WO2017022701A1 - 光学部材、及び、ナノインプリント用の重合性組成物 - Google Patents
光学部材、及び、ナノインプリント用の重合性組成物 Download PDFInfo
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- WO2017022701A1 WO2017022701A1 PCT/JP2016/072464 JP2016072464W WO2017022701A1 WO 2017022701 A1 WO2017022701 A1 WO 2017022701A1 JP 2016072464 W JP2016072464 W JP 2016072464W WO 2017022701 A1 WO2017022701 A1 WO 2017022701A1
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- acryloylmorpholine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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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
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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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
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
Definitions
- the present invention relates to an optical member and a polymerizable composition for nanoimprinting. More specifically, the present invention relates to an optical member having a concavo-convex structure of nanometer size, and a polymerizable composition for nanoimprint that is suitably used as a material for the optical member.
- Patent Documents 1 to 3 Various optical members having antireflection properties have been studied (see, for example, Patent Documents 1 to 3).
- an optical member having a nanometer-sized uneven structure has excellent antireflection properties (see, for example, Patent Documents 4 to 8).
- Patent Documents 4 to 8 According to such a concavo-convex structure, since the refractive index continuously changes from the air layer to the substrate, the reflected light can be dramatically reduced.
- Examples of such an optical member include a configuration in which a polymer layer having antireflection properties is disposed on a base material.
- a base material the base material containing a triacetyl cellulose (TAC) is used from a viewpoint which has the outstanding optical characteristic (for example, transparency), for example.
- TAC triacetyl cellulose
- other types of base materials for example, a base material containing polyethylene terephthalate (PET), methyl methacrylate
- PET polyethylene terephthalate
- MMA substrate including
- the primer treatment when the primer treatment is performed, not only the manufacturing cost increases, but also there is a problem that an environmental load is applied. Moreover, it turned out that the base material containing a triacetyl cellulose has a high hygroscopic property, and a hygroscopic property is higher in the state which is not primed. In particular, it has been found that there is a problem in that the adhesiveness with the polymer layer tends to be lowered because the moisture is remarkably easily absorbed under high humidity.
- the conventional optical member having a base material containing triacetyl cellulose is subjected to primer treatment to reduce the adhesion between the base material containing triacetyl cellulose and the polymer layer due to moisture absorption. There was a problem of suppressing it. However, no means for solving the above problem has been found.
- Patent Document 4 describes that a substrate containing triacetyl cellulose and a cured product of an active energy ray-curable resin composition having a fine concavo-convex structure are in close contact with each other. There was no description about the fall of property, and the said subject was not solved. Similarly, the inventions described in Patent Documents 1 to 3 and 5 to 8 do not solve the above problems.
- the present invention has been made in view of the above-described situation, and an object thereof is to provide an optical member in which a decrease in adhesion between a substrate containing triacetyl cellulose and a polymer layer due to moisture absorption is suppressed. It is. Moreover, it aims at providing the polymeric composition for nanoimprints which comprises the polymer layer which suppresses the fall of adhesiveness with the base material containing a triacetyl cellulose by moisture absorption.
- the inventors of the present invention have studied various optical members in which the decrease in adhesion between the substrate containing the triacetyl cellulose and the polymer layer due to moisture absorption is suppressed, and the polymerizable composition constituting the polymer layer is,
- the polymerizable composition constituting the polymer layer is,
- a monofunctional monomer having a tertiary amide group increases the binding force with triacetyl cellulose.
- the hygroscopicity is lowered according to the fluorine-containing compound having a reactive group.
- the polymerizable composition contains a polyfunctional acrylate, a monofunctional monomer, and a fluorine-containing compound at a predetermined ratio, so that the adhesion between the substrate containing triacetyl cellulose and the polymer layer due to moisture absorption is increased. It was found that the decrease in the amount was suppressed. As a result, the inventors have conceived that the above problems can be solved brilliantly and have reached the present invention.
- one embodiment of the present invention includes a base material, and a polymer layer that is in direct contact with the base material and has a concavo-convex structure provided on the surface with a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light.
- Triacetyl cellulose is present at least on the surface of the base material on the polymer layer side, and the polymer layer is formed from a polymerizable composition that is polymerized by irradiation with active energy rays.
- the composition is 30 parts by weight or more and 75 parts by weight or less of polyfunctional acrylate, 25 parts by weight or more and 60 parts by weight or less of a monofunctional monomer having a tertiary amide group, and 0% of a fluorine-containing compound having a reactive group.
