WO2013151119A1 - Composition durcissable sous énergie active pour formation de couche optique - Google Patents

Composition durcissable sous énergie active pour formation de couche optique Download PDF

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Publication number
WO2013151119A1
WO2013151119A1 PCT/JP2013/060293 JP2013060293W WO2013151119A1 WO 2013151119 A1 WO2013151119 A1 WO 2013151119A1 JP 2013060293 W JP2013060293 W JP 2013060293W WO 2013151119 A1 WO2013151119 A1 WO 2013151119A1
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meth
weight
acrylate
composition
component
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PCT/JP2013/060293
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English (en)
Japanese (ja)
Inventor
和正 稲田
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東亞合成株式会社
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Priority to JP2014509200A priority Critical patent/JP5839116B2/ja
Publication of WO2013151119A1 publication Critical patent/WO2013151119A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B29C39/006—Monomers or prepolymers

Definitions

  • the present invention relates to an active energy ray-curable composition for forming an optical layer.
  • the composition of the present invention includes a lens sheet such as a Fresnel lens and a lenticular lens, a prism sheet for a backlight of a liquid crystal display device, a plastic lens, and an antiglare sheet. It can be used for optical films or sheets used in various optical materials such as screens and wavelength selective reflection films, and can be suitably used for heat ray reflective films or sheets, and belongs to these technical fields.
  • a fine shape made of a cured product of the active energy ray-curable composition is formed on a transparent plastic substrate by mold transfer to produce an optical film or sheet (hereinafter simply referred to as “optical film”) such as a lens sheet.
  • optical film such as a lens sheet.
  • the technique is widely known (for example, Patent Documents 1 to 3). In these techniques, moldability (coating property, permeability to a fine shape, and mold releasability from a mold) and adhesion of a cured product to a transparent plastic substrate are required. Furthermore, it is necessary that curability, transparency, refractive index, toughness, heat resistance and curl are small depending on the application.
  • Patent Documents 4 and 5 disclose an optical film that selectively directs and reflects light in a specific wavelength band, for example, infrared rays, and a heat ray retroreflective film that is attached to a window is exemplified as an application example. Yes.
  • Patent Documents 4 and 5 as a method for producing an optical film, a fine uneven shape made of a cured product of an active energy ray-curable composition is formed on a substrate by mold transfer, and then wavelength selection is performed thereon.
  • an inorganic film such as a metal or metal oxide is formed, and the other substrate is laminated through the active energy ray-curable composition so as to fill the unevenness, and the active energy ray is again applied. Illustrated is a method of manufacturing by irradiation and curing.
  • the active energy ray-curable composition for mold transfer for producing such an optical film has good moldability (coating property, permeability to fine shape, and mold releasability).
  • moldability coating property, permeability to fine shape, and mold releasability.
  • it is required to maintain a relatively high elastic modulus even at a high temperature of about 100 ° C.
  • heat may be applied in the process of forming the inorganic film, or pressure may be applied at a high temperature when the other substrate is laminated while filling the unevenness.
  • the storage elastic modulus E ′ at 100 ° C. in the dynamic viscoelastic spectrum (1 Hz) is 3 ⁇ 10 7 Pa or more (Patent Document 5).
  • the substrate is a polyethylene terephthalate (hereinafter referred to as “PET”) film.
  • PET polyethylene terephthalate
  • the liquid soot is exposed to light from which high-energy ultraviolet rays of about 315 nm or less are cut in contact with air.
  • This liquid soot is not cured by one rotation of the roll-shaped mold, but is cured after several tens to several hundreds of rotations (after several tens to several hundreds of times of ultraviolet irradiation).
  • the deposit that is slowly cured by irradiation with ultraviolet rays through the substrate under air has a strong adhesion to the mold and is difficult to peel off with an adhesive tape or the like.
  • the uncured stain on the liquid jar is a mold that is released from the mold when the next liquid is covered and cured.
  • the coating width slightly narrows, and the mold may rotate several tens to several hundreds of revolutions.
  • the soiled part of the cocoon is repeatedly exposed to ultraviolet rays through the base material in the air, and is cured very slowly to become a firmly adhered dirt.
  • Swelling and peeling by solvent immersion is useful as a method for removing such tightly adhered soot stains without damaging the mold.
  • a composition that maintains a relatively high elastic modulus even at a high temperature of about 100 ° C. has a relatively high crosslinking density and tends to be difficult to swell and peel by solvent immersion.
  • the application of the optical film is a heat ray reflective film to be attached to a window
  • weather resistance is also required.
  • the optical film is applied to the indoor side of the window and the UV absorbent is included in the adhesive used when the optical film is applied to the window, the remarkable weather resistance as in outdoor use is not necessary. However, it is still exposed to light incident from the end of the film and moisture due to condensation, so that good weather resistance is required.
  • the present invention has been made in view of these problems, and is excellent in moldability during mold transfer to a substrate, adhesion to the substrate, and transparency and toughness of the cured product. Even if it is thin, the curl is small, the storage elastic modulus E ′ at 100 ° C. in the dynamic viscoelastic spectrum (1 Hz) is 3 ⁇ 10 7 Pa or more, and the dirt adhered by a large amount of ultraviolet rays through the base material in the air.
  • An object of the present invention is to provide an active energy ray-curable composition that can be easily removed by swelling and peeling with a solvent (excellent in mold cleaning properties).
