JP4632088B2 - Forming sheet - Google Patents

Description

  The present invention relates to a shaping sheet that can be suitably used for the production of shaped articles such as optical lenses, projection screens, and embossing sheets for building materials.

  Optical sheets used for optical lenses, projection screens and the like are manufactured by manufacturing methods such as injection molding, extrusion molding, and press molding. However, these manufacturing methods have problems that it is difficult to form a large-sized sheet, and that many dies are required for mass production.

  For this reason, a sheet (shaped sheet) obtained by laminating a resin layer containing an active energy ray-curable resin composition such as an ultraviolet curable resin on a sheet-like base material such as polyethylene terephthalate is used. 2. Description of the Related Art A manufacturing method (press shaping method) is known in which a lens pattern is continuously shaped on one or both sides of a sheet by pressing (pressing) a shaped lens mold or the like. As the resin composition used here, for example, an active energy ray-curable resin composition containing a thermoplastic polymer, a monomer having one or more unsaturated double bonds in the molecule, and a photopolymerization initiator is proposed. (For example, refer to Patent Document 1).

  In Patent Document 1, in order to accurately transfer the shape of the cylindrical mold, it is necessary to use a low molecular weight acrylic resin or the like as the thermoplastic polymer. However, by using a low molecular weight resin, the mold and the adhesiveness become too good, causing a problem that the mold is difficult to separate from the shaping sheet (difficult to separate the mold), which causes the productivity to deteriorate.

JP-A-7-128503

  Accordingly, the problem to be solved by the present invention is to provide a shaping sheet that has good shaping properties and that is easily separated from the sheet after shaping.

The present inventors have made extensive studies to solve the above problems, and have found the following findings (1) to (3).
(1) A soft resin layer is not formed on a sheet-shaped resin substrate (A), but on a sheet-shaped resin substrate (A), which is not a sheet for shaping in which a single resin layer is laminated as in the sheet for shaping disclosed in Patent Document 1. The shaping sheet in which the hard resin layer is laminated on the soft resin layer has a good shapeability by the soft resin layer, and the mold is formed from the sheet after shaping by the hard resin layer. Easy to leave.
(2) The soft resin layer contains an active energy ray-curable resin having a weight average molecular weight of 8,000 to 30,000, and the entire weight average molecular weight of the coating film forming component is 5,000 to 20. If the layer (B) of the active energy ray-curable resin composition is 1,000, the shape of the mold can be accurately transferred.
(3) As the hard resin layer, if it is a layer (C) of a resin composition containing 3% by weight or more of a component having a weight average molecular weight of 50,000 or more based on the weight of the film-forming component, a sheet after shaping The mold is easy to leave.
The present invention has been completed based on the above findings.

  That is, the present invention contains an active energy ray-curable resin having a weight average molecular weight of 8,000 to 30,000 in the sheet-like resin substrate (A), and the entire weight average molecular weight of the coating film forming component. 3% by weight or more of the layer (B) of the active energy ray-curable resin composition having a weight average molecular weight of 50,000 or more based on the weight of the film forming component The layer (C) of the resin composition to contain is laminated | stacked in order of (A) / (B) / (C), and the sheet | seat for shaping characterized by the above-mentioned is provided.

  The shaping sheet of the present invention can be applied with a fine shaping pattern and has good mold release after shaping, which contributes to improvement in productivity.

The present invention is described in detail below.
As the sheet-shaped resin substrate (A) used in the present invention, a sheet-shaped resin substrate composed of a polyester-based resin represented by polyethylene terephthalate, a sheet-shaped resin substrate composed of an acrylic resin represented by polymethyl methacrylate, Resin layer of active energy ray-curable resin composition formed by being laminated and shaped on both sides or one side of these substrates, such as a sheet-like resin substrate made of polycarbonate resin, which is a substrate that transmits active energy rays When irradiating an active energy ray with respect to this, it is preferable because it can be cured by irradiation from one side of the sheet. The thickness of the sheet-shaped resin substrate is not particularly limited and is determined according to the use, but is preferably 38 to 500 μm, more preferably 50 to 250 μm. Moreover, in order to improve adhesiveness with a resin layer, the sheet-like resin base material to which the surface was subjected to easy-adhesion processing, such as corona discharge processing, plasma processing, and primer processing, is preferable.

  The active energy ray-curable resin composition constituting the layer (B) in the present invention contains an active energy ray-curable resin having a weight average molecular weight of 8,000 to 30,000, and the entire coating film forming component. It is necessary to be an active energy ray-curable resin composition having a weight average molecular weight of 5,000 to 20,000. A layer of an active energy ray-curable resin composition that does not contain an active energy ray-curable resin having a weight average molecular weight greater than 5,000 is not preferable because it has fluidity and cannot retain a shaped shape after release. The layer of the active energy ray-curable resin composition containing the active energy ray-curable resin having a weight average molecular weight of more than 30,000 is not preferable because it is too hard to transfer the shaped shape sufficiently. The active energy ray-curable resin constituting the layer (B) more preferably contains a component having a weight average molecular weight of 10,000 to 20,000.

