any one of claims 3 to 5, wherein the N-vinyl compound is at least one compound selected from the group consisting of N-vinyl pyrrolidone and N-vinyl caprolactam. object.
7. The curable composition according to any one of claims 1 to 6, comprising a monofunctional (meth) acrylate compound.
8. The curable composition according to claim 7, wherein the content of the monofunctional (meth) acrylate compound is 1% by mass or more and 80% by mass or less based on the total mass of the curable composition.
9. The curable composition according to any one of claims 1 to 8, comprising a photopolymerization initiator.
10. The urethane (meth) acrylate compound is not contained, or the content of the urethane (meth) acrylate compound is more than 0% by mass and less than 4% by mass with respect to the total mass of the curable composition. Item 10. The curable composition according to any one of Items 9.
11. Preparing the curable composition according to any one of claims 1 to 10, and
    The manufacturing method of hardened | cured material including the process of hardening | curing the said curable composition in the state which has the temperature nonuniformity of the range of 0.5 to 10 degreeC.
12. A laminated sheet having a cured product of the curable composition according to any one of claims 1 to 10.
13. An optical member having a cured product of the curable composition according to any one of claims 1 to 10.
14. A lenticular sheet having a cured product of the curable composition according to any one of claims 1 to 10.
15. A three-dimensional structure which is a three-dimensional molded product of the laminated sheet according to claim 12.
16. The elongation at break at 100 ° C. is 6% or more and 80% or less,
    Cured product having a molecular weight between crosslinking points of 20 g / mol or more and 2,000 g / mol or less.
17. The cured product according to claim 16, wherein the distribution of molecular weight between crosslinking points is 1% or more and 30% or less.

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