WO2018070538A1 - Curable composition, cured product and production method therefor, laminated sheet, optical member, lenticular sheet, and three-dimensional structure - Google Patents

Curable composition, cured product and production method therefor, laminated sheet, optical member, lenticular sheet, and three-dimensional structure Download PDF

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WO2018070538A1
WO2018070538A1 PCT/JP2017/037273 JP2017037273W WO2018070538A1 WO 2018070538 A1 WO2018070538 A1 WO 2018070538A1 JP 2017037273 W JP2017037273 W JP 2017037273W WO 2018070538 A1 WO2018070538 A1 WO 2018070538A1
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curable composition
meth
mass
composition according
acrylate compound
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PCT/JP2017/037273
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French (fr)
Japanese (ja)
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貴康 永井
直之 師岡
冨澤　秀樹
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富士フイルム株式会社
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Priority to JP2018545087A priority Critical patent/JPWO2018070538A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F220/68—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/02—Simple or compound lenses with non-spherical faces
    • G02B3/06—Simple or compound lenses with non-spherical faces with cylindrical or toric faces

Definitions

  • 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.
  • a desired geometrical optical performance is obtained mainly by forming a fine structure with a resin material.
  • 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.
  • the cured product has high temperature stretchability. It is not sufficient, and the cured product may be cracked or three-dimensionally molded or the cured product itself may be damaged. Further, in the invention described in Patent Document 1, since a thermoplastic resin is used for the lens portion that is subjected to molding, for example, when three-dimensionalization is performed by vacuum molding or the like, the shape is formed by heat during molding. May not be stably maintained, and the structure of the lenticular sheet may not be maintained after molding.
  • the problem to be solved by one embodiment of the present invention is to provide a curable composition that is excellent in scratch resistance and high-temperature stretchability 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 scratch resistance and high-temperature stretchability, 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 obtained by curing the curable composition.
  • the curable composition according to the present disclosure includes a bifunctional or trifunctional (meth) acrylate compound having a central skeleton having a three-fold symmetry axis, and a monofunctional (meth) acrylate having a glass transition temperature of 0 ° C. or higher.
  • the compound is contained and 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 the present disclosure is suitably used as a curable composition for forming a lenticular sheet (particularly a lenticular lens in a lenticular sheet).
  • the curable composition according to the present disclosure contains a bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis.
  • the compound in which the central skeleton of the compound in the present disclosure has a three-fold symmetry axis means that after the C 3 rotation operation is performed on the central skeleton of a molecule, the shape is the conformation before the C 3 rotation operation is performed.
  • the central skeleton in the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a three-fold symmetry axis is a skeleton having a ring structure from the viewpoint of scratch resistance and high-temperature stretchability of the obtained cured product. It is more preferable that it is a structure selected from the group consisting of an isocyanuric ring structure, a triazine ring structure, a triphenylene ring structure, and a benzene ring structure, and it consists of an isocyanuric ring structure, a triazine ring structure, and a triphenylene ring structure. A structure selected from the group is more preferable, and an isocyanuric ring structure is particularly preferable.
  • Preferred examples of the bifunctional or trifunctional (meth) acrylate compound having the isocyanuric ring structure include compounds represented by the following formula ICT or formula ICD from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product. More preferred are compounds represented by the following formula ICT.
  • R 1C , R 2C and R 3C are preferably hydrogen atoms.
  • R 4C is preferably an alkyl group, a hydroxyalkyl group, or —L 6C — ( OL 7 C ) nd —OH, and is preferably a hydroxyalkyl group or —L 6C — ( OL 7 C ) nd It is more preferably —OH, further preferably a hydroxyalkyl group, and particularly preferably a hydroxyethyl group.
  • bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure examples include isocyanuric acid alkylene oxide-modified tri (meth) acrylate, isocyanuric acid alkylene oxide-modified di (meth) acrylate, and tri (meth) acryloxy.
  • examples include alkylated isocyanurates, di (meth) acryloxyalkylated isocyanurates, and di (meth) acrylated isocyanurates.
  • At least one compound selected from the group consisting of isocyanuric acid ethylene oxide-modified tri (meth) acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate is preferable, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate. Is particularly preferred.
  • difunctional or trifunctional (meth) acrylate compound having the isocyanuric ring structure commercially available products Aronix M-315, M-313, and M-215 manufactured by Toagosei Co., Ltd. are preferably used. it can.
  • the glass transition temperature of the homopolymer in the monofunctional (meth) acrylate compound is preferably 20 ° C. or higher, and preferably 60 ° C. or higher, from the viewpoint of scratch resistance and high temperature stretchability of the resulting cured product. Is more preferably 60 ° C. or higher and 200 ° C. or lower, and particularly preferably 110 ° C. or higher and 200 ° C. or lower.
  • the monofunctional (meth) acrylate compound whose glass transition temperature of the said homopolymer is 0 degreeC or more is a monofunctional (meth) acrylate compound which has an alicyclic structure which has a 2 or more ring.
  • the alicyclic structure is at least 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 scratch resistance and high-temperature stretchability of the resulting cured product.
  • One type of ring structure is preferred, and a tricyclodecane ring structure is more preferred.
  • 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.
  • the curable composition concerning this indication may contain urethane (meth) acrylate compound individually by 1 type, it may contain 2 or more types, but it is preferable not to contain.
  • the curable composition according to the present disclosure does not contain a urethane (meth) acrylate compound from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product, or the content thereof is that of the curable composition. It is preferably 2% by mass or less with respect to the total mass, and is not contained, or the content is more preferably 1% by mass or less with respect to the total mass of the curable composition, It is particularly preferred not to do so.
  • 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.
  • 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. And the elongation at break represented by the following formula was measured.
  • the rubber component preferably contains acrylic rubber from the viewpoints of dispersion stability and scratch resistance and high-temperature stretchability of the resulting cured product. More preferably, it is contained in an amount of at least 100% by mass.
  • the arithmetic average particle diameter of the rubber particles is preferably from 0.05 ⁇ m to 10 ⁇ m, more preferably from 0.1 ⁇ m to 1 ⁇ m, and more preferably from 0.1 ⁇ m to 0.8 ⁇ m from the viewpoint of dispersion stability. More preferably, it is more preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • the arithmetic average particle diameter of the rubber particles is a particle of 100 fine particles arbitrarily selected from images taken using a microscope (for example, a scanning electron microscope) after separating the rubber particles from the curable composition. The diameter (equivalent circle diameter) is measured and can be obtained by arithmetic averaging.
  • the quantification of the rubber component in the curable composition according to the present disclosure can be performed by a method in which the rubber component is separated and measured.
  • cured material can be implemented with the following method. Cut a cured product or a sample taken from the cured product to prepare a cross-section, soak it in a 0.5% by mass ruthenium tetroxide aqueous solution at 25 ° C. for 15 hours, stain with ruthenium, and use a transmission electron microscope (TEM). The cross section is observed at 30,000 times. Since the rubber component is dyed darkly by ruthenium dyeing, this area is observed, and the content of the rubber component is obtained by dividing by the area of the observation field. The above measurement is carried out in 10 arbitrarily selected visual fields, and this average value is taken as the rubber component content.
  • 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 substrate, and further improves the high temperature stretchability of the cured product at the time of molding.
  • the N-vinyl compound is preferably a monofunctional N-vinyl compound and preferably has a ring structure.
  • the N-vinyl compound is at least one compound selected from the group consisting of N-vinyl pyrrolidone and N-vinyl caprolactam from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product.
  • N-vinylpyrrolidone is more preferable.
  • examples of N-vinylpyrrolidone include N-vinyl-2-pyrrolidone.
  • Examples of N-vinylcaprolactam include N-vinyl- ⁇ -caprolactam.
  • 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, from the viewpoint of high-temperature stretchability 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 curable composition which concerns on this indication may contain other ethylenically unsaturated compounds other than having mentioned above.
  • a known polymerizable compound particularly a known ethylenically unsaturated compound can be used.
  • the curable composition according to the present disclosure preferably includes a polymerization initiator from the viewpoint of curability.
  • a polymerization initiator a known photopolymerization initiator and a known thermal polymerization initiator can be used.
  • a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.
  • 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. may be used.
  • the curable composition according to the present disclosure may contain other components such as an organic solvent and inorganic particles as necessary.
  • 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.
  • the inorganic particles include so-called filler particles such as silicon dioxide (silica).
  • 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 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.
  • 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.
  • the laminated sheet which concerns on this indication is a laminated sheet which has the hardened
  • the laminated sheet which concerns on this indication has a resin base material and the hardened
  • the lenticular sheet according to the present disclosure has a cured product obtained by curing the curable composition according to the present disclosure.
  • the cured product in the lenticular sheet according to the present disclosure is preferably a lenticular lens.
  • 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.
  • 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.
  • 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
  • the y direction indicates the longitudinal direction of the lens.
  • 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.
  • 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.
  • UV ultraviolet
  • the lenticular sheet produced in the lenticular sheet production step is three-dimensionally molded.
  • the lenticular sheet can be molded, and the lenticular sheet may be subjected to a molding process using a mold such as a mold.
  • the above-described vacuum molding can be performed using a vacuum molding technique widely known in the molding field.
  • the vacuum molding may be performed using Formech 508FS manufactured by Nippon Shikki Kogyo Co., Ltd.
  • the mean three are a hydroxy group, an average of three represents a 6-acryloxy-hexyl group.
  • NVP Wired Chemical Industries, Ltd .: N-vinyl-2-pyrrolidone
  • NVC manufactured by Tokyo Chemical Industry Co., Ltd .: N-vinyl- ⁇ -caprolactam
  • Example 8 and Example 9 are compared, when a monofunctional (meth) acrylate compound having an alicyclic structure is used, it is more excellent in scratch resistance and high-temperature stretchability.
  • Example 10, and Example 11 are compared, the content of the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a three-fold symmetry axis is 15 with respect to the total mass of the curable composition. When it is at least 60% by mass, it is more excellent in scratch resistance and high-temperature stretchability.
  • Example 3 and Example 12 are compared, by further including a resin having a (meth) acryloyl group at the terminal, it is more excellent in scratch resistance and high temperature stretchability.
  • Example 1, Example 14, and Example 15 are compared, it is more excellent in high temperature stretchability by further including a rubber component.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

This curable composition contains a bifunctional or trifunctional (meth)acrylate compound, the central backbone of which has an axis of 3-fold rotational symmetry, and a monofunctional (meth)acrylate compound, the homopolymer of which has a glass transition temperature of 0°C or more, wherein the curable composition does not contain a urethane(meth)acrylate compound, or the contained amount of a urethane(meth)acrylate compound is more than 0 mass% but less than 4 mass% with respect to the total mass of the curable composition. Also, provided are a cured product of the curable composition and a production method for the cured product, and a laminated sheet, optical member, lenticular sheet, and three-dimensional structure which have the cured product obtained by curing the curable composition.

Description

硬化性組成物、硬化物及びその製造方法、積層シート、光学部材、レンチキュラーシート、並びに、３次元構造物Curable composition, cured product and method for producing the same, laminated sheet, optical member, lenticular sheet, and three-dimensional structure
　本開示は、硬化性組成物、硬化物及びその製造方法、積層シート、光学部材、レンチキュラーシート、並びに、３次元構造物に関する。 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.
　従来、硬化性組成物は、重合性樹脂と開始剤とを含有し、熱や光などにより重合反応を起こすことにより硬化し、様々な用途で幅広く用いられている。
　また、硬化性組成物を硬化して得られる硬化物を積層した積層シートは、光学部材、ガスバリアフィルム、保護フィルム、光学フィルタ、反射防止フィルム等、広く利用されている。
　更に、硬化性組成物を硬化して得られる硬化物は、反射防止膜、透明画素、透明絶縁膜、平坦化膜などの種々の部材に用いられる。
　近年、光学部材の種類は多岐にわたり、上記光学部材における光学構造は、例えば、表面形状が平坦なものに限らず、液晶用バックライトの輝度向上レンズや拡散レンズ、ビデオプロジェクションテレビのスクリーンに用いられるフレネルレンズ、マイクロレンズなどが挙げられる。こうしたデバイスでは主に樹脂材料により微細構造をなすことで所望の幾何光学的な性能を得ている。
　また、上記光学構造としては、見る角度によって異なる画像を表示する媒体として、半円筒形の表面を有する凸状レンズが並列したレンチキュラーレンズを用いたレンチキュラーシートが知られている。
　レンチキュラーシートは、一般に、レンチキュラーレンズの裏面側（凸状レンズの半円筒形の表面と反対側の面）に、インターレースされた複数の画像を組合せた画像列群（レンチキュラー画像）が配置され、画像列群をレンチキュラーレンズを通して観察した場合に、観察する角度によって画像列群のうちの１種又は２種以上の画像を表示することができる。 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.
　そのため、光学材料及び光学スクリーン等をはじめ、様々な商業用途での利用が期待されている。ところが、従来から提案されている用途は、シート又はフィルム等の２次元形態での利用がほとんどであり、立体形状に成形された３次元形態への適用は多くない。 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.
　３次元形態への適用が試みられた技術としては、例えば、光学スクリーン用樹脂材料を成型した光学スクリーン用シートに係る発明が提案されている（例えば、特許文献１参照）。
　一方、光学用途の例として、形状精度等に優れた光導波路の作製において、（メタ）アクリロイル基を有するマクロマー、アクリレート、及び重合開始剤等を含有する硬化性組成物を用いる技術が開示されている（例えば、特許文献２参照）。また、フィルム用途において硬化性組成物を適用する例として、多官能アクリレート、シリカ粒子、及び高分子量モノマー等を含有する組成によりハードコート性を付与する技術に関する開示がある（例えば、特許文献３参照）。 As a technique for which application to a three-dimensional form has been attempted, for example, an invention relating to an optical screen sheet obtained by molding a resin material for an optical screen has been proposed (see, for example, Patent Document 1).
On the other hand, as an example of optical applications, a technique using a curable composition containing a macromer having a (meth) acryloyl group, an acrylate, a polymerization initiator and the like in the production of an optical waveguide having excellent shape accuracy and the like is disclosed. (For example, refer to Patent Document 2). Further, as an example of applying a curable composition in film applications, there is a disclosure relating to a technique for imparting hard coat properties by a composition containing polyfunctional acrylates, silica particles, high molecular weight monomers, and the like (see, for example, Patent Document 3). ).
特開２００５－２０６７４２号公報JP 2005-206742 A 特開２００８－１１６９７１号公報JP 2008-116971 A 特開２００１－２８７３０８号公報JP 2001-287308 A
　しかしながら、従来より提案されている硬化性組成物を用いて硬化物、又は、上記硬化物を有する積層シートを作製し、更に真空成型等により立体成型しようとすると、上記硬化物の高温延伸性が十分ではなく、立体成型時に上記硬化物に亀裂（クラック）が生じたり、硬化物自体が破損する場合がある。
　また、特許文献１に記載された発明では、成型に供されるレンズ部分には熱可塑性樹脂が使用されているため、例えば真空成形等を施して立体化する場合において、成形時の熱で形状を安定的に保ちにくく、成形後にレンチキュラーシートの構造を維持できない場合がある。 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 cured product has high temperature stretchability. It is not sufficient, and the cured product may be cracked or three-dimensionally molded or the cured product itself may be damaged.
Further, in the invention described in Patent Document 1, since a thermoplastic resin is used for the lens portion that is subjected to molding, for example, when three-dimensionalization is performed by vacuum molding or the like, the shape is formed by heat during molding. May not be stably maintained, and the structure of the lenticular sheet may not be maintained after molding.
　本発明の一実施形態が解決しようとする課題は、得られる硬化物の耐擦傷性及び高温延伸性に優れる硬化性組成物を提供することである。
　本発明の他の実施形態が解決しようとする課題は、耐擦傷性及び高温延伸性に優れる硬化物及びその製造方法を提供することである。
　本発明の更に他の実施形態は、上記硬化性組成物を硬化してなる硬化物を有する積層シート、光学部材、レンチキュラーシート、及び、３次元構造物を提供することである。 The problem to be solved by one embodiment of the present invention is to provide a curable composition that is excellent in scratch resistance and high-temperature stretchability 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 scratch resistance and high-temperature stretchability, 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 obtained by curing the curable composition.
