WO2019012895A1 - Feuille stratifiée et procédé de production associé, et structure tridimensionnelle et procédé de production associé - Google Patents

Feuille stratifiée et procédé de production associé, et structure tridimensionnelle et procédé de production associé Download PDF

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Publication number
WO2019012895A1
WO2019012895A1 PCT/JP2018/022418 JP2018022418W WO2019012895A1 WO 2019012895 A1 WO2019012895 A1 WO 2019012895A1 JP 2018022418 W JP2018022418 W JP 2018022418W WO 2019012895 A1 WO2019012895 A1 WO 2019012895A1
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group
meth
laminated sheet
acrylate
cured product
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PCT/JP2018/022418
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English (en)
Japanese (ja)
Inventor
橋本　斉和
直之 師岡
貴康 永井
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富士フイルム株式会社
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Priority to JP2019528998A priority Critical patent/JP6782843B2/ja
Publication of WO2019012895A1 publication Critical patent/WO2019012895A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • 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 present disclosure relates to a laminated sheet and a method of manufacturing the same, and a three-dimensional structure and a method of manufacturing the same.
  • a curable composition contains a polymerizable resin and an initiator, is cured by causing a polymerization reaction by heat, light or the like, and is widely used in various applications.
  • curing a curable composition is widely utilized, such as an optical member, a gas barrier film, a protective film, an optical filter, an antireflection film.
  • a cured product obtained by curing the curable composition is used for various members such as an antireflective film, a transparent pixel, a transparent insulating film, and a flattening film.
  • the optical structure in the optical members is not limited to those having a flat surface shape, for example, and is used for brightness improving lenses for liquid crystal backlights, diffusion lenses, and screens of video projection televisions
  • a Fresnel lens, a micro lens, etc. are mentioned.
  • the desired geometrical optical performance is obtained by forming the fine structure mainly with a resin material.
  • a lenticular sheet using a lenticular lens in which convex lenses having semi-cylindrical surfaces are arranged in parallel is known as a medium for displaying an image different depending on a viewing angle.
  • an image row group (lenticular image) in which a plurality of interlaced images are combined is disposed on the back surface side (surface opposite to the semi-cylindrical surface of the convex lens) of the lenticular lens.
  • the row group is observed through the lenticular lens, one or more images of the image row group can be displayed according to the angle to be observed. Therefore, utilization in various commercial applications including optical materials and optical screens is expected.
  • the applications that have been proposed conventionally are mostly used in a two-dimensional form such as a sheet or a film, but are not often applied to a three-dimensional form molded into a three-dimensional shape.
  • a laminated film as a decorative film those described in Japanese Patent No. 469 2553 or Japanese Patent No. 4720832 can be mentioned.
  • Another embodiment of the present invention is to provide a lamination sheet which is excellent in abrasion resistance and trimming nature, and its manufacturing method.
  • Another embodiment of the present invention is to provide a three-dimensional structure using the above-mentioned laminated sheet and a method of manufacturing the same.
  • the laminated sheet which has a hardened
  • the laminated sheet as described in said ⁇ 1> whose molecular weight between crosslinking points of the ⁇ 2> above-mentioned hardened
  • cured material is 1 to 30%.
  • ⁇ 4> The laminated sheet according to any one of the above ⁇ 1> to ⁇ 3>, wherein at least one layer of the laminated base material is an acrylic resin layer.
  • ⁇ 5> The laminated sheet according to any one of the above ⁇ 1> to ⁇ 4>, wherein at least one layer of the laminated base material is a polycarbonate resin layer.
  • ⁇ 6> The above ⁇ 1> to ⁇ 5, wherein the cured product contains a resin having at least one ring structure selected from the group consisting of isocyanuric ring structure, tricyclodecane ring structure, triazine ring, and cyclohexane ring structure.
  • ⁇ 7> The laminated sheet according to any one of the above ⁇ 1> to ⁇ 6>, wherein the cured product contains a resin having a structural unit having a nitrogen atom-containing group.
  • the structural unit having a group containing the nitrogen atom is selected from the group consisting of a structural unit represented by the following formula 1, a structural unit represented by the following formula 2, and a structural unit represented by the following formula 3
  • the laminated sheet as described in said ⁇ 7> containing at least 1 type of structural unit.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • X 2 Is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms
  • at least one of R 5 , R 6 and R 7 contains a nitrogen atom bonded to a carbon atom of the hydrocarbon group
  • X 2 and R 5 , R 6 and R 7 may be the same or different, and may form a ring with each other.
  • At least one ring structure selected from the group consisting of an isocyanuric ring structure, a tricyclodecane ring structure, a triazine ring, and a cyclohexane ring structure, and a structural unit represented by the following formula 1,
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • X 2 Is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms
  • at least one of R 5 , R 6 and R 7 contains a nitrogen atom bonded to a carbon atom of the hydrocarbon group
  • X 2 and R 5 , R 6 and R 7 may be the same or different, and may form a ring with each other.
  • ⁇ 10> The laminated sheet according to any one of the above ⁇ 1> to ⁇ 9>, wherein the cured product is an optical member.
  • the optical member is a lens.
  • the laminated sheet according to ⁇ 11>, wherein the lens is a cylindrical lens.
  • ⁇ 14> A three-dimensional structure which is a three-dimensional molded article of the laminated sheet according to any one of the above ⁇ 1> to ⁇ 13>.
  • a step of applying a curable composition onto a laminated base consisting of two or more different resin layers, and a step of irradiating the active radiation to cure the curable composition to form a cured product The manufacturing method of the lamination sheet as described in any one of said ⁇ 1>- ⁇ 13> containing.
  • ⁇ 16> A method for producing a three-dimensional structure, comprising three-dimensionally molding the laminated sheet according to any one of the above ⁇ 1> to ⁇ 13>.
  • the present invention it is possible to provide a laminated sheet excellent in wear resistance and trimming property, and a method of manufacturing the same.
  • a hydrocarbon group such as an alkyl group, an aryl group, an alkylene group and an arylene group in the present disclosure may have a branch or a ring structure unless otherwise specified.
  • “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation) unless otherwise noted.
  • the laminated sheet which concerns on this indication has a hardened
  • the laminated sheet according to the present disclosure is suitably used as an optical member sheet, and more suitably used as a lenticular sheet.
  • the substrate used in the present disclosure is a laminated substrate composed of two or more different resin layers.
  • the laminated base used in the present disclosure is a base as a support material, and any resin can be selected according to the purpose and the like.
  • a sheet-like or film-like substrate can be suitably used as the laminated substrate.
  • acrylic resin, polyester resin, polycarbonate resin (PC), vinyl chloride resin (PVC), an acrylonitrile butadiene styrene copolymer (ABS resin), etc. are mentioned preferably. .
  • the thickness of the laminated base material is not particularly limited, and is preferably in the range of 50 ⁇ m to 300 ⁇ m, and more preferably in the range of 50 ⁇ m to 200 ⁇ m from the viewpoint of uniform molding (shape) at high temperatures. Within the above range, the laminated base material is not easily torn, cracks are not easily generated during handling (for example, during transportation) during molding, and it is also difficult to be broken during three-dimensional molding.
  • the thickness of each resin layer is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m, from the viewpoint of three-dimensional moldability, abrasion resistance, and trimming property.
  • Such a laminated base material may be laminated in a molten state during film formation (for example, using a multi-manifold die or feed block die), and a resin extruded from a die or the like is laminated on a solidified resin film
  • the solidified resin films may be thermocompression-bonded to each other.
  • the laminated sheet according to the present disclosure three-dimensional formability is further improved by using the laminated base as a base. This is presumed to be due to the following reason.
  • the glass transition temperatures (Tg) are different. For this reason, when three-dimensional molding is performed at Tg of one resin or more and Tg of the other resin, one resin is molded and deformed because of Tg or more, but the flowability is large and the hole is easily opened at the time of molding extension. However, since the other layer is below Tg, there is no large flow and the generation of holes can be suppressed.
  • the temperature difference of Tg of the resin to be laminated is preferably 10 ° C. or more and 90 ° C.
  • the temperature difference of said Tg points out the difference of the highest Tg and the lowest Tg.
  • PET Polyethylene terephthalate
  • the number of resin layers in the laminated base material is preferably 2 or more and 8 or less, more preferably 2 or more and 5 or less, and more preferably 2 or more and 4 or less from the viewpoint of three-dimensional moldability, abrasion resistance, trimability
  • the following is more preferable.
  • a laminated base material having at least one acrylic resin layer is preferable from the viewpoint of three-dimensional moldability, abrasion resistance and trimming property.
  • a (meth) acrylic compound is often used for the cured product, and if the structures of both materials are similar, the adhesion between the two becomes better, and both are separated by the impact during trimming and become thinner It is presumed that it is possible to suppress that the layer is easily cracked (cracks are easily formed).
  • stacking base material it is preferable to have a polycarbonate resin layer of at least 1 layer from a viewpoint of abrasion resistance and trimming property.
  • the thickness ratio of each resin layer in the laminated base material is preferably 51% or more and 95% or less of the thickness of the entire layer from the viewpoint of three-dimensional moldability, abrasion resistance and trimming property, and is preferably 55% or more
  • the thickness is more preferably 90% or less, and still more preferably 60% to 85%.
  • each resin layer in the laminated base material preferably has a resin content of 80% by mass or more based on the total mass of the resin layer, It is more preferable that it is 90 mass% or more, and it is still more preferable that it is 95 mass% or more.
