JP4900685B2 - Active energy ray-curable resin composition for shaping, shaping sheet and shaped article - Google Patents

Description

  The present invention provides an active energy ray-curable resin composition for shaping and a resin sheet for shaping that can be suitably used for the production of shaped articles such as optical lenses, projection screens, embossing sheets for building materials, and the like. The present invention relates to a shaped article comprising the shaping sheet.

  As manufacturing methods of optical sheets used for optical lenses, projection screens, and the like, manufacturing methods such as injection molding, extrusion molding, and press molding are known. 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 manufacturing method is known in which an active energy ray-curable resin composition such as an ultraviolet curable resin is used, and a lens is continuously formed on one or both surfaces of a sheet-like substrate by a cylindrical lens mold or the like. As the resin composition used here, 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).

  However, in the active energy ray-curable resin composition disclosed in Patent Document 1, an acrylic resin such as polyethyl methacrylate is used as a thermoplastic polymer in order to obtain a shaped article such as an optical lens having good mechanical properties. As a result, when the resin is dissolved in a solvent to form a uniform solution and cast on a sheet-like base material, the solvent is removed by evaporation to be laminated on the sheet base material. There is a problem that foaming is likely to occur due to steam and it is difficult to form a uniform coating film. Even if foaming due to the solvent vapor during the lamination to the sheet base material can be prevented, the viscosity of the active energy ray-curable resin composition is high during the subsequent shaping by the cylindrical mold, and the heating is performed. Even when trying to shape at a higher temperature, in the active energy ray curable resin composition using an acrylic resin such as polyethyl methacrylate as the thermoplastic polymer, the sheet-like resin base material is not affected by deformation due to heat. Since the decrease in viscosity due to heating in a temperature range that is not affected is small, improvement in formability cannot be expected, and the shape of the cylindrical mold cannot be accurately transferred. In order to prevent these problems, an active energy ray-curable resin composition that is easy to prevent foaming and has a moderately large decrease in viscosity due to heating when a low molecular weight acrylic resin or the like is used as the thermoplastic polymer. However, there is a problem that the final cured product becomes brittle, resulting in a cured product having inferior mechanical properties, and an active energy ray-curable resin composition having a good balance between the formability and the mechanical properties of the cured product. There is a problem that it is difficult to obtain.

JP-A-7-128503 (page 2-5)

  Further, as a method for producing a resin composite suitable for a protective film or a coating material, for example, an energy ray curable composition in which (A) an energy ray polymerizable compound and (B) a chain polymer are uniformly mixed is applied. A first irradiation step of irradiating the shaped product with energy rays to form the shaped product into a transparent solid semi-cured product having no fluidity, and a temperature at the time of irradiation of the semi-cured product in the first irradiation step There is known a method for producing a resin composite including a second irradiation step of further irradiating energy rays at a high temperature and at a temperature equal to or higher than the glass transition temperature of the semi-cured product (see, for example, Patent Document 2). .)

  As the energy ray curable composition preferably used when obtaining a shaped product in Patent Document 2, for example, (B) a composition using a polyester polymer as a chain polymer, specifically, for example, An example of Patent Document 2 discloses an energy beam curable resin composition using (B) a polymer wholly aromatic polyester as a chain polymer. However, in the energy beam curable composition considered preferable in Patent Document 2, it is difficult to mix (A) the energy beam polymerizable compound and (B) the chain polymer, and the shapeability is not sufficient. In addition, the solvent solubility is poor, and there is a problem that a strongly soluble solvent having a strong influence on the human body and the environment, for example, a halogen-based hydrocarbon such as methylene chloride must be used.

  Moreover, when preparing the resin composition disclosed in Patent Document 1 and Patent Document 2 without using an organic solvent or the like (in a solvent-free system), a high temperature, for example, a temperature of 100 ° C. or higher is used. The mixture is heated and melted and mixed in a state where the viscosity of the mixture system is lowered to obtain a uniform resin composition. However, the resin compositions disclosed in Patent Document 1 and Patent Document 2 have insufficient heat stability and have a problem of causing gelation of the composition due to high-temperature heating.

Japanese Patent Laid-Open No. 2002-200563 (Page 2, Page 17)

  Therefore, the problem to be solved by the present invention is to provide an active energy ray-curable resin composition for a shaped sheet, which has an excellent balance between the formability and the mechanical properties of the cured product, and has a good thermal stability, and the activity for shaping. A shaped sheet in which an energy ray curable resin composition is laminated on one or both sides of a sheet-like resin base material, and a shaped article obtained by shaping the shaped sheet and then curing it by irradiation with active energy Is to provide.

