WO2011158725A1 - インクジェット印刷法に用いる紫外線硬化樹脂組成物、及びこれを用いて得た光学素子 - Google Patents
インクジェット印刷法に用いる紫外線硬化樹脂組成物、及びこれを用いて得た光学素子 Download PDFInfo
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- WO2011158725A1 WO2011158725A1 PCT/JP2011/063206 JP2011063206W WO2011158725A1 WO 2011158725 A1 WO2011158725 A1 WO 2011158725A1 JP 2011063206 W JP2011063206 W JP 2011063206W WO 2011158725 A1 WO2011158725 A1 WO 2011158725A1
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00278—Lenticular sheets
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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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
Definitions
- the present invention relates to a resin composition that can be applied by an inkjet printing method and has an ultraviolet curing property. Specifically, the obtained cured product is excellent in transparency and hardness, and particularly has a refractive index.
- the present invention relates to an ultraviolet curable resin composition suitable for an optical element having a ratio exceeding 1.5.
- the present invention also relates to an optical element such as a lenticular lens sheet or a microlens sheet obtained by applying and curing the ultraviolet curable resin composition on a support substrate by an ink jet printing method.
- Microlenses and lenticular lens sheets are elements used in liquid crystal display backlight units, rear projection displays, projection screens, stereoscopic display, and the like.
- convex lenses are formed in the form of dots or stripes on the surface of a transparent substrate such as glass or plastic sheet.
- Patent Document 1 a three-dimensional display using a time-division light direction control backlight.
- the principle of this method is that the backlight LD of the display is a time-division light direction control backlight 1 that can change the direction LD of the light emitted from the backlight in a time-sharing manner at high speed using a lenticular lens.
- the corresponding image is displayed on the transmissive display 2.
- an image giving binocular parallax in the directions of the left and right eyes (LE, RE) is presented, and switching of this direction is performed at an invisible speed, so that a three-dimensional image can be displayed to the observer.
- the image resolution is the same as that of the LCD, the high resolution of the LCD can be used as it is, and manufacturing and high resolution are facilitated.
- the surface shape of the lenticular lens is a spherical surface, and the following methods have been adopted as processing means. That is, (1) injection molding of molten or semi-molten thermoplastic resin, (2) embossing while heating the sheet (refer to Patent Document 2), (3) ultraviolet curing by placing ultraviolet curing resin in a mold ( Patent Document 3), (4) UV-curing resin is screen-printed and ultraviolet-cured (see Patent Document 4).
- these methods require a mold with high processing accuracy, or require a printing plate, and the mold or the plate and the lens surface are always in contact with each other. It is difficult to eliminate the fear, and it can be said that this is a manufacturing method that reflects scratches on a mold or the like.
- Patent Document 5 a method of forming a microlens using an inkjet or the like has been proposed. That is, in manufacturing a light guide plate for a backlight used in a liquid crystal display device, hemispherical specular dots that prevent diffusion or scattering of incident light are formed on one or both sides of a plastic that is a base material of the light guide plate. Regarding the method. According to this, it has the advantage that it is not necessary to manufacture a metal mold
- Patent Documents 6 and 7 disclose divinyl aromatic compounds (a) and monovinyl aromatic compounds (b) in an organic solvent at a temperature of 20 to 100 ° C. in the presence of a Lewis acid catalyst and an initiator having a specific structure.
- a soluble polyfunctional vinyl aromatic copolymer obtained by polymerization is disclosed.
- this soluble polyfunctional vinyl aromatic copolymer is excellent in solvent solubility and processability, and it is disclosed that the cured
- Patent Document 8 describes that this is a material suitable for an optical material. However, none of them are intended to be compatible with the inkjet process.
- JP 2004-20684 A Japanese Patent Laid-Open No. 9-114024 JP 2002-365405 A JP 2000-155380 A JP 2005-249882 A JP 2004-123873 A Japanese Patent Laying-Open No. 2005-213443 JP 2008-231280 A
- the conventional method mainly uses a mold or a printing plate.
- the contact with the surface was inevitable, and the problem was a decrease in yield due to foreign matter contamination and scratches.
- the present invention has been made to solve such problems, and the object of the present invention is to cure the ultraviolet ray suitable for the inkjet process so that an optical element can be obtained without using a mold or a plate.
- the object is to provide a resin composition.
- an ultraviolet curable resin composition having a specific composition is excellent in coating properties in an ink jet printing method, and therefore, non-maskless or non-mold-less.