　上記課題を解決するための手段には、以下の態様が含まれる。
＜１＞　中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物、及び、
　ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物を含有し、
　ウレタン（メタ）アクリレート化合物を含有しないか、又は、ウレタン（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、０質量％を超え４質量％未満である
　硬化性組成物。
＜２＞　上記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物が、イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物である上記＜１＞に記載の硬化性組成物。
＜３＞　上記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物が、イソシアヌル環構造を有する３官能（メタ）アクリレート化合物である上記＜１＞又は＜２＞に記載の硬化性組成物。
＜４＞　上記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、１０質量％以上６０質量％以下である上記＜１＞～＜３＞のいずれか１つに記載の硬化性組成物。
＜５＞　上記単官能（メタ）アクリレート化合物のホモポリマーのガラス転移温度が、６０℃以上である上記＜１＞～＜４＞のいずれか１つに記載の硬化性組成物。
＜６＞　上記単官能（メタ）アクリレート化合物が、脂環構造を有する上記＜１＞～＜５＞のいずれか１つに記載の硬化性組成物。
＜７＞　ゴム成分を、硬化性組成物の全質量に対し、１質量％以上３０質量％以下更に含む上記＜１＞～＜６＞のいずれか１つに記載の硬化性組成物。
＜８＞　末端に（メタ）アクリロイル基を有する樹脂を更に含む上記＜１＞～＜７＞のいずれか１つに記載の硬化性組成物。
＜９＞　上記末端に（メタ）アクリロイル基を有する樹脂の含有量が、硬化性組成物の全質量に対し、５質量％以上４５質量％以下である上記＜８＞に記載の硬化性組成物。
＜１０＞　Ｎ－ビニル化合物を更に含む上記＜１＞～＜９＞のいずれか１つに記載の硬化性組成物。
＜１１＞　上記Ｎ－ビニル化合物が、Ｎ－ビニルピロリドン、及び、Ｎ－ビニルカプロラクタムよりなる群から選ばれた少なくとも１種の化合物である上記＜１０＞に記載の硬化性組成物。
＜１２＞　上記Ｎ－ビニル化合物の含有量が、硬化性組成物の全質量に対し、５質量％以上４０質量％以下である上記＜１０＞又は＜１１＞に記載の硬化性組成物。
＜１３＞　光重合開始剤を更に含む上記＜１＞～＜１２＞のいずれか１つに記載の硬化性組成物。
＜１４＞　上記＜１＞～＜１３＞のいずれか１つに記載の硬化性組成物を硬化してなる硬化物。
＜１５＞　上記＜１＞～＜１３＞のいずれか１つに記載の硬化性組成物を準備する工程、及び、上記硬化性組成物を硬化する工程を含む硬化物の製造方法。
＜１６＞　上記＜１＞～＜１３＞のいずれか１つに記載の硬化性組成物の硬化物を有する積層シート。
＜１７＞　上記＜１＞～＜１３＞のいずれか１つに記載の硬化性組成物の硬化物を有する光学部材。
＜１８＞　上記＜１＞～＜１３＞のいずれか１つに記載の硬化性組成物の硬化物を有するレンチキュラーシート。
＜１９＞　上記＜１８＞に記載のレンチキュラーシートの立体成型物である３次元構造物。 Means for solving the above problems include the following aspects.
<1> a bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis, and
Containing a monofunctional (meth) acrylate compound whose homopolymer has a glass transition temperature of 0 ° C. or higher,
The curable composition which does not contain a urethane (meth) acrylate compound, 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.
<2> The curing according to <1>, wherein the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is a bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure. Sex composition.
<3> The bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is the trifunctional (meth) acrylate compound having an isocyanuric ring structure. Curable composition.
<4> The content of the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is 10% by mass or more and 60% by mass or less with respect to the total mass of the curable composition < The curable composition according to any one of 1> to <3>.
<5> The curable composition according to any one of <1> to <4>, wherein the homopolymer of the monofunctional (meth) acrylate compound has a glass transition temperature of 60 ° C. or higher.
<6> The curable composition according to any one of <1> to <5>, wherein the monofunctional (meth) acrylate compound has an alicyclic structure.
<7> The curable composition according to any one of <1> to <6>, further including a rubber component in an amount of 1% by mass to 30% by mass with respect to the total mass of the curable composition.
<8> The curable composition according to any one of <1> to <7>, further including a resin having a (meth) acryloyl group at a terminal.
<9> The curable composition according to <8>, wherein the content of the resin having a (meth) acryloyl group at the terminal is 5% by mass to 45% by mass with respect to the total mass of the curable composition. .
<10> The curable composition according to any one of <1> to <9>, further including an N-vinyl compound.
<11> The curable composition according to <10>, wherein the N-vinyl compound is at least one compound selected from the group consisting of N-vinylpyrrolidone and N-vinylcaprolactam.
<12> The curable composition according to <10> or <11>, wherein the content of the N-vinyl compound is 5% by mass or more and 40% by mass or less with respect to the total mass of the curable composition.
<13> The curable composition according to any one of <1> to <12>, further including a photopolymerization initiator.
<14> A cured product obtained by curing the curable composition according to any one of <1> to <13>.
<15> A method for producing a cured product comprising a step of preparing the curable composition according to any one of <1> to <13> and a step of curing the curable composition.
<16> A laminated sheet having a cured product of the curable composition according to any one of <1> to <13>.
<17> An optical member having a cured product of the curable composition according to any one of <1> to <13>.
<18> A lenticular sheet having a cured product of the curable composition according to any one of the above items <1> to <13>.
<19> A three-dimensional structure which is a three-dimensional molded product of the lenticular sheet according to <18>.
　本発明の一実施形態によれば、得られる硬化物の耐擦傷性及び高温延伸性に優れる硬化性組成物を提供することができる。
　また、本発明の他の実施形態によれば、耐擦傷性及び高温延伸性に優れる硬化物及びその製造方法を提供することができる。
　更に、本発明の更に他の実施形態によれば、上記硬化性組成物を硬化してなる硬化物を有する積層シート、光学部材、レンチキュラーシート、及び、３次元構造物を提供することができる。 According to one embodiment of the present invention, it is possible to provide a curable composition excellent in scratch resistance and high-temperature stretchability of the obtained cured product.
Moreover, according to other embodiment of this invention, the hardened | cured material excellent in scratch resistance and high temperature stretchability, and its manufacturing method can be provided.
Furthermore, according to still another embodiment of the present invention, a laminated sheet, an optical member, a lenticular sheet, and a three-dimensional structure having a cured product obtained by curing the curable composition can be provided.
本開示におけるレンチキュラーシートの一例を示す概略図である。It is the schematic which shows an example of the lenticular sheet in this indication.
　以下、本開示について詳細に説明する。
　なお、本明細書中、「ｘｘ～ｙｙ」の記載は、ｘｘ及びｙｙを含む数値範囲を表す。
　本明細書において、「（メタ）アクリル」は、アクリル及びメタクリルの両方を包含する概念で用いられる語であり、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルの両方を包含する概念として用いられる語である。
　また、本明細書中の「工程」の用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば本用語に含まれる。
　本開示におけるアルキル基、アリール基、アルキレン基及びアリーレン基等の炭化水素基は、特に断りのない限り、分岐を有していても、環構造を有していてもよい。
　また、本開示において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　また、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　また、本開示における重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特に断りのない限り、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、ＴＳＫｇｅｌ　Ｇ２０００ＨｘＬ（何れも東ソー（株）製の商品名）のカラムを使用したゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析装置により、溶媒ＴＨＦ（テトラヒドロフラン）、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。 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.
（硬化性組成物）
　本開示に係る硬化性組成物は、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物、及び、ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物を含有し、ウレタン（メタ）アクリレート化合物を含有しないか、又は、ウレタン（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、０質量％を超え４質量％未満である。
　本開示に係る硬化性組成物は、レンチキュラーシート（特にレンチキュラーシートにおけるレンチキュラーレンズ）形成用硬化性組成物として好適に用いられる。 (Curable composition)
The curable composition according to the present disclosure includes a bifunctional or trifunctional (meth) acrylate compound having a central skeleton having a three-fold symmetry axis, and a monofunctional (meth) acrylate having a glass transition temperature of 0 ° C. or higher. The compound is contained and 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 the present disclosure is suitably used as a curable composition for forming a lenticular sheet (particularly a lenticular lens in a lenticular sheet).
　本発明者らが詳細な検討を行った結果、上記硬化性組成物とすることにより、得られる硬化物の耐擦傷性及び高温延伸性に優れることを見出した。
　詳細な機構は不明であるが、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物は、多官能による架橋点の形成により耐擦傷性が向上するだけでなく、中心骨格間で、双極子―双極子相互作用、又は、π－π相互作用が生じ、より耐擦傷性に優れ、また、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物であることにより、架橋密度が適度となり、高温延伸性にも優れると推定している。
　また、ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物を含むことにより、その硬化物の高温における柔軟性から高温延伸性に優れるとともに、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物により生じる双極子－双極子相互作用と架橋密度とを適度に制御でき、耐擦傷性と高温延伸性とが両立できると推定している。
　更に、本発明者らは、機構は不明であるが、ウレタン（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、４質量％以上であると、得られる硬化物の耐擦傷性に劣ることを見出した。
　ウレタン（メタ）アクリレート化合物の含有量を、硬化性組成物の全質量に対し、４質量％未満に抑えることにより、得られる硬化物の耐擦傷性及び高温延伸性に優れる。 As a result of detailed studies by the present inventors, it was found that by using the above curable composition, the obtained cured product was excellent in scratch resistance and high temperature stretchability.
Although the detailed mechanism is unknown, the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a three-fold symmetry axis not only improves the scratch resistance by the formation of crosslinking points by polyfunctionality, but also the central skeleton. A dipole-dipole interaction or π-π interaction occurs between them, and is more excellent in scratch resistance, and a bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a three-fold symmetry axis. It is presumed that the cross-linking density becomes moderate and the high-temperature stretchability is excellent.
In addition, by including a monofunctional (meth) acrylate compound whose homopolymer has a glass transition temperature of 0 ° C. or higher, the cured product is excellent in high-temperature stretchability from flexibility at high temperatures, and the central skeleton has a three-fold symmetry axis. It is presumed that the dipole-dipole interaction produced by the bifunctional or trifunctional (meth) acrylate compound possessed and the crosslink density can be appropriately controlled, and that both scratch resistance and high temperature stretchability can be achieved.
Furthermore, although the mechanism is unclear, the inventors of the present invention have a urethane (meth) acrylate compound content of 4% by mass or more based on the total mass of the curable composition. It was found that the scratch resistance is poor.
By suppressing the content of the urethane (meth) acrylate compound to less than 4% by mass with respect to the total mass of the curable composition, the obtained cured product is excellent in scratch resistance and high-temperature stretchability.
　以下、本開示に係る硬化性組成物に用いられる各成分について、詳述する。 Hereinafter, each component used in the curable composition according to the present disclosure will be described in detail.
＜中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物＞
　本開示に係る硬化性組成物は、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物を含有する。
　本開示における化合物の中心骨格が３回対称軸を有する化合物とは、ある分子の中心骨格において、Ｃ３回転操作を実施した後に、その形が、Ｃ３回転操作実施前の形と、配座異性体に関係なく、区別がつかないものである場合に、Ｃ３対称要素を有する化合物であるものをいう。Ｃ３回転は、角２π／３（ラジアン）又は角３６０゜／３＝１２０°によって、分子における中心骨格を通過している軸に対しての単一の回転である。
　また、本開示における化合物の対称性は、配座異性体等の厳密な立体構造の対称性まで規定するものではなく、例えば、下記に示す構造であれば、それぞれ、中心骨格が３回対称軸を有するものとする。 <Bifunctional or trifunctional (meth) acrylate compound whose central skeleton has a 3-fold symmetry axis>
The curable composition according to the present disclosure contains a bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis.
The compound in which the central skeleton of the compound in the present disclosure has a three-fold symmetry axis means that after the C 3 rotation operation is performed on the central skeleton of a molecule, the shape is the conformation before the C 3 rotation operation is performed. regardless isomers, if one intends indistinguishable, refers to a compound having a C 3 symmetry elements. C 3 rotation, the angular 2 [pi / 3 (rad) or angular 360 ° / 3 = 120 °, a single rotation of an axis passing through the central skeleton in the molecule.
Further, the symmetry of the compound in the present disclosure does not define the strict stereostructure symmetry such as a conformer. For example, in the structure shown below, the central skeleton has a three-fold symmetry axis, respectively. It shall have.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　なお、Ｒは、化合物の中心骨格が３回対称軸を有していれば、同一の化学構造である基であっても、同一でない化学構造を有する基であってもよい。 Note that R may be a group having the same chemical structure or a group having a non-identical chemical structure as long as the central skeleton of the compound has a three-fold symmetry axis.
　上記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物における中心骨格としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、環構造を有する骨格であることが好ましく、イソシアヌル環構造、トリアジン環構造、トリフェニレン環構造、及び、ベンゼン環構造よりなる群から選ばれた構造であることがより好ましく、イソシアヌル環構造、トリアジン環構造、及び、トリフェニレン環構造よりなる群から選ばれた構造であることが更に好ましく、イソシアヌル環構造が特に好ましい。
　すなわち、上記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物は、得られる硬化物の耐擦傷性及び高温延伸性の観点から、イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物であることが特に好ましい。
　また、本開示における中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物は、イソシアヌル環構造以外のウレタン結合を含まないことが好ましい。 The central skeleton in the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a three-fold symmetry axis is a skeleton having a ring structure from the viewpoint of scratch resistance and high-temperature stretchability of the obtained cured product. It is more preferable that it is a structure selected from the group consisting of an isocyanuric ring structure, a triazine ring structure, a triphenylene ring structure, and a benzene ring structure, and it consists of an isocyanuric ring structure, a triazine ring structure, and a triphenylene ring structure. A structure selected from the group is more preferable, and an isocyanuric ring structure is particularly preferable.
That is, the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is a bifunctional or trifunctional compound having an isocyanuric ring structure from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product. Particularly preferred is a (meth) acrylate compound.
Moreover, it is preferable that the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton in the present disclosure has a 3-fold symmetry axis does not include a urethane bond other than the isocyanuric ring structure.
　上記イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物は、耐擦傷性の観点から、イソシアヌル環構造を有する３官能（メタ）アクリレート化合物であることが好ましい。 The bifunctional or trifunctional (meth) acrylate compound having the isocyanuric ring structure is preferably a trifunctional (meth) acrylate compound having an isocyanuric ring structure from the viewpoint of scratch resistance.
　上記イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、下記式ＩＣＴ又は式ＩＣＤで表される化合物が好ましく挙げられ、下記式ＩＣＴで表される化合物がより好ましく挙げられる。 Preferred examples of the bifunctional or trifunctional (meth) acrylate compound having the isocyanuric ring structure include compounds represented by the following formula ICT or formula ICD from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product. More preferred are compounds represented by the following formula ICT.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式ＩＣＴ及び式ＩＣＤ中、Ｌ１Ｃ、Ｌ２Ｃ及びＬ３Ｃは互いに異なっていてもよい、アルキレン基、又は、－Ｌ４Ｃ－（Ｏ－Ｌ５Ｃ）ｎｔ－を表し、Ｌ４Ｃ及びＬ５Ｃは互いに異なっていてもよい、アルキレン基を表し、ｎｔは１以上の整数を表し、Ｒ１Ｃ、Ｒ２Ｃ及びＲ３Ｃは互いに異なっていてもよい、水素原子、又は、メチル基を表し、Ｒ４Ｃは、水素原子、アルキル基、ヒドロキシアルキル基、又は、－Ｌ６Ｃ－（Ｏ－Ｌ７Ｃ）ｎｄ－ＯＨを表し、Ｌ６Ｃ及びＬ７Ｃは互いに異なっていてもよい、アルキレン基を表し、ｎｄは１以上の整数を表す。 In formula ICT and formula ICD, L 1C , L 2C and L 3C may be different from each other, and represent an alkylene group or —L 4C — ( OL 5 C ) nt — where L 4C and L 5C are Represents an alkylene group which may be different, nt represents an integer of 1 or more, R 1C , R 2C and R 3C represent a hydrogen atom or a methyl group which may be different from each other, and R 4C represents Represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or —L 6C — ( OL 7 C ) nd —OH, L 6C and L 7C may be different from each other, and represent an alkylene group, and nd is 1 or more Represents an integer.