  In the present invention, the weight average molecular weight of the coating film forming component refers to that obtained by measuring a component that forms a coating film after curing with resin or the like by gel permeation chromatography.

  The layer of the active energy ray-curable resin composition having an average weight average molecular weight of the coating film forming component of the active energy ray-curable resin composition constituting the layer (B) is less than 5,000 is fluid. Therefore, it is not preferable because the shaped shape cannot be retained after release. The layer of the active energy ray-curable resin composition having an overall weight average molecular weight of the coating film forming component of more than 20,000 is not preferable because it is too hard to transfer the shaped shape sufficiently. The total weight average molecular weight of the coating film forming component of the active energy ray-curable resin composition constituting the layer (B) is preferably 6,000 to 15,000, more preferably 6,500 to 13,000.

  The active energy ray curable resin contained in the active energy ray curable resin composition constituting the layer (B) is particularly an active energy ray curable resin having a weight average molecular weight of 8,000 to 30,000. There is no restriction, and examples thereof include unsaturated polyester, polyester acrylate, urethane acrylate, epoxy acrylate, acrylic acrylate, and silicon acrylate. Among these, polyester-based active energy ray-curable resins are preferable because of easy viscosity adjustment and excellent cured properties, and unsaturated polyester resins are more preferable.

  The unsaturated polyester resin is preferable because a sufficient crosslinking density can be obtained after curing by irradiation with active energy rays. Further, it may be a branched unsaturated polyester resin.

  Examples of the unsaturated polyester resin include those obtained by using a polycarboxylic acid component and a polyol component as essential components.

  The polycarboxylic acid component is not particularly limited. For example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecenyl succinic acid, n-dodecyl succinic acid, malonic acid, maleic acid, fumaric acid, citracone Acid, itaconic acid, glutaconic acid, cyclohexanedicarboxylic acid, diphthalic acid such as orthophthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof; trifunctional or higher carboxylic acid such as trimellitic acid, trimetic acid, pyromellitic acid, or The anhydride etc. are mentioned. Also, lower alkyl carboxylic acid esters having 1 to 4 carbon atoms can be used as the polycarboxylic acid component. These polycarboxylic acid components can be used alone or in combination of two or more. Of these, when maleic acid and / or fumaric acid is used as part or all of the polycarboxylic acid component, unsaturated double bonds can be introduced into the resulting polyester resin, and polymerizable vinyl compounds ( Since the polyester resin excellent in compatibility with V) is obtained, it is more preferable. If necessary, monocarboxylic acids such as benzoic acid, p-toluic acid, and p-tert-butylbenzoic acid can be used in combination.

The polyol component is not particularly limited. For example, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butane. Dihydric alcohols such as diol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol A, alkylene oxide adducts of bisphenols; glycerin, trimethylolethane, trimethylol Examples thereof include trivalent or higher-valent alcohols such as propane, trishydroxyethyl isocyanurate, and pentaerythritol. These polyol components can be used alone or in combination of two or more. Among these, when a bisphenol and / or its alkylene oxide adduct is used as part or all of the polyol component, the complex viscosity (η *) at a frequency of 1 Hz of the component excluding the solvent is 1 × 10 ⁴ dPa. A polyester resin that has a temperature (T4) at which s is 30 ° C. or higher and a temperature (T6) at which the complex viscosity (η *) at a frequency of 1 Hz is 1 × 10 ⁶ dPa · s can be easily controlled to 100 ° C. or lower. Is more preferable.

  Accordingly, as the polyester resin (R), for example, maleic acid and / or fumaric acid is used as part or all of the polycarboxylic acid component, and bisphenols and / or alkylene thereof are used as part or all of the polyol component. Those obtained using an oxide adduct are particularly preferred.

  In addition, when manufacturing a polyester resin using these polycarboxylic acid components and a polyol component, esterification catalysts, such as dibutyltin oxide, can be used suitably.

  When the polyester resin is used as the active energy ray curable resin contained in the active energy ray curable resin constituting the layer (B), for example, the polyester resin having a number average molecular weight of 5,000 to 20,000 is, for example, the poly A carboxylic acid component, a polyol component and, if necessary, an esterification catalyst are placed in a flask, mixed and heated, and reacted for 4 to 48 hours while stirring gradually in a range of 200 to 250 ° C. under a nitrogen stream. It can be prepared by a method to be performed.