- An optical element can be obtained by contact, and it is possible to manufacture an optical element having a wide variety of lens shapes at a low cost, and the obtained cured product has characteristics such as a refractive index suitable for the optical element. As a result, the present invention was completed.
- the present invention is a copolymer obtained by copolymerizing component (A): divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 1 to 80 mol%,
- component (A) divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 1 to 80 mol%
- the following formula (a1) derived from divinyl aromatic compound (a) (Wherein R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms), the content of the structural unit containing an unreacted vinyl group is a structural unit derived from all monomers.
- the blending amount of component (A) is 5 to 45% by weight, the blending amount of component (B) is 55 to 94% by weight, the blending amount of component (C) is 0.97 to 20% by weight, and (D) component An ultraviolet curable resin composition used in an ink jet printing method, wherein the blending amount is 0.03 to 1% by mass and the component curable by ultraviolet rays is 90% by mass or more.
- the present invention is an optical element obtained by coating the ultraviolet curable resin composition on a support substrate by an inkjet printing method and further curing the composition with ultraviolet rays.
- the ultraviolet curable resin composition of the present invention comprises the component (A), the component (B), the component (C), and the component (D), and the blending amount of the component (A) is 5 to 45% by mass.
- the blending amount of component B) is 55 to 94% by mass
- the blending amount of component (C) is 0.97 to 20% by mass
- the blending amount of component (D) is 0.03 to 1% by mass.
- the components (A), (B) and (C) function as a photosensitive resin composition.
- the component (B) is a liquid component prepared to have a viscosity suitable for ink jet coating
- the component (A) provides a refractive index of 1.5 or more necessary for an optical element.
- the component (A) is a copolymer obtained by copolymerizing divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 1 to 80 mol%, and divinyl
- the content of the structural unit containing an unreacted vinyl group represented by the above formula (a1) derived from the aromatic compound (a) constitutes the copolymer.
- a soluble polyfunctional vinyl aromatic copolymer (hereinafter also referred to as copolymer (A)) in an amount of 10 to 90 mol% based on the total number of moles of structural units derived from the monomer.
- the copolymer (A) has a structural unit (a) derived from the divinyl aromatic compound (a) and a structural unit (b) derived from the monovinyl aromatic compound (b), and the above formula
- the structural unit (a1) represented by (a1) is a kind of the structural unit (a) and occupies a part of the structural unit (a).
- the copolymer (A) is soluble means that it is soluble in the photocurable polyfunctional (meth) acrylate of the component (B).
- the copolymer (A) is a soluble polyfunctional vinyl aromatic copolymer obtained by copolymerizing a monomer containing a divinyl aromatic compound, the branched structural unit derived from the divinyl aromatic compound, although it has other structural units, the abundance of cross-linked structural units is limited to the extent that it is soluble. That is, it is a polyfunctional vinyl aromatic copolymer having a certain amount of the structural unit (a1).
- the unreacted vinyl group in the structural unit (a1) is also referred to as a pendant vinyl group, which exhibits polymerizability, and therefore can be polymerized by further polymerization treatment to give a solvent-insoluble photocured resin.
- the number of terminals can be increased by increasing the number of branched structural units.
- the above soluble polyfunctional vinyl aromatic copolymers it is disclosed by the said patent document 7, 8, 9 grade
- the copolymer (A) is obtained by copolymerizing 20 to 99 mol% of the divinyl aromatic compound (a) and 1 to 80 mol% of the monovinyl aromatic compound (b). It has a structural unit derived from the divinyl aromatic compound (a) corresponding to the composition ratio of the monomer and a structural unit derived from the monovinyl aromatic compound (b).
- the copolymer (A) preferably contains 25 to 95 mol% of the structural unit (a) derived from the divinyl aromatic compound based on the structural units derived from all the monomers. More preferably, it is 30 to 90 mol%.
- the structural unit (a) is less than 20 mol%, the heat resistance of the cured product is insufficient, which is not preferable.
- the structural unit (a) derived from the divinyl aromatic compound (a) exceeds 99 mol%, the solubility is lowered, which is not preferable.
- the divinyl aromatic compound (a) generates a structural unit (a1) having a pendant vinyl group in addition to branching or crosslinking the copolymer (A), and has a heat resistance when the copolymer (A) is cured. It plays an important role as a cross-linking component for the expression of.