　上記Ｌ１Ｃ、Ｌ２Ｃ及びＬ３Ｃは互いに異なっていてもよい、アルキレン基であることが好ましく、炭素数２～８のアルキレン基であることがより好ましく、エチレン基であることが特に好ましい。
　上記Ｌ４Ｃ及びＬ６Ｃは互いに異なっていてもよい、炭素数２～８のアルキレン基であることが好ましく、エチレン基であることがより好ましい。
　上記Ｌ５Ｃ及びＬ７Ｃは互いに異なっていてもよい、エチレン基、又は、プロピレン基であることが好ましく、エチレン基、又は、１，２－プロピレン基であることがより好ましく、エチレン基であることが特に好ましい。
　上記ｎｔ及びｎｄは互いに異なっていてもよい、１～２０の整数であることが好ましく、１～８の整数であることがより好ましく、１～４の整数であることが特に好ましい。
　上記Ｒ１Ｃ、Ｒ２Ｃ及びＲ３Ｃは、水素原子であることが好ましい。
　上記Ｒ４Ｃは、アルキル基、ヒドロキシアルキル基、又は、－Ｌ６Ｃ－（Ｏ－Ｌ７Ｃ）ｎｄ－ＯＨであることが好ましく、ヒドロキシアルキル基、又は、－Ｌ６Ｃ－（Ｏ－Ｌ７Ｃ）ｎｄ－ＯＨであることがより好ましく、ヒドロキシアルキル基であることが更に好ましく、ヒドロキシエチル基であることが特に好ましい。 L 1C , L 2C and L 3C may be different from each other, preferably an alkylene group, more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an ethylene group.
L 4C and L 6C are preferably an alkylene group having 2 to 8 carbon atoms, which may be different from each other, and more preferably an ethylene group.
L 5C and L 7C may be different from each other, preferably an ethylene group or a propylene group, more preferably an ethylene group or a 1,2-propylene group, and an ethylene group. Is particularly preferred.
The nt and nd may be different from each other, preferably an integer of 1 to 20, more preferably an integer of 1 to 8, and particularly preferably an integer of 1 to 4.
R 1C , R 2C and R 3C are preferably hydrogen atoms.
R 4C is preferably an alkyl group, a hydroxyalkyl group, or —L 6C — ( OL 7 C ) nd —OH, and is preferably a hydroxyalkyl group or —L 6C — ( OL 7 C ) nd It is more preferably —OH, further preferably a hydroxyalkyl group, and particularly preferably a hydroxyethyl group.
　上記イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物として具体的には、イソシアヌル酸アルキレンオキサイド変性トリ（メタ）アクリレート、イソシアヌル酸アルキレンオキサイド変性ジ（メタ）アクリレート、トリ（メタ）アクリルオキシアルキル化イソシアヌレート、ジ（メタ）アクリルオキシアルキル化イソシアヌレート、ジ（メタ）アクリル化イソシアヌレート等が挙げられる。
　中でも、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、及び、イソシアヌル酸エチレンオキサイド変性ジ（メタ）アクリレートよりなる群から選ばれた少なくとも１種の化合物が好ましく、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレートが特に好ましい。 Specific examples of the bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure include isocyanuric acid alkylene oxide-modified tri (meth) acrylate, isocyanuric acid alkylene oxide-modified di (meth) acrylate, and tri (meth) acryloxy. Examples include alkylated isocyanurates, di (meth) acryloxyalkylated isocyanurates, and di (meth) acrylated isocyanurates.
Among them, at least one compound selected from the group consisting of isocyanuric acid ethylene oxide-modified tri (meth) acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate is preferable, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate. Is particularly preferred.
　また、上記イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物は、市販品である東亞合成（株）製アロニックスＭ－３１５、Ｍ－３１３、及び、Ｍ－２１５も好適に用いることができる。 As the difunctional or trifunctional (meth) acrylate compound having the isocyanuric ring structure, commercially available products Aronix M-315, M-313, and M-215 manufactured by Toagosei Co., Ltd. are preferably used. it can.
　中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物の分子量は、２００以上１，５００以下であることが好ましい。
　本開示に係る硬化性組成物は、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物を、１種単独で含んでいても、２種以上を含んでいてもよい。
　本開示に係る硬化性組成物における中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物の含有量としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、硬化性組成物の全質量に対して、５質量％以上７０質量％以下が好ましく、１０質量％以上６５質量％以下がより好ましく、１０質量％以上６０質量％以下であることが更に好ましく、１５質量％以上６０質量％以下であることが特に好ましい。 The molecular weight of the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is preferably 200 or more and 1,500 or less.
The curable composition according to the present disclosure may include one or more bifunctional or trifunctional (meth) acrylate compounds having a central skeleton having a three-fold symmetry axis, or may include two or more.
As content of the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton in the curable composition according to the present disclosure has a three-fold symmetry axis, from the viewpoint of scratch resistance and high temperature stretchability of the obtained cured product, 5 mass% or more and 70 mass% or less are preferable with respect to the total mass of a curable composition, 10 mass% or more and 65 mass% or less are more preferable, It is more preferable that they are 10 mass% or more and 60 mass% or less, It is particularly preferable that the content is not less than mass% and not more than 60 mass%.
＜ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物＞
　本開示に係る硬化性組成物は、ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物を含有する。
　単官能（メタ）アクリレート化合物のホモポリマーのガラス転移温度（Ｔｇ）とは、単官能（メタ）アクリレート化合物を重合して得られるホモポリマー（単独重合体）のガラス転移温度を意味する。具体的には、単官能（メタ）アクリレート化合物に重合開始剤を添加して、重量平均分子量５０，０００のホモポリマーを得る。ホモポリマーのガラス転移温度（Ｔｇ）は、ＡＳＴＭ　Ｄ３４１８－８に準拠して、示差走査熱量計により測定する。
　なお、分子量によってガラス転移温度（Ｔｇ）が変化するが、重量平均分子量１０，０００以上の場合には、分子量によるＴｇの変動は無視できる程度である。 <Monofunctional (meth) acrylate compound whose homopolymer has a glass transition temperature of 0 ° C. or higher>
The curable composition which concerns on this indication contains the monofunctional (meth) acrylate compound whose glass transition temperature of a homopolymer is 0 degreeC or more.
The glass transition temperature (Tg) of a homopolymer of a monofunctional (meth) acrylate compound means the glass transition temperature of a homopolymer (homopolymer) obtained by polymerizing a monofunctional (meth) acrylate compound. Specifically, a polymerization initiator is added to the monofunctional (meth) acrylate compound to obtain a homopolymer having a weight average molecular weight of 50,000. The glass transition temperature (Tg) of the homopolymer is measured with a differential scanning calorimeter according to ASTM D3418-8.
Although the glass transition temperature (Tg) varies depending on the molecular weight, when the weight average molecular weight is 10,000 or more, the variation in Tg due to the molecular weight is negligible.
　また、上記単官能（メタ）アクリレート化合物におけるホモポリマーのガラス転移温度は、得られる硬化物の耐擦傷性及び高温延伸性の観点から、２０℃以上であることが好ましく、６０℃以上であることがより好ましく、６０℃以上２００℃以下であることが更に好ましく、１１０℃以上２００℃以下であることが特に好ましい。 In addition, the glass transition temperature of the homopolymer in the monofunctional (meth) acrylate compound is preferably 20 ° C. or higher, and preferably 60 ° C. or higher, from the viewpoint of scratch resistance and high temperature stretchability of the resulting cured product. Is more preferably 60 ° C. or higher and 200 ° C. or lower, and particularly preferably 110 ° C. or higher and 200 ° C. or lower.
　また、ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物としては、ベンジル（メタ）アクリレート、１－ナフチル（メタ）アクリレート、２－ナフチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ブチルメタクリレート、メチル（メタ）アクリレート、２－ヒドロキシエチルメタクリレート等が挙げられる。 Monofunctional (meth) acrylate compounds having a homopolymer glass transition temperature of 0 ° C. or higher include benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, and stearyl (meth). Examples include acrylate, hexadecyl (meth) acrylate, lauryl (meth) acrylate, t-butyl (meth) acrylate, n-butyl methacrylate, methyl (meth) acrylate, 2-hydroxyethyl methacrylate and the like.
　上記ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物は、得られる硬化物の耐擦傷性及び高温延伸性の観点から、脂環構造（脂肪族環構造）を有する単官能（メタ）アクリレート化合物であることが好ましく、脂肪族炭化水素環構造を有する単官能（メタ）アクリレート化合物であることがより好ましい。
　また、上記ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物は、２つ以上の環を有する脂環構造を有する単官能（メタ）アクリレート化合物であることが好ましい。
　上記脂環構造としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、トリシクロデカン環構造、シクロヘキサン環構造、ノルボルネン環構造、及び、アダマンタン環構造よりなる群から選ばれた少なくとも１種の環構造が好ましく、トリシクロデカン環構造がより好ましい。 The monofunctional (meth) acrylate compound in which the homopolymer has a glass transition temperature of 0 ° C. or higher is a monofunctional (meth) acrylate compound having an alicyclic structure (aliphatic ring structure) from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product. It is preferably a functional (meth) acrylate compound, more preferably a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure.
Moreover, it is preferable that the monofunctional (meth) acrylate compound whose glass transition temperature of the said homopolymer is 0 degreeC or more is a monofunctional (meth) acrylate compound which has an alicyclic structure which has a 2 or more ring.
The alicyclic structure is at least 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 scratch resistance and high-temperature stretchability of the resulting cured product. One type of ring structure is preferred, and a tricyclodecane ring structure is more preferred.
　ホモポリマーのガラス転移温度が０℃以上である脂環構造を有する単官能（メタ）アクリレート化合物として、具体的には、ジシクロペンタニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレートなどのトリシクロデカン環構造を有する（メタ）アクリレート化合物、シクロヘキシル（メタ）アクリレートなどのシクロヘキサン環構造を有する（メタ）アクリレート化合物、イソボロニル（メタ）アクリレートなどのノルボルネン環構造を有する（メタ）アクリレート化合物、１－アダマンチル（メタ）アクリレートなどのアダマンタン環構造を有する（メタ）アクリレート化合物等が挙げられる。
　中でも、得られる硬化物の耐擦傷性及び高温延伸性の観点から、トリシクロデカン環構造を有する（メタ）アクリレート化合物が好ましく、ジシクロペンタニル（メタ）アクリレートがより好ましい。 As monofunctional (meth) acrylate compounds having an alicyclic structure whose homopolymer glass transition temperature is 0 ° C. or higher, specifically, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate (Meth) acrylate compounds having a tricyclodecane ring structure such as (meth) acrylate compounds having a cyclohexane ring structure such as cyclohexyl (meth) acrylate, and (meth) acrylate compounds having a norbornene ring structure such as isobornyl (meth) acrylate And (meth) acrylate compounds having an adamantane ring structure such as 1-adamantyl (meth) acrylate.
Among these, a (meth) acrylate compound having a tricyclodecane ring structure is preferable, and dicyclopentanyl (meth) acrylate is more preferable from the viewpoint of scratch resistance and high-temperature stretchability of the obtained cured product.
　本開示に係る硬化性組成物は、ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物を、１種単独で含んでいても、２種以上を含んでいてもよい。
　本開示に係る硬化性組成物におけるホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物の含有量としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、硬化性組成物の全質量に対して、０．５質量％以上５０質量％以下が好ましく、１０質量％以上４０質量％以下がより好ましく、１５質量％以上３５質量％以下が特に好ましい。 The curable composition concerning this indication may contain the monofunctional (meth) acrylate compound whose glass transition temperature of a homopolymer is 0 degreeC or more individually by 1 type, or may contain 2 or more types.
As content of the monofunctional (meth) acrylate compound whose glass transition temperature of the homopolymer in the curable composition according to the present disclosure is 0 ° C. or higher, from the viewpoint of scratch resistance and high temperature stretchability of the obtained cured product, 0.5 mass% or more and 50 mass% or less are preferable with respect to the total mass of a curable composition, 10 mass% or more and 40 mass% or less are more preferable, and 15 mass% or more and 35 mass% or less are especially preferable.
＜ウレタン（メタ）アクリレート化合物＞
　本開示に係る硬化性組成物は、ウレタン（メタ）アクリレート化合物を含有しないか、又は、ウレタン（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、０質量％を超え４質量％未満である。
　本開示におけるウレタン（メタ）アクリレート化合物は、１以上のウレタン結合及び１以上の（メタ）アクリロイル基を有する化合物である。ただし、本開示におけるウレタン（メタ）アクリレート化合物のウレタン結合には、イソシアヌル環構造を含まないものとする。
　ウレタン（メタ）アクリレート化合物は、単官能であっても、多官能であってもよいが、２官能～１５官能のものが好ましく挙げられる。
　また、ウレタン（メタ）アクリレート化合物の重量平均分子量は、１，０００以上１００，０００以下であることが好ましい。 <Urethane (meth) acrylate compound>
The curable composition according to the present disclosure does not contain a urethane (meth) acrylate compound, or the content of the urethane (meth) acrylate compound exceeds 0% by mass with respect to the total mass of the curable composition. It is less than mass%.
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.
　ウレタン（メタ）アクリレート化合物としては、例えば、ポリエチレングリコール、ポリテトラメチルグリコール等のポリエーテルポリオール；コハク酸、アジピン酸、アゼライン酸、セバシン酸、フタル酸、テトラヒドロ（無水）フタル酸、ヘキサヒドロ（無水）フタル酸等の二塩基酸とエチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール等のジオールの反応によって得られるポリエステルポリオール；ポリε－カプロラクトン変性ポリオール；ポリメチルバレロラクトン変性ポリオール；エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール等のアルキルポリオール；エチレンオキシド付加ビスフェノールＡ、プロピレンオキシド付加ビスフェノールＡ等のビスフェノールＡ骨格アルキレンオキシド変性ポリオール；エチレンオキシド付加ビスフェノールＦ、プロピレンオキシド付加ビスフェノールＦ等のビスフェノールＦ骨格アルキレンオキシド変性ポリオール、又はそれらの混合物とトリレンジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の有機ポリイソシアネートと２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリレートから製造されるウレタン（メタ）アクリレート化合物、１，５，５－トリメチル－１－［（１－メタクリロイルオキシプロパン－２－イル）カルバモイルメチル］－３－（１－メタクリロイルオキシプロパン－２－イル）カルバモイルシクロヘキサン、１，５，５－トリメチル－１－［（２－メタクリロイルオキシエチル）カルバモイルメチル］－３－（２－メタクリロイルオキシエチル）カルバモイルシクロヘキサン等が挙げられる。 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.
　また、ウレタン（メタ）アクリレート化合物の市販品としては、日本合成化学工業（株）製の紫光シリーズ、新中村化学工業（株）製のＵ－２ＰＰＡ、Ｕ－４ＨＡ、Ｕ－６ＨＡ、Ｕ－６ＬＰＡ、Ｕ－１５ＨＡ、Ｕ－３２４Ａ、ＵＡ－１２２Ｐ、ＵＡ５２０１、ＵＡ－５１２等；サートマー・ジャパン（株）製のＣＮ９６４Ａ８５、ＣＮ９６４、ＣＮ９５９、ＣＮ９６２、ＣＮ９６３Ｊ８５、ＣＮ９６５、ＣＮ９８２Ｂ８８、ＣＮ９８１、ＣＮ９８３、ＣＮ９９６、ＣＮ９００２、ＣＮ９００７、ＣＮ９００９、ＣＮ９０１０、ＣＮ９０１１、ＣＮ９１７８、ＣＮ９７８８、ＣＮ９８９３、ダイセル・サイテック（株）製のＥＢ２０４、ＥＢ２３０、ＥＢ２４４、ＥＢ２４５、ＥＢ２７０、ＥＢ２８４、ＥＢ２８５、ＥＢ８１０、ＥＢ４８３０、ＥＢ４８３５、ＥＢ４８５８、ＥＢ１２９０、ＥＢ２１０、ＥＢ２１５、ＥＢ４８２７、ＥＢ４８３０、ＥＢ４８４９、ＥＢ６７００、ＥＢ２０４、ＥＢ８４０２、ＥＢ８８０４、ＥＢ８８００－２０Ｒ等が挙げられる。 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.