  The active energy ray-curable resin composition constituting the layer (C) in the present invention needs to be a resin composition containing 3% by weight or more of a resin having a weight average molecular weight of 50,000 or more based on the weight of the coating film forming component. is there. A layer of a resin composition containing only 3% by weight or less of a resin having a weight average molecular weight of 50,000 or more is not preferable because mold adhesion is exhibited at the forming temperature. The resin composition constituting the layer (C) more preferably contains a number average molecular weight of 80,000 to 300,000.

  In the active energy ray-curable resin composition constituting the layer (C) in the present invention, the content of the resin having a weight average molecular weight of 50,000 or more is preferably 5% by weight or more based on the weight of the coating film forming component.

  Therefore, the resin composition constituting the layer (C) is more preferably a resin composition containing 5% by weight of a resin having a weight average molecular weight of 80,000 to 300,000 based on the weight of the coating film forming component.

  Examples of the resin composition constituting the layer (C) include a resin composition containing 3% by weight or more of a thermoplastic resin having a weight average molecular weight of 50,000 or more based on the weight of the film-forming component, and a weight average molecular weight. A resin composition containing 3% by weight or more of an active energy ray-curable resin having a weight of 50,000 or more based on the weight of the coating film forming component.

  Examples of the thermoplastic resin resin include acrylic resins and saturated polyester resins. Examples of the active energy ray curable resin include an active energy ray curable resin used to form the layer (B). When using the active energy ray curable resin, the same active energy ray curable resin as that used for forming the layer (B) may be used, or a different one may be used. Examples of the resin composition constituting the layer (C) include a resin composition containing 3% by weight or more of a thermoplastic resin having a weight average molecular weight of 50,000 or more based on the weight of the film forming component, and a weight average molecular weight of 50. A resin composition containing 3% by weight or more of an active energy ray-curable resin of 1,000 or more based on the weight of the coating film forming component is preferable.

  It is preferable that the active energy ray-curable resin composition constituting the layer (B) and the layer (C) contains an unsaturated polyester and a polymerizable vinyl compound since cured properties are good. Examples of the polymerizable vinyl compound include various polymerizable vinyl monomers and polymerizable vinyl oligomers such as β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, β -Hydroxyethyl (meth) acryloyl phosphate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Polypropylene glycol di (meth) acrylate, bisphenol A alkylene oxide modified di (meth) acrylate, bisphenol F alkylene oxide modified di (meth) acrylate, bisphenol S alkylene oxide modified di (meth) acrylate, trimethylolpropane di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylic such as meth) acrylate, tris [2- (meth) acryloyloxyethyl] isocyanurate Monomer; polyester (meth) acrylate, bisphenol type epoxy (meth) acrylate, novolac type epoxy (meth) acrylate, (meth) acrylic oligomer such as urethane (meth) acrylate. These polymerizable vinyl monomers and polymerizable vinyl oligomers can each be used alone, but usually the use of a polymerizable vinyl monomer alone is preferred, and the combined use of a polymerizable vinyl monomer and a polymerizable vinyl oligomer is preferred. And a combination of a polymerizable vinyl oligomer are particularly preferred. The polymerizable vinyl oligomer is preferably an oligomer having a number average molecular weight of 200 or more and 2,000 or less and smaller than the number average molecular weight (Mn) of the polyester resin (R).

  Further, among these polymerizable vinyl compounds (V), a sufficient crosslink density can be obtained after curing by irradiation with active energy rays, so that the molecule has 2 to 6 unsaturated double bonds (meth). Acrylic compounds such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Acrylate), pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris [2- (meth) acryloyloxyethyl] It is preferable to use isocyanurate as an essential component.

  In the present invention, the coating film forming component is a component that forms a coating film by curing an active energy ray-curable resin, an additive, or the like, and does not include components such as a solvent that does not constitute the coating film.

  The active energy ray-curable resin composition constituting the layer (B) used in the present invention and the resin composition constituting the layer (C) contain a photopolymerization initiator, other additives, a solvent, etc. as necessary. You can also At this time, the same thing may be used in a layer (B) and a layer (C), and a different thing may be used.

  Examples of the photopolymerization initiator include 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2, 2-dimethoxy-1,2-jephenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin ethyl ether, bis (2 , 4,6-Trimethylbenzoyl) -phenylphosphine oxide, isopropylthioxanthone, o-benzoyl Examples thereof include methyl benzoate, [4- (methylphenylthio) phenyl] phenylmethanone, benzophenone, and p-dimethylaminobenzoic acid isoamyl ethyl ester, among which 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-jephenylethane-1-one, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferred. The amount of the photopolymerization initiator used is usually 10 parts by weight or less based on 100 parts by weight of the total of the polyester resin (R) and the polymerizable vinyl compound (V) (or a resin component that is cured by irradiation with active energy rays). The amount is preferably 0.1 to 6 parts by weight.