- An optical member containing 1 part by weight or more and 10 parts by weight or less may be used.
- Another embodiment of the present invention is a polyfunctional acrylate having 30 to 75 parts by weight and a monofunctional monomer having a tertiary amide group of 25 to 60 parts by weight and a reactive group. It may be a polymerizable composition for nanoimprinting containing 0.1 to 10 parts by weight of a fluorine-containing compound and polymerizing by irradiation with active energy rays.
- the optical member by which the fall of the adhesiveness of the base material containing a triacetyl cellulose and a polymer layer by moisture absorption was suppressed can be provided.
- the polymeric composition for nanoimprint which comprises the polymer layer which suppresses the fall of adhesiveness with the base material containing a triacetyl cellulose by moisture absorption can be provided.
- FIG. 5 is a schematic cross-sectional view for explaining the manufacturing process of the optical member of the embodiment (steps a to d).
- FIG. 1 is a schematic cross-sectional view illustrating an optical member according to an embodiment.
- the optical member 1 includes a base material 2 and a polymer layer 3 that is in direct contact with the base material 2.
- the polymer layer 3 has a concavo-convex structure in which a plurality of convex portions (projections) 4 are provided at a pitch P (distance between vertices of adjacent convex portions 4) P that is equal to or less than the wavelength of visible light. Therefore, the optical member 1 corresponds to an antireflection member having a moth-eye structure (breast-like structure). Thereby, the optical member 1 can show the excellent antireflection property (low reflectivity) by a moth-eye structure.
- Triacetyl cellulose is present on at least the surface of the substrate 2 on the polymer layer 3 side.
- triacetyl cellulose refers to cellulose acetate having an acetylation degree of 58% or more, and preferably refers to cellulose acetate having an acetylation degree of 61% or more.
- the surface of the substrate 2 on the polymer layer 3 side may not be subjected to surface treatment, and may be subjected to surface treatment such as washing treatment as long as it does not change the chemical structure of triacetylcellulose. Also good.
- the surface of the substrate 2 on the polymer layer 3 side is not subjected to a surface treatment such as a saponification treatment that changes the chemical structure of triacetylcellulose. Whether or not the substrate 2 has been subjected to a surface treatment that changes the chemical structure of triacetyl cellulose can be verified by the following method, for example.
- the base material 2 before the polymer layer 3 is arranged on the surface is prepared, or the polymer layer 3 is removed from the optical member 1 by a physical method. Expose the surface. Then, FT-IR measurement using the ATR method (total reflection measurement method) is performed on the surface of the base material 2 and the surface of the base material containing triacetyl cellulose that has not been separately prepared.
- the base material 2 may be composed only of triacetyl cellulose. If the chemical structure of the triacetyl cellulose present on the surface of the base material 2 on the polymer layer 3 side does not change, plastic other than triacetyl cellulose may be used. An additive such as an agent may be included as appropriate.
- the shape of the substrate 2 is not particularly limited, and examples thereof include a film shape and a sheet shape.
- a film-like substrate 2 may be used, and a triacetyl cellulose film (TAC film) is preferably used.
- TAC film triacetyl cellulose film
- the form in which the base material 2 comprises a part of polarizing plate is preferable.
- the thickness of the base material 2 is not specifically limited, From a viewpoint of ensuring transparency and workability, it is preferable that they are 50 micrometers or more and 100 micrometers or less.
- the polymer layer 3 is formed from a polymerizable composition (polymerizable composition 5 in FIG. 2 described later) that is polymerized by irradiation with active energy rays.
- active energy rays refer to ultraviolet rays, visible rays, infrared rays, plasma, and the like.
- the polymerizable composition is preferably one that is polymerized by ultraviolet rays.
- the polymerizable composition has a polyfunctional acrylate of 30 parts by weight or more and 75 parts by weight or less of a monofunctional monomer having a tertiary amide group (hereinafter also simply referred to as a monofunctional monomer) of 25 parts by weight or more and 60 parts by weight.
- a fluorine-containing compound having a reactive group hereinafter also simply referred to as a fluorine-containing compound
- the polymeric composition for nanoimprints which comprises the polymer layer 3 which suppresses the fall of adhesiveness with the base material 2 by moisture absorption is obtained.