　本開示に係る硬化性組成物は、ウレタン（メタ）アクリレート化合物を、１種単独で含んでいても、２種以上を含んでいてもよいが、含まないことが好ましい。
　本開示に係る硬化性組成物は、得られる硬化物の耐擦傷性及び高温延伸性の観点から、ウレタン（メタ）アクリレート化合物を、含有しないか、又は、その含有量が、硬化性組成物の全質量に対して、２質量％以下であることが好ましく、含有しないか、又は、その含有量が、硬化性組成物の全質量に対して、１質量％以下であることがより好ましく、含有しないことが特に好ましい。 Although the curable composition concerning this indication may contain urethane (meth) acrylate compound individually by 1 type, it may contain 2 or more types, but it is preferable not to contain.
The curable composition according to the present disclosure does not contain a urethane (meth) acrylate compound from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product, or the content thereof is that of the curable composition. It is preferably 2% by mass or less with respect to the total mass, and is not contained, or the content is more preferably 1% by mass or less with respect to the total mass of the curable composition, It is particularly preferred not to do so.
＜ゴム成分＞
　本開示に係る硬化性組成物は、得られる硬化物の耐擦傷性及び高温延伸性の観点から、ゴム成分を含むことが好ましく、硬化性組成物の全質量に対し、ゴム成分を１質量％以上３０質量％以下含むことがより好ましく、３質量％以上２５質量％以下であることが更に好ましく、４質量％以上１０質量％以下であることが特に好ましい。
　本開示におけるゴム成分は、ゴム弾性を有する樹脂、すなわち、エラストマーであればよく、いわゆる、狭義のゴムだけでなく、熱可塑性エラストマーであってもよい。
　本開示における「ゴム」とは、ガラス転移温度（Ｔｇ）が０℃以下である樹脂である。
　具体的には、硬化性組成物又は硬化物を下記条件で示差走査熱分析（ＤＳＣ）測定し、低温側に現れるＴｇ（比熱の不連続変化点）を求める。
　硬化性組成物又は硬化物を１０ｍｇサンプリングし２００℃まで１０℃／分で昇温した後、－５０℃で－２００℃まで冷却、これを１０℃／分で昇温しながらＤＳＣ測定しＴｇを求める。
　また、本開示において、硬化物がゴム成分を有することは、硬化物の１００℃における破断伸度が１００％以上であることからも示すことができる。ゴム成分を含まない硬化物であれば、１００℃における破断伸度が１００％以上となることはない。
　硬化物の１００℃における破断伸度が１００％以上であることを示す方法としては、後述する破断伸度の測定方法により測定してもよいし、下記に示す方法により確認してもよい。
　硬化物を、膜厚５０μｍ×長さ５０ｍｍ×幅１０ｍｍの大きさとしたサンプル片を作製し、得られたサンプル片を１８０度折り曲げる。これにより外周部は１００％伸長される。この状態で包埋し、断面を切削し、０．５質量％四酸化ルテニウム水溶液に２５℃で１５時間浸漬してルテニウム染色し、透過型電子顕微鏡（ＴＥＭ）により３万倍で撮影する。撮影した像を観察し、外周部の内部に破壊が発生していないものは、破断伸度が１００％以上である。 <Rubber component>
The curable composition according to the present disclosure preferably contains a rubber component from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product, and the rubber component is 1% by mass with respect to the total mass of the curable composition. It is more preferably 30% by mass or less, further preferably 3% by mass or more and 25% by mass or less, and particularly preferably 4% by mass or more and 10% by mass or less.
The rubber component in the present disclosure may be a resin having rubber elasticity, that is, an elastomer, and may be not only a so-called rubber in a narrow sense but also a thermoplastic elastomer.
The “rubber” in the present disclosure is a resin having a glass transition temperature (Tg) of 0 ° C. or lower.
Specifically, a differential scanning calorimetry (DSC) measurement is performed on the curable composition or the cured product under the following conditions to determine Tg (discontinuous change point of specific heat) that appears on the low temperature side.
10 mg of the curable composition or cured product was sampled, heated to 200 ° C. at 10 ° C./min, cooled to −200 ° C. to −200 ° C., and DSC measurement was performed while raising the temperature at 10 ° C./min. Ask.
In the present disclosure, the fact that the cured product has a rubber component can also be indicated by the fact that the elongation at break of the cured product at 100 ° C. is 100% or more. If it is a hardened | cured material which does not contain a rubber component, the breaking elongation in 100 degreeC will not become 100% or more.
As a method of indicating that the breaking elongation at 100 ° C. of the cured product is 100% or more, it may be measured by a measuring method of breaking elongation described later, or may be confirmed by the following method.
A sample piece in which the cured product has a thickness of 50 μm × length 50 mm × width 10 mm is produced, and the obtained sample piece is bent 180 degrees. Thereby, an outer peripheral part is expanded 100%. It is embedded in this state, the cross section is cut, immersed in an aqueous 0.5% by mass ruthenium tetroxide solution at 25 ° C. for 15 hours, stained with ruthenium, and photographed at a magnification of 30,000 with a transmission electron microscope (TEM). When the photographed image is observed and no fracture occurs inside the outer peripheral portion, the elongation at break is 100% or more.
　本開示における破断伸度は、以下の方法により測定するものとする。
　硬化性組成物を入手できる場合は、硬化性組成物を、疎水化処理された２枚のガラス板間に挟み込み、下記条件にて紫外線（ＵＶ）照射、又は、熱硬化するまで加熱し、ガラス板から剥がして膜厚５０μｍの樹脂硬化膜（単膜）を作製する。
　ＵＶ照射は、紫外線（ＵＶ）照射装置（ＥＸＥＣＵＲＥ　３０００、ＨＯＹＡ　ＣＡＮＤＥＯ　ＯＰＴＲＯＮＩＣＳ（株）製）を用い、ＵＶ照射量１．０Ｊ／ｃｍ２の条件にて硬化するまで照射する。
　得られた樹脂硬化膜（単膜）を、長さ５０ｍｍ×幅１０ｍｍの大きさに打ち抜いてサンプル片を作製し、ＴＥＮＳＩＬＯＮ　ＲＴＣ－１２２５Ａ（（株）エー・アンド・デイ製）を用い、下記の条件にて引張試験を行って下記式で表される破断伸度を測定した。
　樹脂硬化膜（単膜）を、長さ５０ｍｍ×幅１０ｍｍの大きさに打ち抜いてサンプル片を作製し、ＴＥＮＳＩＬＯＮ　ＲＴＣ－１２２５Ａ（エー・アンド・デイ社製）を用い、下記の条件にて引張試験を行って下記式で表される破断伸度を測定した。破断伸度を３回測定し、それらの平均値を破断伸度とした。測定結果を表１又は表２に示す。
　破断伸度（％）＝１００×（延伸で破断した長さ－チャック間距離）／（チャック間距離）
－条件－
・チャック間距離：３０ｍｍ
・サンプル片の温度：１００℃
・引張速度：１ｍｍ／秒 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 .
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.
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. 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
　硬化物から破断伸度を測定する場合は、硬化物を長さ５０ｍｍ×幅１０ｍｍの大きさに加工し、サンプル片を作製して、上記と同様の方法により、１００℃における破断伸度を測定する。この測定において、下記の本開示における硬化膜の好ましい厚みの範囲では、厚みの破断伸度への影響はない。
　なお、本開示に係る硬化性組成物を膜状に硬化した硬化膜の厚みは、１０μｍ以上１００μｍ以下が好ましく、１５μｍ以上８０μｍ以下がより好ましく、２０μｍ以上６０μｍ以下が更に好ましい。上記範囲であると、取扱い性に優れるとともに、成型加工性に優れる。 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.
　上記ゴム成分に用いられるゴムとしては、例えば、スチレンブタジエンゴム、アクリロニトリルブタジエンゴム、ブタジエンゴム、イソプレンゴム、クロロプレンゴム、エチレンプロピレンゴム、エチレンプロピレンジエン共重合ゴム（ＥＰＤＭ）、エチレンブテンゴム、エチレンオクテンゴム、ブチルゴム、アクリルゴム、シリコーンゴム、塩素化ポリエチレン等の化学的に合成された合成ゴム、天然ゴム等を挙げることができる。
　また、上記ゴム成分に用いられる熱可塑性エラストマーとしては、例えば、ウレタン系熱可塑性エラストマー、エステル系熱可塑性エラストマー、アミド系熱可塑性エラストマー、シリコーン系熱可塑性エラストマー等を挙げることができる。
　更に、ゴム成分としては、国際公開第２０１４／１６２３６９号の段落０１２４～０２８５の記載のもの、国際公開第２０１５／１５６３２３号の段落００２４～００６８に記載のもの、及び、特許第５４０１０２９号公報の段落００１６～００２０に記載のものも使用できる。
　本開示に係る硬化性組成物は、ゴム成分を１種単独で含んでいても、２種以上含んでいてもよい。 Examples of the rubber used in the rubber component include styrene butadiene rubber, acrylonitrile butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, ethylene propylene rubber, ethylene propylene diene copolymer rubber (EPDM), ethylene butene rubber, and ethylene octene rubber. And chemically synthesized synthetic rubbers such as butyl rubber, acrylic rubber, silicone rubber, chlorinated polyethylene, and natural rubber.
Examples of the thermoplastic elastomer used for the rubber component include urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based thermoplastic elastomers, and silicone-based thermoplastic elastomers.
Further, examples of the rubber component include those described in paragraphs 0124 to 0285 of International Publication No. 2014/162369, those described in paragraphs 0024 to 0068 of International Publication No. 2015/156323, and paragraphs of Japanese Patent No. 5401629. Those described in 0016 to 0020 can also be used.
The curable composition according to the present disclosure may include one rubber component alone or two or more rubber components.
　中でも、ゴム成分としては、分散安定性、並びに、得られる硬化物の耐擦傷性及び高温延伸性の観点から、アクリルゴムを含むことが好ましく、アクリルゴムを、ゴム成分の全質量に対し、５０質量％以上１００質量％以下含むことがより好ましい。 Among these, the rubber component preferably contains acrylic rubber from the viewpoints of dispersion stability and scratch resistance and high-temperature stretchability of the resulting cured product. More preferably, it is contained in an amount of at least 100% by mass.
　また、本開示に係る硬化性組成物において、ゴム成分は、分散安定性の観点から、粒子形状で含まれることが好ましい。すなわち、本開示に係る硬化性組成物は、ゴム成分として、ゴム粒子を含むことが好ましい。ゴム成分を粒子状で添加すると、ゴム粒子どうしの接触点が生成し連続相を形成すると考えられ、これがネットワークを形成し網目状になり、これがクッション層となって成型加工時の衝撃を和らげ、高温延伸性に優れるものと推定される。
　ゴム粒子の算術平均粒径は、分散安定性の観点から、０．０５μｍ以上１０μｍ以下であることが好ましく、０．１μｍ以上１μｍ以下であることがより好ましく、０．１μｍ以上０．８μｍ以下であることが更に好ましく、０．１μｍ以上０．５μｍ以下であることが特に好ましい。
　上記ゴム粒子の算術平均粒径は、硬化性組成物からはゴム粒子を分離して、顕微鏡（例えば、走査型電子顕微鏡）を用いて撮影された画像から任意に選択した１００個の微粒子の粒径（円相当径）を測定し、それらを算術平均して求めることができる。なお、円相当径とは、観察時の粒子の投影面積と同じ投影面積をもつ真円を想定したときの円の直径である。
　また、硬化物から上記ゴム粒子の算術平均粒径を求める方法としては、後述するゴム成分の定量方法における断面観察において、観察されるゴム粒子のうち、粒径の大きい１００個のゴム粒子の粒径（円相当径）を測定し、平均をとることにより算出することができる。 In the curable composition according to the present disclosure, the rubber component is preferably included in the form of particles from the viewpoint of dispersion stability. That is, the curable composition according to the present disclosure preferably includes rubber particles as a rubber component. When the rubber component is added in the form of particles, it is thought that the contact points between the rubber particles are generated and a continuous phase is formed, which forms a network and forms a mesh, which becomes a cushion layer and softens the impact during molding, It is estimated that it is excellent in high temperature stretchability.
The arithmetic average particle diameter of the rubber particles is preferably from 0.05 μm to 10 μm, more preferably from 0.1 μm to 1 μm, and more preferably from 0.1 μm to 0.8 μm from the viewpoint of dispersion stability. More preferably, it is more preferably 0.1 μm or more and 0.5 μm or less.
The arithmetic average particle diameter of the rubber particles is a particle of 100 fine particles arbitrarily selected from images taken using a microscope (for example, a scanning electron microscope) after separating the rubber particles from the curable composition. The diameter (equivalent circle diameter) is measured and can be obtained by arithmetic averaging. The equivalent circle diameter is a diameter of a circle assuming a true circle having the same projected area as the projected area of particles at the time of observation.
In addition, as a method for obtaining the arithmetic average particle diameter of the rubber particles from the cured product, 100 rubber particles having a large particle diameter among the observed rubber particles in the cross-sectional observation in the rubber component quantification method described later. It can be calculated by measuring the diameter (equivalent circle diameter) and taking the average.
　本開示に係る硬化性組成物におけるゴム成分の定量は、ゴム成分を分離して、測定する方法で実施できる。
　また、硬化物におけるゴム成分の定量は、下記の方法で実施できる。
　硬化物、又は、硬化物から採取したサンプルを切削して断面切片を作製し、０．５質量％四酸化ルテニウム水溶液に２５℃で１５時間浸漬してルテニウム染色し、透過型電子顕微鏡（ＴＥＭ）により、３万倍で断面切片を観察する。
　ゴム成分は、ルテニウム染色により暗く染色されるため、この面積を観測し、観測視野の面積で割りゴム成分の含有率を求める。
　任意に選んだ１０視野において、上記測定を行い、この平均値をゴム成分の含有率とする。 The quantification of the rubber component in the curable composition according to the present disclosure can be performed by a method in which the rubber component is separated and measured.
Moreover, the fixed quantity of the rubber component in hardened | cured material can be implemented with the following method.
Cut a cured product or a sample taken from the cured product to prepare a cross-section, soak it in a 0.5% by mass ruthenium tetroxide aqueous solution at 25 ° C. for 15 hours, stain with ruthenium, and use a transmission electron microscope (TEM). The cross section is observed at 30,000 times.
Since the rubber component is dyed darkly by ruthenium dyeing, this area is observed, and the content of the rubber component is obtained by dividing by the area of the observation field.
The above measurement is carried out in 10 arbitrarily selected visual fields, and this average value is taken as the rubber component content.
　このような特定量のゴム成分を含む硬化膜（硬化樹脂層）は、基材の上に形成して使用することが好ましく、例えば、基材上に成型せずにフラットな膜を形成すると、ハードコート膜として使用できる。また、本開示に係る硬化性組成物を硬化した本開示に係る硬化物は、伸長性に優れるため、フラット膜を立体成型することも好ましい。
　更に、基材上に本開示に係る硬化性組成物を塗布した後、凹凸等の形状を付与することも好ましい。例えば、半円柱状に賦型するとレンチキュラーレンズとして使用でき、三角柱状に賦型するとプリズムシート又は輝度向上膜として使用でき、半球状に多数賦型するとマイクロレンズシートとして使用でき、また、国際公開第２０１５／１０２１００号の図４Ａのようなノコギリ刃状の形状を同心円状に形成するとプリズムシートとして利用できる。 Such a cured film containing a specific amount of rubber component (cured resin layer) is preferably used by forming it on a substrate, for example, when a flat film is formed on the substrate 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.