  Examples of the other additives include a release agent for improving the releasability in the release step, a colorant such as a pigment and a dye, an antioxidant, a light diffusing agent, and a thermal polymerization inhibitor. .

  Among these other additives, prevention of thermal polymerization and storage stability during the production of the active energy ray-curable resin composition constituting the layer (B) used in the present invention and the resin composition constituting the layer (C). In order to maintain the heat resistance, it is desirable to add a thermal polymerization inhibitor. Although it does not specifically limit as a thermal polymerization inhibitor, If a typical thing is illustrated, hydroquinone, hydroquinone monomethyl ether, tert- butyl catechol, p-benzoquinone, phenothiazine, etc. will be mentioned. The amount of the thermal polymerization inhibitor used is usually 2 parts by weight or less based on 100 parts by weight of the total of the polyester resin (R) and the polymerizable vinyl compound (V) (or a resin component cured by heating), preferably 0.05 to 1 part by weight.

  Furthermore, a release agent can also be contained in the active energy ray-curable resin composition used in the present invention. By including a mold release agent, the mold is brought into close contact with the shaping sheet, pressurized and shaped, and then the releasability can be improved without cooling, so the cooling step is omitted. Can contribute to improving the manufacturing efficiency of shaped sheets.

  Examples of the mold release agent include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder; fluorine-based or phosphate ester-based surfactant; fluorine-containing resin; silicone compound, and the like. . Of these, silicone compounds are preferred.

  As the silicone compound, for example, polyether-modified and / or polyester-modified silicone compounds such as polyether-modified silicone compounds, polyester-modified silicone compounds, polyether-modified and polyester-modified silicone compounds can be preferably used.

  Examples of the polyether-modified and / or polyester-modified silicone compound include compounds in which a polyether chain and / or a polyester chain are introduced at the terminal and / or side chain of the polysiloxane. A co-modified silicone compound in which introduction of an organic group such as an epoxy group or amino group other than the polyester chain is also used may be used. Moreover, if it has a (meth) acryloyl group in a molecule | numerator, sufficient crosslinking density can be obtained after hardening by active energy ray irradiation, and it is preferable.

  Examples of the polyether-modified silicone compound include KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015. , KF-6004, X-22-4272, X-22-4952, X-22-6266, X-22-3667, X-22-4741, X-22-3939A, X-22-3908A [more; Shin-Etsu Manufactured by Chemical Industries Co., Ltd.], BYK-300, BYK-302, BYK-306, BYK-310, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK- 344, BYK-375, BYK-377, BYK-UV3510, BYK-301, BYK-307, BYK-32 BYK-341, BYK-345, BYK-346, BYK-347, BYK-348 (above; manufactured by Big Chemie), SILWET L-77, SILWET L-720, SILWET L-7001, SILWET L-7002, SILWET L -7604, SILWET Y-7006, SILWET FZ-2101, SILWET FZ-2104, FZ-2105, SILWET FZ-2110, SILWET FZ-2118, SILWET FZ-2120, SILWET FZ-2122, SILWET FZ-2123, SILWET FZ-123 2130, SILWET FZ-2154, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2163, SILWET FZ-2164, S LWET FZ-2166, SILWET FZ-2191, SILWET FZ-2203, SILWET FZ-2207, SILWET 2208, SILWET FZ-3737, SILWET Y-7499, SILWET FZ-3789, SF8472, BY16-004, H7428, SF4428, H4428S BY16-036, SH3749, SH3748, SH8400, SF8410 [above; manufactured by Toray Dow Corning Silicone Co., Ltd.], L032, L051, L066 [above; manufactured by Asahi Kasei Wacker Silicone Co., Ltd.], and the like. Moreover, as what has one or more (meth) acryloyl groups in a molecule | numerator especially, BYK-UV3500, BYK-UV3570, BYK-UV3530 (above; BYK-Chemie company make) etc. are mentioned, for example.

  Examples of the polyester-modified silicone compound include BYK-310, BYK-315, BYK-370 and the like, and particularly those having one or more (meth) acryloyl groups in the molecule include, for example, , BYK-UV3570 (manufactured by Big Chemie) and the like. These polyether-modified or polyester-modified silicone compounds (S) can be used alone or in combination of two or more.

  The polyether-modified or polyester-modified silicone compound is used in a range in which the compatibility of the active energy ray-curable resin composition is maintained so that transparency suitable for optical parts can be secured. The range in which the content of the active energy ray-curable resin composition in the coating film forming component is 0.1 to 15% by weight is preferable, and the range in which the content is 1 to 10% by weight is more preferable. This amount is large compared to the case of a release agent such as a silicone compound used in general casting polymerization. This is an active energy ray-curable resin composition that is blended so that the viscosity is high enough to prevent the resin layer from flowing before and after shaping while maintaining shapeability, in the case of general cast polymerization This is because the bleedability of the release agent (the property that the low molecular components in the resin ooze out on the surface) becomes poorer than that of the mold release agent, so that the release property can be expressed even under such a low bleed condition.