- the optical member 1 in which a decrease in adhesion between the base material 2 and the polymer layer 3 due to moisture absorption is suppressed is obtained.
- polyfunctional acrylate examples include pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated (4 mol adduct) bisphenol A diacrylate, and the like. It is done.
- pentaerythritol triacrylate examples include polyfunctional acrylate (product name: A-TMM-3LM-N) manufactured by Shin-Nakamura Chemical Co., Ltd.
- Examples of known ethoxylated pentaerythritol tetraacrylates include polyfunctional acrylates (product name: ATM-35E) manufactured by Shin-Nakamura Chemical Co., Ltd.
- Known examples of 1,6-hexanediol diacrylate include, for example, polyfunctional acrylate (product name: A-HD-N) manufactured by Shin-Nakamura Chemical Co., Ltd.
- Known examples of tripropylene glycol diacrylate include polyfunctional acrylate (product name: APG-200) manufactured by Shin-Nakamura Chemical Co., Ltd.
- ethoxylated (4 mol adduct) bisphenol A diacrylate examples include, for example, polyfunctional acrylate (product name: A-BPE-4) manufactured by Shin-Nakamura Chemical Co., Ltd.
- the polyfunctional acrylate may be composed of only one kind of polyfunctional acrylate, or may be composed of a combination of plural kinds of polyfunctional acrylates.
- the content of the polyfunctional acrylate is 30 parts by weight or more and 75 parts by weight or less.
- the content of the polyfunctional acrylate is less than 30 parts by weight, the content of the monofunctional monomer and the fluorine-containing compound is relatively increased.
- the polarity of the polymer layer 3 becomes too high, or the amount of the tertiary amide group is relatively reduced due to the increase in the amount of fluorine atoms on the surface of the polymer layer 3 on the substrate 2 side. Therefore, the adhesiveness between the base material 2 and the polymer layer 3 decreases due to moisture absorption.
- the content of the polyfunctional acrylate is more than 75 parts by weight, the content of the monofunctional monomer and the fluorine-containing compound is relatively decreased.
- the amount of tertiary amide groups in the polymer layer 3 becomes too small, or the amount of fluorine atoms in the polymer layer 3 becomes too small and the hygroscopicity is increased. Adhesiveness between the substrate 2 and the polymer layer 3 is lowered.
- the polyfunctional acrylate is composed of a combination of a plurality of types of polyfunctional acrylates, the total content of each polyfunctional acrylate is defined as the content of the polyfunctional acrylate.
- the monofunctional monomer has a tertiary amide group. Since the tertiary amide group has a strong hydrogen bonding force, it strongly binds to the hydroxyl group, ester structure, and ether structure of triacetyl cellulose present on the surface of the substrate 2 on the polymer layer 3 side. Therefore, according to the monofunctional monomer which has a tertiary amide group, the polymeric composition for nanoimprints which comprises the polymer layer 3 with high adhesiveness with the base material 2 is obtained. As a result, the optical member 1 having high adhesion between the substrate 2 and the polymer layer 3 is obtained. On the other hand, since the primary amide group and the secondary amide group have high polarity and low bonding strength, the adhesion with the substrate 2 is lower than that of the tertiary amide group.
- Examples of the monofunctional monomer having a tertiary amide group include N-acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylmethacrylamide, N-methoxy-N-methyl-3 -Phenyl-acrylamide and the like.
- Known examples of N-acryloylmorpholine include monofunctional monomers (product name: ACMO (registered trademark)) manufactured by KJ Chemicals.
- Known examples of N, N-dimethylacrylamide include monofunctional monomers (product name: DMAA (registered trademark)) manufactured by KJ Chemicals.
- N, N-diethylacrylamide examples include monofunctional monomers (product name: DEAA (registered trademark)) manufactured by KJ Chemicals.
- Examples of known N, N-dimethylmethacrylamide include monofunctional monomers (product code: D0745) manufactured by Tokyo Chemical Industry Co., Ltd.
- Known examples of N-methoxy-N-methyl-3-phenyl-acrylamide include monofunctional monomers (N-methoxy-N-methyl-3-phenyl-acrylamide) manufactured by Sigma-Aldrich.
- the monofunctional monomer may be composed of only one type of monofunctional monomer, or may be composed of a combination of a plurality of types of monofunctional monomers.