  • an active energy ray-curable composition that is excellent in adhesion to polyethylene terephthalate (hereinafter referred to as “adhesive PET”) subjected to easy adhesion treatment, which is commonly used as a substrate in optical applications, is provided.
  • adheresive PET polyethylene terephthalate
  • the present inventors have found that di (meth) acrylate of an alkylene oxide adduct of bisphenol A or bisphenol F, one aromatic group and one (meth) per molecule.
  • the inventors have found that a composition containing a compound having an acryloyl group and a specific urethane (meth) acrylate in a specific ratio has excellent performance, and has completed the present invention.
  • the present invention will be described in detail.
  • an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group
  • an acrylate or methacrylate is represented as a (meth) acrylate.
  • the moldability when transferring the fine shape of the mold to the substrate is excellent, the adhesion to the substrate and the transparency of the cured product are excellent, and the curl is small even if the substrate is thin, about It is possible to provide an active energy ray-curable composition that maintains its shape even at a high-temperature process of 100 ° C., and that is excellent in detergency with a solvent when dirt adheres to the mold. Furthermore, the active energy ray-curable composition having good weather resistance can be provided.
  • this invention can be used for various optical materials, such as various lens sheets, a plastic lens, an anti-glare sheet, a screen, and a wavelength selective reflection film, and it is preferably used for a heat ray reflective film stuck on a window. be able to.
  • the present invention relates to an active energy ray-curable composition for forming an optical layer containing the following components (A) to (D) in the following proportions, with the total composition as 100% by weight.
  • component (A) Di (meth) acrylate of an alkylene oxide adduct of bisphenol A or bisphenol F (hereinafter referred to as “component (A)”): 20 to 65% by weight
  • component (B) Compound containing one aromatic group and one (meth) acryloyl group in one molecule [hereinafter referred to as “component (B)”]: 5 to 40% by weight
  • component (B) a (meth) acrylate of an alkylene oxide adduct of phenol is preferable.
  • component (C) is preferably a compound having a weight average molecular weight of 1,000 to 40,000.
  • composition of the present invention preferably further contains the following components in the following proportions.
  • component (E) A radical photopolymerization initiator (hereinafter referred to as “component (E)”) is 0.01 to 10% by weight based on 100% by weight of the entire composition.
  • component (D) As component (D), (D1) (meth) acryloylmorpholine (hereinafter referred to as “component (D1)”) is 3 to 30% by weight based on 100% by weight of the entire composition.
  • component (D2) a compound having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl equivalent of 250 g / mol or less [hereinafter referred to as “component (D2)” ] 5 to 40% by weight based on 100% by weight of the whole composition (F)
  • An ultraviolet absorber (hereinafter referred to as “component (F)”) is 0.1 to 5% by weight based on 100% by weight of the entire composition.
  • Component (A) is a di (meth) acrylate of an alkylene oxide adduct of bisphenol A or bisphenol F.
  • di (meth) acrylate of an alkylene oxide adduct of bisphenol A is preferable.
  • an acrylate is preferable because it is excellent in curability and adhesiveness to the easy-adhesion PET when the irradiation amount of active energy rays is small.
  • alkylene oxide examples include ethylene oxide and propylene oxide.
  • ethylene oxide is preferable because it is excellent in curability and adhesion to easily-adhesive PET when the irradiation amount of active energy rays is small.
  • the added mole number of alkylene oxide is preferably 2 to 6 moles on average and more preferably 3 to 5 moles per mole of bisphenol A or bisphenol F. When the added mole number is 2 or more, the curability is excellent, and when the added mole number is 6 or less, the storage elastic modulus at 100 ° C. is maintained high.
  • the content ratio of the component (A) is 20 to 65% by weight, preferably 30 to 50% by weight, based on 100% by weight of the entire composition.
  • the content ratio of the component (A) is less than 20% by weight, the curability, the mold cleaning property, and the toughness of the cured product are deteriorated.
  • the content rate of (A) component exceeds 65 weight%, the adhesiveness to a base material, especially the adhesiveness to easy-adhesion PET will fall.
  • the component (B) is a compound containing one aromatic group and one (meth) acryloyl group in one molecule.
  • the aromatic group include a phenyl group, an alkylphenyl group, a biphenyl group, and a p-cumylphenyl group.
  • a compound having one aromatic ring such as a phenyl group and an alkylphenyl group is preferable because it can reduce the viscosity of the composition and has excellent adhesion to the substrate.
  • component (B) examples include (meth) acrylate of phenol ethylene oxide adduct and (meth) acrylate of phenol alkylene oxide adduct such as (meth) acrylate of phenol propylene oxide adduct; ethylene of nonylphenol (Meth) acrylates of alkylene oxide adducts of alkylphenols such as (meth) acrylates of oxide adducts and (meth) acrylates of propylene oxide adducts of nonylphenol; (meth) acrylates of ethylene oxide adducts of p-cumylphenol and (meth) acrylates of alkylene oxide adducts of p-cumylphenol such as (meth) acrylates of propylene oxide adducts of p-cumylphenol; (Meth) acrylates of biphenyl alkylene oxide adducts such as (meth) acrylates of side adducts and (meth)
  • (meth) acrylates of phenol alkylene oxide adducts are preferable.
  • an acrylate is preferable because it is excellent in curability and adhesion to a substrate when the irradiation amount of active energy rays is small, particularly adhesion to easily-adhesive PET.