  In the shaping sheet of the present invention, the layer (B) and the layer (C) are arranged in the order of (A) / (B) / (C) on the sheet-like resin base material (A). . In order to laminate the layer (B) or the layer (C), for example, a resin composition such as an active energy ray-curable resin composition is added to toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl as necessary. Dissolve in a solvent such as isobutyl ketone, ethanol, isopropyl alcohol, etc. to make a uniform solution, cast it on a sheet-shaped resin substrate using various coaters, then volatilize and remove the solvent in a drying furnace, etc., uniformly Examples thereof include a method in which a mixed resin composition such as an active energy ray-curable resin composition is heated to lower the viscosity, and then applied onto a sheet-like resin substrate and then cooled and solidified. Among these, the former is more preferable in the former because it is difficult to completely remove the solvent particularly during thick film coating. In addition, when making into a solution using a solvent, it is preferable to melt | dissolve so that it may become 40 weight% in conversion of solid content, and it is more preferable to melt | dissolve so that it may become 50 weight% or more.

  Even if the layer (B) and the layer (C) are laminated in the order of (A) / (B) / (C) only on one side of the sheet-like resin base material (A), the shaping sheet of the present invention is laminated. It may be good or may be laminated on both sides.

  As thickness of the said layer (B), 10-1000 micrometers is preferable from the point of the thin film formation of a shaping sheet, and a shaping property, and 50-200 micrometers is more preferable. Moreover, as thickness of the said layer (C), 5-100 micrometers is preferable from the point of a shapeability, and 10-50 micrometers is more preferable. At this time, the total thickness of the layer (B) and the layer (C) is usually 10 μm to 1 mm, preferably 50 to 500 μm. The maximum depth of the mold is preferably 1 to 5 times. Further, the thickness of the layer (B) is preferably 0.5 to 5 times the thickness of the layer (C), more preferably 50 to 200 μm from the viewpoint of mold shape reproducibility.

The shaping sheet of the present invention can be made into a shaped product by shaping it and then curing it by irradiation with active energy. The shaping sheet is shaped by shaping the shaping active energy ray-curable resin composition layer laminated on one or both sides of the sheet-like resin substrate. For example, in the shaping sheet of the present invention, the complex viscosity (η ^* ) at a frequency of 1 Hz of the active energy ray-curable resin composition layer for solvent-free shaping is 1 × 10 ⁴ to 1 × 10 ⁶ dPa · s. s, preferably the complex viscosity (η ^* ) at a frequency of 1 Hz is about 1 × 10 ⁵ dPa · s, for example, 0.63 × 10 ^{5 to} 1.58 × 10 ⁵ dPa · s. Then, it is brought into contact with a planar shaping mold, shaped by pressing, then irradiated with an active energy ray and cured, and then released to obtain a shaped article such as an optical lens sheet, or the same as described above The forming sheet is heated and applied by continuous pressing using a roll-shaped forming die as shown in Patent Document 1 and other documents (for example, JP-A-1-159627). Form and release, then irradiate with active energy rays Examples thereof include a method of obtaining a shaped product such as an optical lens sheet by curing. As the light source of the active energy ray used for curing at this time, various types of light sources such as a low-pressure or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a carbon arc lamp can be used.

  The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples. The parts in the examples are based on weight unless otherwise specified.

Example 1
812 parts of propylene oxide adduct of bisphenol A [BAP2 glycol manufactured by Nippon Emulsifier Co., Ltd.] and 272 parts of fumaric acid are reacted for 8 hours at 215 ° C. in the presence of 1.1 parts of dibutyltin oxide, and unsaturated in the molecule. A polyester resin (R1) having a double bond and having a number average molecular weight (Mn) of 2,300 and a softening point of 100 ° C. was obtained.

  The number average molecular weight (Mn) of the polyester resin was determined as a solvent by using a high-speed GPC device HLC-8220GPC manufactured by Tosoh Corporation and a column manufactured by Tosoh Corporation (TSKgel SuperHZ4000, SuperHZ3000, SuperHZ2000, SuperHZ1000, one each). Using tetrahydrofuran, the flow rate was 0.350 ml / min. The number average molecular weight in terms of polystyrene obtained by measuring under the conditions (the same applies hereinafter).