The present inventors have made extensive studies to solve the above problems, and have found the following findings (1) to (5).
(1) In the energy ray curable resin that is preferred in Patent Document 2, the number average molecular weight of the wholly aromatic polyester used as the (B) chain polymer is as large as about 16,000, which is shaped. This is one of the causes of insufficient solubility and solvent solubility.

(2) A temperature at which the complex viscosity (η *) at a frequency of 1 Hz of the components excluding the solvent is 1 × 10 ⁴ dPa · s, which is an active energy ray-curable resin composition containing a polyester resin and a polymerizable vinyl compound. In the resin composition having a temperature of 30 ° C. or higher, the resin layer made of the shaping active energy ray-curable resin composition laminated on the sheet-shaped resin base material has a film thickness by flow before reaching the shaping step. Less likely to change.

(3) An active energy ray-curable resin composition obtained by using a bifunctional vinyl compound (V1) having a bisphenol skeleton as the polymerizable vinyl compound, and having a complex viscosity (η *) at a frequency of 1 Hz. In a resin composition having a temperature of 1 × 10 ⁶ dPa · s of 100 ° C. or lower, the heating temperature when it is heated and melted and laminated on a sheet-like resin substrate can be as low as about 40 to 110 ° C., for example. . Moreover, it is excellent also in the stability with respect to a heat | fever, and the polymerizable vinyl type compound in a composition cannot be gelatinized easily, and can be laminated | stacked uniformly.

(4) The active energy ray-curable resin composition having the performances of (2) and (3) above, that is, the complex viscosity (η *) at a frequency of 1 Hz of the component excluding the solvent is 1 × 10 ⁴ dPa · s. The resin composition having a temperature of 30 ° C. or higher and a complex viscosity (η *) of 1 × 10 ⁶ dPa · s at a frequency of 1 Hz of 100 ° C. or lower has a number average molecular weight of 1 as a polyester resin. It can be easily obtained by using a polyester resin of 8,000 to 8,000.

(5) Complex viscosity (η) at a frequency of 1 Hz of a component containing a polyester resin (R) having a number average molecular weight (Mn) of 1,000 to 8,000 and a polymerizable vinyl compound (V1) and excluding the solvent. *) The temperature (T4) at which 1 × 10 ⁴ dPa · s becomes 1 × 10 ⁴ dPa · s is 30 ° C. or higher, and the temperature (T6) at which the complex viscosity (η *) at 1 Hz is 1 × 10 ⁶ dPa · s is 100 ° C. or lower. The active energy ray-curable resin composition is excellent in mechanical properties of the cured product. And it may be possible to cast on a sheet-like resin base material by heating moderately without using a solvent. Even when a solvent is used to make a solution, it can be dissolved without using a highly soluble solvent, and the amount of solvent used may be small, so that the solvent can be removed by evaporation after casting on a sheet-like substrate. When foaming is difficult to occur. In addition, since the viscosity decrease due to heating in a temperature range where the sheet-shaped resin substrate is not affected by deformation due to heat is reasonably large, the formability by heating (reproduces accurately even in the shape of a fine mold, and its shape Performance) is easy to improve, and the balance between the formability and the mechanical properties of the cured product is good.
The present invention has been completed based on the above findings.

That is, the present invention includes a complex viscosity at a frequency of 1 Hz of a component containing a polyester resin (R) having a number average molecular weight (Mn) of 1,000 to 8,000 and a polymerizable vinyl compound (V) and excluding a solvent. The temperature (T4) at which the rate (η *) is 1 × 10 4 dPa · s is 30 ° C. or higher, and the temperature (T 6) at which the complex viscosity (η *) is 1 × 10 6 dPa · s at a frequency of 1 Hz is 100 ° C. or lower. A shaping active energy ray-curable resin composition, wherein the polyester resin (R) is a polyester resin obtained using a polycarboxylic acid component and a polyol component as essential components, and a part of the polycarboxylic acid component or a polyester resin obtained by using maleic acid and / or fumaric acid as the whole, the polymerizable vinyl compound (V) is having a bisphenol skeleton There is provided a vehicle for the active energy ray curable resin composition which is a bifunctional vinyl compound of (V1).

  In addition, the present invention provides a shaping sheet, wherein the shaping active energy ray-curable resin composition is laminated on one or both sides of a sheet-like resin base material, and for this shaping The present invention provides a shaped article obtained by shaping a sheet and then curing it by irradiation with active energy.