＜Ｎ－ビニル化合物＞
　本開示に係る硬化性組成物は、Ｎ－ビニル化合物を含有することが好ましい。Ｎ－ビニル化合物は、基材との密着性の向上に寄与し、かつ、硬化物の、成型時における高温延伸性をより向上させる。
　上記Ｎ－ビニル化合物としては、単官能Ｎ－ビニル化合物であることが好ましく、また、環構造を有することが好ましい。
　中でも、Ｎ－ビニル化合物としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、Ｎ－ビニルピロリドン、及び、Ｎ－ビニルカプロラクタムよりなる群から選ばれた少なくとも１種の化合物であることが好ましく、Ｎ－ビニルピロリドンがより好ましい。
　Ｎ－ビニル化合物のうち、Ｎ－ビニルピロリドンの例としては、Ｎ－ビニル－２－ピロリドン等が挙げられる。また、Ｎ－ビニルカプロラクタムの例としては、Ｎ－ビニル－ε－カプロラクタム等が挙げられる。 <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 substrate, and further improves the high temperature stretchability of the cured product at the time of molding.
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-vinyl pyrrolidone and N-vinyl caprolactam from the viewpoint of scratch resistance and high-temperature stretchability 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.
　本開示に係る硬化性組成物は、Ｎ－ビニル化合物を、１種単独で含んでいても、２種以上を含んでいてもよい。
　本開示に係る硬化性組成物におけるＮ－ビニル化合物の含有量としては、得られる硬化物の耐擦傷性及び高温延伸性、並びに、シリンドリカルレンズの形状保持性の観点から、硬化性組成物の全質量に対して、３質量％以上６０質量％以下が好ましく、５質量％以上５０質量％以下がより好ましく、５質量％以上４０質量％以下が更に好ましく、２０質量％以上３５質量％以下が特に好ましい。 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 scratch resistance and high-temperature stretchability of the resulting cured product and shape retention of the cylindrical lens. 3 mass% or more and 60 mass% or less are preferable with respect to mass, 5 mass% or more and 50 mass% or less are more preferable, 5 mass% or more and 40 mass% or less are still more preferable, and 20 mass% or more and 35 mass% or less are especially. preferable.
＜末端に（メタ）アクリロイル基を有する樹脂＞
　本開示に係る硬化性組成物は、末端に（メタ）アクリロイル基を有する樹脂を含有することが好ましい。上記樹脂は、分子鎖の末端に（メタ）アクリロイル基を有しているため、イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物等の多官能重合性化合物と併用することで、硬化性組成物全体における架橋密度を制御し、得られる硬化物の耐擦傷性及び高温延伸性により優れる。 <Resin having a (meth) acryloyl group at the terminal>
The curable composition according to the present disclosure preferably contains 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, it is cured by using in combination with a polyfunctional polymerizable compound such as a bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure. The crosslink density in the entire composition is controlled, and the resulting cured product is more excellent in scratch resistance and high temperature stretchability.
　上記樹脂としては、末端に（メタ）アクリロイル基を有するポリマーであればよく、例えば、（メタ）アクリル樹脂、ポリスチレン、ポリスチレン・メタクリレート（ＭＳ樹脂）、ポリスチレン・アクリロニトリル（ＡＳ樹脂）、ポリプロピレン、ポリエチレン、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタレート、ポリ塩化ビニル（ＰＶＣ）、熱可塑性エラストマー、又は、これらの共重合体、シクロオレフィンポリマー等の、主鎖構造の末端に（メタ）アクリロイル基を少なくとも１つ有するポリマーを挙げることができる。中でも、得られる硬化物の耐擦傷性及び高温延伸性の観点から、末端に（メタ）アクリロイル基を有する（メタ）アクリル樹脂、又は、末端に（メタ）アクリロイル基を有するポリスチレンが好ましく、末端に（メタ）アクリロイル基を有する（メタ）アクリル樹脂がより好ましい。
　また、末端に（メタ）アクリロイル基を有する（メタ）アクリル樹脂としては、耐擦傷性の観点から、末端に（メタ）アクリロイル基を有するポリメチルメタクリレートが好ましい。
　更に、末端に（メタ）アクリロイル基を有する樹脂は、末端にメタクリロイル基を有することが好ましい。
　また、末端に（メタ）アクリロイル基を有する樹脂は、主鎖の末端に（メタ）アクリロイル基を有する樹脂であることが好ましく、主鎖の片末端に（メタ）アクリロイル基を有する樹脂であることがより好ましい。
　なお、本開示において、「主鎖」とは樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは主鎖から枝分かれしている炭素鎖を表す。 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 scratch resistance and high temperature stretchability of the obtained 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, and the terminal is preferable. A (meth) acrylic resin having a (meth) acryloyl group is more preferred.
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 scratch 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. .
　末端に（メタ）アクリロイル基を有する樹脂としては、例えば、東亞合成（株）製のマクロモノマーシリーズ（例：マクロモノマーＡＡ－６（メタクリロイル基を有するポリメチルメタクリレート）、マクロモノマーＡＳ－６又はＡＳ－６Ｓ（メタクリロイル基を有するポリスチレン）、マクロモノマーＡＮ－６Ｓ（メタクリロイル基を有するポリスチレン・アクリロニトリル）、マクロモノマーＡＢ－６（メタクリロイル基を有するポリブチルメタクリレート）等を用いることができる。 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.
　末端に（メタ）アクリロイル基を有する樹脂の数平均分子量としては、得られる硬化物の高温延伸性の観点から、１，０００以上１０，０００以下が好ましく、３，０００以上１０，０００以下がより好ましく、５，０００以上１０，０００以下が更に好ましい。
　なお、本開示における樹脂は、数平均分子量１，０００以上のものであることが好ましい。 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, from the viewpoint of high-temperature stretchability 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.
　末端に（メタ）アクリロイル基を有する樹脂のガラス転移温度（Ｔｇ）としては、得られる硬化物の耐擦傷性の観点から、５０℃以上が好ましく、８０℃以上がより好ましい。また、得られる硬化物の樹脂基材への密着性及び高温延伸性の観点から、Ｔｇは２５０℃未満が好ましく、２００℃以下がより好ましい。
　本開示においては、末端に（メタ）アクリロイル基を有する樹脂等のガラス転移温度（Ｔｇ）は、ＡＳＴＭ　Ｄ３４１８－８に準拠して、示差走査熱量計により測定するものとする。 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 scratch resistance of the resulting cured product. In addition, from the viewpoint of adhesion of the obtained cured product to the resin substrate and high temperature stretchability, Tg is preferably less than 250 ° C, and more preferably 200 ° C or less.
In the present disclosure, the glass transition temperature (Tg) of a resin having a (meth) acryloyl group at the terminal is measured by a differential scanning calorimeter in accordance with ASTM D3418-8.
　本開示に係る硬化性組成物は、末端に（メタ）アクリロイル基を有する樹脂を、１種単独で含んでいても、２種以上を含んでいてもよい。
　本開示に係る硬化性組成物における末端に（メタ）アクリロイル基を有する樹脂の含有量としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、硬化性組成物の全質量に対して、０．５質量％以上５０質量％以下が好ましく、５質量％以上４５質量％以下がより好ましく、１５質量％以上３５質量％以下が特に好ましい。 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 based on the total mass of the curable composition from the viewpoint of scratch resistance and high-temperature stretchability of the obtained cured product. 0.5 mass% or more and 50 mass% or less is preferable, 5 mass% or more and 45 mass% or less are more preferable, and 15 mass% or more and 35 mass% or less are especially preferable.
　また、本開示に係る硬化性組成物は、上述した以外の他のエチレン性不飽和化合物を含んでいてもよい。
　他のエチレン性不飽和化合物としては、公知の重合性化合物、特に公知のエチレン性不飽和化合物を用いることができる。 Moreover, the curable composition which concerns on this indication may contain other ethylenically unsaturated compounds other than having mentioned above.
As another ethylenically unsaturated compound, a known polymerizable compound, particularly a known ethylenically unsaturated compound can be used.
　本開示に係る硬化性組成物は、他のエチレン性不飽和化合物を、１種単独で含んでいても、２種以上を含んでいてもよい。
　本開示に係る硬化性組成物は、得られる硬化物の高温延伸性の観点から、他のエチレン性不飽和化合物を、含有しないか、又は、その含有量が、硬化性組成物の全質量に対して、２０質量％以下であることが好ましく、含有しないか、又は、その含有量が、硬化性組成物の全質量に対して、１０質量％以下であることがより好ましく、含有しないか、又は、その含有量が、硬化性組成物の全質量に対して、５質量％以下であることが更に好ましく、含有しないか、又は、その含有量が、硬化性組成物の全質量に対して、１質量％以下であることが特に好ましい。 The curable composition concerning this indication may contain the other ethylenically unsaturated compound individually by 1 type, or may contain 2 or more types.
The curable composition according to the present disclosure does not contain other ethylenically unsaturated compounds from the viewpoint of high-temperature stretchability of the resulting cured product, or the content thereof is the total mass of the curable composition. On the other hand, it is preferably 20% by mass or less, not contained, or the content thereof is more preferably 10% by mass or less, based on the total mass of the curable composition. Or it is further more preferable that the content is 5 mass% or less with respect to the total mass of a curable composition, or it does not contain, or the content is with respect to the total mass of a curable composition. 1% by mass or less is particularly preferable.
＜重合開始剤＞
　本開示に係る硬化性組成物は、硬化性の観点から、重合開始剤を含むことが好ましい。
　重合開始剤としては、公知の光重合開始剤、及び、公知の熱重合開始剤を用いることができる。
　中でも、得られる硬化物の耐擦傷性及び高温延伸性の観点から、光重合開始剤が好ましく、光ラジカル重合開始剤がより好ましい。 <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 scratch resistance and high-temperature stretchability of the resulting cured product, a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.
　光ラジカル重合開始剤としては、構造上の制限は特になく、例えば、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、１－ヒドロキシシクロヘキシルフェニルケトン、１－［４－（２－ヒドロキシエトキシ）フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル］フェニル｝－２－メチルプロパン－１－オン、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン等を挙げることができる。 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.
　光ラジカル重合開始剤は、上市されている市販品を用いてもよく、市販品の具体例として、ＢＡＳＦ社製のイルガキュアシリーズ（例：ＩＲＧＡＣＵＲＥ　ＴＰＯ、ＩＲＧＡＣＵＲＥ　８１９、ＩＲＧＡＣＵＲＥ　６５１、ＩＲＧＡＣＵＲＥ　１８４、ＩＲＧＡＣＵＲＥ　１１７３、ＩＲＧＡＣＵＲＥ　２９５９、ＩＲＧＡＣＵＲＥ　１２７、ＩＲＧＡＣＵＲＥ　９０７等）が挙げられる。 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.).
　熱重合開始剤としては、公知のアゾ系化合物、公知の過酸化物系化合物等が挙げられる。上記アゾ系化合物としては、アゾビス系化合物を挙げることができる。また、上記過酸化物系化合物としては、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネート等を挙げることができる。 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.
　本開示に係る硬化性組成物は、重合開始剤を、１種単独で含んでいても、２種以上を含んでいてもよい。
　本開示に係る硬化性組成物における重合開始剤の含有量としては、得られる硬化物の耐擦傷性及び高温延伸性の観点から、硬化性組成物の全質量に対して、０．０５質量％以上１０質量％以下が好ましく、０．１質量％以上１０質量％以下がより好ましく、０．１質量％以上５質量％以下が更に好ましく、０．５質量％以上３質量％以下が特に好ましい。 The curable composition concerning this indication may contain the polymerization initiator individually by 1 type, or may contain 2 or more types.
The content of the polymerization initiator in the curable composition according to the present disclosure is 0.05% by mass with respect to the total mass of the curable composition from the viewpoint of scratch resistance and high temperature stretchability of the obtained cured product. 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.
－他の成分－
　本開示に係る硬化性組成物は、上記の成分以外に、必要に応じて、有機溶剤、無機粒子等の他の成分が含まれていてもよい。
　有機溶剤としては、トルエン、メチルエチルケトン等が挙げられる。本開示に係る硬化性組成物は、上記の（メタ）アクリル化合物等の重合性化合物を含有するため、重合性化合物が溶剤としての機能を兼ね、別途有機溶剤を含有していなくてもよい。
　無機粒子としては、二酸化珪素（シリカ）等のいわゆるフィラーと称される粒子が挙げられる。無機粒子の例として、上市されている市販品として日産化学工業（株）製のオルガノシリカゾルＭＥＫ－ＳＴシリーズ（例：ＭＥＫ－ＳＴ－４０、ＭＥＫ－ＳＴ－Ｌ等）が挙げられる。 -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.
　本開示に係る硬化性組成物は、活性エネルギー線により硬化可能な組成物であることが好ましい。「活性エネルギー線」とは、その照射により硬化性組成物中に重合開始種を発生させるエネルギーを付与できる放射線であり、α線、γ線、Ｘ線、紫外線、可視光線、電子線などを包含する。中でも、硬化感度及び装置の入手容易性の観点から、紫外線及び電子線が好ましく、紫外線がより好ましい。
　また、本開示に係る硬化性組成物は、水及び揮発性溶剤をできるだけ含有しないことが好ましく、含有していたとしても、硬化性組成物の全質量に対し、５質量％以下であることが好ましく、１質量％以下であることがより好ましく、０．５質量％以下であることが更に好ましい。 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.
Moreover, it is preferable that the curable composition according to the present disclosure does not contain water and a volatile solvent as much as possible, and even if it is contained, it may be 5% by mass or less based on the total mass of the curable composition. Preferably, it is 1 mass% or less, more preferably 0.5 mass% or less.
　また、本開示における硬化性組成物は、得られる硬化物のガラス転移温度（Ｔｇ）が、得られる硬化物の耐擦傷性及び高温延伸性の観点から、９０℃を超えることが好ましく、９５℃以上２００℃以下であることがより好ましく、１００℃以上１８０℃以下であることが更に好ましい。 Moreover, the curable composition in the present disclosure preferably has a glass transition temperature (Tg) of the obtained cured product of more than 90 ° C. from the viewpoint of scratch resistance and high temperature stretchability 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.
（硬化物、及び、光学部材）
　本開示に係る硬化物は、本開示に係る硬化性組成物を硬化してなる硬化物（本開示に係る硬化性組成物の硬化物）である。
　本開示に係る硬化物は、光学部材として好適に用いることができ、凸状レンズとしてシリンドリカルレンズ、プリズム、半球状のマイクロレンズ、フレネルレンズなどがより好適に用いることができ、複数の凸状レンズ（シリンドリカルレンズ）が並列したレンチキュラーレンズとして特に好適に用いることができる。
　また、本開示に係る光学部材は、本開示に係る硬化物を有するものである。
　本開示に係る硬化物の製造方法は、特に制限はなく、本開示に係る硬化性組成物を準備する工程、及び、上記硬化性組成物を硬化する工程を含む製造方法であることが好ましい。また、例えば、本開示に係る硬化性組成物の硬化は、光硬化（活性エネルギー線の照射による硬化）であっても、熱硬化であってもよいが、光硬化であることが好ましい。 (Cured product and optical member)
The cured product according to the present disclosure is a cured product (cured product of the curable composition according to the present disclosure) obtained by curing the curable composition according to the present disclosure.
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 which concerns on this indication has the hardened | cured material which concerns on this indication.
The manufacturing method of the hardened | cured material which concerns on this indication does not have a restriction | limiting in particular, It is preferable that it is a manufacturing method including the process of preparing the curable composition which concerns on this indication, and the process of hardening | curing the said curable composition. Further, for example, the curing of the curable composition according to the present disclosure may be photocuring (curing by irradiation with active energy rays) or heat curing, but is preferably photocuring.