- divinyl aromatic compound (a) examples include divinylbenzene (including both m- and p-isomers), divinylnaphthalene (including each isomer), divinylbiphenyl (including each isomer), and the like. However, it is not limited to these. Moreover, these can be used individually or in combination of 2 or more types. In particular, divinylbenzene (including both m- and p-isomers) is preferable from the viewpoint of cost and availability, and when higher heat resistance is required, divinylnaphthalene (each isomer) Or divinylbiphenyl (including each isomer) is preferably used.
- the divinyl aromatic compound (a) acts as a means for increasing the refractive index of the cured product as well as heat resistance.
- the structural unit (a1) represented by the formula (a1) is derived from the divinyl aromatic compound (a), it is possible to understand R 1 in the formula (a1) from the divinyl aromatic compound (a). it can. That is, when divinylbenzene is used as the divinyl aromatic compound, R 1 is a phenylene group, and other divinyl aromatic compounds such as divinylbiphenyl are understood to be residues generated by removing two vinyl groups therefrom. .
- One monovinyl aromatic compound (b) is used together with the divinyl aromatic compound (a) to improve the solubility of the copolymer (A).
- the monovinyl aromatic compound (b) include styrene, a nuclear alkyl substituted monovinyl aromatic compound, an ⁇ -alkyl substituted monovinyl aromatic compound, a ⁇ -alkyl substituted styrene, an alkoxy substituted styrene, and the like. Is not to be done.
- styrene ethylvinylbenzene (including both m- and p-isomers), or Ethyl vinyl biphenyl (including each isomer) is preferable from the viewpoint of cost and availability.
- styrene ethylvinylbenzene (including both m- and p-isomers), or Ethyl vinyl biphenyl (including each isomer) is preferable from the viewpoint of cost and availability.
- the copolymer (A) is a trivinyl aromatic compound, trivinyl as long as the effects of the present invention are not impaired.
- Structural units derived from other monomer components (c) such as aliphatic compounds, divinyl aliphatic compounds, monovinyl aliphatic compounds and the like can be introduced.
- the other monomer component (c) examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diene. Examples thereof include, but are not limited to, acrylate and butadiene. These can be used alone or in combination of two or more.
- the structural unit (c) derived from the other monomer component (c) is the total amount of the structural unit (a) derived from the monomer component (a) and the structural unit (b) derived from the monomer component (b). Is used within a range of less than 30 mol%.
- the number average molecular weight Mn (wherein Mn is a number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) of the copolymer (A) is preferably 500 to 20000, more preferably 500 to 10,000. It is. If Mn is 100,000 or more, gel is likely to be formed, and the viscosity increases, which is not desirable. Further, the molecular weight distribution (Mw / Mn) obtained from Mn and the weight average molecular weight Mw is preferably 2 to 10.
- the soot copolymer (A) can be obtained by cationic copolymerization of the above monomers in the presence of one or more promoters selected from (I) Lewis acid catalysts and (II) ester compounds. *
- the divinyl aromatic compound (a) is 20 to 99 mol%, preferably 25 to 95 mol%, more preferably 30 to 90 mol%, and the monovinyl aromatic compound 80 A monomer component containing ⁇ 1 mol%, preferably 75 to 5 mol%, more preferably 70 to 10 mol% is copolymerized.
- the other monomer component (c) can be used in an amount of less than 30 mol% as described above.
- the (I) Lewis acid catalyst used in the production of the copolymer (A) is a compound comprising a metal ion (acid) and a ligand (base), and can receive an electron pair. Can be used without any particular restrictions. At that time, a co-catalyst or a molecular weight distribution regulator (chain transfer agent) may be added.
- the method for recovering the copolymer after stopping the polymerization reaction is not particularly limited. For example, a commonly used method such as a steam stripping method or precipitation with a poor solvent may be used.
- component (B) As the component (B), a photocurable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is used.
- component (B) examples include polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, and ditrimethylol.
- examples of the polyglycidyl compound include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, and glycerin polyethoxyglycidyl ether. , Trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, and the like.
- component (B) examples include polyfunctional urethane acrylate which is a reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate compound.
- the hydroxyl group-containing polyfunctional (meth) acrylate include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate.
- examples include range isocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and p-phenylene diisocyanate.
- components (B) may be used alone or in admixture of two or more.