The active energy ray-curable resin composition for shaping according to the present invention is excellent in the mechanical properties of a cured product. Moreover, it is excellent in thermal stability and hardly gels even when heated. Furthermore, it may be possible to cast on a sheet-like resin substrate by heating appropriately without using a solvent. Even when a solvent is used to make a solution, it can be dissolved without using a highly soluble solvent, and the amount of solvent used may be small, so foaming does not easily occur when the solvent is removed by evaporation after casting. . Moreover, it is easy to improve the formability by heating, the balance between the formability and the mechanical properties of the cured product is good, and the mechanical properties are accurately transferred to the shape of the mold including the lens pattern. A cured product is easily obtained.
In this specification, “acrylic acid” and “methacrylic acid” are collectively referred to as (meth) acrylic acid, and “acrylate” and “methacrylate” are collectively referred to as (meth) acrylate.

The present invention is described in detail below.
The polyester resin (R) used in the present invention is required to be a polyester resin having a number average molecular weight (Mn) of 1,000 to 8,000, and in particular, the sheet-like resin base material is affected by heat deformation. The active energy ray-curable resin composition for shaping is obtained with a reasonably large decrease in viscosity due to heating at a temperature range not subjected to heat treatment, for example, 30 to 100 ° C., and a better balance between the shaping properties and the mechanical properties of the cured product. In addition, since the solvent solubility is good, it is preferably a polyester resin having a number average molecular weight (Mn) of 1,500 to 5,000. Further, the polyester resin (R) used in the present invention preferably has a softening point of 80 to 150 ° C. by the ring and ball method. A polyester resin having a number average molecular weight (Mn) of less than 1,000 is not preferable because the mechanical properties of the cured product are lowered and become brittle, and a polyester resin having a number average molecular weight (Mn) of more than 8,000 is not preferable. Mixing with other components such as the monomer (M) having a double bond is difficult, and shapeability is lowered, which is not preferable. Further, in the case of a polyester resin having a number average molecular weight (Mn) of less than 1,000 or a polyester resin having a number average molecular weight (Mn) of more than 8,000, the complex of the components excluding the solvent of the active energy ray-curable resin composition at a frequency of 1 Hz. Temperature (T4) at which the viscosity (η *) is 1 × 10 ⁴ dPa · s is 30 ° C. or higher, and temperature (T6) at which the complex viscosity (η *) is 1 × 10 ⁶ dPa · s at a frequency of 1 Hz. Is not preferable because it is difficult to control the temperature to be 100 ° C. or lower.

  As the polyester resin (R), those having an unsaturated double bond are preferable because a sufficient crosslinking density can be obtained after curing by irradiation with active energy rays. Further, it may be a branched polyester resin.

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

Examples of the polycarboxylic acid component, if example embodiment, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecenyl succinic acid, n- dodecyl succinic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, Examples thereof include dicarboxylic acids such as cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, and terephthalic acid, or anhydrides thereof; trifunctional or higher carboxylic acids such as trimellitic acid, trimetic acid, and pyromellitic acid, or anhydrides thereof. 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, the Rukoto with maleic acid and / or fumaric acid as part or all of the polycarboxylic acid component can be introduced an unsaturated double bond in the resulting polyester resin, The polymerizable vinyl compound (V It is more preferable because a polyester resin excellent in compatibility with (A) is obtained. 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 a 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 · s. A polyester resin that can be easily controlled to a temperature (T6) at which the temperature (T4) becomes 30 ° C. or higher and the complex viscosity (η *) at a frequency of 1 Hz becomes 1 × 10 6 dPa · s (T6) to 100 ° C. or lower is obtained. To 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.

  The polymerizable vinyl compound (V) used in the present invention is a bifunctional vinyl compound (V1) having a bisphenol skeleton. As the vinyl compound (V1), for example, a (meth) acrylic compound can be preferably used. Among (meth) acrylic compounds, for example, di (meth) acrylates of alkylene oxide modified bisphenol A such as diacrylate of alkylene oxide modified bisphenol A, dimethacrylate of alkylene oxide modified bisphenol A; di (meth) acrylate of alkylene oxide modified bisphenol F; Di (meth) acrylates of alkylene oxide modified bisphenol F such as acrylate, alkylene oxide modified bisphenol F dimethacrylate, etc .; Dioxide of alkylene oxide modified bisphenol S, alkylene oxide modified bisphenol S such as dimethacrylate of alkylene oxide modified bisphenol S Bifunctional having an alkylene oxide-modified bisphenol skeleton such as di (meth) acrylates It can be preferably used a nil-based compound.