Next, in a separable flask, 74 parts of the obtained polyester resin (R1), 13 parts of bisphenol A propylene oxide 4 mol adduct diacrylate [BPP-4 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], side chain polyether-modified dimethylsiloxane 9 parts of [KF-615A made by Shin-Etsu Chemical Co., Ltd.] and 4 parts of 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE 651 made by Ciba Specialty Chemicals] were mixed at 120 ° C. And degassing under reduced pressure to obtain a uniform active energy ray-curable resin composition.
The obtained active energy ray-curable resin composition contains an active energy ray-curable resin having a weight average molecular weight of 11785, and the average number average molecular weight of the coating film forming component is 1260, which is the average of the coating film forming component. The weight average molecular weight was 7780.

  A 100 μm-thick polyethylene terephthalate film [Toyobo Co., Ltd., Toyobo Ester Film A4300] was applied on one side with an applicator using the obtained active energy beam-curable resin composition, and a 100 μm-thick active energy beam A shaping sheet (S1) in which a curable resin composition layer was laminated on one side of a sheet-like resin base material was obtained.

  In addition, when the molecular weight distribution of the active energy ray-curable resin composition used for the preparation of the shaping sheet (S1) was measured by GPC, it was as shown in Table 1 (1). The overall weight average molecular weight of the coating film forming component was 7780.

  In addition, application with an applicator using an active energy ray-curable resin composition obtained on one side of a 38 μm thick release-treated polyethylene terephthalate film [Separator release film SP-PET-03-BU manufactured by Tosero Co., Ltd.] The shaping active sheet (S2) in which the active energy ray-curable resin composition layer for shaping having a thickness of 50 μm was laminated on one side of the sheet-like resin base material was obtained. Furthermore, the shaping sheet (S3) was obtained by irradiating the obtained shaping sheet (S2) with 50 mJ / cm 2 of ultraviolet rays using an ultraviolet lamp.

  A part of the resin layer of the obtained shaped sheet (S3) was cut off with a cutter knife. When this molecular weight distribution was analyzed by GPC, it was a weight average molecular weight distribution as shown in Table 1 (1). From this result, the resin layer of the shaping sheet (S3) was irradiated with an active energy ray-curable resin having a weight average molecular weight of 50,000 or more based on the weight of the coating film forming component by ultraviolet irradiation of 50 mJ / cm 2. It turns out that it contains 5.4%.

  After the resin layer surfaces of the obtained shaping sheet (S1) and shaping sheet (S3) were bonded together, the separator release film SP-PET-03-BU was peeled off to produce the shaping sheet of the present invention. did. This is abbreviated as a shaping sheet (S4).

A shaped sheet (S4) is fixed to a metal roll heated to 80 ° C. so that the resin composition layer is on the mold side, and cylindrical grooves having an opening width of 144 μm and a depth of 78 μm are formed in parallel. When the roll is molded and the mold is released using a roll heated to 85 ° C. at a pressure of 1200 kPa and a speed of 2 m / min, the mold can be released without the resin adhering to the mold. Met. Next, ultraviolet rays of 1000 mJ / cm ² were irradiated by an ultraviolet lamp to transfer a mold pattern to the active energy ray-curable resin composition, and a cured shaped sheet (Sc4) was obtained.

  The cured shaped sheet (Sc4) was able to transfer a shaped shape of about 60 μm to a flat mold in which cylindrical grooves with a mold depth of 78 μm were formed in parallel.

Example 2
669 parts of propylene oxide adduct of bisphenol A [BA-P4U manufactured by Nippon Emulsifier Co., Ltd.] and 495 parts of ethylene oxide adduct of bisphenol A [PM8701L manufactured by Japan Emulsifier Co., Ltd.], 297 parts of isophthalic acid, 139 parts of fumaric acid And a polyester resin having an unsaturated double bond in the molecule, a number average molecular weight (Mn) of 2,500, and a softening point of 85 ° C. in the presence of 1.1 parts of dibutyltin oxide at 235 ° C. for 8 hours. R2) was obtained.

Next, in a separable flask, 75 parts of the obtained polyester resin (R2), 9 parts of bisphenol A propylene oxide 4 mol adduct diacrylate [BPP-4 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], side chain polyether-modified dimethylsiloxane 9 parts of [KF-615A made by Shin-Etsu Chemical Co., Ltd.] and 4 parts of 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE 651 made by Ciba Specialty Chemicals] were mixed at 120 ° C. And degassing under reduced pressure to obtain a uniform active energy ray-curable resin composition. The obtained active energy ray-curable resin composition contains an active energy ray-curable resin having a weight average molecular weight of 13521, and the overall number average molecular weight of the coating film forming component is 1540, and the average weight of the coating film forming component The average molecular weight was 9220. Further, the temperature (T6) at which the complex viscosity (η ^* ) at a frequency of 1 Hz of the obtained active energy ray-curable resin composition is 1 × 10 ⁶ dPa · s is 15 ° C., and the complex viscosity (η at a frequency of 1 Hz) ^* ) Is 1 × 10 ⁵ dPa · s at a temperature (T5) of 25 ° C., and the temperature (T4) at which the complex viscosity (η ^* ) is 1 × 10 ⁴ dPa · s at a frequency of 1 Hz of the components excluding the solvent is It was 44 degreeC and the temperature difference (T4-T6) was 29 degreeC.