  • elastomers for imparting flexibility for example, those described in Patents 4720832 and 4692553
  • UV agents for imparting light resistance for example, JP-A 2010-234640, JP-A-2011-31498, JP-A-2011-93258, JP-A-2011-110916, etc.
  • particles for imparting slipperiness for example, silica, alumina, crosslinked
  • PMMA fine particles of PMMA or the like: for example, those described in paragraph 0049 of Japanese Patent No. 469253.
  • acrylic resin film (Acryprene HBS010P, thickness: 125 ⁇ m) manufactured by Mitsubishi Rayon Co., Ltd., Toray (Toray) Co., Ltd. polyethylene terephthalate resin film (Lumirror S10, thickness: 100 ⁇ m), Teijin Kasei Co., Ltd. polycarbonate resin film (Iupilon H-3000, thickness 125 ⁇ m), Sumika Acrylics Co., Ltd. acrylic (PMMA) resin (Technoloy S001, thickness 139 ⁇ m), Sumika Acrylics Co., Ltd.
  • acrylic resin film (Acryprene HBS010P, thickness: 125 ⁇ m) manufactured by Mitsubishi Rayon Co., Ltd., Toray (Toray) Co., Ltd. polyethylene terephthalate resin film (Lumirror S10, thickness: 100 ⁇ m), Teijin Kasei Co., Ltd. polycarbonate resin film (Iupilon H-3000, thickness 125 ⁇ m), Sumika Acrylics Co
  • PC polycarbonate
  • PMMA PC laminated resin
  • Toray Industries, Inc. ABS resin (Toyolac 900- 52: Thickness 125 [mu] m)
  • Okamoto Co. transparent vinyl chloride resin prowder pretend transparent grade, it can be used thickness 100 [mu] m) and the like.
  • the laminated sheet which concerns on this indication has a hardened
  • the breaking elongation at 100 ° C. of the cured product is 6% or more and 500% or less, preferably 15% or more and 400% or less, and 20% or more and 300% or less from the viewpoint of three-dimensional moldability and wear resistance. It is more preferable that
  • the breaking elongation in the present disclosure is to be measured by the following method. Peel the cured product from the substrate.
  • an adhesive tape may be attached to both the substrate and the cured layer, and both may be pulled apart, or the sheet with the cured film may be dipped in a solvent that dissolves the substrate to isolate the cured product layer.
  • the cured product layer is crosslinked and does not dissolve. Examples of the solvent for dissolving the substrate include acetone, methyl ethyl ketone (MEK) and the like).
  • the resulting cured product is dried to a residual solvent content of 1% by weight or less, and then it is unidirectional (when the cured product has a structure such as a lens, its longitudinal direction) and in the orthogonal direction
  • the sample pieces are prepared by processing each into a size of 50 mm long ⁇ 10 mm wide, and using TENSILON RTC-1225A (manufactured by A & D Co., Ltd.), a tensile test is performed under the following conditions, and the following formula is obtained
  • Elongation at break (%) 100 ⁇ (Length broken at stretching-distance between chucks) / (distance between chucks) -conditions- -Distance between chucks: 30 mm ⁇ Temperature of sample piece: 100 ° C ⁇ Tensing speed: 1 mm / sec
  • the thickness of the cured product is preferably 10 ⁇ m to 100 ⁇ m, more preferably 15 ⁇ m to 80 ⁇ m, and still more preferably 20 ⁇ m to 60 ⁇ m. While it is excellent in the handleability as it is the said range, it is excellent in moldability.
  • the cross-linking molecular weight of the cured product is preferably 20 g / mol or more and 2,000 g / mol or less, and more preferably 50 g / mol or more and 1,500 g / mol or less from the viewpoint of three-dimensional moldability and abrasion resistance. Is more preferably 100 g / mol or more and 1,200 g / mol or less.
  • the molecular weight between crosslinking points indicates the size of the network of the crosslinked structure.
  • the molecular weight between crosslinking points in the present disclosure is to be measured by the following method.
  • the same sample piece used for the measurement of the breaking elongation is prepared, heated to a temperature (250 ° C.) to be a rubber region, and DMA (Dynamic Mechanical Analyzer: Rheogel-E4000HP manufactured by UBM Co., Ltd.) is used.
  • a strain of 0.01% is applied at 10 Hz and measured to obtain a storage elastic modulus (E ').
  • E ' storage elastic modulus
  • Mc molecular weight between crosslinking points
  • Mc 3 ⁇ ⁇ ⁇ R ⁇ T / E ′
  • Mc g / mol
  • the distribution of molecular weight between crosslinking points of the cured product is preferably 1% to 30%, more preferably 2% to 25%, and further preferably 3% to 20%. preferable.
  • the distribution is 1% or more, the three-dimensional moldability is more excellent, and when the distribution is 30% or less, the wear resistance is more excellent.
  • the distribution of molecular weight between crosslinking points in the present disclosure is to be measured by the following method.
  • the measurement of the molecular weight between crosslinking points was carried out for 10 sample pieces used for the measurement of molecular weight between crosslinking points, and the difference between the maximum value and the minimum value among the values of molecular weight between crosslinking points measured for 10 sample pieces Divided by the average value, and the value shown as a percentage is taken as the distribution of molecular weight between crosslinking points.
  • the glass transition temperature (Tg) of the cured product is preferably more than 90 ° C., more preferably 95 ° C. or more and 200 ° C. or less, and more preferably 100 ° C. or more and 180 ° C. from the viewpoint of three-dimensional moldability and abrasion resistance. It is further preferable that the temperature is not higher than ° C.
  • the glass transition temperature (Tg) of the cured product, resin and the like in the present disclosure is determined from the main maximum peak measured using a differential scanning calorimeter (manufactured by Perkin Elmer, Inc .: DSC-7) in accordance with ASTM D 3418-8. be able to.
  • the temperature correction of the detection section of this device uses the melting point of indium and zinc, and the heat of heat correction uses the heat of fusion of indium.
  • the sample uses an aluminum pan and sets an empty pan for control. The temperature is raised at a temperature rising rate of 10 ° C./min, held at 200 ° C. for 5 minutes, lowered from 200 ° C. to 20 ° C. with liquid nitrogen at ⁇ 10 ° C./min, held at 20 ° C. for 5 minutes, and again 20
  • the onset temperature analyzed from the endothermic curve at the time of the second temperature increase obtained by raising the temperature from 10 ° C. to 200 ° C. at 10 ° C./min was defined as Tg.
  • the cured product is preferably in the form of a film.
  • a flat film is formed without being molded on the laminated substrate, it can be used as a hard coat film.
  • the lamination sheet which concerns on this indication is excellent in the extensibility of hardened
  • it can be used as a lenticular lens when it is molded in a semi-cylindrical shape, it can be used as a prism sheet or a brightness enhancement film when it is molded in a triangular prism, it can be used as a microlens sheet when it is molded in many hemispheres If a sawtooth-like shape as shown in FIG. 4A of 2015/102100 is formed concentrically, it can be used as a prism sheet.
  • the cured product preferably contains a resin having a ring structure from the viewpoint of steric moldability and abrasion resistance, and is selected from the group consisting of an isocyanuric ring structure, a tricyclodecane ring structure, a triazine ring, and a cyclohexane ring structure. It is more preferable to include a resin having at least one ring structure, and further preferably include a resin having at least one ring structure selected from the group consisting of an isocyanuric ring structure and a tricyclodecane ring structure, It is particularly preferred to include a resin having an isocyanuric ring structure.
  • cured material contains resin which has a structural unit which has group which contains a nitrogen atom from a three-dimensional moldability and abrasion resistance viewpoint.
  • group containing nitrogen atom is not particularly limited as long as it has a nitrogen atom, and examples thereof include an amino group, an amide group, an imino group, and a cyano group, and an imidazole ring group and an imidazoline ring group And pyrrolidine ring group, pyrazole ring group, morpholine ring group, and heterocyclic group such as triazine ring group.
  • the structural unit having a group containing the nitrogen atom is a structural unit represented by the following formula 1, a structural unit represented by the following formula 2, and a structure represented by the following formula 3 from the viewpoint of adhesion and three-dimensional formability.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • X 2 Is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms
  • at least one of R 5 , R 6 and R 7 contains a nitrogen atom bonded to a carbon atom of the hydrocarbon group
  • X 2 and R 5 , R 6 and R 7 may be the same or different, and may form a ring with each other.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms
  • X 1 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms
  • R 1 , R 2 , R 3 , R 4 and X 1 may be the same or different and each other is a ring You may form.
  • the structural unit represented by the above formula 1 is a monomer unit formed by polymerizing N-vinylcaprolactam (more specifically, N-vinyl- ⁇ -caprolactam), and is represented by the above formula 2
  • the structural unit is a monomer unit formed by polymerizing N-vinylpyrrolidone (more specifically, N-vinyl-2-pyrrolidone).
  • the structural unit represented by the said Formula 3 is a monomer unit formed by polymerizing the compound represented by Formula (II) mentioned later
  • the structural unit represented by said Formula 4 is a formula (I) mentioned later. It is a monomer unit formed by polymerizing the compound represented by 1.).
  • R 5, R 6 and R 7 in the above formula 3 has the same meaning as X 2, R 5, R 6 and R 7 in the compound represented by formula (II) described below, a preferred embodiment also the same is there.