  Among the (meth) acrylic compounds, di (meth) acrylate represented by the following general formula (1) is most preferable.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６はそれぞれ水素原子またはメチル基であり、これらは同一であっても異なっていても良い。ｍ_１とｍ_２は整数であり、１≦ｍ１＋ｍ２≦２０である。）

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom or a methyl group, and these may be the same or different. M ₁ and m ₂ are An integer, 1 ≦ m1 + m2 ≦ 20)

  Examples of commercially available di (meth) acrylates represented by the general formula (1) include, for example, Aronix M-208, Aronix M-210, Aronix M-211B [above, manufactured by Toa Gosei Co., Ltd.], Light Acrylate BP -4EA, light acrylate BP-4PA, light ester BP-2EM [manufactured by Kyoeisha Chemical Co., Ltd.], NK ester A-BPE-4, NK ester BPE-100, NK ester BPE-200, NK ester BPE-500 [Above, Shin-Nakamura Chemical Co., Ltd.], Kayarad R-551, Kayarad R-712 [above, Nippon Kayaku Co., Ltd.], Beam Set 750 [Arakawa Chemical Industries, Ltd.], SR-348 SR-349, SR480, SR-601 [above, manufactured by Kayaku Sartomer Co., Ltd.], New Frontier BPE 4. New Frontier BPE-10, New Frontier BPE-20, New Frontier BPEM-20, New Frontier BPP-4 [above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], Biscote # 700 [Osaka Organic Chemical Co., Ltd.] ], Photomer 4025, photomer 4028 (manufactured by Sannopco), Evecril 150, Evekril 1150, BPA (EO3) DMA [manufactured by Daicel UC Corporation], Blemmer ADBE-200, Blemmer PDBE-200, Blemmer ADBP Series, Blemmer PDBP series, Blemmer ADBEP series, Blemmer PDBEP series [above, manufactured by NOF Corporation] and the like.

  In the present invention, another vinyl polymer may be used in combination with the vinyl polymer (V1) to such an extent that the effects of the present invention are not impaired. Examples of other vinyl compounds include 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, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl Propanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di (Meth) acrylic monomers such as pentaerythritol hexa (meth) acrylate and tris [2- (meth) acryloyloxyethyl] isocyanurate; polyester (meth) acrylate, novolac epoxy (meth) acrylate, urethane (meth) acrylate, etc. (Meth) acrylic oligomers and the like.

The shaping active energy ray-curable resin composition of the present invention contains the polyester resin (R) and the vinyl compound (V1), and has a complex viscosity (η *) at a frequency of 1 Hz of components other than the solvent. The temperature (T4) at which 1 × 10 ⁴ dPa · s is obtained is 30 ° C. or higher, and the temperature (T6) at which the complex viscosity (η *) at a frequency of 1 Hz is 1 × 10 ⁶ dPa · s is 100 ° C. or lower. is required. When the temperature (T4) is lower than 30 ° C., the resin layer made of the active energy ray-curable resin composition for shaping laminated on the sheet-like resin base material has a film thickness by flow before reaching the shaping step. It is not preferable because a change is easily generated. If the temperature (T6) is higher than 100 ° C., the heating temperature at the time of heating and melting and laminating on the sheet-like resin base material has to be increased. As a result, the active energy ray-curable resin composition for shaping is obtained. Polyethylene terephthalate with a low softening point as a result of the gelation of the polymerizable vinyl compound in the inside, making it difficult to uniformly laminate, and the need to increase the heating temperature during shaping. This is not preferable because there is a possibility that the sheet-like resin base material is thermally deformed.

  The temperature (T4) of the active energy ray-curable resin composition for shaping of the present invention is preferably 40 ° C or higher, and more preferably 55 ° C or higher. Further, the temperature (T6) is preferably 80 ° C. or lower, and more preferably 60 ° C. or lower. Among them, a shaping active energy ray-curable resin composition having a temperature (T4) of 40 ° C. or higher and a temperature (T6) of 80 ° C. or lower is preferable, the temperature (T4) is 55 ° C. or higher, and The shaping active energy ray-curable resin composition having a temperature (T6) of 60 ° C. or lower is more preferable.

  The active energy ray-curable resin composition for shaping according to the present invention comprises the polyester resin (R) and the vinyl compound (V1) as essential components, and if necessary, other resins other than the polyester resin (R). , Photopolymerization initiators, those containing other additives, solvents and the like.