  • the component (B) is a (meth) acrylate of an alkylene oxide adduct of phenol
  • ethylene oxide has curability and adhesion to a substrate when the irradiation amount of active energy rays is small, In particular, it is preferable because of its excellent adhesion to easily-adhesive PET.
  • the number of moles of alkylene oxide added is preferably 1 to 4 moles on average, more preferably 1 to 3 moles, and particularly preferably 2 moles per mole of phenol. When the added mole number is 1 or more, the curability is excellent, and when the added mole number is 4 or less, the toughness of the cured product becomes good.
  • the number of added moles is 2 moles, the odor and skin irritation of the composition are lowered, and the adhesion to the substrate, particularly the adhesion to the easy-adhesion PET and the toughness of the cured product are also good. Become.
  • the content ratio of the component (B) is 5 to 40% by weight, preferably 5 to 30% by weight, based on 100% by weight of the entire composition.
  • the content ratio of the component (B) is less than 5% by weight, the adhesion to the substrate, particularly the adhesion to the easy-adhesion PET and the mold cleaning properties are deteriorated.
  • the content rate of (B) component exceeds 40 weight%, the storage elastic modulus in high temperature will fall.
  • Component (C) The component (C) is composed of a diisocyanate compound having no aromatic ring (hereinafter referred to as “compound (C1)”) and a polyester diol having a number average molecular weight of 500 to 3000 (hereinafter referred to as “compound (C2)”. And urethane (meth) acrylate which is a reaction product of a hydroxyl group-containing mono (meth) acrylate (hereinafter referred to as “compound (C3)”). Component (C) is a compound having two (meth) acryloyl groups.
  • the compound (C1) is a diisocyanate compound having no aromatic ring, and is an aliphatic diisocyanate such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate (hereinafter referred to as “isophorone diisocyanate”).
  • IPDI alicyclic diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate), norbornane diisocyanate and ⁇ , ⁇ '-diisocyanate dimethylcyclohexane, isocyanurate of hexamethylene diisocyanate, isocyanurate of IPDI, etc. And polyisocyanates.
  • IPDI and hexamethylene diisocyanate are preferable.
  • the compound (C2) is a polyester diol having a number average molecular weight (hereinafter referred to as “Mn”) of 500 or more and 3000 or less.
  • Mn number average molecular weight
  • Examples of the compound (C2) include ester compounds of dicarboxylic acid and diol, polycaprolactone diol, and the like.
  • Specific examples of suitable dicarboxylic acids include adipic acid, sebacic acid, succinic acid, phthalic acid, and tetrahydrophthalic acid.
  • Examples of the diol include ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol and hexanediol.
  • Mn of the compound (C2) needs to be 500 or more and 3000 or less.
  • Mn is 500 or more, the mold cleaning property can be improved, and when it is 3000 or less, the transparency of the cured product can be improved.
  • particularly preferable Mn is 700 to 1700.
  • Mn means a value obtained from a hydroxyl value.
  • the compound (C3) is a hydroxyl group-containing mono (meth) acrylate.
  • compound (C3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and caprolactone adducts thereof.
  • an acrylate is preferable because it is excellent in curability and adhesion to a substrate when the irradiation amount of active energy rays is small, particularly adhesion to easily-adhesive PET.
  • Component (C) A component may be manufactured by the conventional method. For example, a method of reacting compound (C1) with compound (C2) to produce an isocyanate group-containing compound and then reacting this with compound (C3), compound (C1), compound (C2) and compound (C3 ) Are reacted at the same time.
  • Component (C) is preferably an oligomer.
  • the weight average molecular weight is preferably 1,000 to 40,000, more preferably 1,000 to 15,000.
  • the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.
  • the content ratio of the component (C) is 5 to 30% by weight, more preferably 10 to 25% by weight, based on 100% by weight of the entire composition.
  • the content ratio of the component (C) is less than 5% by weight, the mold cleaning property and the toughness of the cured product are deteriorated.
  • the content rate of (C) component exceeds 30 weight%, coating property and the permeability of the liquid to a metal mold
  • (D) Component In the composition of the present invention, the component (D) [other than the components (A) to (C) is optionally added for the purpose of adjusting the physical properties of the composition and various physical properties of the cured composition. And a compound having an ethylenically unsaturated group].
  • the content ratio of the component (D) is 0 to 60% by weight, more preferably 10 to 45% by weight, based on 100% by weight of the entire composition. When the content ratio of the component (D) exceeds 60% by weight, any of moldability, adhesion, curl, high temperature elastic modulus, mold cleaning property and weather resistance is deteriorated.
  • component (D3) a compound having an ethylenically unsaturated group other than the components (D1) and (D2) (hereinafter referred to as “component (D3)”) may be included.
  • component (D3) a compound having an ethylenically unsaturated group other than the components (D1) and (D2)
  • Component (D1) is (meth) acryloylmorpholine.
  • the component (D1) can be preferably used when it is desired to increase the adhesion to the substrate, particularly the adhesion to the easily-adhesive PET, without reducing the elastic modulus at high temperature.
  • the content ratio of the component (D1) is preferably 3 to 30% by weight, more preferably 7 to 20% by weight, based on 100% by weight of the entire composition.
  • the content ratio of the component (D1) is preferably 3 to 30% by weight, more preferably 7 to 20% by weight, based on 100% by weight of the entire composition.
  • Component (D2) is a compound having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl equivalent of 250 g / mol or less.