- a preferred one is a diacrylate or triacrylate compound having a viscosity of 30 mPa ⁇ sec or less at 20 ° C. to 45 ° C.
- those having a boiling point exceeding 200 ° C. are preferably used.
- the photopolymerization initiator of component (C) will be described.
- the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- (methylthio) Acetophenones such as phenyl] -2-morpholinopropan-1-one; ant such as 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinone
- tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester
- an accelerator such as a benzoic acid derivative.
- photopolymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur® 116, 1173 (above, Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO, LR8883, LR8970 (above BASF), Ubekrill P36 (UCB) and the like.
- surfactant of the component (D) commercially available silicon surfactants, fluorine surfactants, nonionic surfactants and the like can be used alone or in admixture of two or more.
- fluorochemical surfactant DIC's MegaFuck series may be used.
- the addition amount of the surfactant is 0.03% by mass to 1% by mass with respect to the total resin composition, and the surface tension of the inkjet ultraviolet curable resin composition at the inkjet head temperature during coating is 20 to 32 mN /%. Add to m. If the surface tension exceeds 32 mN / m, the discharge amount may not be stable at the initial stage of inkjet discharge, and may not be discharged. When the surface tension is less than 20 mN / m, the nozzle surface is contaminated and the landing accuracy is lowered.
- the blending amount of the above essential components is such that the blending amount of the component (A) is 5 to 45% by weight, the blending amount of the component (B) is 55 to 94% by weight, and the blending amount of the component (C) is 0.97 to 20%.
- the blending amount of the component (D) is 0.03 to 1% by mass, and 90% by mass or more of the component that is cured by ultraviolet rays is contained.
- containing 90% by mass or more of a component that is cured by UV means that the total amount of the component (A), the component (B), and the component (C) is 90% by mass or more. .
- the refractive index required as an optical element may not be 1.5 or more.
- the viscosity upper limit of 40 mPa ⁇ sec (20 ° C. to 45 ° C.) suitable for ink jet discharge is exceeded, and it is difficult to obtain a stable discharge amount.
- the compounding quantity of (B) component exceeds 95 mass%, the refractive index of 1.5 or more may not be obtained like the case of (A) component.
- the viscosity upper limit of 40 mPa ⁇ sec (20 ° C. to 45 ° C.) suitable for ink jet discharge is exceeded.
- the blending amount of the component (C) is less than 0.97% by mass, the tack of the cured product is not eliminated with a substantial ultraviolet ray irradiation amount. If it exceeds 20% by mass, the cured product becomes brittle, and yellowing during heating becomes a problem.
- the blending amount of the component (D) is less than 0.03% by mass, the discharge amount at the start of ink jet discharge is not stable, and there are disadvantages such as the occurrence of bulges during line drawing. If it exceeds 1% by mass, the ink jet nozzle is contaminated and the droplet landing accuracy is lowered.
- a cured product comprising the ultraviolet curable resin composition of the present invention is used for optical applications, dimensional stability during curing is important. Therefore, it is preferable to contain 90% by mass or more of a component having a boiling point of 200 ° C. or higher under atmospheric pressure in the resin composition. If it is less than 90% by mass, the volume is not stabilized by evaporation after ejection. In addition, as described above, the reason why the cured ultraviolet curable component is contained by 90% by mass or more is that when the cured component is less than 90% by mass, characteristics such as a change in refractive index in a use environment of the cured product are not stable. .
- the resin composition thus obtained has a viscosity of 5 to 40 mP ⁇ sec and a surface tension of 20 to 32 mN / m at a head temperature of 20 to 45 ° C., more preferably so that stable ejection can be achieved by an ink jet printing method. It is prepared to be 20 to 30 mN / m.
- An ink jet head suitable for coating such a resin composition is a piezo method, and XAAR, SUPETRA, Konica Minolta, Toshiba Tec, Ricoh Printing, and the like can be used. Electrostatic ink jet heads are also commercially available, but in this case the viscosity tolerance is also increased.
- the droplets ejected from the ink jet are drawn in the form of dots and lines on the support substrate.
- the cured surface has a convex shape.
- the component having a boiling point of 200 ° C. or higher under the atmospheric pressure of the ink jet resin composition is 90% by mass or more, and the cured ultraviolet curing component is 90% by mass or more.
- a preferable result is obtained such that the film has a convex shape on the support substrate and is cured.
- the static contact angle formed by the resin composition and the support substrate is 5 ° or more and 30 ° or less, preferably 20 ° or less.