  If the change in viscosity with respect to the temperature of the active energy ray-curable resin composition for shaping is too rapid, the influence of slight temperature fluctuations in the shaping process on the shapeability cannot be ignored. It is more preferable that the active energy ray-curable resin composition for forming has an appropriate temperature sensitivity. Specifically, the temperature difference (T4−T6) between the temperature (T4) and the temperature (T6) is as follows. It is preferably 20 ° C. or higher, and more preferably 20 to 50 ° C. At this time, the temperature (T5) at which the complex viscosity (η *) at a frequency of 1 Hz shows 1 × 10 5 dPa · s is preferably 30 to 100 ° C., and more preferably 40 to 80 ° C.

The polyester resin (R) and the polymerizable vinyl compound (V1) are a complex viscosity (η *) at a frequency of 1 Hz of components other than the solvent in the shaping active energy ray-curable resin composition to be obtained. ) Is 1 × 10 ⁴ dPa · s (T4) is 30 ° C. or more, and the complex viscosity (η *) at a frequency of 1 Hz is 1 × 10 ⁶ dPa · s (T6) is 100 ° C. or less. In such a range, the mixture may be mixed at an arbitrary ratio. Among them, the weight ratio (R / V1) is in the range of 40/60 to 90/10. Temperature (T6)] is preferably 20 ° C. or higher, and the active energy ray-curable resin composition for shaping having the temperature (T5) of 30 to 100 ° C. is preferable. In addition, the combination of the polyester resin (R) and the vinyl compound (V1) can be freely selected. However, when the use of the shaped product obtained as the final product is an optical article, the composition can provide transparency. It is preferable.

In the present invention, the complex viscosity (η ^* ) at a frequency of 1 Hz of components other than the solvent of the shaping active energy ray-curable resin composition is measured using a rheometer RS500 manufactured by HAAKE Corporation, measuring frequency: 6.28 rad. / Sec. (1 Hz), measurement start temperature: 25 ° C., measurement end temperature: 150 ° C., temperature increase rate: 2 ° C./min. It is obtained by measuring the active energy ray-curable resin composition for shaping that does not contain a solvent under the above conditions. Moreover, temperature (T4), temperature (T5), and temperature (T6) can each be calculated | required from the chart of the measurement result of the temperature change of the said complex viscosity ((eta) *).

  As described above, the shaping active energy ray-curable resin composition of the present invention may contain other resins other than the polyester resin (R), a photopolymerization initiator, other additives, and the like as necessary. Examples of the resin other than the polyester resin (R) include acrylic resin, urethane resin, epoxy resin, and polycarbonate. The amount of these other resins used is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the polyester resin (R).

  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-ben Examples include methyl ylbenzoate, [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.

  Furthermore, 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. Can be mentioned.

  Among these other additives, in order to prevent thermal polymerization during production of the shaping active energy ray-curable resin composition of the present invention and maintain storage stability, 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.

  Various methods can be used to produce a shaped product using the active energy ray-curable resin composition for shaping of the present invention. For example, the following method etc. are mentioned.

  Method 1: The shaping sheet obtained by the method described later and the flat or roll-shaped mold on which the shaping pattern is formed are heated, respectively, and the active energy ray-curable resin composition layer of the shaping sheet is the gold. After the mold is brought into intimate contact with the shaping sheet so as to be on the mold side, pressurization is performed to form, then the active energy ray-curable resin composition is cured by irradiation with active energy rays, and then released. .

  Method 2: The shaping sheet obtained by the method to be described later and the flat or roll-shaped mold on which the shaping pattern is formed are heated, respectively, so that the active energy ray-curable resin composition layer of the shaping sheet is a mold. The mold is brought into close contact with the shaping sheet so as to be on the mold side, pressed and shaped, and then released, and then the active energy ray-curable resin composition is cured by irradiation with active energy rays.

  In the method 2, the mold can be brought into close contact with the shaping sheet, pressed and shaped, and then cooled to improve the releasability.

  The shaping active energy ray-curable resin composition of the present invention may contain a release agent. In particular, by including a mold release agent, the mold can be brought into close contact with the shaping sheet in the method 2 and pressurizing to form the mold, so that the mold release can be improved without cooling. The cooling step can be omitted, which contributes to improving the manufacturing efficiency of the shaped sheet.

  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, H4428, 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 in the nonvolatile content of the active energy ray-curable resin composition is 1 to 15% by weight is preferable, and the range in which the content is 3 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.