  • the component (D2) can be preferably used when a high elastic modulus at a high temperature is required for the cured product of the composition.
  • component (D2) include tri (meth) acrylate of an isocyanuric acid alkylene oxide adduct, trimethylolpropane tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate, and pentaerythritol. And triacrylate and triacrylate of pentaerythritol alkylene oxide adduct, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa and penta (meth) acrylate.
  • polyester (meth) acrylate in addition to the above compound, polyester (meth) acrylate, epoxy (epoxy) having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl equivalent of 250 g / mol or less.
  • examples include meth) acrylate, urethane (meth) acrylate, and silsesquioxane having a (meth) acryloyl group.
  • an acrylate is preferable because it is excellent in curability and adhesion to a substrate when the irradiation amount of active energy rays is small, particularly adhesion to easily-adhesive PET.
  • the alkylene oxide ethylene oxide is preferable because it is excellent in curability and adhesion to a substrate when the irradiation amount of active energy rays is small, particularly adhesion to easily-adhesive PET.
  • polyester (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl equivalent of 250 g / mol or less include succinic acid, maleic acid, phthalic acid, tetrahydro Examples thereof include acid anhydrides such as phthalic acid and hexahydrophthalic acid, polyols such as trimethylolpropane, pentaerythritol and dipentaerythritol, and esterification reaction products of (meth) acrylic acid. Besides these, poly (meth) acrylates of dendrimer polyols and the like can also be mentioned.
  • epoxy (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl equivalent of 250 g / mol or less include trimethylolpropane triglycidyl ether and pentaerythritol tetra Examples include addition reaction products of a compound having an epoxy group such as glycidyl ether and (meth) acrylic acid.
  • urethane (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl equivalent of 250 g / mol or less include polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate. And addition reaction products such as polyfunctional (meth) acrylate having a hydroxyl group such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.
  • Preferred specific examples of the component (D2) include tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylol, which are alkylene oxide adducts of isocyanuric acid, in that they are excellent in moldability and elastic modulus at high temperature.
  • a more preferable specific example of the component (D2) is tri (meth) acrylate of an isocyanuric acid alkylene oxide adduct in that the curl of the molded product is small.
  • pentaerythritol tri- or tetra (meth) acrylate may be mentioned in terms of increasing the high-temperature elastic modulus more effectively.
  • the component (D2) is not necessarily required when the storage elastic modulus E ′ at 100 ° C. and 1 Hz may be 3 ⁇ 10 7 Pa or more. However, when it is desired to increase the high temperature elastic modulus, for example, when the storage elastic modulus E ′ at 100 ° C. and 1 Hz is desired to be 1 ⁇ 10 8 Pa or more, it is preferable to contain 5 to 40% by weight of the component (D2).
  • the content ratio of the component (D2) is preferably 5 to 40% by weight based on 100% by weight of the entire composition. (D2) By making the content rate of a component into 5 weight% or more, the improvement effect of a 100 degreeC elasticity modulus can be show
  • the more preferable content of the component (D2) is 5 to 25% by weight from the viewpoint of satisfying both the improvement of the elastic modulus at 100 ° C. and the mold cleaning property.
  • the component (D3) is a compound having an ethylenically unsaturated group other than the components (D1) and (D2).
  • various compounds can be used as long as they are compounds having an ethylenically unsaturated group other than the components (A) to (C) and the components (D1) and (D2).
  • the compound (D3) having one ethylenically unsaturated group per molecule include (meth) acrylic acid, Michael addition dimer of acrylic acid, and ⁇ -carboxy-polycaprolactone mono (Meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, ethyl carbitol (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl (meth) acrylate, Michael addition polymer of acrylic acid and tetrahydro Products of esterification of rufuryl alcohol, isobornyl (meth)
  • specific examples of the compound having two ethylenically unsaturated groups in one molecule include di (meth) acrylate of an alkylene oxide adduct of bisphenol Z and an alkylene oxide adduct of bisphenol S.
  • polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like other than the component (D2) are included.
  • the content ratio of the component (D3) is preferably 0 to 20% by weight based on 100% by weight of the entire composition.
  • composition of the present invention contains the above-described essential components (A) to (C) and a desired component (D), and various components can be blended as necessary.
  • preferred components include (E) component (photo radical polymerization initiator) and (F) component (ultraviolet absorber).
  • E component
  • F component
  • ultraviolet absorber ultraviolet absorber
  • Component (E) When the composition of the present invention is cured by visible light, ultraviolet light, or the like, it is preferable to incorporate a photoradical polymerization initiator of component (E). When the composition of the present invention is cured by an electron beam, it is not necessary to add the component (E). As the component (E), various compounds can be used.
  • component (E) examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo ⁇ 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propanone ⁇ and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenone compounds such as phenyl ⁇ -2-methyl-propan-1-one; benzophenone compounds such as benzophenone,
  • the content of the component (E) is preferably 0.01 to 10% by weight, more preferably 0.1 to 7% by weight, still more preferably 0.5 to 5% by weight, based on 100% by weight of the entire composition. It is. By making the content of the component (E) 0.01% by weight or more, curability can be improved. Moreover, by making content of (E) component 10 weight% or less, yellowing of hardened
  • Component (F) is an ultraviolet absorber.
  • the component (F) is added for the purpose of suppressing oxidative deterioration due to light during product use. It is preferable.