  • R 1, R 2, R 3 , R 4 and X 1 in the above formula 4, in the compound of formula (I) to be described later, in R 1, R 2, R 3 , R 4 and X 1 as defined Preferred embodiments are also the same.
  • the structural unit having a group containing a nitrogen atom is preferably a structural unit formed by polymerizing a polymerizable compound having a functional group containing a nitrogen atom described later and a polymerizable group.
  • the resin may have a single type of structural unit having a group containing the nitrogen atom or may have two or more types.
  • the resin may have either or both of the structural unit represented by the above formula 1 and the structural unit represented by the above formula 2. It is preferable to have the constitutional unit represented or the constitutional unit represented by the above-mentioned formula 2.
  • the content of the structural unit having a group containing a nitrogen atom in the resin is preferably 1% by mass to 60% by mass with respect to the total mass of the specific resin from the viewpoint of heat resistance and adhesion.
  • the content is more preferably 5% by mass to 35% by mass, still more preferably 2% by mass to 30% by mass, and particularly preferably 2.5% by mass to 9% by mass.
  • the cured product has at least one ring structure selected from the group consisting of an isocyanuric ring structure, a tricyclodecane ring structure, a triazine ring, and a cyclohexane ring structure from the viewpoint of stereoformability and abrasion resistance,
  • it comprises a resin having at least one structural unit selected from the group consisting of a structural unit represented by the above formula 1, a structural unit represented by the above formula 2, and a structural unit represented by the above formula 3 preferable.
  • cured material contains resin which has a crosslinked structure from a heat resistant viewpoint.
  • the crosslinked structure can be easily introduced into a specific resin by copolymerizing a polyfunctional polymerizable compound such as a polyfunctional (meth) acrylate compound described later.
  • the above-mentioned resin preferably has an acrylic resin chain, and more preferably has a polymethyl methacrylate chain.
  • the said resin has a graft chain from a heat resistant and adhesive viewpoint.
  • the graft chain is preferably an acrylic resin chain, and more preferably a polymethyl methacrylate chain.
  • the number average molecular weight Mn of the acrylic resin chain is preferably 1,000 or more and 20,000 or less, and more preferably 2,000 or more and 10,000 or less.
  • the glass transition temperature (Tg) of the above-mentioned resin is preferably more than 90 ° C., more preferably 95 ° C. or more and 200 ° C. or less, and more preferably 100 ° C. or more and 180 ° C. It is more preferable that it is the following.
  • the content of the resin in the cured product is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the cured product, from the viewpoints of transparency, heat resistance, and adhesion.
  • the content is 95% by mass or more.
  • the upper limit of content is 100 mass%.
  • the laminated sheet according to the present disclosure may have the above-mentioned cured product only on one side of the above-mentioned laminated base, or may have it on both sides of the above-mentioned laminated base, but the designability and the range of applications It is preferable to have the said hardened
  • the above-mentioned cured product may be provided on the entire surface of at least one surface of the above-mentioned laminated base material, or may be provided only on a part thereof.
  • the cured product is preferably an optical member, and more preferably has a desired shape that can be suitably used as an optical member.
  • the optical member examples include, as convex lenses, cylindrical lenses, prism lenses, hemispherical microlenses, Fresnel lenses, and lenticular lenses in which a plurality of convex lenses (cylindrical lenses) are arranged in one direction.
  • the member may be in the form of dots (dots) or columns (lines), but is preferably columns having a large contact area with the laminated base material.
  • the cross section of the column in the column is not particularly limited, such as polygonal and semicircular, but it is more preferable to be semicircular so as to easily disperse the residual stress generated in the member.
  • the cured product (optical member) is preferably a lens, and more preferably a cylindrical lens.
  • the size of the lenticular lens is preferably 50 ⁇ m to 1,000 ⁇ m, more preferably 80 ⁇ m to 600 ⁇ m, and still more preferably 100 ⁇ m to 300 ⁇ m.
  • the height of the lenticular lens is preferably 10 ⁇ m to 500 ⁇ m, more preferably 15 ⁇ m to 400 ⁇ m, and still more preferably 20 ⁇ m to 300 ⁇ m.
  • the size of the lenticular lens becomes appropriate, and when winding in a roll shape or cutting out a laminated sheet and stacking it as a sheet, the lenticular lens In addition, damage to the print layer, which will be described later, caused by the contact with the above, and a decrease in adhesion of the print layer are suppressed. Furthermore, when the sheet is wound into a roll shape or the laminated sheet is cut out and stacked as a single sheet, the slidability of the lenticular lens and the print layer becomes good, and the handleability becomes good.
  • cured material is formed by hardening
  • the laminated sheet according to the present disclosure may have a print layer on the side opposite to the side on which the cured product of the laminated base material is disposed, from the viewpoint of design. Formation of a printing layer is performed by a conventional method according to the intended purpose of a lamination sheet. Examples of printing methods for forming the printing layer include offset printing method, screen printing method, inkjet printing method, lithographic printing method, flexographic printing method, gravure printing method, printing method using a printing roll, and the like. Among them, the offset printing method, the ink jet method and the like are preferable from the viewpoint of the accuracy of thin lines of the lenticular changing printing.
  • the printing can be performed, for example, by applying an ultraviolet curable ink (UV ink) onto the surface of the laminated substrate using a screen printer, an inkjet recording device, or the like.
  • an ultraviolet curable ink for example, a UV ink containing a (meth) acrylate compound can be used.
  • it can carry out using an offset printing apparatus.
  • offset printing a multicolor image is formed by using a plurality of devices.
  • oil-based offset ink or ultraviolet curing offset ink can be used as printing ink, for example.
  • printing can be performed using a synthetic rubber printing roll equipped with a metal doctor blade.
  • the ink applied to the surface of the laminated substrate is filled between the printing roll and the doctor blade, and when the printing roll rotates, the uncured ink adheres to the surface of the laminated substrate in contact with the printing roll.
  • printing can also be performed on the convex portion of the laminated sheet.
  • printing can be performed by moving the lamination sheet in the same direction as the rotation direction of the printing roll by a conveyance device of the lamination sheet at a specific speed such as 5 m / min.
  • an ink suitable for the printing method may be selected and used.
  • the viscosity of the ink used for printing is not particularly limited. For example, in the case of a lithographic printing ink, 15 Pa ⁇ s to 30 Pa ⁇ s, in the case of a flexographic printing ink, 1 Pa ⁇ s to 5 Pa ⁇ s, a screen printing ink If it is, it can be in the range of 2 Pa ⁇ s to 5 Pa ⁇ s, and if it is an ink for gravure printing, it can be in the range of 1 Pa ⁇ s to 5 Pa ⁇ s or the like. The viscosity of the ink is not limited to these ranges.
  • a known ink receiving layer may be provided on the surface of the laminated base on which the printing layer is to be formed.
  • the ink receiving layer may be formed according to the characteristics of the printing ink used for forming the printing layer. From the viewpoint of enhancing the adhesion between the substrate and the print layer, the surface of the substrate on which the print layer is to be formed may be subjected to surface treatment (for example, corona discharge treatment).
  • the ink receiving layer may be provided, for example, by applying a preparation liquid for forming the ink receiving layer to a substrate.
  • the application of the preparation liquid can be performed, for example, by application.
  • the preparation liquid preferably contains a solid component and a solvent for forming the ink receiving layer.
  • the ink receiving layer preferably contains a resin, and at least a part of the resin is preferably crosslinked by a crosslinking agent. Therefore, the aspect containing resin and a crosslinking agent as a solid component contained in preparation liquid is preferable.
  • the resin used to form the ink receiving layer is preferably at least one resin selected from the group consisting of polyester resins, acrylic resins and urethane resins, and is particularly advantageous when forming parallax images by offset printing is there.
  • thermoplastic resin layer (also referred to as a “backing layer”) on the printing layer from the viewpoint of three-dimensional moldability and protection of the printing layer during injection molding described later.
  • thermoplastic resins used for the thermoplastic resin layer include olefin-based thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); vinyl chloride, chlorinated vinyl resin, etc.
  • Halogen-containing thermoplastic resins such as polymethyl methacrylate; polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer etc.
  • Plastic resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyamides such as nylon 6, nylon 66 and nylon 610; Polyacetal; Polycarbonate resin; Polyphenylene oxide; Nsurufido; polyetheretherketone; polysulfone; polyether sulfone; polyoxyethylene benzylidene alkylene; polyamideimide, acrylic resins.
  • styrene thermoplastic resins are preferable, and acrylonitrile-butadiene-styrene copolymer (ABS resin) is particularly preferable, from the viewpoints of three-dimensional moldability and protection of the printing layer at the time of injection molding.
  • the thickness of the thermoplastic resin layer is preferably 0.10 mm to 0.50 mm, and is 0.20 mm to 0.45 mm, from the viewpoint of followability at the time of heat molding and protection of the printing layer at the time of injection molding. Is more preferable, and 0.35 mm to 0.45 mm is particularly preferable.
  • thermoplastic resin layer does not have a restriction
  • a method of attaching a thermoplastic resin sheet to the print layer with a hot melt adhesive is preferable. That is, the laminated sheet according to the present disclosure preferably has a hot melt layer made of a hot melt adhesive between the print layer and the thermoplastic resin layer.
  • the adhesive used in the present disclosure, in particular a hot melt adhesive is not particularly limited, and any known adhesive can be used. Depending on the situation, it may be selected appropriately.
  • the thickness of the hot melt layer is not particularly limited as long as sufficient adhesion can be obtained.