  The shaping sheet of the present invention is such that the above-mentioned shaping active energy ray-curable resin composition is laminated on one side or both sides of a sheet-like resin substrate. The sheet-like resin base material used for this shaping sheet is not particularly limited. For example, a sheet-like resin base material made of a polyester-based resin typified by polyethylene terephthalate, typified by polymethyl methacrylate. A base material that transmits active energy rays, such as a sheet-like resin base material made of acrylic resin and a sheet-like resin base material made of polycarbonate resin, is laminated and shaped on both sides or one side of these base materials. When the active energy ray is irradiated to the resin layer of the active energy ray-curable resin composition, it is preferable that the active energy ray-curable resin composition 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 thickness of the active energy ray-curable resin composition layer for solvent-free shaping laminated on one side or both sides of the sheet-like resin base material is not particularly limited and is determined according to its use. However, it is usually 10 μm to 1 mm, preferably 50 to 500 μm, and preferably 1 to 5 times the maximum depth of the mold.

  The method of laminating the active energy ray-curable resin composition for shaping on one side or both sides of the sheet-like resin substrate is not particularly limited, but for example, an active energy ray-curable resin composition is required. Depending on the solution, dissolve in a solvent such as toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropyl alcohol, etc. to make a uniform solution, and cast on a sheet-shaped resin substrate using various coaters After removing the solvent by evaporating in a drying oven, etc., the uniformly mixed active energy ray-curable resin composition for shaping is heated to lower the viscosity and then applied onto the sheet-like resin substrate. And a method of solidifying by cooling. 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 resin content may be 40 weight% in conversion of a part, and it is more preferable to melt | dissolve so that it may become 50 weight% or more.

The shaping sheet of the present invention can be formed 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 g of propylene oxide adduct of bisphenol A [BAP2 glycol manufactured by Nippon Emulsifier Co., Ltd.] and 272 g of fumaric acid were reacted at 215 ° C. for 8 hours in the presence of 1.1 g of dibutyltin oxide, and unsaturated double bond in the molecule A polyester resin (R1) 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), urethane acrylate oligomer [Unidic V-4260 manufactured by Dainippon Ink & Chemicals, Inc., number average molecular weight 1,700, average number of unsaturated groups 3 ] 4 parts, diacrylate of propylene oxide 4 mol adduct of bisphenol A [New Frontier BPP-4 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 18 parts, and 2,2-dimethoxy-1,2-diphenylethane-1 -4 parts of ON [IRGACURE 651 manufactured by Ciba Specialty Chemicals] were mixed, heated and stirred at 130 ° C, and degassed under reduced pressure to obtain a uniform active energy ray-curable resin composition for shaping. The temperature (T6) at which the complex viscosity (η ^* ) at a frequency of 1 Hz of the obtained active energy ray-curable resin composition for shaping becomes 1 × 10 ⁶ dPa · s is 37 ° C. and the complex viscosity at a frequency of 1 Hz ( The temperature (T5) at which η ^* ) is 1 × 10 ⁵ dPa · s is 55 ° C., and the temperature (T4) at which the complex viscosity (η ^* ) is 1 × 10 ⁴ dPa · s at a frequency of 1 Hz after solvent removal is The temperature difference (T4−T6) was 35 ° C.

  When the obtained active energy ray-curable resin composition for shaping was heated and the temperature of the composition reached 150 ° C., the viscosity was measured to be 26 dPa · s. After allowing the composition to stand at a temperature of 150 ° C. for 24 hours, the viscosity was again measured and found to be 26 dPa · s. Gelation could not be confirmed by observing the appearance. Thereby, it became clear that the active energy ray-curable resin composition for shaping according to the present invention is excellent in heat stability.

  Next, the obtained active energy ray-curable resin composition for shaping, the polyethylene terephthalate film A4300, and the applicator were preheated to 110 ° C., and the polyethylene terephthalate film was heated on a hot plate controlled at 110 ° C. An active energy ray-curable resin composition for shaping is applied on one side with an applicator, and an active energy ray-curable resin composition layer for shaping having a thickness of 100 μm is laminated on one side of a sheet-like resin substrate. A forming sheet (S2) was obtained.

The obtained shaping sheet (S1) and a planar mold in which rectangular grooves having a bottom width of 93 μm, an upper width of 103 μm, and a depth of 40 μm are formed in parallel with an interval of a width of 47 μm, After heating to ° C and bringing the shaping sheet into contact with the mold so that the active energy ray-curable resin composition layer for shaping is on the mold side, a pressure of 98 kPa is applied for 2 seconds for shaping The sheet was shaped. Next, the sheet is peeled off from the mold by cooling to 40 ° C., and further irradiated with ultraviolet rays of 1000 mJ / cm ² by an ultraviolet lamp, and the mold pattern is transferred to the active energy ray-curable resin composition and cured. A shaped sheet (Sc1) was obtained.