  • component (F) examples include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bis-butyroxyphenyl) -1,3,5-triazine, 2 -(2-hydroxy-4 [1-Octyl
  • the content ratio of the component (F) is preferably 0.1 to 5% by weight, more preferably 0.2 to 2% by weight, based on 100% by weight of the entire composition.
  • component (F) When the component (F) is added to the composition of the present invention, it is preferable to use a phosphine oxide compound having absorption up to visible light or near visible light as the component (E).
  • composition of the present invention includes a light stabilizer, a silane coupling agent, a surface conditioner, a radical polymerization inhibitor, an antioxidant, etc. You may mix
  • a light stabilizer may be added for the purpose of suppressing oxidative deterioration due to light during product use.
  • a hindered amine light stabilizer HALS is preferable.
  • HALS include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4 -Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine Decanoic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like.
  • those having a low basicity of hindered amine are preferable from the viewpoint of the stability of the composition, and specifically, a so-called NOR type having an amino ether group is more preferable.
  • a preferable addition ratio is 0.01 to 2% by weight in the composition, and more preferably 0.1 to 1% by weight.
  • a silane coupling agent can be added to the composition of the present invention for the purpose of enhancing the adhesion between the cured surface of the composition of the present invention and the inorganic film formed thereon.
  • the silane coupling agent does not exhibit the adhesion to the inorganic film during mold transfer, but it is hydrolyzed and condensed by moisture in the air to adhere to the inorganic film. Can be preferably used in order to increase.
  • silane coupling agent a compound having a radical polymerizable unsaturated group and an alkoxysilyl group is preferable.
  • a compound having a (meth) acryloyl group and a methoxysilyl group or an ethoxysilyl group is preferable.
  • a silane coupling agent is added, a preferable addition ratio is 0.1 to 10% by weight in the composition, and more preferably 0.5 to 5% by weight.
  • the composition of the present invention has a leveling agent, a wettability improver, etc. for the purpose of improving the leveling property of the coating film at the time of coating or improving the permeability of the liquid into the microstructure of the mold.
  • a surface conditioner can be added.
  • various types such as a silicone type and a fluorine type can be used.
  • a surface conditioner containing a (meth) acryloyl group in the molecule may be used for the purpose of suppressing the transition to the inorganic film interface and the decrease in adhesion.
  • a preferable addition ratio is 0.01 to 0.5% by weight in the composition, and more preferably 0.02 to 0.2% by weight.
  • a radical polymerization inhibitor may be added for the purpose of suppressing gelation during long-term storage or gelation in a machine used for production.
  • the radical polymerization inhibitor may be sufficient if it is contained in the monomer or oligomer that is the raw material for blending, but a radical polymerization inhibitor may be additionally added to ensure the suppression of gelation.
  • radical polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, phenothiazine, naphthoquinone, anthraquinone, N-nitrosophenylhydroxylamine, ammonium salt of N-nitrosophenylhydroxylamine, aluminum salt of N-nitrosophenylhydroxylamine, dibutyl Examples include copper dithiocarbamate, copper chloride, and copper sulfate.
  • the content of the radical polymerization inhibitor is preferably 0.01 to 0.5% by weight, more preferably 0.02 to 0.2% by weight in the composition.
  • An antioxidant may be added to the composition of the present invention for the purpose of suppressing deterioration due to oxidation during product use.
  • As the antioxidant there are a primary antioxidant and a secondary antioxidant. By using these in combination, a high antioxidant effect is obtained.
  • the primary antioxidant examples include 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6 -Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.
  • secondary antioxidants include didodecyl 3,3′-thiodipropionate, 4,6-bis (octylthiomethyl) -o-cresol, tris (2,4-di-tert-butylphenyl) Phosphite etc. are mentioned.
  • the preferable addition ratio is the total of the primary antioxidant and the secondary antioxidant, and is 0.1 to 5% by weight in the composition, more preferably 0.2 to 2% by weight. %.
  • composition of the present invention various substances may be blended in addition to the above components as long as the performance of the present invention is not impaired.
  • a silane coupling agent is added to the composition of the present invention
  • a catalyst that promotes the hydrolysis reaction of alkoxysilyl groups may be added.
  • colloidal silica surface-modified with a (meth) acryloyl group may be blended.
  • a polymer may be added for the purpose of suppressing curling of the cured film.
  • composition of the present invention comprises the components (A) to (C) as essential, the component (D) as an optional component, and contains these in the proportions described above. Preferably, it further comprises (E) to (F) components.
  • a conventional method may be used, and examples thereof include a method of stirring and mixing the components (A) to (D) and, if necessary, other components. If the components (A) to (D) and other components have a high viscosity at room temperature or are solid or the composition does not become liquid at room temperature, the composition may be heated after stirring and mixing. good.
  • the heating temperature is preferably 30 to 100 ° C.
  • the viscosity of the composition of the present invention may be appropriately set according to the purpose, and is preferably 50 to 3,000 mPa ⁇ s at 25 ° C., more preferably 100 to 2,000 mPas, from the viewpoint of excellent moldability. ⁇ S, more preferably 200 to 1,000 mPa ⁇ s. By setting the viscosity at 25 ° C. to 50 mPa ⁇ s or more, it can be applied to a film thickness necessary to fill the uneven shape. Moreover, the permeability
  • lens sheets such as Fresnel lenses and lenticular lenses, prism sheets for backlights of liquid crystal display devices, plastic lenses, and anti-glare products such as liquid crystal displays. It can be used for various optical materials such as a sheet, a projector screen, and a wavelength selective reflection film. Further, the wavelength selective reflection film can be used for a heat ray reflective film. More specifically, examples of the lens sheet include uses such as a video projector, a projection television, and a liquid crystal display.