  • the laminated sheet according to the present disclosure may further have a protective layer on the cured product in order to protect the cured product, which is an optical member or the like, from scratches and the like.
  • a protective layer a thermoplastic resin is mentioned suitably.
  • the sheet or film of the thermoplastic resin used for the thermoplastic resin layer mentioned above can be used suitably for formation of a protective layer, and the said sheet or film may be stuck.
  • the thickness of the protective layer is preferably in the range of 30 ⁇ m to 400 ⁇ m from the viewpoint of sheet handling.
  • the shape of the protective layer may or may not follow the shape of the cured product. For example, a sheet-like protective layer may be provided on the cured product without following the shape of the cured product.
  • the protective layer may be in close contact with at least a part of the cured product. Also, the formation of the protective layer may be before or after the formation of the printing layer.
  • the lamination sheet which concerns on this indication may have another well-known structure other than the structure mentioned above.
  • the lenticular sheet may be a lenticular decorative sheet having an ink receiving layer and a lenticular image.
  • a lenticular sheet is a display medium that displays an image different according to the viewing angle by having a lenticular lens in which convex cylindrical lenses having semi-cylindrical surfaces are arranged in one direction on an image suitable for lenticular display Display body).
  • FIG. 1 is a schematic view showing an example of a lenticular sheet.
  • the lenticular sheet 10 shown in FIG. 1 is a semicylindrical shape of a lenticular lens 12 in which a plurality of convex lenses (cylindrical lenses) 12A having a semicylindrical surface are arranged in one direction and a convex lens 12A of the lenticular lens 12. And a lenticular image 14 disposed on the side opposite to the front surface.
  • the x direction indicates the width direction of the lens
  • the y direction indicates the longitudinal direction of the lens.
  • the lenticular sheet preferably has a lenticular lens layer in which a plurality of cylindrical lenses having a semi-cylindrical surface are arranged in parallel.
  • the width per cylindrical lens is not particularly limited, and the pitch width of the lens may be selected depending on the purpose.
  • the width per cylindrical lens is usually represented by LPI (Line Per Inch), which represents the number of lenses per inch (2.54 cm). For example, 100 LPI indicates that 100 cylindrical lenses (100 rows) are arranged in parallel, and the lens pitch is 254 ⁇ m. As the number of lines per inch (the number of arranged lenses) increases, the lens pitch decreases and the definition improves.
  • a low definition lenticular sheet (for example, 60 LPI etc.) is suitable for use as a poster or the like displaying a pattern with a relatively distant viewing position, but for the purpose of reading small text information such as a business card, It is preferable that the lenses constituting the lenticular lens layer are arranged in parallel at least 100 rows per one inch. On the other hand, from the viewpoint of the resolution of the lenticular image, it is more preferable that the number of arrangement of the convex lenses constituting the lenticular lens layer is 200 or less (200 LPI) per 2.54 cm.
  • the lenticular image 14 is a display image sequence 14A, 14B for displaying two display images separately, and an interpolation image sequence 14C inserted between adjacent display image sequences 14A, 14B.
  • image sequence groups including. Specifically, the display image sequences 14A and 14B extracted in stripes from each display image are arranged adjacent to each other for each convex lens 12A at the corresponding position, and the adjacent display image sequences 14A, The color (interpolated color) between the color of one of the adjacent display image sequences 14A and 14B and the other color at the position where the colors of the adjacent display image sequences 14A and 14B are different from each other between 14B. An interpolated image sequence 14C is inserted.
  • curable composition below, although an example of the curable composition which can be used suitably for formation of the said hardened
  • cured material is obtained by containing these components suitably.
  • the curable composition used in the present disclosure preferably contains a polymerizable compound.
  • a polymerizable compound an ethylenically unsaturated compound is preferable.
  • Preferred examples of the ethylenically unsaturated compound include polyfunctional (meth) acrylate compounds having a ring structure, and N-vinyl compounds.
  • the curable composition used in the present disclosure contains a polyfunctional (meth) acrylate compound having a ring structure, and an N-vinyl compound, from the viewpoint of the steric moldability and the abrasion resistance of the resulting cured product. Is preferred.
  • the curable composition used for this indication contains the polyfunctional (meth) acrylate compound which has ring structure from a stereoformability and abrasion resistance viewpoint of the cured
  • the above ring structure is not particularly limited, but is an aliphatic hydrocarbon ring structure which may partially have a hetero atom as a ring member, and fat which may partially have a hetero atom as a ring member Preferred examples include fused ring structures in which two or more aromatic hydrocarbon rings are fused. Further, the aliphatic hydrocarbon ring is preferably a 5- or 6-membered ring.
  • a nitrogen atom is especially preferable.
  • the ring structure selected from the group consisting of an isocyanuric ring structure, a tricyclodecane ring structure, a triazine ring, and a cyclohexane ring structure from the viewpoint of stereoformability and abrasion resistance of a cured product obtained.
  • One ring structure is preferable, an isocyanuric ring structure or a tricyclodecane ring structure is more preferable, and an isocyanuric ring structure is particularly preferable.
  • the polyfunctional (meth) acrylate compound which has a ring structure in this indication does not contain urethane bonds other than isocyanuric ring structure.
  • the polyfunctional (meth) acrylate compound having the above ring structure is not particularly limited as long as it is bifunctional or more, but is trifunctional to hexafunctional from the viewpoint of three-dimensional moldability and abrasion resistance of a cured product to be obtained Is preferred, trifunctional or tetrafunctional is more preferred, and trifunctional is particularly preferred.
  • polyfunctional (meth) acrylate compound having the above ring structure examples include tricyclodecanedimethanol di (meth) acrylate, di (meth) acryloxyalkylated isocyanurate, isocyanuric acid ethylene oxide (hereinafter, ethylene oxide Also referred to as "EO") modified tri (meth) acrylate, ethylene oxide modified with isocyanuric acid ethylene oxide di (meth) acrylate and the like.
  • EO ethylene oxide Also referred to as "EO”
  • isocyanuric acid ethylene oxide modified tri (meth) acrylate is particularly preferable.
  • the molecular weight of the polyfunctional (meth) acrylate compound having the above ring structure is preferably 200 or more and 1,500 or less.
  • the curable composition used in the present disclosure may contain the polyfunctional (meth) acrylate compound having a ring structure singly or in combination of two or more.
  • the content of the polyfunctional (meth) acrylate compound having a ring structure in the curable composition used in the present disclosure is the total mass of the curable composition from the viewpoint of three-dimensional moldability and abrasion resistance of the resulting cured product 1 mass% or more and 75 mass% or less are preferable, 10 mass% or more and 70 mass% or less are more preferable, and 15 mass% or more and 40 mass% or less are more preferable.
  • the curable composition used in the present disclosure is a polymerizable compound having a nitrogen atom-containing group and a polymerizable group other than the polyfunctional (meth) acrylate compound having the above ring structure (hereinafter also referred to as "specific polymerizable compound") It is preferable to contain.
  • the "polymerizable group” is preferably a group having an ethylenically unsaturated bond.
  • the specific polymerizable compound from the viewpoint of adhesion and thermoforming, at least one selected from the group consisting of N-vinyl compounds and compounds represented by formula (I) or formula (II) described later It is preferably one compound, more preferably at least one compound selected from the group consisting of an N-vinyl compound and a compound represented by the formula (II) described later, N-vinyl compound It is particularly preferable that it is at least one compound selected from the group consisting of pyrrolidone and N-vinylcaprolactam.
  • N-vinylpyrrolidone include N-vinyl-2-pyrrolidone and the like.
  • N-vinylcaprolactam include N-vinyl- ⁇ -caprolactam and the like.
  • the molecular weight of the specific polymerizable compound is preferably 300 or less, more preferably 250 or less, still more preferably 150 or less, and particularly preferably 100 or less from the viewpoint of adhesion and thermoformability.
  • the lower limit of the molecular weight of the specific polymerizable compound is not particularly limited, but is preferably 50 or more.
  • the molecular weight of the specific polymerizable compound is determined from the chemical formula by arithmetic calculation.
  • the specific polymerizable compound preferably has a component ( ⁇ p) of the polar term of the SP value in the range of 5 MPa (1/2) to 15 MPa (1/2) .
  • ⁇ p of the polymerizable compound is close to ⁇ p of the substrate, excellent adhesion is exhibited.
  • a resin substrate having ⁇ p of 5 MPa (1/2) to 15 MPa (1/2) is preferable as a substrate. Details of the resin base will be described later.
  • the base material is, for example, polymethyl methacrylate (PMMA)
  • PMMA polymethyl methacrylate
  • the ⁇ p of PMMA is 10.5 MPa (1/2) , and thus the effect of improving adhesion of the cured product to the base material by containing the specific polymerizable compound is high.
  • the ⁇ p of the specific polymerizable compound 7MPa (1/2) ⁇ 13MPa ( 1/2) are preferred, 10.5MPa (1/2) ⁇ 11MPa ( 1/2) is preferred.
  • the component ( ⁇ p) of the polar term of the SP value is a value calculated by the Hansen solubility parameter.
  • the Hansen solubility parameter is composed of intermolecular dispersive energy ( ⁇ d), intermolecular polarity energy ( ⁇ p), and intermolecular hydrogen bonding energy ( ⁇ h).
  • HSPiP version 4.1.07 software for calculation.