  The obtained active energy ray-curable resin composition, polyethylene terephthalate film A4300, and applicator were preheated to 95 ° C., and the active energy ray-curable type was placed on one side of the polyethylene terephthalate film on a hot plate controlled at 95 ° C. The resin composition was applied with an applicator to obtain a shaping sheet (S5) in which an active energy ray-curable resin composition layer having a thickness of 100 μm was laminated on one side of a sheet-like resin substrate.

  In addition, when the weight average molecular weight distribution of the active energy ray-curable resin composition used for the preparation of the shaping sheet (S5) was measured by GPC, it was as shown in Table 2 (1). The average weight average molecular weight of the coating film forming component was 9221.

  Moreover, 9 parts of acrylic resin LG21 [Mitsubishi Chemical Corporation] was dissolved in 41 parts of THF to obtain a resin solution (Sol 1). The resin solution (Sol1) is applied with an applicator on a release-treated polyethylene terephthalate film [Separator release film SP-PET-03-BU manufactured by Tosero Co., Ltd.] having a thickness of 38 μm, and after drying, the thickness of the resin layer is A 10 μm shaping sheet (S6) was obtained.

  A part of the resin layer of the obtained shaping sheet (S6) was cut off with a cutter knife. When this weight average molecular weight distribution was analyzed by GPC, it was a weight average molecular weight distribution as shown in Table 2 (2). From this result, it can be seen that a layer of a resin composition containing 94.9% of a resin having a weight average molecular weight of 57267 is laminated on the resin sheet (S6).

  After the resin layer surfaces of the obtained shaping sheet (S5) and shaping sheet (S6) were bonded together, the separator release film SP-PET-03-BU was peeled off to produce the shaping sheet of the present invention. . This is abbreviated as a shaping sheet (S7).

A flat mold in which a shaped sheet (S7) is fixed to a metal roll at room temperature so that the resin composition layer is on the mold side, and cylindrical grooves having an opening width of 144 μm and a depth of 78 μm are formed in parallel. When roll forming and mold releasing were performed using a roll heated to 85 ° C. at a pressure of 1200 kPa and a speed of 2 m / min, the resin could be released without adhering to the mold. Next, ultraviolet rays of 1000 mJ / cm ² were irradiated by an ultraviolet lamp, the mold pattern was transferred to the active energy ray-curable resin composition, and a cured shaped sheet (Sc7) was obtained.

  The cured shaped sheet (Sc7) was able to transfer a shaped shape of about 40 μm to a flat mold in which cylindrical grooves with a mold depth of 78 μm were formed in parallel.

Example 3
9 parts of styrene resin TS-20 [manufactured by Dainippon Ink & Chemicals, Inc.] was dissolved in 41 parts of THF to obtain a resin solution (Sol 2). The resin solution (Sol2) is applied on an exfoliated polyethylene terephthalate film [Separator release film SP-PET-03-BU manufactured by Tosero Co., Ltd.] having a thickness of 38 μm with an applicator, and after drying, the thickness of the resin layer is A 10 μm resin sheet (S8) was obtained.

  A part of the resin layer of the obtained shaping sheet (S8) was cut off with a cutter knife. When this weight average molecular weight distribution was analyzed by GPC, it was a weight average molecular weight distribution as shown in Table 3 (1). From this result, it can be seen that the resin sheet (S6) is laminated with a resin composition layer containing 98.16% of a resin having a weight average molecular weight of 256156 based on the weight of the coating film forming component. The number average molecular weight of this layer was 12200.

  After the resin layer surfaces of the shaping sheet (S5) and the shaping sheet (S8) prepared in Example 2 were bonded together, the separator release film SP-PET-03-BU was peeled off, and the shaping according to the present invention was performed. A sheet was created. This is abbreviated as a shaping sheet (S9).

  The molecular weight distribution of the shaping sheet (S8) is shown below.

A shaping sheet (S9) is fixed to a metal roll at room temperature so that the shaping active energy ray-curable resin composition layer is on the mold side, and cylindrical grooves with an opening width of 144 μm and a depth of 78 μm are parallel. When the roll was formed and the mold was released using a roll heated to 85 ° C. at a pressure of 1200 kPa and a speed of 2 m / min on the flat mold prepared in the above, the resin did not adhere to the mold. It was possible to release the mold. Next, ultraviolet rays of 1000 mJ / cm ² were irradiated by an ultraviolet lamp to transfer a mold pattern to the active energy ray-curable resin composition, and a cured shaped sheet (Sc9) was obtained.