（積層シート、及び、レンチキュラーシート）
　本開示に係る積層シートは、本開示に係る硬化性組成物の硬化物を有する積層シートであればよく、具体的には、基材及び基材上に本開示に係る硬化性組成物の硬化物を少なくとも有するものであることが好ましい。
　また、本開示に係る積層シートは、本開示に係る硬化物を有する積層シートである。
　中でも、本開示に係る積層シートは、樹脂基材と、上記樹脂基材の少なくとも一方の面に設けられた本開示に係る硬化性組成物の硬化物とを有することが好ましい。
　本開示に係る積層シートが有する本開示に係る硬化性組成物の硬化物の形状は、特に制限はなく、所望の形状であればよく、膜状であっても、後述するシリンドリカルレンズのような半円柱状のものが並んだ形状であっても、マイクロレンズのように半球状のものが並んだ形状であってもよい。
　本開示に係る積層シートは、ハードコート膜を有する積層シート、立体成型用積層シート、輝度向上膜を有する積層シート、レンチキュラーシート、プリズムシート、マイクロレンズシート、フレネルレンズシート、フライアイレンズ等として好適に用いることができる。 (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.
　本開示に係るレンチキュラーシートは、本開示に係る硬化性組成物を硬化してなる硬化物を有する。
　本開示に係るレンチキュラーシートにおける上記硬化物は、レンチキュラーレンズであることが好ましい。
　また、本開示に係るレンチキュラーシートは、樹脂基材と、樹脂基材の少なくとも一方面に配置されたシリンドリカルレンズと、を有することが好ましく、上記樹脂基材のシリンドリカルレンズを有する側の反対側に記録層を有することがより好ましい。また、記録層に例えばインクジェット法等の公知の記録方法により画像（以下、加飾画像ともいう。）を付与することができる態様が好ましい。 The lenticular sheet according to the present disclosure has a cured product obtained by curing the curable composition according to the present disclosure.
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.
　本開示に係るレンチキュラーシートは、例えば図１に示すように、記録層を付設してレンチキュラー画像が付される構成のレンチキュラー加飾シートであってもよい。レンチキュラー加飾シートは、レンチキュラー表示に適した画像上に、半円筒形の表面を有する凸状のシリンドリカルレンズが並列したレンチキュラーレンズを有することにより、見る角度によって異なる画像を表示する表示媒体（レンチキュラー表示体）である。図１は、レンチキュラー加飾シート（レンチキュラーシート）の一例を示す概略図である。 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).
　図１に示すレンチキュラー加飾シート１０は、半円筒形状の表面を有する複数の凸状レンズ（シリンドリカルレンズ）１２Ａが並列したレンチキュラーレンズ１２と、レンチキュラーレンズ１２の凸状レンズ１２Ａの半円筒形状の表面とは反対側（裏面側ともいう。）に配置されたレンチキュラー画像１４と、を有している。
　なお、ｘ方向は、レンズの幅方向を示し、ｙ方向は、レンズの長手方向を示している。 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.
　本開示に係るレンチキュラーシートは、半円筒形状の表面を有する複数の凸状レンズ（シリンドリカルレンズ）が並列したレンチキュラーレンズ層を有していることが好ましい。シリンドリカルレンズ１本当たりの幅は、特に限定されず、目的によってレンズのピッチ幅を選択すればよい。シリンドリカルレンズ１本当たりの幅は、通常、１インチ（２．５４ｃｍ）当たりのレンズ数を表すＬＰＩ（Ｌｉｎｅ　Ｐｅｒ　Ｉｎｃｈ）で表されることが多い。例えば１００ＬＰＩは、１インチ当たり１００本（１００列）のシリンドリカルレンズが並列することを示しており、レンズのピッチは２５４μｍである。１インチ当たりの線数（レンズの配列数）は、値が大きいほどレンズのピッチは小さくなり、精細度が向上する。
　精細度の低いレンチキュラーシート（例えば６０ＬＰＩなど）は、観察位置が比較的遠い図柄を表示するポスターなどに使うには適している。名刺など小さい文字情報を読ませることを目的とする場合は、レンチキュラーレンズ層を構成するレンズが、２．５４ｃｍ（１インチ）当たり１００列以上並列していることが好ましい。一方、レンチキュラー画像の解像度の観点から、レンチキュラーレンズ層を構成する凸状レンズの配列数は、２．５４ｃｍ当たり２００列（２００ＬＰＩ）以下であることがより好ましい。 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.
　従来、レンチキュラー材料は、シート又はフィルム等の形態で用いられることが多く、立体形状にして用いる試みは少ない。ところが、従来のレンチキュラーシートは、例えばレンズ部分に用いられる樹脂成分は熱可塑性樹脂であることが一般的であり、立体形状に成型する場合の熱で変形しやすく、形状を維持し得る耐熱性が不足しやすい。一方、樹脂成分として熱硬化性樹脂を用いる技術も提案されているが、熱硬化性樹脂は一般に、架橋構造を有するために変形させる場合の延伸性が乏しい傾向にある。そのため、立体成型時において高温に曝された場合の熱変形こそ生じにくいが、立体成型時に延ばされた際に亀裂（クラック）等を招来しやすい懸念がある。
　本開示に係るレンチキュラーシートは、本開示に係る硬化性組成物を硬化してなるレンチキュラーレンズを有することにより、高温延伸性に優れ、立体成型性に優れる。 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 includes a lenticular lens obtained by curing the curable composition according to the present disclosure, and thus has excellent high-temperature stretchability and excellent three-dimensional moldability.
＜樹脂基材＞
　本開示に用いられる樹脂基材は、支持材としての基材であり、任意の樹脂を目的等に応じて選択することができる。樹脂基材は、シート状又はフィルム状の基材を好適に用いることができる。
　樹脂基材の例としては、アクリル樹脂、ポリエステル樹脂等のシート又はフィルムが挙げられる。
　樹脂基材の厚みは、特に制限はなく、５０μｍ以上３００μｍ以下の範囲が好ましく、高温で均一に成型（賦形）する観点から、５０μｍ以上２００μｍ以下の範囲がより好ましい。上記範囲であると、樹脂基材が破れにくく、成型加工時における取扱い中（例えば、運搬中）に割れが発生しにくく、３次元成型時にも割れにくい。 <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.
　樹脂基材は、上市されている市販品を用いてもよく、例えば、三菱レイヨン（株）製のアクリル樹脂フィルム（アクリプレンＨＢＳ０１０Ｐ、厚み：１２５μｍ）、東レ（株）製のポリエチレンテレフタレート樹脂フィルム（ルミラーＳ１０、厚み：１００μｍ）、帝人化成（株）製のポリカーボネート樹脂フィルム（ユーピロンＨ－３０００、厚み１２５μｍ）等を用いることができる。 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.
＜記録層＞
　本開示に係るレンチキュラーシートにおいて、樹脂基材のシリンドリカルレンズを有する側の反対側には、レンチキュラー表示される画像（レンチキュラー画像）を記録するための記録層を有していてもよい。
　樹脂基材の記録層が設けられる面は、樹脂基材と記録層との接着力を高める観点から、表面処理（例えばコロナ放電処理等）が施されてもよい。記録層は、例えば、記録層を形成するための調製液を樹脂基材に付与することにより設けられてもよい。
　調製液の付与は、例えば、塗布により行うことができる。
　調製液は、記録層を形成するための固形成分と溶媒とを含むことが好ましい。記録層は、樹脂を含むことが好ましく、樹脂の少なくとも一部は架橋剤で架橋されていることが好ましい。したがって、調製液に含まれる固形成分として樹脂及び架橋剤を含む態様が好ましい。
　樹脂としては、ポリエステル、アクリル樹脂及びウレタン樹脂よりなる群から選択された少なくとも１種の樹脂であることが好ましく、特にオフセット印刷により視差画像を形成する場合に有利である。 <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.
　図１では、レンチキュラー画像１４は、２つの表示用画像をそれぞれ別々に表示するための表示用画像列１４Ａ，１４Ｂと、隣接する表示用画像列１４Ａ，１４Ｂの間に挿入された補間画像列１４Ｃと、を含む画像列群から構成されている。
　具体的には、各表示用画像からストライプ状に抽出された表示用画像列１４Ａ，１４Ｂが対応する位置の凸状レンズ１２Ａごとに隣接して配列されており、隣接する表示用画像列１４Ａ，１４Ｂの間に、隣接する表示用画像列１４Ａ，１４Ｂの色が互いに異なる位置において、隣接する表示用画像列１４Ａ，１４Ｂの一方の色と他方の色との間にある色（補間色）を有する補間画像列１４ｃが挿入されている。 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.
（３次元構造物）
　本開示に係る３次元構造物は、本開示に係る積層シートの（好ましくは、熱成型又は真空成型などの手法により立体成型した）立体成型物である。
　また、本開示に係る３次元構造物は、本開示に係るレンチキュラーシートの立体成型物であることが好ましい。
　本開示に係る３次元構造物は、本開示に係る積層シートを用いて製造されたものであれば、立体成型方法に特に制限されるものではない。
　本開示に係るレンチキュラーシートを用いる３次元構造物の製造方法としては、例えば、本開示に係る硬化性組成物を成型し、活性エネルギー線を照射して硬化させ、樹脂基材上にシリンドリカルレンズを有するレンチキュラーシートを作製する工程（以下、「レンチキュラーシート作製工程」ともいう。）と、作製されたレンチキュラーシートを立体成型（好ましくは真空成型或いは加圧成型）することでレンチキュラーの立体成型体を得る工程（以下、「立体成型工程」ともいう。）とを含む方法が好ましく挙げられる。 (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 to the three-dimensional molding method as long as the three-dimensional structure 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.
　比較的高い温度に曝される成型に際して、立体成型性に優れる本開示に係るレンチキュラーシートが用いられるので、成型の際の熱で溶融して形状変形を生じにくく、かつ、成型時に延ばされた際に生じやすい亀裂（クラック）等の発生も抑えられる。 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.
－レンチキュラーシート作製工程－
　上記レンチキュラーシート作製工程では、本開示に係る硬化性組成物を成型し、活性エネルギー線を照射して硬化させ、樹脂基材上にシリンドリカルレンズを有するレンチキュラーシートを作製する。
　本開示に係る硬化性組成物の詳細については、既述の通りであり、好ましい態様も同様である。 -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.
　また、本開示に係る硬化性組成物は、光ラジカル重合開始剤を含有することが好ましい。活性エネルギー線が照射されることでラジカルが発生し、重合性化合物の重合反応が進行することによって硬化する。これにより、本開示に係る硬化性組成物の硬化物であるシリンドリカルレンズが形成される。
　シリンドリカルレンズの成型に当たり、硬化性組成物を硬化させる前にあらかじめ樹脂基材を硬化性組成物と接触させた後、硬化性組成物の硬化を行うようにしてもよい。樹脂基材と硬化性組成物とを接触させた状態で硬化させることで、硬化収縮による密着性の向上がより期待でき、組成に由来する密着効果に加え、樹脂基材に対する密着性の向上がより効果的に図られる。
　シリンドリカルレンズの樹脂基材に対する密着の観点から、樹脂基材に接触された硬化性組成物を硬化させることで、密着性により優れたシリンドリカルレンズを有するレンチキュラーシートが得られる。 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.
　本工程では、硬化前にまず、硬化性組成物を、目的とするシリンドリカルレンズの形状に成型する。成型は、目的とする形状が得られる方法であれば特に制限されないが、成型効率及び成型精度の観点から、金型又は木型等の型を用いた成型が好ましい。
　具体的には、例えば、所望とするレンズ形状に加工された金型を用意し、金型に硬化性組成物を流し込み、必要に応じて乾燥させた後、硬化性組成物を硬化させてもよい。これにより、目的とする形状に成型された成型物が安定的に得られる。 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.
　活性エネルギー線を発生させるための光源としては、水銀ランプ、メタルハライドランプ、ＵＶ蛍光灯、ガスレーザー、固体レーザー等が広く知られている。また、光源として半導体紫外発光デバイスを適用してもよく、小型、高寿命、高効率、及び低コストの点で、ＬＥＤ（Light Emitting Diode）及びＬＤ（Laser Diode）も好適である。
　光源としては、メタルハライドランプ、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、水銀キセノンランプ、ＬＥＤ又は青紫レーザーが好ましい。中でも、波長３６５ｎｍ、４０５ｎｍ若しくは４３６ｎｍの光照射が可能な超高圧水銀ランプ、波長３６５ｎｍ、４０５ｎｍ若しくは４３６ｎｍの光照射が可能な高圧水銀ランプ、波長３６５ｎｍ、４０５ｎｍ若しくは４３６ｎｍの光照射が可能な水銀キセノンランプ、又は、波長３５５ｎｍ、３６５ｎｍ、３８５ｎｍ、３９５ｎｍ若しくは４０５ｎｍの光照射が可能なＬＥＤがより好ましく、波長３５５ｎｍ、３６５ｎｍ、３８５ｎｍ、３９５ｎｍ又は４０５ｎｍの光照射が可能なＬＥＤが特に好ましい。 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 ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury xenon 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, and a mercury xenon lamp capable of irradiating with a wavelength of 365 nm, 405 nm, or 436 nm. Alternatively, an LED capable of 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 light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is particularly preferable.
　活性エネルギー線の照射量は、レンチキュラーレンズ用硬化性組成物の組成及び使用量により適宜選択すればよく、０．３Ｊ／ｃｍ２以上５Ｊ／ｃｍ２以下とすることが好ましい。 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.
　活性エネルギー線の照射には、上記の活性エネルギー線を照射可能な光源を備えた公知の装置を選択して行うことができる。例えば、ＨＯＹＡ　ＣＡＮＤＥＯ　ＯＰＴＲＯＮＩＣＳ（株）製のＥＸＥＣＵＲＥ　３０００等の紫外線（ＵＶ）照射装置を用いてもよい。 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.
－立体成型工程－
　上記立体成型工程では、レンチキュラーシート作製工程で作製されたレンチキュラーシートを立体成型する。本工程では、レンチキュラーシートを成型できればよく、金型等の型を用いた成型加工に供されてもよい。 -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.
　立体成型は、熱成型又は真空成型などが好適に挙げられる。
　真空成型する方法としては、特に制限されるものではないが、立体成型を、真空下の加熱した状態で行う方法が好ましい。
　真空とは、室内を真空引きし、１００Ｐａ以下の真空度とした状態を指す。
　立体成型する際の温度は、６０℃以上の温度域が好ましく、８０℃以上の温度域がより好ましく、１００℃以上の温度域が更に好ましい。立体成型する際の温度の上限は、２００℃が好ましい。
　立体成型する際の温度とは、立体成型に供されるレンチキュラーシートの温度を指し、レンチキュラーシートの表面に熱電対を付すことで測定される。 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.
　上記の真空成型は、成型分野で広く知られている真空成型技術を利用して行うことができ、例えば、日本製図器工業（株）製のＦｏｒｍｅｃｈ５０８ＦＳを用いて真空成型してもよい。 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.
　以下、本発明の実施形態を実施例により更に具体的に説明するが、本開示はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 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.
　以下に実施例及び比較例で使用した化合物を示す。 The compounds used in Examples and Comparative Examples are shown below.
＜中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物＞
・Ｍ－３１５（東亞合成（株）製：イソシアヌル酸ＥＯ変性トリアクリレート（イソシアヌル環構造を有する３官能アクリレート化合物）
・Ｍ－２１５（東亞合成（株）製：イソシアヌル酸ＥＯ変性ジアクリレート（イソシアヌル環構造を有する２官能アクリレート化合物）
・ＴＰ－Ａ（合成物、下記化合物）
　ＴＰ－Ａは以下の手順で合成した。 <Bifunctional or trifunctional (meth) acrylate compound whose central skeleton has a 3-fold symmetry axis>
M-315 (manufactured by Toagosei Co., Ltd .: isocyanuric acid EO-modified triacrylate (trifunctional acrylate compound having an isocyanuric ring structure)
M-215 (manufactured by Toagosei Co., Ltd .: isocyanuric acid EO-modified diacrylate (bifunctional acrylate compound having an isocyanuric ring structure))
・ TP-A (composite, the following compound)
TP-A was synthesized by the following procedure.