  • the compound represented by the following formula (I) or formula (II) can be mentioned suitably from a thermoformability and a curable viewpoint.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
  • R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • X 1 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
  • R 1 , R 2 , R 3 , R 4 and X 1 may be the same or different, and may form a ring with each other.
  • Examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms as R 1 and R 2 include alkyl groups such as methyl, ethyl, propyl, butyl and hexyl groups. . Among them, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 2 carbon atoms is more preferable. As a hydrocarbon group, an alkyl group is preferable. Among the above, R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom.
  • hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R 3 and R 4 , for example, alkyl such as methyl group, ethyl group, isopropyl group, t-butyl group, hexyl group and the like And cycloalkyl groups such as cyclopentyl and cyclohexyl.
  • R 3 and R 4 may be bonded to each other to form a ring.
  • the ring formed by combining R 3 and R 4 is preferably a saturated heterocyclic ring.
  • substituent group T As a substituent which a hydrocarbon group may have, the group in the substituent group T shown below is mentioned.
  • An alkyl group preferably having 1 to 10, more preferably 1 to 8, particularly preferably 1 to 6 carbon atoms (also referred to as “carbon atom number”), and examples thereof include methyl, ethyl, isopropyl and tert.
  • alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2) And particularly preferably 2 to 6, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group and the like), an alkynyl group (preferably having 2 to 10 carbon atoms, more preferably The number is preferably 2 to 8, particularly preferably 2 to 6, and examples thereof include propargyl and 3-pentynyl), aryl groups (preferably having carbon atoms) And more preferably 6 to 15, particularly preferably 6 to 12, and examples thereof include a phenyl group, a biphenyl group and a naphthyl group), an amino group (preferably having a carbon number of 0 to 15, and more preferably And particularly
  • It has 2 to 15 carbon atoms, more preferably 2 to 10, and particularly preferably 2 to 8, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group, and an aryloxycarbonyl group (preferably having a carbon number of 7 to 6).
  • acyloxycarbonyl group and the like examples thereof include a phenyloxycarbonyl group and the like
  • an acyloxy group preferably having 2 to 15 carbon atoms, more preferably 2 to 10, particularly preferably Preferably 2 to 8, and examples thereof include an acetoxy group, a benzoyloxy group, etc.
  • an acylamino It is preferably a group having 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples include acetylamino and benzoylamino. ),
  • alkoxycarbonylamino group preferably having 2 to 15 carbon atoms, more preferably 2 to 10, and particularly preferably 2 to 8 carbon atoms, such as methoxycarbonylamino group and the like
  • aryloxycarbonylamino group preferably having 2 to 15 carbon atoms.
  • the carbon number is 7 to 15, more preferably 7 to 13, particularly preferably 7 to 10, and examples thereof include a phenyloxycarbonylamino group and the like), and a sulfonylamino group (preferably having a carbon number of 1 to 15) It is preferably 1 to 10, particularly preferably 1 to 8, and examples thereof include a methanesulfonylamino group, a benzenesulfonylamino group and the like), a sulfamoyl group (preferably having a carbon number of 0 to 15, more preferably 0 to 10).
  • sulfamoyl group methyl sulfa And dimethylsulfamoyl, phenylsulfamoyl and the like
  • carbamoyl preferably having 1 to 15 carbon atoms, more preferably 1 to 10, particularly preferably 1 to 8 carbon atoms, and the like And carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like
  • alkylthio group preferably having 1 to 15 carbon atoms, more preferably 1 to 10, particularly preferably 1 to 8 carbon atoms, And methylthio, ethylthio and the like
  • arylthio preferably having 6 to 20 carbon atoms, more preferably 6 to 15, and particularly preferably 6 to 12 carbon atoms, such as phenylthio).
  • a sulfonyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 16, particularly preferably It is 1 to 12, and examples thereof include a mesyl group, a tosyl group, etc.), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12), for example methanesulfinyl Group, benzenesulfinyl group etc., ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms), for example ureido group, methyl ureido group, phenyl ureido Groups, etc.), phosphoric acid amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid
  • nitrogen atom, oxygen atom, sulfur atom specifically imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like can be mentioned. ).
  • R 3 and R 4 are preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a hydrocarbon group having 1 to 6 carbon atoms.
  • a hydrocarbon group an alkyl group is preferable.
  • the saturated heterocyclic ring includes a pyrrolidine ring, a piperidine ring, a morpholine ring and the like.
  • R 3 and R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 are bonded to each other Also preferred are morpholine rings formed.
  • hydrocarbon group having 1 to 5 carbon atoms which may have a substituent in X 1 examples include alkyl groups such as methyl, ethyl, propyl and butyl. Among them, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 or 2 carbon atoms is more preferable. As a hydrocarbon group, an alkyl group is preferable. As a substituent which may be possessed by a hydrocarbon group, groups in the aforementioned substituent group T can be mentioned. Among the above, X 1 is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • X 2 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
  • At least one of R 5 , R 6 and R 7 contains a nitrogen atom bonded to a carbon atom of a hydrocarbon group.
  • X 2 , R 5 , R 6 and R 7 may be the same or different, and may form a ring with each other.
  • Examples of the optionally substituted hydrocarbon group having 1 to 6 carbon atoms as R 5 and R 6 include alkyl groups such as methyl, ethyl, propyl, butyl and hexyl. . Among them, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 2 carbon atoms is more preferable. As a hydrocarbon group, an alkyl group is preferable. Among the above, R 5 and R 6 are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
  • examples of the optionally substituted hydrocarbon group having 1 to 20 carbon atoms as R 7 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group. . Among them, R 7 is preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms. As a hydrocarbon group, an alkyl group is preferable. Among the above, R 7 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As a substituent which said hydrocarbon group may have, the group in the substituent group T as stated above is mentioned.
  • R 5 , R 6 and R 7 is a group containing a nitrogen atom, that is, it contains a nitrogen atom bonded to a carbon atom of a hydrocarbon group
  • R 5 , R 6 and R 7 At least one is preferably a hydrocarbon group substituted with a nitrogen-containing group or a cyano group.
  • the hydrocarbon group substituted with a nitrogen-containing group is preferably a C 1-10 alkyl group substituted with a nitrogen-containing group.
  • the hydrocarbon group substituted with a nitrogen-containing group in R 5 , R 6 and R 7 is preferably —C n H 2 n NR 11 R 12 .
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —COOR 13 , and R 13 represents an alkyl group having 1 to 4 carbon atoms.
  • R 11 and R 12 may be bonded to each other to form a ring.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 11 , R 12 and R 13 include a methyl group, an ethyl group, an isopropyl group and a t-butyl group.
  • Examples of the C1-C10 alkyl group substituted with a nitrogen-containing group include 1-cyanoethyl group, cyanomethyl group, N, N-dimethylaminoethyl group, methoxycarbonylaminoethyl group and the like.
  • Examples of the hydrocarbon group having 1 to 5 carbon atoms which may have a substituent in X 2 include, for example, alkyl groups such as methyl, ethyl, propyl and butyl.
  • a hydrocarbon group of -4 is preferable, more preferably a hydrocarbon group having 1 to 2 carbon atoms.
  • As a hydrocarbon group an alkyl group is preferable.
  • X 2 is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
  • the content of the specific polymerizable compound is preferably 1% by mass to 60% by mass, and more preferably 5% by mass to 50% by mass, with respect to the total mass of the curable composition, from the viewpoint of heat resistance and adhesion. Is more preferable, and 10% by mass to 40% by mass is particularly preferable.
  • the curable composition used in the present disclosure preferably contains a monofunctional (meth) acrylate compound from the viewpoint of the three-dimensional moldability and the abrasion resistance of the resulting cured product.
  • a monofunctional (meth) acrylate compound a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure and a (meth) acryloyl group at the end, from the viewpoint of stereoformability and abrasion resistance of the resulting cured product
  • resins having a group are preferred.
  • the curable composition used in the present disclosure preferably contains a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure, from the viewpoint of three-dimensional moldability and abrasion resistance of the resulting cured product.
  • the aliphatic hydrocarbon ring structure is selected from the group consisting of a tricyclodecane ring structure, a cyclohexane ring structure, a norbornene ring structure, and an adamantane ring structure from the viewpoints of stereoformability and abrasion resistance of a cured product to be obtained At least one ring structure is preferred, and a tricyclodecane ring structure is more preferred.
  • a monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure it has a tricyclodecane ring structure such as dicyclopentanyl (meth) acrylate and dicyclopentanyl oxy (meth) acrylate (Meth) acrylate compounds, (meth) acrylate compounds having a cyclohexane ring structure such as cyclohexyl (meth) acrylate, (meth) acrylate compounds having a norbornene ring structure such as isoboronyl (meth) acrylate, 1-adamantyl (meth) acrylate, etc.
  • a tricyclodecane ring structure such as dicyclopentanyl (meth) acrylate and dicyclopentanyl oxy (meth) acrylate (Meth) acrylate compounds
  • (meth) acrylate compounds having a cyclohexane ring structure such as cyclohexyl (meth) acryl
  • (meth) acrylate compounds having an adamantane ring structure of Among them, a (meth) acrylate compound having a tricyclodecane ring structure is preferable, and dicyclopentanyl (meth) acrylate is more preferable, from the viewpoint of three-dimensional moldability and abrasion resistance of a cured product to be obtained.
  • the curable composition used in the present disclosure may contain one kind of monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure alone, or may contain two or more kinds.