  • the composition of the present invention is used for forming an optical layer.
  • a usage method a conventional method for producing an optical material may be used. Specifically, the composition is applied to a mold having a concavo-convex shape (lens shape) and bonded to a film or sheet substrate (hereinafter collectively referred to as “film substrate”), or a film substrate. And a method of applying an active energy ray from the film substrate side and curing the composition after applying the composition to the substrate and pasting with a mold. Since the composition of this invention has the said effect, it can be preferably used for manufacture of the optical material manufactured through the said mold transcription
  • film substrates examples include PET (polyethylene terephthalate), polymethyl methacrylate, polymethyl methacrylate-styrene copolymer film, polyethylene naphthalate, polyarylate, polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, Plastic films such as polyetherimide, polyetherketone, polyimide, polymethylpentene, cycloolefin polymer, polyethylene, polypropylene, and triacetylcellulose are preferable, and a glass-based substrate can be used if necessary.
  • PET polyethylene terephthalate
  • polymethyl methacrylate polymethyl methacrylate-styrene copolymer film
  • polyethylene naphthalate polyarylate
  • polyacrylonitrile polycarbonate
  • polysulfone polyethersulfone
  • Plastic films such as polyetherimide, polyetherketone, polyimide, polymethylpentene, cycloolefin polymer, polyethylene, polyprop
  • the film substrate is preferably transparent or translucent (for example, milky white).
  • the thickness of the film substrate is generally 20 to 200 ⁇ m.
  • the composition of the present invention is applied to a mold called a stamper having a target lens shape, and a layer of the composition is provided. A transparent substrate onto which the lens sheet is transferred is adhered onto the substrate. Alternatively, the composition is applied to a transparent substrate and brought into close contact with the mold. Next, active energy rays are irradiated from the transparent substrate side to cure the composition, and then peel from the mold.
  • a coating method it may be appropriately set according to the purpose, and conventionally known bar coat, applicator, doctor blade, knife coater, comma coater, reverse roll coater, die coater, gravure coater, micro gravure coater, etc.
  • the coating method is mentioned.
  • Examples of the active energy ray for curing the composition of the present invention include visible light, ultraviolet light, and electron beam, and light containing ultraviolet light or ultraviolet light is preferable.
  • Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, and an LED.
  • a new type using a DC power supply current can also be suitably used.
  • a high pressure mercury lamp, a metal halide lamp, and an electrodeless lamp are particularly preferable because they are excellent in curability.
  • the irradiation energy of ultraviolet rays should be appropriately set according to the type and composition of the ultraviolet irradiation device.
  • the irradiation energy in the UV-A region is 100 to 5,000 mJ. / Cm 2 is preferable, and 500 to 2,000 mJ / cm 2 is more preferable.
  • the composition of the present invention is poured between a mold having a target lens shape and a transparent substrate.
  • active energy rays are irradiated from the transparent substrate side to cure the composition, and thereafter, the mold is removed from the mold.
  • the material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and resins such as epoxy resins. It is preferable that the mold is made of metal in view of the long life of the mold.
  • Optical Film or Sheet The composition of the present invention is used for forming an optical layer, and is applied to a plastic film or sheet (hereinafter simply referred to as “plastic film”) for forming the optical layer as described above. It is preferably used for the production of an optical film (optical film or sheet) in which an optical layer is formed by a cured product of a linear curable composition.
  • the optical film may be manufactured by a conventional method, and an optical film manufacturing method in which the following steps 1 to 3 are sequentially performed is preferable.
  • Step 1 Apply the above-mentioned active energy ray-curable composition for forming an optical layer to a mold having a fine uneven shape, and bond the coated surface and a plastic film, or as described above for a plastic film.
  • Step 2 Applying the active energy ray-curable composition for forming an optical layer, and bonding a coated surface and a mold having a fine uneven shape
  • Step 2 Irradiating active energy rays from the plastic film side
  • Step 3 Process to remove mold
  • step 1 the active energy ray-curable composition for forming an optical layer described above is applied to a mold having a fine concavo-convex shape, and the coated surface and a plastic film are bonded, or the plastic film is bonded to the plastic film.
  • This is a step of applying the active energy ray-curable composition for forming an optical layer, and bonding a coated surface and a mold having a fine uneven shape.
  • the mold include the same ones as described above.
  • Examples of the coating method include the same methods as described above.
  • the plastic in the plastic film include the plastic films described above, and among them, PET is preferable.
  • a film that has been subjected to an easy adhesion treatment can be used for the purpose of improving the adhesion to the cured composition.
  • the easy adhesion treatment include a treatment for modifying the surface of a hardly adhesive plastic by corona discharge treatment, a treatment for providing an easy adhesion layer on the surface, and the like.
  • Step 2 is a step of irradiating active energy rays from the plastic film side.
  • the active energy ray for curing the composition of the present invention include visible light, ultraviolet light, and electron beam, and light containing ultraviolet light or ultraviolet light is preferable.
  • the ultraviolet irradiation apparatus include the same apparatus as described above, and the same apparatus as described above is preferable. Further, as the ultraviolet irradiation energy, the same irradiation energy as described above is preferable.
  • Step 3 is a step of removing the mold.