  The obtained shaped sheet (Sc1) is free from breakage during mold release and subsequent handling, and has excellent mechanical properties. The shape of the shaped sheet (Sc1) is a laser microscope (VK-8510, an ultra-deep shape measuring microscope manufactured by Keyence Corporation). The width of the flat portion of the upper portion of the rectangular shape corresponding to the bottom portion (width 93 μm) of the rectangular groove was 90 μm or more, and it was confirmed that the mold shape was accurately transferred. .

Example 2
In a separable flask, 74 parts of the polyester resin (R1) obtained in Example 1, urethane acrylate oligomer [Unidick V-4260 manufactured by Dainippon Ink & Chemicals, Inc., number average molecular weight 1,700, average number of unsaturated groups 3 pieces] 4 parts, diacrylate of 20 mol adduct of bisphenol A with ethylene oxide [New Frontier BPE-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], and 2,2-dimethoxy-1,2-diphenylethane 4 parts of -1-one [IRGACURE 651 manufactured by Ciba Specialty Chemicals] were mixed, heated and stirred at 130 ° C., and degassed under reduced pressure to obtain a uniform active energy ray-curable resin composition for shaping. The temperature (T6) at which the complex viscosity (η ^* ) at a frequency of 1 Hz of the obtained active energy ray-curable resin composition for shaping is 1 × 10 ⁶ dPa · s is 30 ° C., and the complex viscosity at a frequency of 1 Hz ( The temperature (T5) at which η ^* ) is 1 × 10 ⁵ dPa · s is 41 ° C., and the temperature at which the complex viscosity (η ^* ) is 1 × 10 ⁴ dPa · s at a frequency of 1 Hz of the components excluding the solvent (T4). Was 58 ° C, and the temperature difference (T4-T6) was 28 ° C.

  When the obtained active energy ray-curable resin composition for shaping was heated and the temperature of the composition reached 150 ° C., the viscosity was measured and found to be 24 dPa · s. After leaving the composition at a temperature of 150 ° C. for 12 hours, the viscosity was measured again and found to be 24 dPa · s. Gelation could not be confirmed by observing the appearance. Thereby, it became clear that the active energy ray-curable resin composition for shaping according to the present invention is excellent in heat stability.

  Next, using the obtained active energy ray-curable resin composition for shaping, the active energy ray-curable resin composition layer for shaping having a thickness of 100 μm was formed into a sheet-like resin group in the same manner as in Example 1. A shaping sheet (S2) laminated on one side of the material was obtained.

The obtained shaping sheet (S2) and a flat mold in which rectangular grooves having a bottom width of 93 μm, an upper width of 103 μm, and a depth of 40 μm are formed in parallel with an interval of a width of 47 μm are respectively 45 After heating to ° C and bringing the shaping sheet into contact with the mold so that the active energy ray-curable resin composition layer for shaping is on the mold side, a pressure of 98 kPa is applied for 2 seconds for shaping The sheet was shaped. Next, the sheet is peeled off from the mold by cooling to 30 ° C., and further irradiated with ultraviolet rays of 1000 mJ / cm ² by an ultraviolet lamp, and the mold pattern is transferred to the active energy ray-curable resin composition and cured. A shaped sheet (Sc2) was obtained.

  The obtained shaped sheet (Sc2) has no mechanical damage during mold release or subsequent handling, and has excellent mechanical properties. When the shape was measured using a laser microscope, the bottom of the rectangular groove (width) The width of the upper flat portion of the rectangular shape corresponding to 93 μm was 90 μm or more, and it was confirmed that the mold shape was accurately transferred.

Comparative Example 1
In a separable flask, 65 parts acrylic resin (Dainippon Ink & Chemicals Co., Ltd. Fined A-251) with a number average molecular weight (Mn) of 7,300, urethane acrylate oligomer [Dainippon Ink & Chemicals Co., Ltd. Unidic V-4260] 28 parts, 3 parts KAYARAD DPHA, and 4 parts IRGACURE 651 were melt mixed and degassed under reduced pressure to obtain a uniform comparative active energy ray-curable resin composition for comparison. The temperature (T6) at which the complex viscosity (η ^* ) at a frequency of 1 Hz after removal of the solvent of the obtained comparative active energy ray-curable resin composition for comparison was 1 × 10 ⁶ dPa · s was 52 ° C., after removal of the solvent. The temperature (T5) at which the complex viscosity (η ^* ) at a frequency of 1 Hz is 1 × 10 ⁵ dPa · s is 70 ° C., and the complex viscosity (η ^* ) at a frequency of 1 Hz after solvent removal is 1 × 10 ⁴ dPa · s. The temperature (T4) was 85 ° C, and the temperature difference (T4-T6) was 33 ° C.