  • the content of the monofunctional (meth) acrylate compound having an aliphatic hydrocarbon ring structure in the curable composition used in the present disclosure is a curable composition from the viewpoint of three-dimensional moldability and abrasion resistance of the resulting cured product. 0.5 mass% or more and 50 mass% or less are preferable with respect to the total mass of a thing, 5 mass% or more and 45 mass% or less are more preferable, 10 mass% or more and 40 mass% or less are especially preferable.
  • the curable composition used in the present disclosure preferably contains a resin having a (meth) acryloyl group at an end. Since the above-mentioned resin has a (meth) acryloyl group at the end of the molecular chain, the crosslink density in the entire curable composition can be obtained by using it in combination with another polymerizable compound, particularly a polyfunctional (meth) acrylate compound. It is controlled, and it is excellent in the three-dimensional moldability and abrasion resistance of the hardened
  • the resin may be a polymer having a (meth) acryloyl group at its terminal, and examples thereof include (meth) acrylic resin, polystyrene, polystyrene / methacrylate (MS resin), polystyrene / acrylonitrile (AS resin), polypropylene, polyethylene, Polymers having at least one (meth) acryloyl group at the end of the main chain structure, such as polyethylene terephthalate, glycol-modified polyethylene terephthalate, polyvinyl chloride (PVC), thermoplastic elastomers, or copolymers thereof, cycloolefin polymers, etc. Can be mentioned.
  • a (meth) acrylic resin having a (meth) acryloyl group at an end or a polystyrene having a (meth) acryloyl group at an end is preferable from the viewpoint of three-dimensional moldability and abrasion resistance of a cured product obtained.
  • (Meth) acrylic resin having a (meth) acryloyl group is more preferable.
  • polymethyl methacrylate having a (meth) acryloyl group at an end is preferable from the viewpoint of abrasion resistance.
  • the resin which has a (meth) acryloyl group at the terminal 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 the resin having a (meth) acryloyl group at one end of the main chain Is more preferred.
  • the “main chain” represents a relatively long bond chain in the molecule of the polymer compound constituting the resin
  • the “side chain” represents a carbon chain branched from the main chain. .
  • Examples of the resin having a (meth) acryloyl group at an end include macromonomer series (eg, macromonomer AA-6 (polymethyl methacrylate having a methacryloyl group) manufactured by Toagosei Co., Ltd., macromonomer AS-6 or AS) -6S (polystyrene having a methacryloyl group), macromonomer AN-6S (polystyrene / acrylonitrile having a methacryloyl group), macromonomer AB-6 (polybutyl methacrylate having a methacryloyl group), and the like can be used.
  • macromonomer series eg, macromonomer AA-6 (polymethyl methacrylate having a methacryloyl group) manufactured by Toagosei Co., Ltd., macromonomer AS-6 or AS) -6S (polystyrene having a methacryloyl group), macromon
  • 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 three-dimensional moldability of the cured product obtained Preferably, 5,000 or more and 10,000 or less are more preferable.
  • the resin in the present disclosure preferably has a number average molecular weight of 1,000 or more.
  • the glass transition temperature (Tg) of the resin having a (meth) acryloyl group at the end is preferably 50 ° C. or more, more preferably 80 ° C. or more, from the viewpoint of the abrasion resistance of the obtained cured product. Further, from the viewpoint of adhesion of the cured product to a resin substrate obtained and the three-dimensional moldability, Tg is preferably less than 250 ° C., and more preferably 200 ° C. or less.
  • the curable composition used in the present disclosure may contain a single type of resin having a (meth) acryloyl group at an end, or may contain two or more types.
  • the content of the resin having a (meth) acryloyl group at the end of the curable composition used in the present disclosure is the total mass of the curable composition from the viewpoint of three-dimensional moldability and abrasion resistance of the resulting cured product.
  • 0.5 mass% or more and 50 mass% or less are preferable, 5 mass% or more and 45 mass% or less are more preferable, and 10 mass% or more and 40 mass% or less are particularly preferable.
  • the curable composition used in the present disclosure may contain a monofunctional (meth) acrylate compound (other monofunctional (meth) acrylate compound) other than the urethane (meth) acrylate described above and later described.
  • monofunctional (meth) acrylate compounds include 2-ethyl-2-butylpropanediol (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl ( Ta)
  • the curable composition used in the present disclosure may contain other monofunctional (meth) acrylate compounds singly or in combinations of two or more.
  • the curable composition used in the present disclosure does not contain another monofunctional (meth) acrylate compound or the content of the curable composition is from the viewpoint of the abrasion resistance of the resulting cured product.
  • the content is 20 mass% or less with respect to the total mass, or it is not contained, or it is more preferable that the content is 10 mass% or less with respect to the total mass of a curable composition, It is more preferable that the content thereof is 5% by mass or less based on the total mass of the curable composition, or the content does not contain or the content of the total mass of the curable composition It is particularly preferable that the amount is 1 mass% or less.
  • the curable composition used for this indication may contain a monofunctional (meth) acrylate compound individually by 1 type, and may contain 2 or more types.
  • the content of the monofunctional (meth) acrylate compound in the curable composition used in the present disclosure is, relative to the total mass of the curable composition, from the viewpoint of three-dimensional moldability and abrasion resistance of the resulting cured product, 1 mass% or more and 80 mass% or less are preferable, 15 mass% or more and 75 mass% or less are more preferable, and 30 mass% or more and 70 mass% or less are particularly preferable.
  • the curable composition used in the present disclosure may contain a urethane (meth) acrylate compound.
  • the urethane (meth) acrylate compound in the present disclosure is a compound having one or more urethane bonds and one or more (meth) acryloyl groups.
  • 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 is preferably bifunctional to 15 functional.
  • the weight average molecular weight of the urethane (meth) acrylate compound is preferably 1,000 or more and 100,000 or less.
  • 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 (anhydride) phthalic acid, hexahydro (anhydride) 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, etc.
  • polyether polyols such as polyethylene glycol and polytetramethyl glycol
  • succinic acid, adipic acid, azelaic acid, sebacic acid phthalic acid, tetrahydro (anhydride) phthalic acid, hexahydro (
  • Polyester polyols obtained by the method; poly ⁇ -caprolactone modified polyols; polymethyl valerolactone modified polyols; ethylene glycol, propylene glycol, 1,4-butanediyl Alkyl polyols such as 1,6-hexanediol and neopentyl glycol; bisphenol A skeleton alkylene oxide modified polyols such as ethylene oxide added bisphenol A, propylene oxide added bisphenol A; ethylene oxide added bisphenol F, propylene oxide added bisphenol F and the like Bisphenol F skeleton alkylene oxide modified polyol, or a mixture thereof and tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, organic polyisocyanate such as diphenylmethane diisocyanate, xylylene diisocyanate and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Hydroxy group containing (meth)
  • urethane (meth) acrylate compound a purple light series made by Nippon Synthetic Chemical Industry Co., Ltd., U-2PPA made by Shin-Nakamura Chemical Co., Ltd., U-4HA, U-6HA, U-6LPA U-15HA, U-324A, UA-122P, UA5201, UA-512, etc .; CN 964A 85, CN 964, CN 959, CN 962, J 996, CN 963, CN 982 B 88, CN 981, CN 983, CN 996, CN 9002, CN 964, CN 964, CN 959 CN9007, CN9009, CN9010, CN9011, CN9178, CN9788, CN9893, EB 204, EB230, EB244, EB245, EB270, EB284, EB285, EB810, EB483 manufactured by Daicel Cytech Co
  • the curable composition used for this indication may contain a urethane (meth) acrylate compound individually by 1 type, and may contain 2 or more types.
  • the curable composition used in the present disclosure does not contain a urethane (meth) acrylate compound from the viewpoint of three-dimensional moldability of a cured product to be obtained, or the content thereof is the total mass of the curable composition.
  • the content is more preferably 1% by mass or less, and particularly preferably not contained, with respect to the total mass of the curable composition.
  • the curable composition used in the present disclosure includes a polyfunctional (meth) acrylate compound having a ring structure and a polyfunctional (meth) acrylate compound (other polyfunctional (meth) acrylate compound) other than a urethane (meth) acrylate compound. May be included.
  • polyfunctional (meth) acrylate compounds include diethylene glycol monoethyl ether di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene Oxide-modified 1,6-hexanediol di (meth) acrylate, ECH modified 1,6-hexanediol di (meth) acrylate, aryloxy polyethylene glycol (meth) acrylate, 1,9-nonanediol di (meth) acrylate, ECH Modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, pro Len oxide (hereinafter also referred to as “
  • the curable composition used in the present disclosure may contain other multifunctional (meth) acrylate compounds singly or in combination of two or more.
  • the curable composition used in the present disclosure does not contain other polyfunctional (meth) acrylate compounds, or the content of the curable composition is that of the curable composition from the viewpoint of three-dimensional formability of the resulting cured product.
  • the content is 20 mass% or less with respect to the total mass, or it is not contained, or it is more preferable that the content is 10 mass% or less with respect to the total mass of a curable composition, It is more preferable that the content thereof is 5% by mass or less based on the total mass of the curable composition, or the content does not contain or the content of the total mass of the curable composition It is particularly preferable that the amount is 1% by mass or less.
  • the curable composition used in the present disclosure may contain other ethylenically unsaturated compounds other than those described above.
  • known polymerizable compounds particularly known ethylenically unsaturated compounds can be used.
  • the curable composition used in the present disclosure preferably contains a polymerization initiator from the viewpoint of curability.