- the ultraviolet curable resin composition of the present invention can be applied by an ink jet printing method, has an ultraviolet curable property, and the obtained cured product is excellent in transparency and hardness.
- the refractive index exceeds 1.5, it is a material suitable for an optical element.
- an optical element such as a lenticular lens sheet or a microlens sheet can be obtained by coating the ultraviolet curable resin composition of the present invention on a support substrate using an inkjet printing method and curing the composition by ultraviolet irradiation.
- a projection display, a stereoscopic display, etc. can be formed using this optical element.
- the number average molecular weight Mn of the obtained copolymer A was 2690, the weight average molecular weight Mw was 5160, and Mw / Mn was 1.92.
- a resonance line derived from the end of 2-phenoxyethyl methacrylate was observed in copolymer A.
- the introduction amount (a) of structural units derived from 2-phenoxyethyl methacrylate of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis result and the number average molecular weight in terms of standard polystyrene was 3.2 (pieces / molecule). It was. Further, it contained 60.0 mol% of structural units derived from divinylbenzene and 40.0 mol% in total of structural units derived from styrene and ethylvinylbenzene. The vinyl group content contained in the copolymer A was 37 mol%. As a result of TMA measurement, Tg was 272 ° C. and softening temperature was 300 ° C. or higher.
- GPC manufactured by Tosoh Corporation, HLC-8120GPC
- tetrahydrofuran was used as a solvent
- a flow rate was 1.0 ml / min
- a column temperature was 38 ° C.
- a calibration curve using monodisperse polystyrene was used.
- UV curable resin composition (P1) 15 parts of the above-mentioned phenylethyl methacrylate-terminated PDV (polydivinylbenzene), 5 parts of trimethylolpropane triacrylate, 9 parts of 2-hydroxyethyl acrylate, 50 parts of 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate 20 parts, 7 parts Irgacure 184 (manufactured by Ciba Specialty), 0.05 parts Adeka Stub AO-60 (manufactured by Adeka), 1.1 parts diethylene glycol diacetate solution containing 10% surfactant BYK378 (manufactured by Big Chemie) are mixed.
- the solution was made into a uniform solution and filtered through a 0.2 ⁇ m microfilter to prepare an ultraviolet curable resin ink (P1).
- P1 This had a viscosity of 19.9 mPa ⁇ sec, a surface tension of 25.1 mN / m, and a density of 1055 kg / m 3 .
- KM512L was used as an inkjet head, and a UV-LED in-line exposure head was loaded 50 mm behind the inkjet head. Using one nozzle of KM512L, drawing was performed at a stage speed of 125 mm / second and a dot pitch of 75 ⁇ m / drop, and UV-LED inline exposure was performed on the stage immediately after the drawing. The integrated exposure amount at this time is 40 mJ / cm 2 .
- the measuring method of the physical-property value shown in Table 1 and Table 2 is as follows. Viscosity: measured at 23 ° C. using an E-type viscometer. Contact angle: Using OCH200 manufactured by Data Physics, 0.5 ⁇ l of the ultraviolet curable resin composition (P and Q) was dropped on the surface of the partition wall coating film, and the contact angle after 1 second was measured (measurement temperature: 23 ° C.). Surface tension: measured by a platinum substrate immersion method. Refractive index: A cured film was prepared, and a refractive index at a wavelength of 589 nm was measured at 25 ° C. using an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.
- Transmittance Using a cured film having a thickness of 5 ⁇ m, a 400 nm object light transmittance was measured with a spectrophotometer U3200 (manufactured by Hitachi, Ltd.). Hardened product shape: observed with optical microscope and SEM.
- Example 4 A 5-inch non-alkali glass substrate (AN-100 manufactured by Asahi Glass) was washed with acetone and dried, and then a substrate I-2 having a contact angle with the resin ink P1 of 12 ° was prepared.
- a continuous discharge test of ultraviolet curable resin ink (P1) for 10 minutes was performed at a driving frequency of 4.8 kHz and an applied voltage of 18.54 V. No nozzle clogging was observed, and good discharge characteristics were exhibited.
- a dot speed is drawn at a stage speed of 125 mm / second and a dot pitch of 75 ⁇ m / drop.