  When the viscosity of the obtained active energy ray-curable resin composition for shaping was heated and the temperature of the composition reached 150 ° C., it was 30 dPa · s. After leaving the composition at a temperature of 150 ° C. for 2 hours, the viscosity was measured again and found to be 65 dPa · s. When the appearance was observed, gel-like spots had already occurred, which was incompatible with the resin composition for coating. Furthermore, when it was allowed to stand for 1 hour while being maintained at 150 ° C., the entire resin was gelled. This revealed that the comparative active energy ray-curable resin composition for shaping was low in stability against heat.

  Next, a shaping sheet (S1 ′) was prepared in the same manner as in Example 1 except that the obtained comparative active energy ray-curable resin composition was used. Extruding and ultraviolet irradiation were performed in the same manner as in Example 1 except that the forming sheet and the mold before shaping were each heated at 70 ° C. to obtain a shaped sheet (Sc1 ′).

  The cured resin layer of the obtained shaped sheet (Sc1 ′) was very fragile, and immediately after release from the sheet-like transparent resin substrate made of polyethylene terephthalate, it was easily cracked.

Claims (12)

The complex viscosity (η *) at a frequency of 1 Hz of a component containing a polyester resin (R) having a number average molecular weight (Mn) of 1,000 to 8,000 and a polymerizable vinyl compound (V) and excluding the solvent is Shaping at a temperature (T4) of 1 × 10 ⁴ dPa · s is 30 ° C. or higher and a complex viscosity (η *) at a frequency of 1 Hz is 1 × 10 ⁶ dPa · s (T6) of 100 ° C. or lower Active energy ray-curable resin composition, wherein the polyester resin (R) is a polyester resin obtained using a polycarboxylic acid component and a polyol component as essential components, and a part of the polycarboxylic acid component A polyester resin obtained by using maleic acid and / or fumaric acid as a whole, wherein the polymerizable vinyl compound (V) has a bisphenol skeleton. System Compound (V1) for vehicles, characterized the radiation-curable resin composition to be produced. The temperature (T5) at which the complex viscosity (η *) at a frequency of 1 Hz is 1 × 10 ⁵ dPa · s is 40 to 80 ° C., and the temperature difference between the temperature (T4) and the temperature (T6) (T4−T6) The active energy ray-curable resin composition for shaping according to claim 1, wherein The polyester resin (R) is a polyester resin obtained by using a polycarboxylic acid component and a polyol component as essential components, and a bisphenol and / or an alkylene oxide adduct thereof is used as part or all of the polyol component. The active energy ray-curable resin composition for shaping according to claim 1, which is a polyester resin obtained. The active energy ray-curable resin composition for shaping according to any one of claims 1 to 3, wherein the vinyl compound (V1) is a (meth) acrylic compound. The active energy ray-curable resin composition for shaping according to any one of claims 1 to 3, wherein the polyester resin (R) is a polyester resin having a number average molecular weight (Mn) of 1,500 to 5,000. The active energy ray-curable resin composition for shaping according to any one of claims 1 to 3, wherein the vinyl compound (V1) is a di (meth) acrylate represented by the following general formula (1).

(Wherein, is _{R 1, R 2, R 3} , R 4, R 5 and R ₆ are each a hydrogen atom or a methyl group, it may be the same or different. _{M 1} and m ₂ are An integer, 1 ≦ m ₁ + m ₂ ≦ 20) The active energy for shaping according to any one of claims 1 to 3, wherein the weight ratio (R / V) of the polyester resin (R) and the polymerizable vinyl compound (V1) is 40/60 to 90/10. A linear curable resin composition. Furthermore, the active energy ray hardening-type resin composition for shaping | molding as described in any one of Claims 1-3 containing a photoinitiator. The said temperature (T4) is 55 degreeC or more, and the said temperature (T6) is 60 degrees C or less, The active energy ray hardening-type resin composition for shaping | molding as described in any one of Claims 1-3. A shaping sheet, wherein the shaping active energy ray-curable resin composition according to claim 1 is laminated on one side or both sides of a sheet-like resin base material. The sheet for shaping according to claim 10, wherein the sheet-like resin substrate is a sheet-like resin substrate of polyethylene terephthalate resin. A shaped article obtained by shaping the shaping sheet according to claim 10 or 11 and then curing it by irradiation with active energy.