  • a polymerization initiator known photopolymerization initiators and known thermal polymerization initiators can be used. Among them, from the viewpoint of the three-dimensional moldability and the abrasion resistance of the cured product to be obtained, a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.
  • the photoradical polymerization initiator is not particularly limited in structure, and examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2,2 -Dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl 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-methyl-propionyl) benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl- 1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, etc. Can.
  • photoradical polymerization initiator commercially available commercial products may be used, and specific examples of the commercial products include IRGACURE series manufactured by BASF (eg, IRGACURE TPO, IRGACURE 819, IRGACURE 651, IRGACURE 184, IRGACURE 1173) , IRGACURE 2959, IRGACURE 127, IRGACURE 907, etc.).
  • IRGACURE series manufactured by BASF eg, IRGACURE TPO, IRGACURE 819, IRGACURE 651, IRGACURE 184, IRGACURE 1173
  • IRGACURE 2959 IRGACURE 127, IRGACURE 907, etc.
  • a well-known azo compound As a thermal polymerization initiator, a well-known azo compound, a well-known peroxide compound, etc. are mentioned. An azobis compound can be mentioned as said azo compound. Moreover, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxy dicarbonate etc. can be mentioned as said peroxide compound.
  • the curable composition used for this indication may contain a polymerization initiator individually by 1 type, and may contain 2 or more types.
  • the content of the polymerization initiator in the curable composition used in the present disclosure is 0.05 mass based on the total mass of the curable composition from the viewpoint of three-dimensional moldability and abrasion resistance of the resulting cured product % Or more and 10% by mass or less is preferable, 0.1% by mass or more and 10% by mass or less is more preferable, 0.1% by mass or more and 5% by mass or less is more preferable, and 0.5% by mass or more and 3% by mass or less is particularly preferable .
  • the curable composition used for this indication may contain other components, such as an organic solvent and an inorganic particle, as needed other than the above-mentioned component.
  • the organic solvent include toluene and methyl ethyl ketone. Since the curable composition used for this indication contains polymeric compounds, such as said (meth) acrylic compound, it does not need to contain an organic solvent separately, a polymeric compound also having a function as a solvent.
  • the inorganic particles include particles called so-called fillers such as silicon dioxide (silica).
  • commercially available commercial products include organosilica sol MEK-ST series (eg, MEK-ST-40, MEK-ST-L, etc.) manufactured by Nissan Chemical Industries, Ltd.
  • the curable composition used in the present disclosure is preferably a composition curable by actinic radiation.
  • actinic radiation is a radiation capable of giving energy to generate a polymerization initiation species in the curable composition by the irradiation, and includes alpha rays, gamma rays, X rays, ultraviolet rays, visible rays, electron rays and the like. . Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable, from the viewpoint of curing sensitivity and availability of the apparatus.
  • the curable composition used in the present disclosure is preferably an active radiation curable type curable composition, and more preferably an oil-based curable composition.
  • the curable composition used in the present disclosure preferably contains as little water and volatile solvent as possible, and even if contained, it is 5% by mass or less based on the total mass of the curable composition.
  • the content is preferably 1% by mass or less, particularly preferably 0.5% by mass or less.
  • the manufacturing method of the lamination sheet concerning this indication does not have a restriction
  • the laminate base and the curable composition in the method of producing a laminate sheet according to the present disclosure those described above can be suitably used.
  • the application amount of the curable composition in the step of applying the curable composition is not particularly limited, and may be an amount capable of forming a desired member.
  • the method for applying the curable composition is not particularly limited, and spin coating method, gravure printing method, flexographic printing method, ink jet method, die coating method, slit die coating method, cap coating method, dipping method, etc. are known. Conventional methods can be used.
  • the curable composition is first mold into a desired cured product shape before curing.
  • the molding is not particularly limited as long as a desired shape can be obtained, but in terms of molding efficiency and molding accuracy, molding using a mold such as a mold or a wood mold is preferable.
  • the curable composition is applied to a laminated base material, dried if necessary, and then the active radiation is applied from the substrate side while a mold is applied with a mold processed into a desired lens shape. And the curable composition may be cured. Thereby, a cured product molded into the target shape is stably obtained.
  • a mercury lamp, a metal halide lamp, a fluorescent lamp, a gas laser, a solid laser and the like are widely known.
  • a semiconductor ultraviolet light emitting device may be applied as a light source, and in terms of small size, high life, high efficiency, and low cost, LEDs (Light Emitting Diodes) and LDs (Laser Diodes) are also suitable.
  • a metal halide lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an LED or a blue-violet laser is preferable.
  • an ultra high pressure mercury lamp capable of light irradiation with a wavelength of 365 nm, 405 nm or 436 nm
  • a high pressure mercury lamp capable of light irradiation with a wavelength of 365 nm, 405 nm or 436 nm
  • LEDs capable of emitting light at wavelengths of 355 nm, 365 nm, 385 nm, 395 nm or 405 nm are particularly preferred.
  • the dose of actinic radiation may be appropriately selected depending on the composition and amount of the curable composition, it is preferable to 0.3 J / cm 2 or more 5 J / cm 2 or less.
  • the irradiation with actinic radiation can be performed by selecting a known device provided with a light source capable of emitting actinic radiation described above.
  • a light source capable of emitting actinic radiation described above.
  • an ultraviolet (UV) irradiation apparatus such as EXECURE 3000 manufactured by HOYA CANDEO OPTRONICS may be used.
  • the manufacturing method of the lamination sheet which concerns on this indication can include arbitrary other processes.
  • printing is performed on the surface of the laminated base opposite to the side having the cured product to form a printed layer, and The process of forming a layer, the process of providing a protective layer on the said hardened
  • the printing method mentioned above is mentioned suitably as a printing method in a process of forming the above-mentioned printing layer.
  • the ink mentioned above is used suitably as an ink used for printing.
  • the process of forming the said printing layer may be performed before irradiation of actinic radiation or after irradiation, it is preferable after irradiation.
  • the formation method of the thermoplastic resin layer mentioned above as a formation method of the thermoplastic resin layer in the process of forming the above-mentioned thermoplastic resin layer is mentioned suitably.
  • the manufacturing method of the lamination sheet which concerns on this indication may further include the process of providing a hot-melt-adhesive on the said printing layer.
  • the formation method of the protective layer mentioned above as a formation method of the protective layer in the process of providing the said protective layer is mentioned suitably.
  • the step of providing the protective layer may be performed before or after irradiation with actinic radiation, but is preferably after irradiation.
  • the curable composition in a state having temperature unevenness in the range of 0.5 ° C. or more and 10 ° C. or less.
  • the temperature range of the temperature non-uniformity when curing in the state having the above temperature non-uniformity is 0.7 from the viewpoint of easily adjusting the three-dimensional moldability and abrasion resistance of the resulting cured product and the molecular weight distribution between crosslinking points. It is preferable that the temperature is not less than 0 ° C.
  • the temperature range of the above-mentioned temperature nonuniformity divides the base material surface of the portion to which the curable composition was given at the time of hardening of a curable composition into 9 equal parts of 3 ⁇ 3 and measures the temperature of each central portion. And the minimum temperature.
  • As a method of forming temperature unevenness it is possible to, for example, change the blowing amount of warm air to the curable composition on the surface of the laminated base material in the width direction, or divide the surface into a plurality of temperature divisions and adjust the temperature.
  • the method of giving temperature distribution using a base material, the method of using the several radiation heat source from which temperature differs, etc. are mentioned.
  • the method of changing the air volume in the width direction can be achieved, for example, by dividing the blowout nozzle and blowing air from a hot air generator set to a plurality of temperatures.
  • a method of changing the temperature of the substrate can be achieved by preparing a plurality of panel heaters and changing their set temperatures.
  • a heat medium can be made to pass through a base material, and temperature distribution can also be provided by providing a baffle plate in this flow path.
  • a plurality of radiant heat sources can also be achieved by changing the temperature of a plurality of radiant heat sources (for example, a halogen lamp, an infrared (IR) heater, a nichrome wire, etc.) provided in the upper and lower portions of the sample.
  • a plurality of radiant heat sources for example, a halogen lamp, an infrared (IR) heater, a nichrome wire, etc.
  • the curing in the step of curing in the state having temperature unevenness may be photo curing (curing by irradiation with actinic radiation) or thermal curing, but photo curing is preferable.
  • the manufacturing method of the lamination sheet which concerns on this indication includes the process of trimming the obtained lamination sheet.
  • trimming processing such as punching processing, drilling processing, cutting processing and the like can be suitably performed to remove unnecessary portions.
  • trimming processing such as punching processing, drilling processing, cutting processing and the like can be suitably performed to remove unnecessary portions.
  • trimming method It can carry out by a well-known method.
  • the three-dimensional structure according to the present disclosure is a three-dimensional molded product (preferably three-dimensionally molded by a technique such as heat molding or vacuum molding) of the laminate sheet according to the present disclosure. Moreover, it is preferable that the three-dimensional structure which concerns on this indication is a three-dimensional molded object of the lenticular sheet which concerns on this indication.
  • the three-dimensional structure according to the present disclosure is not particularly limited to the molding method as long as it is manufactured using the laminated sheet according to the present disclosure.
  • a curable composition used in the present disclosure is molded, irradiated with actinic radiation and cured, and a cylindrical lens is formed on a resin substrate.
  • a process for producing a 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 are performed to obtain a three-dimensional molded lenticular body.