- Examples 5 to 7 As shown in Table 1, UV curable resin compositions (P4 to P6) were prepared and evaluated in the same manner as in Example 1 except that the type and amount of photopolymerization initiator were changed. The results are shown in Table 1. In any case, the inkjet dischargeability was good. Further, line drawing was performed on the alkali-free glass substrate I-1 under the same conditions as in Example 1. It was confirmed that each of them had an upwardly convex spherical lens shape and that the contact line with the substrate was a straight line.
- Example 8 As shown in Table 2, an ultraviolet curable resin composition P8 was prepared in the same manner as in Example 1 except that the surfactant type was changed to fluorine. Line drawing was performed on the alkali-free glass substrate I-1 under the same conditions as in Example 1. It was confirmed that each of them had an upwardly convex spherical lens shape and that the contact line with the substrate was a straight line.
- a drive frequency of 4.8 kHz, an applied voltage of 17.84 V, a head temperature of 35 ° C., and UV-curable resin inks P9 and P10 for 10 minutes continuous discharge test Went No nozzle clogging was observed, and good discharge characteristics were exhibited.
- Example 1 As shown in Table 2, an ultraviolet curable resin composition Q1 was prepared in the same manner as in Example 1 except that the surfactant was removed. A discharge test was performed using a Konica Minolta inkjet head (KM512L, 42pl specification) at a drive frequency of 4.8 kHz and an applied voltage of 17.84 V. When discharge was resumed after waiting, many non-discharge nozzles were seen.
- Konica Minolta inkjet head KM512L, 42pl specification
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Abstract
Description
(式中、R1は炭素数6~30の芳香族炭化水素基を示す。)で表される未反応のビニル基を含有する構造単位の含有量が、全ての単量体由来の構造単位の総モル数に対して10~90モル%である可溶性多官能ビニル芳香族共重合体、
(B)成分:分子中に少なくとも2個の(メタ)アクリロイル基を有する光硬化型多官能(メタ)アクリレート、
(C)成分:光重合開始剤、及び
(D)成分:界面活性剤、
を少なくとも含有し、
(A)成分の配合量が5~45質量%、(B)成分の配合量が55~94質量%、(C)成分の配合量が0.97~20質量%、及び(D)成分の配合量が0.03~1質量%であり、且つ、紫外線で硬化する成分を90質量%以上含有することを特徴とするインクジェット印刷法に用いる紫外線硬化樹脂組成物である。
本発明の紫外線硬化樹脂組成物は、(A)成分、(B)成分、(C)成分、及び(D)成分を含み、(A)成分の配合量が5~45質量%であり、(B)成分の配合量が55~94質量%であり、(C)成分の配合量が0.97~20質量%であり、(D)成分の配合量が0.03~1質量%である。これら構成材料の中で(A)、(B)及び(C)成分は、感光性樹脂組成物として機能する。このうち、(B)成分はインクジェット塗工に適した粘度に調製する液状成分であり、(A)成分は光学素子として必要な1.5以上の屈折率を与えるものである。