１．ブロモアクリレートの合成
　６－ブロモ－１－ヘキサノール７．２ｇ、及び、酢酸エチルの溶液２０ｍｌの溶液を内温５℃以下に冷却したのち、トリエチルアミン２．８ｍｌを添加した。その後、塩化アクリロイル４．０ｇ（３．６ｍｌ）及び酢酸エチル５ｍｌの溶液を、内温０～８℃にて滴下したのち、内温を２５℃まで上げ、４時間撹拌した。
水４０ｍｌ、及び、濃塩酸４ｍｌを加え、洗浄した。有機層を飽和食塩水５０ｍｌで洗浄、分液し、続いて、飽和食塩水５０ｍｌ、７．５質量％重曹水５ｍｌで洗浄、分液した。有機層を無水硫酸マグネシウムで乾燥し、６０分間撹拌した。硫酸マグネシウム濾別した後、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）を１２５ｇ添加し、酢酸エチル溶媒を減圧留去することで、化合物ブロモアクリレートのＤＭＡｃ溶液を得た。 1. Synthesis of Bromoacrylate A solution of 7.2 g of 6-bromo-1-hexanol and 20 ml of ethyl acetate was cooled to an internal temperature of 5 ° C. or lower, and 2.8 ml of triethylamine was added. Thereafter, a solution of 4.0 g (3.6 ml) of acryloyl chloride and 5 ml of ethyl acetate was added dropwise at an internal temperature of 0 to 8 ° C., and then the internal temperature was raised to 25 ° C. and stirred for 4 hours.
40 ml of water and 4 ml of concentrated hydrochloric acid were added and washed. The organic layer was washed with 50 ml of saturated brine and separated, and then washed and separated with 50 ml of saturated brine and 5 ml of 7.5% by mass sodium bicarbonate. The organic layer was dried over anhydrous magnesium sulfate and stirred for 60 minutes. After magnesium sulfate was filtered off, 125 g of N, N-dimethylacetamide (DMAc) was added, and the ethyl acetate solvent was distilled off under reduced pressure to obtain a DMAc solution of the compound bromoacrylate.
２．ＴＰ－Ａの合成
　ブロモアクリレートのＤＭＡｃ溶液１２９ｇに２，３，６，７，１０，１１－ヘキサヒドロキシトリフェニレン０．９２ｇ及び炭酸カリウム２．９ｇを添加し、窒素雰囲気下で内温を１００℃まで上げ、４８時間撹拌した。酢酸エチル１００ｍｌで洗浄、分液した。有機層を無水硫酸マグネシウムで乾燥し、６０分間撹拌した。硫酸マグネシウム濾別した後、酢酸エチル溶媒を減圧留去しＴＰ－Ａを得た。１Ｈ－ＮＭＲでトリフェニレン骨格とアクリロキシ基とのモル当量が１：３であることを確認した。 2. Synthesis of TP-A 0.92 g of 2,3,6,7,10,11-hexahydroxytriphenylene and 2.9 g of potassium carbonate were added to 129 g of a bromoacrylate DMAc solution, and the internal temperature was increased to 100 ° C. in a nitrogen atmosphere. And stirred for 48 hours. Wash and separate with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and stirred for 60 minutes. After filtration through magnesium sulfate, the ethyl acetate solvent was distilled off under reduced pressure to obtain TP-A. It was confirmed by 1 H-NMR that the molar equivalent of the triphenylene skeleton and the acryloxy group was 1: 3.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記式中、６つのＲＴのうち、平均３つがヒドロキシ基を表し、平均３つが６－アクリロキシヘキシル基を表す。 In the above formula, among the six R T, the mean three are a hydroxy group, an average of three represents a 6-acryloxy-hexyl group.
＜他の多官能（メタ）アクリレート化合物＞
・Ｍ－２１１Ｂ（東亞合成（株）製：ＥＯ変性ビスフェノールＡのジアクリレート体）
・Ａ－ＴＭＰＴ（新中村化学工業（株）製：トリメチロールプロパントリアクリレート）
・ｋａｙａｒａｄＤＰＨＡ（日本化薬（株）製：ジペンタエリスリトールヘキサアクリレート）
・Ａ－ＤＣＰ（新中村化学工業（株）製：トリシクロデカンジメタノールジアクリレート）
・エポキシエステル３０００Ａ（共栄社化学（株）製：ビスフェノールＡジグリシジルエーテルのアクリル酸付加物） <Other polyfunctional (meth) acrylate compounds>
M-211B (manufactured by Toagosei Co., Ltd .: EO-modified bisphenol A diacrylate)
・ A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd .: trimethylolpropane triacrylate)
・ KayradDPHA (Nippon Kayaku Co., Ltd .: dipentaerythritol hexaacrylate)
A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd .: tricyclodecane dimethanol diacrylate)
Epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd .: bisphenol A diglycidyl ether acrylic acid adduct)
＜単官能（メタ）アクリレート化合物＞
・ＦＡ－５１３ＡＳ（日立化成工業（株）製ファンクリルＦＡ－５１３ＡＳ、ジシクロペンタニルアクリレート、ホモポリマーのＴｇ＝１２０℃）
・ＩＢ－ＸＡ（共栄社化学（株）製ライトアクリレートＩＢ－ＸＡ、イソボルニルアクリレート、ホモポリマーのＴｇ＝９４℃）
・ＴＢ（共栄社化学（株）製ライトエステルＴＢ、ｔ－ブチルメタクリレート、ホモポリマーのＴｇ＝１０７℃）
・ＮＢ（共栄社化学（株）製ライトエステルＮＢ、ｎ－ブチルメタクリレート、ホモポリマーのＴｇ＝２０℃）
・ＨＥＡ（大阪有機化学工業（株）製、ヒドロキシエチルアクリレート、ホモポリマーのＴｇ＝－１５℃）
・ＰＯ－Ａ（共栄社化学（株）製ライトアクリレートＰＯ－Ａ、フェノキシエチルアクリレート、ホモポリマーのＴｇ＝－２２℃） <Monofunctional (meth) acrylate compound>
-FA-513AS (Hankuri FA-513AS manufactured by Hitachi Chemical Co., Ltd., dicyclopentanyl acrylate, homopolymer Tg = 120 ° C.)
IB-XA (Kyoeisha Chemical Co., Ltd. light acrylate IB-XA, isobornyl acrylate, homopolymer Tg = 94 ° C.)
TB (Kyoeisha Chemical Co., Ltd. light ester TB, t-butyl methacrylate, homopolymer Tg = 107 ° C.)
NB (Kyoeisha Chemical Co., Ltd. light ester NB, n-butyl methacrylate, homopolymer Tg = 20 ° C.)
・ HEA (Osaka Organic Chemical Co., Ltd., hydroxyethyl acrylate, homopolymer Tg = −15 ° C.)
PO-A (Kyoeisha Chemical Co., Ltd. light acrylate PO-A, phenoxyethyl acrylate, homopolymer Tg = −22 ° C.)
＜ウレタン（メタ）アクリレート化合物＞
・ＫＵＡ－４Ｉ（ケーエスエム（株）製：４官能ウレタン（メタ）アクリレート（シクロヘキシル環を有する４官能ウレタンアクリレート）
・８ＵＸ－０１５Ａ（大成ファインケミカル（株）製ウレタン（メタ）アクリレート） <Urethane (meth) acrylate compound>
・ KUA-4I (manufactured by KS Corporation: tetrafunctional urethane (meth) acrylate (tetrafunctional urethane acrylate having a cyclohexyl ring)
・ 8UX-015A (urethane (meth) acrylate manufactured by Taisei Fine Chemical Co., Ltd.)
＜Ｎ－ビニル化合物＞
・ＮＶＰ（和光純薬工業（株）製：Ｎ－ビニル－２－ピロリドン）
・ＮＶＣ（東京化成工業（株）製：Ｎ－ビニル－ε－カプロラクタム） <N-vinyl compound>
・ NVP (Wako Pure Chemical Industries, Ltd .: N-vinyl-2-pyrrolidone)
NVC (manufactured by Tokyo Chemical Industry Co., Ltd .: N-vinyl-ε-caprolactam)
＜他の単官能エチレン性不飽和化合物＞
・ＡＣＭＯ（ＫＪケミカルズ（株）製：アクリロイルモルホリン） <Other monofunctional ethylenically unsaturated compounds>
・ ACMO (KJ Chemicals Co., Ltd .: acryloylmorpholine)
＜ゴム成分＞
・ゴムＡ（アクリルゴム、カネカ（株）製カネエースＭ－２１０、Ｔｇ＝－２０℃、破断伸度＞１００％）
・ゴムＢ（下記作製方法により作製したゴム状重合体、Ｔｇ＝－３０℃、破断伸度＞１００％） <Rubber component>
-Rubber A (acrylic rubber, Kaneace M-210 manufactured by Kaneka Corporation, Tg = −20 ° C., elongation at break> 100%)
・ Rubber B (rubber-like polymer produced by the following production method, Tg = −30 ° C., elongation at break> 100%)
－ゴムＢの作製－
　ガラス製反応容器に、イオン交換水１，７００部、炭酸ナトリウム０．７部、過硫酸ナトリウム０．３部を仕込み、窒素気流下で撹拌後、ペレックスＯＴ－Ｐ（（株）花王製）４．４６部、イオン交換水１５０部、メチルメタクリレート１５０部、アリルメタクリレート０．３部を仕込んだ後、７５℃に昇温し１５０分間撹拌を続けた。
　続いて、ブチルアクリレート６８９部、スチレン１６２部及びアリルメタクリレート１７部の混合物と、過硫酸ナトリウム０．８５部、ペレックスＯＴ－Ｐ７．４部及びイオン交換水５０部の混合物とをそれぞれ別の入口から９０分間にわたり添加し、更に９０分間重合を続けた。
　重合を完了後、更にメチルアクリレート３２６部及びエチルアクリレート１４部の混合物と、過硫酸ナトリウム０．３４部を溶解させたイオン交換水３０部とをそれぞれ別々の口から３０分間にわたって添加した。
　添加終了後、更に６０分間保持し重合を完了した。得られたラテックスを０．５質量％塩化アルミニウム水溶液に投入して重合体を凝集させた。これを温水にて５回洗浄後、乾燥してアクリル系多層弾性体（ゴムＢ）を得た。 -Production of rubber B-
A glass reaction vessel was charged with 1,700 parts of ion-exchanged water, 0.7 part of sodium carbonate and 0.3 part of sodium persulfate, stirred under a nitrogen stream, and then Perex OT-P (manufactured by Kao Corporation) 4 .46 parts, 150 parts of ion-exchanged water, 150 parts of methyl methacrylate, and 0.3 parts of allyl methacrylate were charged, and the temperature was raised to 75 ° C. and stirring was continued for 150 minutes.
Subsequently, a mixture of 689 parts of butyl acrylate, 162 parts of styrene and 17 parts of allyl methacrylate, 0.85 part of sodium persulfate, 7.4 parts of Perex OT-P, and 50 parts of ion-exchanged water are supplied from separate inlets. The addition was made over 90 minutes and the polymerization was continued for another 90 minutes.
After completion of the polymerization, a mixture of 326 parts of methyl acrylate and 14 parts of ethyl acrylate and 30 parts of ion-exchanged water in which 0.34 part of sodium persulfate was dissolved were added from separate ports over 30 minutes.
After completion of the addition, the polymerization was completed by holding for another 60 minutes. The obtained latex was put into a 0.5 mass% aluminum chloride aqueous solution to aggregate the polymer. This was washed 5 times with warm water and then dried to obtain an acrylic multilayer elastic body (rubber B).
＜末端に（メタ）アクリロイル基を有する樹脂＞
・ＡＡ－６（東亞合成（株）製：末端にメタクリロイル基を有するメタクリル樹脂（ポリメチルメタクリレート）、Ｍｎ＝６，０００）
・ＡＳ－６（東亞合成（株）製：末端にメタクリロイル基を有するポリスチレン、Ｍｎ＝６，０００）
・ＡＮ－６Ｓ（東亞合成（株）製：末端にメタクリロイル基を有するスチレン－アクリロニトリル共重合体、Ｍｎ＝６，０００） <Resin having a (meth) acryloyl group at the terminal>
AA-6 (manufactured by Toagosei Co., Ltd .: methacrylic resin having a methacryloyl group at the terminal (polymethyl methacrylate), Mn = 6,000)
AS-6 (manufactured by Toagosei Co., Ltd .: polystyrene having a methacryloyl group at the end, Mn = 6,000)
AN-6S (manufactured by Toagosei Co., Ltd .: styrene-acrylonitrile copolymer having a methacryloyl group at the terminal, Mn = 6,000)
＜樹脂＞
・ポリスチレン（アルドリッチ社製、Ｍｗ＝３５，０００） <Resin>
・ Polystyrene (Aldrich, Mw = 35,000)
＜光重合開始剤＞
・イルガキュア１８４（ＢＡＳＦ社製：１－ヒドロキシシクロヘキシルフェニルケトン）
・イルガキュアＴＰＯ（ＢＡＳＦ社製：２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド） <Photopolymerization initiator>
・ Irgacure 184 (manufactured by BASF: 1-hydroxycyclohexyl phenyl ketone)
・ Irgacure TPO (BASF: 2,4,6-trimethylbenzoyldiphenylphosphine oxide)
＜他の成分＞
・シリカ（ＭＥＫ－ＳＴ）（日産化学工業（株）製シリカ粒子、平均粒径１０ｎｍ～１５ｎｍ）
・トルエン（有機溶剤、東京化成工業（株）製）
・メチルエチルケトン（有機溶剤、東京化成工業（株）製） <Other ingredients>
・ Silica (MEK-ST) (silica particles manufactured by Nissan Chemical Industries, Ltd., average particle size of 10 nm to 15 nm)
・ Toluene (organic solvent, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Methyl ethyl ketone (organic solvent, manufactured by Tokyo Chemical Industry Co., Ltd.)
（実施例１～１２、及び、比較例１～７）
１．硬化性組成物の調製
　表１～表３に示す各成分を混合し、各硬化性組成物をそれぞれ調製した。 (Examples 1 to 12 and Comparative Examples 1 to 7)
1. Preparation of Curable Composition Each component shown in Tables 1 to 3 was mixed to prepare each curable composition.
２．レンチキュラーシートの作製（耐擦傷性評価用）
　基材であるアクリル樹脂フィルム（アクリプレンＨＢＳ０１０Ｐ、フィルム厚１２５μｍ、三菱レイヨン（株）製）上に上記光硬化性樹脂を下記レンズ高さになるように塗布した後、図１に示すように半円筒形状の表面を有する複数本の凸レンズ部１２Ａを持つシリンドリカルレンズ１２が並列したレンチキュラーレンズの形状〔高さ６０μｍ、長手方向ｙの長さ８０ｍｍ、１本のレンズ幅（レンズのピッチ）２００ＬＰＩ（Ｌｉｎｅ　Ｐｅｒ　Ｉｎｃｈ）〕に加工された金型（幅１００ｍｍ×奥行１００ｍｍ）を押し付け、上記光硬化性樹脂を成型しながら、アクリル樹脂フィルムを通して紫外線（ＵＶ）を、ＵＶ照射装置（ＥＸＥＣＵＲＥ　３０００、ＨＯＹＡ　ＣＡＮＤＥＯ　ＯＰＴＲＯＮＩＣＳ（株）製）を用いて、ＵＶ照射量１．０Ｊ／ｃｍ２にて照射した。照射後、脱型して、レンチキュラーシートを作製した。 2. Preparation of lenticular sheet (for scratch resistance evaluation)
After applying the photo-curing resin on the acrylic resin film (Acryprene HBS010P, film thickness 125 μm, manufactured by Mitsubishi Rayon Co., Ltd.) as a base material so as to have the following lens height, 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 60 μm, 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 ultraviolet light (UV) is passed through the acrylic resin film while molding the photo-curing resin, and UV irradiation device (EXECURE 3000, HOYA CANDEO OPTRICS ( UV irradiation dose of 1.0 J / c 2 was irradiated by. After irradiation, the mold was removed to prepare a lenticular sheet.
　なお、レンチキュラーレンズ（シリンドリカルレンズ）の高さの測定は、以下の方法により行った。
　レンチキュラーシートのシリンドリカルレンズを図１のｘｙ平面と垂直方向に裁断し、光学顕微鏡で高さを測定する。ランダムに１０個のシリンドリカルレンズ測定し、平均を高さとした。
　レンチキュラーレンズ（シリンドリカルレンズ）を形成する金型における高さ６０μｍにおいて、レンチキュラーレンズの高さの好ましい範囲は６０μｍ±５μｍである。上記範囲であると、チェンジング等のレンチキュラーレンズの効果がより鮮明に生じる。 The height of the lenticular lens (cylindrical lens) was measured by the following method.