  • an optical film in which an optical layer is formed is obtained.
  • the optical film thus obtained can be used for various optical materials such as the above-described lens sheet, plastic lens, and wavelength selective reflection film.
  • the composition of the present invention can be preferably used for a wavelength selective reflection film, and particularly preferably for a heat ray reflective film.
  • the heat ray reflective film will be described in detail.
  • the composition of this invention can be preferably used for a heat ray reflective film among these optical materials.
  • the optical film may be manufactured by a conventional method, and an optical film manufacturing method in which the following steps 1 ′ to 6 ′ are sequentially performed is preferable.
  • Step 1 ′ Applying the active energy ray-curable composition for forming an optical layer described above to a mold having a fine concavo-convex shape and bonding the coated surface and a plastic film, or a plastic film (1 ) Coating the active energy ray-curable composition for forming an optical layer described above, and bonding a coated surface and a mold having a fine uneven shape to the process step 2 ′: active energy from the plastic film (1) side Step 3 ′ of irradiating a line Step of removing the mold and forming an inorganic film on the transferred cured product having a fine uneven shape
  • Step 4 ′ Filling the fine uneven shape on which the inorganic film is formed
  • Step 6 ′ for bonding the coating surface obtained in Step 4 ′ and the plastic film
  • (2) 6 ′ Made of plastic the film( 2) A process of irradiating active energy rays from the side
  • Step 1 ′ and step 2 ′ are as described above, and examples of the method include the same methods as in step 1 and step 2.
  • Step 3 ′ is a step of removing the mold and forming an inorganic film on the transferred cured product having a fine uneven shape.
  • the inorganic film formed on the concavo-convex shape various compounds can be used depending on the purpose, and metals and metal oxides are preferable. Only one kind of inorganic film may be laminated, or two or more kinds of inorganic films may be laminated in combination.
  • the metal include Au, Ag, Cu, Al, Ni, Cr, Ti, Pd, Co, Si, Ta, W, Mo, and Ge, or an alloy containing two or more of these simple substances. Ag-based, Cu-based, Al-based, Si-based or Ge-based materials are preferable.
  • the metal oxide examples include niobium oxide, tantalum oxide, titanium oxide, zinc oxide, and indium tin oxide.
  • a method for forming the inorganic film is not particularly limited, but a dry process such as vacuum deposition or sputtering is preferable.
  • Step 4 ′ is a step of applying the active energy ray-curable composition for forming an optical layer described above so as to fill the fine uneven shape on which the inorganic film is formed.
  • the composition of the present invention can be used not only in the mold transfer step through the step 1 ′ and the step 2 ′ but also in the step 4 ′.
  • the composition used in Step 4 ′ it is preferable to add a (meth) acrylate compound having a phosphate group for the purpose of improving the adhesion to the inorganic film.
  • the addition ratio is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on 100% by weight of the entire composition.
  • Step 5 ′ is a step of bonding the coated surface obtained in step 4 ′ and the plastic film (2).
  • the plastic film (2) used in step 6 ′ the same film as the plastic film (1) can be used, or a different film can be used.
  • Step 6 ′ is a step of irradiating active energy rays from the plastic film (2) side.
  • the same method as in Step 3 can be mentioned.
  • a heat ray reflective film is obtained, and more specifically, it can be preferably used for a heat ray reflective film to be attached to a window.
  • each component used for the preparation of the active energy ray-curable composition is as follows, and hereinafter, the compound name or each symbol (trade name itself or a part thereof) is displayed.
  • Component M-211B Diacrylate of ethylene oxide 4 mol adduct of bisphenol A, Aronix M-211B manufactured by Toagosei Co., Ltd.
  • Component (B) M-101A: acrylate of phenol ethylene oxide 2-mol adduct, Aronix M-101A manufactured by Toagosei Co., Ltd. BzMA: benzyl methacrylate, Mitsubishi Rayon Co., Ltd. acrylate BZ
  • Component (C) M-1200: Urethane acrylate comprising a polyester diol having an Mn of about 1200, a diisocyanate having no aromatic ring and a hydroxyalkyl acrylate, Mw: about 5,000, Aronix M-1200 manufactured by Toagosei Co., Ltd.
  • (D2) component M-315 triacrylate of ethylene oxide 3 mol adduct of isocyanuric acid, Aronix M-315 manufactured by Toagosei Co., Ltd.
  • M-450 Pentaerythritol tetraacrylate, Aronix M-450 manufactured by Toagosei Co., Ltd.
  • Component (D3) OT-1501 urethane acrylate composed of polyether diol, diisocyanate having no aromatic ring and hydroxyalkyl acrylate, Aronix OT-1501 manufactured by Toagosei Co., Ltd.
  • Component (F) T-479 UV absorber, TINUVIN479 manufactured by BASF Corporation
  • Examples 1 to 8 and Comparative Examples 1 to 7 [Production of active energy ray-curable composition]
  • the components shown in Table 1 and Table 2 were stirred and mixed according to a conventional method to prepare active energy ray-curable compositions.
  • surface represents weight%.
  • the composition of the present invention has all the items of moldability, adhesion to easy-adhesion PET, low curling property, high temperature elastic modulus, mold cleaning property, and weather resistance. It had good performance.
  • Example 1 the mold cleaning property and low curl property were particularly excellent, and since the component (D2) was not included, the high temperature elastic modulus was at a relatively good level ( ⁇ ).