ジビニルベンゼン3320g(25.50モル)、エチルビニルベンゼン1950g(15.0モル)、スチレン1096g(10.5モル)、2-フェノキシエチルメタクリレート6311g(30.6モル)、及びトルエン8650gを30Lの反応器内に投入し、50℃で354.8gの三フッ化ホウ素のジエチルエーテル錯体を添加し、3時間反応させた。重合溶液を炭酸水素ナトリウム水溶液で停止させた後、純水で3回油層を洗浄し、室温で反応混合液を大量のメタノールに投入し、重合体を析出させた。得られた重合体をメタノールで洗浄し、濾別、乾燥、秤量して、共重合体Aを5640g(収率:88.6質量%)得た。
<紫外線硬化樹脂組成物(P1)の調製>
前述のフェニルエチルメタクリレート末端PDV(ポリジビニルベンゼン)15部、トリメチロールプロパントリアクリレート5部、2-ヒドロキシエチルアクリレート9部、1,4-ブタンジオールジアクリレート50部、1,9-ノナンジオールジアクリレート20部、イルガキュア184(チバスペシャリティ製)7部、アデカスタブAO-60(アデカ製)0.05部、界面活性剤BYK378(ビッグケミー社製)10%を含むジエチレングリコールジアセテート溶液1.1部を混合し、均一溶液とし、0.2μmマイクロフィルターによってろ過し、紫外線硬化樹脂インキ(P1)を調製した。これは、粘度19.9mPa・sec、表面張力25.1mN/m、密度1055kg/m3であった。
コニカミノルタ製インクジェットヘッド(KM512L、42pl仕様)を用い、駆動周波数4.8kHz、印加電圧17.84Vにて、紫外線硬化樹脂インキ(P1)の10分間連続吐出試験を行った。ノズル詰まりは全く無く良好な吐出特性を示した。
表1に示すように組成を変えて樹脂組成物インキP2、P3を調製した。物性値を同様に表1に示した。
SR-213;サートマージャパン株式会社製、1,4-ブタンジオールジアクリレート
ライトアクリレート1,9ND-A;共栄社化学株式会社製、1,9-ノナンジオールジアクリレート
ライトエステルHOA;共栄社化学株式会社製、2-ヒドロキシエチルアクリレート
BYK378;ビックケミージャパン株式会社製、シリコン系表面調整剤
SR-351S;サートマージャパン株式会社製、TMPTA(トリメチロールプロパントリアクリレート)
Irgacure819;チバ・スペシャリティ・ケミカルズ社製、イルガキュア819(ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド)
Irgacure184;チバ・スペシャリティ・ケミカルズ社製、イルガキュア184(1-ヒドロキシ-シクロヘキシル-フェニル-ケトン)
Irgacure907;チバ・スペシャリティ・ケミカルズ社製、イルガキュア907(2-メチル-1-〔4-(メチルチオ)フェニル〕‐2‐モルホリノプロパン-1-オン)
ECA;エチルセロソブアセテート
EGDAC;ジエチレングリコールジアセテート
アデカスタプAO-60;アデカ株式会社製、重合禁止剤
メガファックF470;DIC株式会社製、フッ素系界面活性剤
粘度;E型粘度計を用いて23℃で測定した。
接触角;データフィジックス製OCH200を用いて、紫外線硬化樹脂組成物(PならびにQ)0.5μlを隔壁塗膜表面に滴下して1秒後の接触角を測定(測定温度23℃)した。
表面張力;白金基板浸漬法で測定した。
屈折率;硬化膜を作成し、アタゴ社製アッベ屈折率計DR-M2を用いて、25℃で波長589nmの屈折率を測定した。
透過率;硬化膜5μm厚みを用いて、分光光度計U3200(日立製作所製)で400nm物光線透過率を測定した。
硬化物形状;光学顕微鏡ならびにSEMで観察した。
5インチ無アルカリガラス基板(旭硝子製AN-100)をアセトン洗浄、乾燥後、樹脂インキP1との接触角が12°となる基板I-2を調製した。
表1に示すように、光重合開始剤の種類とその添加量を変更した以外は、実施例1と同様にして紫外線硬化樹脂組成物(P4~P6)を調整し、同様に評価した。結果を表1に示す。いずれもインクジェット吐出性は良好であった。また、実施例1と同様な条件でもって無アルカリガラス基板I-1の基板上にライン描画を行った。何れも上に凸の球面レンズ形状を呈していること、基板との接触線が直線であることを確認した。
表2に示すように、界面活性剤種をフッ素系に変えた以外は実施例1と同様にして紫外線硬化樹脂組成物P8を調製した。実施例1と同様な条件でもって無アルカリガラス基板I-1の基板上にライン描画を行った。何れも上に凸の球面レンズ形状を呈していること、基板との接触線が直線であることを確認した。
表2に示すように組成を変えて樹脂組成物インキP9、P10を調製した。物性値を同様に表2に示した。
表2に示すように、界面活性剤を除いた以外は実施例1と同様にして紫外線硬化樹脂組成物Q1を調製した。コニカミノルタ製インクジェットヘッド(KM512L、42pl仕様)を用い、駆動周波数4.8kHz、印加電圧17.84Vにて吐出試験を行ったが、待機後に吐出を再開すると不吐出ノズルが多く見られた。
表2に示すように、A成分を除いた紫外線硬化性樹脂組成物Q2を調製した。実施例1と同様にして硬化膜を作成したところ、その屈折率は1.48であった。
表2に示すように、実施例1で調製した紫外線硬化樹脂組成物(P1)107.05部に対して、にエチルセロソルブアセテート(ECA)(沸点156℃)30部加えて紫外線硬化樹脂組成物(Q3)を調製し、実施例1と同様に塗工試験を行った。その結果、実施例1と比較してガラス基板に対して濡れ拡がり、その高さは安定しなかった。また、硬化後の形状はトップが平らな部分があり、球面形状ではなかった。
Claims (4)