The cylindrical lens of the lenticular sheet is cut in a direction perpendicular to the xy plane in FIG. 1, and the height is measured with an optical microscope. Ten cylindrical lenses were measured at random and the average was taken as the height.
At a height of 60 μm in a mold for forming a lenticular lens (cylindrical lens), a preferred range of the height of the lenticular lens is 60 μm ± 5 μm. Within the above range, the effect of the lenticular lens such as changing occurs more clearly.
３．硬化物の作製
３－１．硬化物積層シートの作製（耐擦傷性評価用）
　硬化性組成物をアクリル樹脂フィルム（アクリプレンＨＢＳ０１０Ｐ、フィルム厚１２５μｍ、三菱レイヨン（株）製）と疎水化処理したガラス板とで挟み込み、上記ＵＶ照射装置を用い、上記アクリル樹脂フィルム越しに１．０Ｊ／ｃｍ２照射し、表裏を返して再度ＵＶ照射量１．０Ｊ／ｃｍ２にてＵＶ照射し、硬化物の積層シートを作製した。上記積層シートにおける硬化物（硬化膜）の膜厚は６０μｍとした。 3. Production of cured product 3-1. Preparation of cured product laminated sheet (for scratch resistance evaluation)
The curable composition was sandwiched between an acrylic resin film (Acryprene HBS010P, film thickness 125 μm, manufactured by Mitsubishi Rayon Co., Ltd.) and a hydrophobized glass plate, and 1.0 J was passed through the acrylic resin film using the UV irradiation device. / Cm 2 was irradiated, the front and back sides were turned over, and UV irradiation was performed again at a UV irradiation amount of 1.0 J / cm 2 to prepare a laminated sheet of cured product. The film thickness of the cured product (cured film) in the laminated sheet was 60 μm.
３－２．硬化物の単膜の作製（高温延伸性評価用）
　硬化性組成物を疎水化処理したガラス板で挟み込み、上記ＵＶ照射装置を用い、上記アクリル樹脂フィルム越しに１．０Ｊ／ｃｍ２、表裏を返して上記アクリル樹脂フィルム無しで再度ＵＶ照射量１．０Ｊ／ｃｍ２にてＵＶ照射し、硬化物の単膜を作製した。上記単膜の膜厚は５０μｍとした。 3-2. Preparation of cured single film (for high temperature stretchability evaluation)
The curable composition was sandwiched between glass plates that had been subjected to a hydrophobization treatment, and the UV irradiation device was used to turn back the front and back, 1.0 J / cm 2 over the acrylic resin film, and again, without the acrylic resin film, the UV irradiation amount was 1. UV irradiation was performed at 0 J / cm 2 to produce a single film of a cured product. The film thickness of the single film was 50 μm.
４．評価方法
＜耐擦傷性＞
　スチールウール＃００００を用いて、２００ｇの荷重で上記レンチキュラーシートの表面を１０往復し、キズの付き具合で評価した。擦る方向は、レンチキュラーシート又は積層シートに対し、ｘ方向、及び、ｙ平行方向の両方でそれぞれ行った。評価基準を以下に示す。なお、ｘ方向のほうが、より厳しい評価となる。
　　Ａ：傷が確認できない
　　Ｂ：傷は確認できるがシートの後ろの景色が透けて見える
　　Ｃ：傷が激しく、白化してしまい後ろの景色が見えない 4). Evaluation method <Abrasion resistance>
Using steel wool # 0000, the surface of the lenticular sheet was reciprocated 10 times with a load of 200 g, and the degree of scratching was evaluated. The rubbing direction was performed in both the x direction and the y parallel direction with respect to the lenticular sheet or the laminated sheet. The evaluation criteria are shown below. The evaluation in the x direction is more severe.
A: Scratches cannot be confirmed B: Scratches can be confirmed, but the scenery behind the sheet can be seen through C: Scratches are severe, whitening occurs and the scenery behind is not visible
＜高温延伸性＞
　作製した硬化物の単膜を、長さ５０ｍｍ×幅１０ｍｍで打ち抜いて、サンプルとし、引張試験を行い、破断伸度を測定した。下記式で表される破断伸度を測定した。破断伸度を３回測定し、それらの平均値を破断伸度とした。
　破断伸度（％）＝１００×（延伸で破断した長さ－チャック間距離）／（チャック間距離）
　装置はＴＥＮＳＩＬＯＮ　ＲＴＣ－１２２５Ａ（（株）エー・アンド・デイ製）、測定条件：チャック間距離３０ｍｍ、温度は１００℃と１２０℃とを各々行い、引張速度１ｍｍ／ｓｅｃとした。評価基準を以下に示す。
　　ＡＡＡ：破断伸度が５０％以上のもの
　　ＡＡ：破断伸度が２５％以上５０％未満のもの
　　Ａ：破断伸度が２０％以上２５％未満のもの
　　Ｂ：破断伸度が１５％以上２０％未満のもの
　　Ｃ：破断伸度が１５％未満のもの
　なお、Ｂ以上が実用上問題のない範囲である。 <High temperature stretchability>
A single film of the produced cured product was punched out with a length of 50 mm and a width of 10 mm to prepare a sample, and a tensile test was performed to measure the elongation at break. 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.
Elongation at break (%) = 100 × (length broken by stretching−distance between chucks) / (distance between chucks)
The apparatus is TENSILON RTC-1225A (manufactured by A & D Co., Ltd.), measurement conditions: distance between chucks is 30 mm, temperatures are 100 ° C. and 120 ° C., respectively, and the tensile speed is 1 mm / sec. The evaluation criteria are shown below.
AAA: Breaking elongation of 50% or more AA: Breaking elongation of 25% or more and less than 50% A: Breaking elongation of 20% or more and less than 25% B: Breaking elongation of 15% or more and 20% Less than C: Break elongation less than 15% Note that B or more is a practically acceptable range.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表１～表３の結果から明らかなように、比較例１～比較例７の硬化性組成物と比較し、本開示に係る硬化性組成物を用いた場合、得られる硬化物の耐擦傷性及び高温延伸性に優れていることが分かる。
　また、実施例１、実施例３及び実施例５を比較すると、ウレタン（メタ）アクリレート化合物を含有しないほうが、耐擦傷性により優れる。
　実施例３及び実施例７を比較すると、イソシアヌル環構造を有する３官能（メタ）アクリレート化合物を含む場合、耐擦傷性により優れる。
　実施例３、実施例８及び実施例９を比較すると、脂環構造を有する単官能（メタ）アクリレート化合物を用いると、耐擦傷性及び高温延伸性により優れる。
　実施例３、実施例１０及び実施例１１を比較すると、中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、１５質量％以上６０質量％以下である場合、耐擦傷性及び高温延伸性により優れる。
　実施例３及び実施例１２を比較すると、末端に（メタ）アクリロイル基を有する樹脂を更に含むことにより、耐擦傷性及び高温延伸性により優れる。
　実施例１、実施例１４及び実施例１５を比較すると、ゴム成分を更に含むことにより、高温延伸性により優れる。 As is clear from the results of Tables 1 to 3, when the curable compositions according to the present disclosure are used as compared with the curable compositions of Comparative Examples 1 to 7, the resulting cured products have scratch resistance. And it turns out that it is excellent in high temperature stretchability.
Moreover, when Example 1, Example 3, and Example 5 are compared, the direction which does not contain a urethane (meth) acrylate compound is more excellent in abrasion resistance.
When Example 3 and Example 7 are compared, when a trifunctional (meth) acrylate compound having an isocyanuric ring structure is included, it is more excellent in scratch resistance.
When Example 3, Example 8, and Example 9 are compared, when a monofunctional (meth) acrylate compound having an alicyclic structure is used, it is more excellent in scratch resistance and high-temperature stretchability.
When Example 3, Example 10, and Example 11 are compared, the content of the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a three-fold symmetry axis is 15 with respect to the total mass of the curable composition. When it is at least 60% by mass, it is more excellent in scratch resistance and high-temperature stretchability.
When Example 3 and Example 12 are compared, by further including a resin having a (meth) acryloyl group at the terminal, it is more excellent in scratch resistance and high temperature stretchability.
When Example 1, Example 14, and Example 15 are compared, it is more excellent in high temperature stretchability by further including a rubber component.
（実施例１７）
　１０ｍｍの直径を有する半球形状を有する型を用いて、使用した硬化性組成物の硬化物の１００℃において、実施例３で得られたレンチキュラーシートを上記半球形状に真空成型した。得られた成型体（３次元構造物）には、割れが生じておらず、実施例３で得られたレンチキュラーシートは、立体成型性に優れるものであった。 (Example 17)
Using a mold having a hemispherical shape having a diameter of 10 mm, the lenticular sheet obtained in Example 3 was vacuum-formed into the above hemispherical shape at 100 ° C. of the cured product of the used curable composition. The obtained molded body (three-dimensional structure) was not cracked, and the lenticular sheet obtained in Example 3 was excellent in three-dimensional moldability.
　２０１６年１０月１３日に出願された日本国特許出願第２０１６－２０１８９２号、及び、２０１７年２月１３日に出願された日本国特許出願第２０１７－０２４３７３号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosures of Japanese Patent Application No. 2016-201892 filed on October 13, 2016 and Japanese Patent Application No. 2017-024373 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・・・レンチキュラー加飾シート（レンチキュラーシート）
１２・・・レンチキュラーレンズ
１２Ａ・・・凸状レンズ
１４・・・レンチキュラー画像
１４Ａ，１４Ｂ・・・表示用画像列
１４Ｃ・・・補間画像列
ｘ・・・レンズの幅方向
ｙ・・・レンズの長手方向 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 (19)

  1. 　中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物、及び、
    　ホモポリマーのガラス転移温度が０℃以上である単官能（メタ）アクリレート化合物を含有し、
    　ウレタン（メタ）アクリレート化合物を含有しないか、又は、ウレタン（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、０質量％を超え４質量％未満である
    　硬化性組成物。     A bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis, and
    Containing a monofunctional (meth) acrylate compound whose homopolymer has a glass transition temperature of 0 ° C. or higher,
    The curable composition which does not contain a urethane (meth) acrylate compound, 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.
  2. 　前記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物が、イソシアヌル環構造を有する２官能又は３官能（メタ）アクリレート化合物である請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is a bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure.
  3. 　前記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物が、イソシアヌル環構造を有する３官能（メタ）アクリレート化合物である請求項１又は請求項２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is a trifunctional (meth) acrylate compound having an isocyanuric ring structure. .
  4. 　前記中心骨格が３回対称軸を有する２官能又は３官能（メタ）アクリレート化合物の含有量が、硬化性組成物の全質量に対し、１０質量％以上６０質量％以下である請求項１～請求項３のいずれか１項に記載の硬化性組成物。 The content of the bifunctional or trifunctional (meth) acrylate compound in which the central skeleton has a 3-fold symmetry axis is 10% by mass to 60% by mass with respect to the total mass of the curable composition. Item 4. The curable composition according to any one of items 3 to 3.
  5. 　前記単官能（メタ）アクリレート化合物のホモポリマーのガラス転移温度が、６０℃以上である請求項１～請求項４のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the homopolymer of the monofunctional (meth) acrylate compound has a glass transition temperature of 60 ° C or higher.
  6. 　前記単官能（メタ）アクリレート化合物が、脂環構造を有する請求項１～請求項５のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 5, wherein the monofunctional (meth) acrylate compound has an alicyclic structure.
  7. 　ゴム成分を、硬化性組成物の全質量に対し、１質量％以上３０質量％以下更に含む請求項１～請求項６のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 6, further comprising a rubber component in an amount of 1% by mass to 30% by mass with respect to the total mass of the curable composition.
  8. 　末端に（メタ）アクリロイル基を有する樹脂を更に含む請求項１～請求項７のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 7, further comprising a resin having a (meth) acryloyl group at a terminal.
  9. 　前記末端に（メタ）アクリロイル基を有する樹脂の含有量が、硬化性組成物の全質量に対し、５質量％以上４５質量％以下である請求項８に記載の硬化性組成物。 The curable composition according to claim 8, wherein the content of the resin having a (meth) acryloyl group at the terminal is 5% by mass or more and 45% by mass or less with respect to the total mass of the curable composition.
  10. 　Ｎ－ビニル化合物を更に含む請求項１～請求項９のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 9, further comprising an N-vinyl compound.
  11. 　前記Ｎ－ビニル化合物が、Ｎ－ビニルピロリドン、及び、Ｎ－ビニルカプロラクタムよりなる群から選ばれた少なくとも１種の化合物である請求項１０に記載の硬化性組成物。 The curable composition according to claim 10, wherein the N-vinyl compound is at least one compound selected from the group consisting of N-vinylpyrrolidone and N-vinylcaprolactam.
  12. 　前記Ｎ－ビニル化合物の含有量が、硬化性組成物の全質量に対し、５質量％以上４０質量％以下である請求項１０又は請求項１１に記載の硬化性組成物。 The curable composition according to claim 10 or 11, wherein the content of the N-vinyl compound is 5% by mass or more and 40% by mass or less based on the total mass of the curable composition.
  13. 　光重合開始剤を更に含む請求項１～請求項１２のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 12, further comprising a photopolymerization initiator.
  14. 　請求項１～請求項１３のいずれか１項に記載の硬化性組成物を硬化してなる硬化物。 A cured product obtained by curing the curable composition according to any one of claims 1 to 13.
  15. 　請求項１～請求項１３のいずれか１項に記載の硬化性組成物を準備する工程、及び、
    　前記硬化性組成物を硬化する工程を含む
    　硬化物の製造方法。     Preparing the curable composition according to any one of claims 1 to 13, and
    The manufacturing method of hardened | cured material including the process of hardening | curing the said curable composition.
  16. 　請求項１～請求項１３のいずれか１項に記載の硬化性組成物の硬化物を有する積層シート。 A laminated sheet having a cured product of the curable composition according to any one of claims 1 to 13.
  17. 　請求項１～請求項１３のいずれか１項に記載の硬化性組成物の硬化物を有する光学部材。 An optical member having a cured product of the curable composition according to any one of claims 1 to 13.
  18. 　請求項１～請求項１３のいずれか１項に記載の硬化性組成物の硬化物を有するレンチキュラーシート。 A lenticular sheet having a cured product of the curable composition according to any one of claims 1 to 13.
  19. 　請求項１８に記載のレンチキュラーシートの立体成型物である３次元構造物。 A three-dimensional structure which is a three-dimensional molded product of the lenticular sheet according to claim 18.
PCT/JP2017/037273 2016-10-13 2017-10-13 Curable composition, cured product and production method therefor, laminated sheet, optical member, lenticular sheet, and three-dimensional structure WO2018070538A1 (en)

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JPS6327518A (en) * 1986-07-21 1988-02-05 Yokohama Rubber Co Ltd:The Ultraviolet curing type resin composition
JPS63270719A (en) * 1987-04-30 1988-11-08 Yokohama Rubber Co Ltd:The Ultraviolet-curable resin composition
JPH09316111A (en) * 1996-05-30 1997-12-09 Japan Synthetic Rubber Co Ltd Photocurable composition and production of mold made of resin
JP2009134000A (en) * 2007-11-29 2009-06-18 Jsr Corp Film-like optical waveguide
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JPS6327518A (en) * 1986-07-21 1988-02-05 Yokohama Rubber Co Ltd:The Ultraviolet curing type resin composition
JPS63270719A (en) * 1987-04-30 1988-11-08 Yokohama Rubber Co Ltd:The Ultraviolet-curable resin composition
JPH09316111A (en) * 1996-05-30 1997-12-09 Japan Synthetic Rubber Co Ltd Photocurable composition and production of mold made of resin
JP2009134000A (en) * 2007-11-29 2009-06-18 Jsr Corp Film-like optical waveguide
JP2015071704A (en) * 2013-10-03 2015-04-16 東洋インキＳｃホールディングス株式会社 Resin composition, active energy ray-polymerizable adhesive, and laminate

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WO2021167061A1 (en) * 2020-02-21 2021-08-26 味の素株式会社 Curable composition

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