  • lenticular sheet production process preferably vacuum molding or pressure molding
  • three-dimensional molding step preferably vacuum molding or pressure molding
  • the lenticular sheet according to the present disclosure which is excellent in three-dimensional moldability, is used at the time of molding exposed to relatively high temperature, it is difficult to cause shape deformation by melting due to heat at the time of molding It is also possible to suppress the occurrence of cracks which are likely to occur at the same time.
  • the curable composition used in the present disclosure is molded, irradiated with actinic radiation to be cured, and a lenticular sheet having a cylindrical lens on a laminated base is produced.
  • the details of the curable composition used in the present disclosure are as described above, and preferred embodiments are also the same.
  • the curable composition used for this indication contains a radical photopolymerization initiator. Irradiation with actinic radiation generates radicals, and the polymerization reaction of the polymerizable compound proceeds to cure. Thereby, a cylindrical lens which is a cured product of the curable composition used in the present disclosure is formed.
  • the curable composition may be cured after the laminate substrate is brought into contact with the curable composition in advance before the curable composition is cured. By curing the laminated substrate and the curable composition in contact with each other, it is possible to further improve the adhesion due to curing shrinkage, and in addition to the adhesion effect derived from the composition, the adhesion to the laminated substrate is improved.
  • the curable composition is molded into the shape of the desired cylindrical lens.
  • the molding is not particularly limited as long as a desired shape can be obtained, but in terms of molding efficiency and molding accuracy, molding using a mold such as a mold or a wood mold is preferable.
  • a mold processed into a desired lens shape may be prepared, the curable composition may be poured into the mold, dried as necessary, and then the curable composition may be cured. Good.
  • a molded product molded into a target shape can be stably obtained.
  • a mercury lamp, a metal halide lamp, a UV fluorescent lamp, a gas laser, a solid laser and the like are widely known.
  • a semiconductor ultraviolet light emitting device may be applied as a light source, and in terms of small size, high life, high efficiency, and low cost, LEDs (Light Emitting Diodes) and LDs (Laser Diodes) are also suitable.
  • a metal halide lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an LED or a blue-violet laser is preferable.
  • an ultra high pressure mercury lamp capable of light irradiation with a wavelength of 365 nm, 405 nm or 436 nm
  • a high pressure mercury lamp capable of light irradiation with a wavelength of 365 nm, 405 nm or 436 nm
  • LEDs capable of emitting light at wavelengths of 355 nm, 365 nm, 385 nm, 395 nm or 405 nm are particularly preferred.
  • the dose of actinic radiation may be appropriately selected depending on the composition and amount of the lenticular lens curable composition, it is preferable to 0.3 J / cm 2 or more 5 J / cm 2 or less.
  • the irradiation with actinic radiation can be performed by selecting a known device provided with a light source capable of emitting actinic radiation described above.
  • a light source capable of emitting actinic radiation described above.
  • an ultraviolet (UV) irradiation apparatus such as EXECURE 3000 manufactured by HOYA CANDEO OPTRONICS may be used.
  • the lenticular sheet manufactured in the lenticular sheet manufacturing process is three-dimensionally molded.
  • the lenticular sheet can be molded, and may be subjected to a molding process using a mold such as a mold.
  • the method of vacuum forming is not particularly limited, but a method of three-dimensional forming in a heated state under vacuum is preferable.
  • the vacuum refers to a state in which the interior is evacuated to a vacuum degree of 100 Pa or less.
  • a temperature range of 60 ° C. or more is preferable, a temperature range of 80 ° C. or more is more preferable, and a temperature range of 100 ° C. or more is more preferable.
  • the upper limit of the temperature for three-dimensional molding is preferably 200.degree.
  • the temperature at the time of three-dimensional molding refers to the temperature of the lenticular sheet subjected to three-dimensional molding, and is measured by attaching a thermocouple to the surface of the lenticular sheet.
  • the above-mentioned vacuum forming can be performed using a vacuum forming technique widely known in the forming field, and for example, it may be formed by vacuum using Formech 508 FS manufactured by Japan-made Utensils Industry Co., Ltd.
  • Multifunctional (meth) acrylate compound having a ring structure A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd .: tricyclodecane dimethanol diacrylate M-315 (manufactured by Toagosei Co., Ltd .: EO isocyanuric acid)
  • Modified triacrylate (trifunctional acrylate compound having isocyanuric ring structure) -KUA-4I manufactured by Kaesem Co., Ltd .: tetrafunctional urethane (meth) acrylate (tetrafunctional urethane acrylate having a cyclohexyl ring) -KUA-6I (manufactured by KAESM Co., Ltd .: 6-functional urethane acrylate containing a cyclohexyl ring)
  • N-vinyl compound / N-vinyl pyrrolidone N-vinyl pyrrolidone (NVP, manufactured by Wako Pure Chemical Industries, Ltd.)
  • NVC N-vinyl- ⁇ -caprolactam
  • Irgacure 184 manufactured by BASF: 1-hydroxycyclohexyl phenyl ketone
  • Irgacure TPO manufactured by BASF: 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide
  • IRGACURE 819 manufactured by BASF: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • Irgacure 651 manufactured by BASF: 2,2-dimethoxy-1,2-diphenylethane-1-one
  • UV irradiation is performed using an ultraviolet (UV) irradiation apparatus (EXECURE 3000, HOYA CANDEO OPTRONICS Co., Ltd.) by blocking oxygen and curing at 25 ° C. under the condition of a UV irradiation amount of 1.0 J / cm 2 Irradiated.
  • UV irradiation apparatus EXECURE 3000, HOYA CANDEO OPTRONICS Co., Ltd.
  • the temperature nonuniformity at the time of hardening achieves the temperature distribution (temperature nonuniformity) of Table 1 or Table 2 by providing a temperature difference to this using the hot plate divided into 9 to the base material which installs the said glass plate. did.
  • Elongation at break (%) 100 ⁇ (Length broken at stretching-distance between chucks) / (distance between chucks) -conditions- -Distance between chucks: 30 mm ⁇ Temperature of sample piece: 100 ° C ⁇ Tensing speed: 1 mm / sec
  • a film was formed in the same manner as the lamination 2 except that the thicknesses of the PMMA layer and the PC layer were 7 ⁇ m and 132 ⁇ m, respectively.
  • a film was formed in the same manner as the lamination 2 except that the thicknesses of the PMMA layer and the PC layer were 68 ⁇ m and 71 ⁇ m, respectively.
  • a film was formed in the same manner as the lamination 2 except that the thicknesses of the PMMA layer and the PC layer were 56 ⁇ m and 144 ⁇ m, respectively.
  • a film was formed in the same manner as the lamination 2 except that the thicknesses of the PMMA layer and the PC layer were 14 ⁇ m and 36 ⁇ m, respectively.
  • -Monolayer film 2 (PC monolayer)- As a polycarbonate resin, Caliber 301-10 manufactured by Sumitomo Dow Co., Ltd. was melted at 275 ° C. using a single-screw extruder, cooled and solidified by a 50 ° C. touch roll, and wound up.
  • the trimming property was evaluated by the following method.
  • the lens layer of a laminated sheet obtained by using a bik blade (Thomson blade) punched into a square shape with a side of 5 cm and having a circular shape with a diameter of 3 mm at each corner (a blade angle of 42 degrees) Or it pierced from the field in which a hardening layer was formed. This was observed with an optical microscope from the side of the lens layer or the hardened layer, and the number of cracks in the lens layer was observed.
  • the evaluation results are shown in Tables 1 and 2.
  • the laminated sheet according to the present disclosure is superior in abrasion resistance and trimability as compared to the laminated sheet using the single-layer base material of the comparative example.
  • Example 1 to Example 4 when a polyfunctional (meth) acrylate compound having the above-mentioned ring structure of 3 to 6 functions is used, the abrasion resistance is excellent.
  • Example 1 and Examples 5 to 9 when the distribution of molecular weight between crosslinking points is 0.5% or more and 10% or less, the three-dimensional moldability and the abrasion resistance are excellent.
  • the laminated sheet according to the present disclosure has three-dimensional formability and abrasion resistance as compared to the laminated sheet using the single-layer base material of the comparative example. It is also excellent in sex.
  • multistage exposure improves the three-dimensional formability, and in multistage exposure, the pre-exposure amount ⁇ post exposure amount improves the breaking elongation. The trimming property is more excellent.
  • Example 14 and Example 19 when forming a hardened
  • Example 20 and Example 21 when the Tg difference of the resin to be laminated is 20 ° C. to 80 ° C., the resin is excellent in three-dimensional moldability, abrasion resistance and trimming property.
  • Lenticular decoration sheet (Lenticular sheet) 12 Lenticular lens 12A: convex lens 14: lenticular image 14A, 14B: display image sequence 14C: interpolation image sequence x: lens width direction y: lens Longitudinal direction

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Abstract

L'invention concerne : une feuille stratifiée comprenant, sur un matériau de base stratifié formé de deux ou plus de deux types différents de couches de résine, un produit durci présentant un allongement à la rupture de 6 à 500 % à 100 °C et un procédé de production associé ; et une structure tridimensionnelle utilisant la feuille stratifiée et un procédé de production associé. Le produit durci présente de préférence un poids moléculaire de 20 à 2 000 g/mol entre des points de réticulation.
PCT/JP2018/022418 2017-07-11 2018-06-12 Feuille stratifiée et procédé de production associé, et structure tridimensionnelle et procédé de production associé WO2019012895A1 (fr)

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