  • the composition of Example 2 containing 20% of M-315 as the component (D2) and the composition of Example 3 containing 29% of M-315 have greatly improved high-temperature elastic modulus and good low curl properties. Met. However, in Example 3 in which the mixing ratio of M-315 was relatively large, the mold cleaning performance was slightly lowered. In the composition of Example 4 containing 10% of M-450 as the component (D2), the high-temperature elastic modulus was effectively improved, the mold cleaning property was excellent, and the low curl property was also good.
  • Example 5 In the composition of Example 5 containing 20% of M-450, the high temperature elastic modulus was greatly improved, but the low curl property was slightly decreased.
  • the composition of Example 6 containing no component (D1) was slightly inferior in adhesion.
  • the compositions of Examples 7 and 8 in which Irg-819 was used as the component (E) and T-479 was added as the component (F) had good weather resistance. In particular, the composition of Example 8 gave an evaluation result of ⁇ or more in all items.
  • Comparative Example 5 The composition of Comparative Example 5 containing no component (A) has poor mold cleaning properties, and the composition of Comparative Example 6 containing component (A) exceeding its upper limit of 60% has poor adhesion. It was. Comparative Example 7 using polyether urethane acrylate in place of component (C) and using BzMA as component (B) had poor weather resistance. Moreover, when the ultraviolet irradiation amount was 1 J / m 2 which was the same as other samples, the adhesion was poor.
  • the composition of the present invention can be used for the production of various optical materials for the purpose of forming an optical layer, and specifically, lens sheets such as Fresnel lenses and lenticular lenses, and prism sheets for backlights of liquid crystal display devices. It can be used for optical films used in various optical materials such as plastic lenses, antiglare sheets, screens, and wavelength selective reflection films, and can be particularly preferably used for heat ray reflection film application to windows.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

(Problème] Fournir une composition durcissable sous énergie active qui peut présenter une excellente aptitude au moulage et une excellente adhérence à une base lorsqu'elle est transférée sur la base à l'aide d'un moule et qui peut fournir un produit durci qui a une excellente transparence et une excellente ténacité, qui peut être seulement légèrement courbée même lorsque la base est mince, peut avoir un module d'élasticité élevé, et présente également une propriété telle que les taches adhérant en tant que résultat de l'irradiation avec une grande quantité de rayons ultraviolets à travers la base sous air peuvent être éliminées facilement avec un solvant. [Solution] Une composition durcissable sous énergie active pour former une couche optique, qui contient à l'intérieur de celle-ci les composants mentionnés ci-dessous (A) à (D) dans les quantités mentionnées ci-dessous : (A) un di (méth) acrylate d'un adduit d'oxyde d'alkylène du bisphénol A ou du bisphénol F dans une quantité de 20 à 65% en poids (en abrégé "%" ci-après) ; (B) un composé ayant un groupe aromatique et un groupe (méth) acryloyle dans une quantité de 5 à 40% (C) ; un (méth) acrylate d'uréthane qui est un produit de réaction d'un composé diisocyanate non-aromatique, un polyester diol ayant une masse moléculaire moyenne en nombre de 500 à 3 000 inclus et un mono (méth) acrylate contenant un groupe hydroxyle dans une quantité de 5 à 30% et (D) un autre composé à insaturation éthylénique dans une quantité de 0 à 60 %.
PCT/JP2013/060293 2012-04-06 2013-04-04 Composition durcissable sous énergie active pour formation de couche optique WO2013151119A1 (fr)

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WO2014119425A1 (fr) * 2013-01-31 2014-08-07 三洋化成工業株式会社 Composition durcissable par rayonnement d'énergie active pour éléments optiques, article durci, et lentille optique et feuille ou film pour lentilles optiques produits au moyen dudit article durci
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WO2018181833A1 (fr) * 2017-03-29 2018-10-04 三井化学株式会社 Composition photodurcissable, ongle artificiel, procédé de génération de données de mise en forme, procédé de production d'ongle artificiel, et système de production d'ongle artificiel
TWI774814B (zh) * 2017-08-09 2022-08-21 日商昭和電工材料股份有限公司 賦形膜及光硬化型組成物
JPWO2019031310A1 (ja) * 2017-08-09 2020-07-02 日立化成株式会社 賦形フィルム及び光硬化型組成物
WO2019031310A1 (fr) * 2017-08-09 2019-02-14 日立化成株式会社 Film à motifs et composition photodurcissable
JP7210844B2 (ja) 2017-08-09 2023-01-24 株式会社レゾナック 賦形フィルム及び光硬化型組成物
WO2019117030A1 (fr) * 2017-12-14 2019-06-20 三菱ケミカル株式会社 Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement
WO2019230977A1 (fr) * 2018-06-01 2019-12-05 東亞合成株式会社 Composition durcissable par del pour photomoulage et son utilisation
CN112204056A (zh) * 2018-06-01 2021-01-08 东亚合成株式会社 光成型用led固化型组合物及其利用
JPWO2019230977A1 (ja) * 2018-06-01 2021-07-15 東亞合成株式会社 光成形用ｌｅｄ硬化型組成物及びその利用
CN112204056B (zh) * 2018-06-01 2023-12-12 东亚合成株式会社 光成型用led固化型组合物及其利用
JP7424287B2 (ja) 2018-06-01 2024-01-30 東亞合成株式会社 光成形用ｌｅｄ硬化型組成物及びその利用

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