  The cured shaped sheet (Sc9) was able to transfer a shaped shape of about 50 μm to a flat mold in which cylindrical grooves with a mold depth of 78 μm were formed in parallel.

  Example 4

  9 parts of phenoxy resin PKHH [manufactured by Sakai Kogyo Co., Ltd.] was dissolved in 41 parts of THF to obtain a resin solution (Sol 3). The resin solution (Sol3) is applied with an applicator on a release-treated polyethylene terephthalate film [Separator release film SP-PET-03-BU manufactured by Tosero Co., Ltd.] having a thickness of 38 μm, and after drying, the thickness of the resin layer is When the thickness was about 5 μm, a shaping sheet (S10) was obtained.

  A part of the resin layer of the obtained shaping sheet (S10) was cut off with a cutter knife. When this weight average molecular weight distribution was analyzed by GPC, it was a weight average molecular weight distribution as shown in Table 4 (1). From this result, it can be seen that the resin sheet (S10) is laminated with a layer of a resin composition containing 94.9% of a resin having a weight average molecular weight of 51016 based on the weight of the coating film forming component. Moreover, the average number average molecular weight of the coating film forming component of the resin composition forming this layer was 12200, the number average molecular weight was 5200, and the weight average molecular weight was 48400.

  After the resin layer surfaces of the shaping sheet (S5) and the shaping sheet (S10) prepared in Example 2 were bonded together, the separator release film SP-PET-03-BU was peeled off and used for shaping according to the present invention. Created a sheet. This is abbreviated as a shaping sheet (S11).

  The molecular weight distribution of the shaping sheet (S10) is shown below.

A shaping sheet (S11) is fixed to a metal roll at room temperature so that the shaping active energy ray-curable resin composition layer is on the mold side, and cylindrical grooves having an opening width of 144 μm and a depth of 78 μm are parallel. When the roll was formed and the mold was released using a roll heated to 85 ° C. at a pressure of 1200 kPa and a speed of 2 m / min on the flat mold prepared in the above, the resin did not adhere to the mold. It was possible to release the mold. Next, ultraviolet rays of 1000 mJ / cm ² were irradiated by an ultraviolet lamp to transfer a mold pattern to the active energy ray-curable resin composition, thereby obtaining a cured shaped sheet (Sc11).

  The cured shaped sheet (Sc11) was able to transfer a shaped shape of about 40 μm to a flat mold in which cylindrical grooves with a mold depth of 78 μm were formed in parallel.

Comparative Example 1
A shaped sheet (Sc4 ′) was prepared in the same manner as Sc4 in the same manner as in Example 1 except that only the shaped sheet (S1) before the ultraviolet irradiation was used, but the shaped sheet (Sc4 ′) Could not be released from the mold, and the desired shaped sheet could not be obtained.

Comparative Example 2
A shaped sheet (Sc5 ′) was prepared in the same manner as Sc4 except that only the shaped sheet (S5) before UV irradiation was used, but the shaped sheet (Sc5 ′) Could not be released from the mold, and the desired shaped sheet could not be obtained.

Claims (6)

The sheet-like resin substrate (A) contains an active energy ray-curable resin having a weight average molecular weight of 8,000 to 30,000, and the entire weight average molecular weight of the coating film forming component is 5,000 to 20 A layer (B) of an active energy ray-curable resin composition having a weight average molecular weight of 50,000 or more, and a layer of a resin composition containing 3% by weight or more of a resin having a weight average molecular weight of 50,000 or more based on the weight of a film forming component ( C) is laminated in the order of (A) / (B) / (C). The sheet-like resin substrate (A) is at least one sheet-like resin substrate selected from the group consisting of a sheet-like polyethylene terephthalate resin substrate, a sheet-like acrylic resin substrate, and a sheet-like polycarbonate resin substrate. 1. The shaping sheet according to 1. The layer (B) contains an active energy ray-curable resin having a weight average molecular weight of 10,000 to 20,000, and the entire weight average molecular weight of the coating film forming component is 6,000 to 15,000. A layer of an active energy ray-curable resin composition, wherein the layer (C) is a resin composition layer containing 5% by weight or more of a resin having a weight average molecular weight of 50,000 or more based on the weight of a film-forming component. The shaping sheet according to claim 1. The sheet for shaping according to claim 1, wherein the resin composition constituting the layer (B) is an active energy ray-curable resin composition containing an unsaturated polyester and a polymerizable vinyl compound. The shaping sheet according to claim 4, wherein the polymerizable vinyl compound is a (meth) acrylic compound having 2 to 6 unsaturated double bonds. The sheet for shaping according to any one of claims 1 to 5, wherein the layer (B) is a layer having a thickness of 10 to 1000 µm, and the layer (C) is a layer having a thickness of 5 to 100 µm.