- (A)成分:ジビニル芳香族化合物(a)20~99モル%及びモノビニル芳香族化合物(b)1~80モル%を共重合して得られる共重合体であって、ジビニル芳香族化合物(a)に由来する下記式(a1)
(式中、R1は炭素数6~30の芳香族炭化水素基を示す。)で表される未反応のビニル基を含有する構造単位の含有量が、全ての単量体由来の構造単位の総モル数に対して10~90モル%である可溶性多官能ビニル芳香族共重合体、
(B)成分:分子中に少なくとも2個の(メタ)アクリロイル基を有する光硬化型多官能(メタ)アクリレート、
(C)成分:光重合開始剤、及び
(D)成分:界面活性剤、
を少なくとも含有し、
(A)成分の配合量が5~45質量%、(B)成分の配合量が55~94質量%、(C)成分の配合量が0.97~20質量%、及び(D)成分の配合量が0.03~1質量%であり、且つ、紫外線で硬化する成分を90質量%以上含有することを特徴とするインクジェット印刷法に用いる紫外線硬化樹脂組成物。 - 沸点200℃以上の成分を90質量%以上含有する請求項1に記載の紫外線硬化樹脂組成物。
- 表面張力が20~32mN/mである請求項1又は2に記載の紫外線硬化樹脂組成物。
- インクジェット印刷法により、支持基板上に上記請求項1~3のいずれかに記載の紫外線硬化樹脂組成物を塗工し、さらに紫外線硬化させて得たことを特徴とする光学素子。
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JP2013163360A (ja) * | 2012-02-13 | 2013-08-22 | Konica Minolta Inc | 光学部材及び光学部材の製造方法 |
JP2014080014A (ja) * | 2012-09-27 | 2014-05-08 | Dainippon Toryo Co Ltd | 基材とレンズ状粒子との複合材料及びその製造方法 |
JP2015194547A (ja) * | 2014-03-31 | 2015-11-05 | 日東電工株式会社 | 光学部品用樹脂組成物およびそれを用いた光学部品 |
JP2017516162A (ja) * | 2014-05-16 | 2017-06-15 | ヘプタゴン・マイクロ・オプティクス・プライベート・リミテッドHeptagon Micro Optics Pte. Ltd. | 複製による光学素子の製造および対応する複製ツール並びに光学装置 |
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CN108290432B (zh) * | 2015-12-07 | 2020-06-30 | 富士胶片株式会社 | 光栅印刷品的制造方法 |
CN111187539B (zh) * | 2019-03-21 | 2022-05-03 | 广东聚华印刷显示技术有限公司 | 紫外光固化墨水 |
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WO2009110453A1 (ja) * | 2008-03-04 | 2009-09-11 | 新日鐵化学株式会社 | 多官能ビニル芳香族共重合体、その製造方法及び樹脂組成物 |
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JP2013163360A (ja) * | 2012-02-13 | 2013-08-22 | Konica Minolta Inc | 光学部材及び光学部材の製造方法 |
JP2014080014A (ja) * | 2012-09-27 | 2014-05-08 | Dainippon Toryo Co Ltd | 基材とレンズ状粒子との複合材料及びその製造方法 |
JP2015194547A (ja) * | 2014-03-31 | 2015-11-05 | 日東電工株式会社 | 光学部品用樹脂組成物およびそれを用いた光学部品 |
JP2017516162A (ja) * | 2014-05-16 | 2017-06-15 | ヘプタゴン・マイクロ・オプティクス・プライベート・リミテッドHeptagon Micro Optics Pte. Ltd. | 複製による光学素子の製造および対応する複製ツール並びに光学装置 |
US10379262B2 (en) | 2014-05-16 | 2019-08-13 | Ams Sensors Singapore Pte. Ltd. | Manufacture of optical elements by replication and corresponding replication tools and optical devices |
Also Published As
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JP5797648B2 (ja) | 2015-10-21 |
US8796352B2 (en) | 2014-08-05 |
JPWO2011158725A1 (ja) | 2013-08-19 |
CN102971350B (zh) | 2014-08-13 |
TWI507425B (zh) | 2015-11-11 |
CN102971350A (zh) | 2013-03-13 |
US20130071632A1 (en) | 2013-03-21 |
KR20130121808A (ko) | 2013-11-06 |
TW201211074A (en) | 2012-03-16 |
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