- the monofunctional monomer preferably includes at least one monomer selected from the group consisting of N-acryloylmorpholine, N, N-dimethylacrylamide, and N, N-diethylacrylamide.
- the content of the monofunctional monomer having a tertiary amide group is 25 parts by weight or more and 60 parts by weight or less.
- the content of the monofunctional monomer is less than 25 parts by weight, the amount of the tertiary amide group in the polymer layer 3 becomes too small, so that the adhesion between the substrate 2 and the polymer layer 3 is caused by moisture absorption. Will fall.
- the content of the monofunctional monomer is more than 60 parts by weight, the polarity of the polymer layer 3 becomes too high, so that the adhesion between the substrate 2 and the polymer layer 3 is reduced due to moisture absorption.
- the content of the monofunctional monomer is preferably 30 parts by weight or more and 55 parts by weight or less, and 35% by weight. More preferably, it is at least 50 parts by weight.
- the monofunctional monomer is composed of a combination of a plurality of types of monofunctional monomers, the total content of each monofunctional monomer is defined as the content of the monofunctional monomer.
- the fluorine-containing compound has a reactive group.
- the fluorine-containing compound contains a fluorine-containing monomer as a constituent component.
- the fluorine-containing compound may further contain other monomer components such as an acrylate monomer.
- the reactive group refers to a site that reacts with other components by external energy such as light and heat. Examples of such reactive groups include alkoxysilyl groups, silyl ether groups, silanol groups obtained by hydrolysis of alkoxysilyl groups, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. Is mentioned.
- the reactive group is preferably an alkoxysilyl group, a silyl ether group, a silanol group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group from the viewpoints of reactivity and handling properties, and a vinyl group or an allyl group.
- An acryloyl group or a methacryloyl group is more preferable, and an acryloyl group or a methacryloyl group is still more preferable.
- the fluorine-containing compound having a reactive group According to the fluorine-containing compound having a reactive group, the fluorine atom is oriented and fixed on the surface of the polymer layer 3 opposite to the substrate 2, and the hygroscopicity can be lowered. As a result, it is possible to suppress a decrease in adhesion between the base material 2 and the polymer layer 3 due to moisture absorption.
- the polymerizable composition contains a fluorine-containing compound, even if the content of the monofunctional monomer is increased and the polarity becomes too high, the substrate 2 and the polymer layer 3 due to moisture absorption. A decrease in adhesion can be suppressed.
- the surface energy of the polymer layer 3 can be lowered, and the optical member 1 having excellent water repellency can be obtained by combining with the moth-eye structure.
- the optical member 1 having excellent antifouling properties against hydrophilic dirt can be obtained.
- a water contact angle is often used as an index indicating the degree of water repellency.
- a larger water contact angle indicates higher water repellency.
- the contact angle of water with respect to the surface of the polymer layer 3 opposite to the substrate 2 (surface of the concavo-convex structure) is preferably 60 ° or more. .
- the fluorine-containing compound includes, in addition to the reactive group, a moiety containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group It is preferable to have.
- a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are respectively an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group, and an oxyalkanediyl group. It is a substituent in which at least part of the hydrogen atoms it has are substituted with fluorine atoms.
- a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are all substituents mainly composed of fluorine atoms and carbon atoms, and are branched in the structure. Part may be present, and a plurality of these substituents may be linked.
- R f1 is a moiety containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.
- R 2 represents an alkanediyl group, an alkanetriyl group, or an ester structure, urethane structure, ether structure, or triazine structure derived therefrom.
- D 1 represents a reactive group.
- fluorine-containing monomer represented by the general formula (A) examples include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, and 2-perfluorobutyl.
- the fluoropolyether moiety is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkyldiyl group, etc., and has a structure represented by the following general formula (B) or (C).
- n1 is an integer of 1 to 3
- n2 to n5 are 1 or 2
- k, m, p, and s are integers of 0 or more.
- a preferable combination of n1 to n5 is a combination in which n1 is 2 or 3, and n2 to n5 is 1 or 2, and a more preferable combination is n1 is 3, n2 and n4 are 2, and n3 and n5 are 1 or 2. 2 is a combination.
- the number of carbon atoms contained in the fluoropolyether moiety is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and still more preferably 6 or more and 8 or less.
- the number of carbon atoms is less than 4, there is a concern that the surface energy is reduced.
- the number of carbon atoms is more than 12, there is a concern that the solubility in a solvent is lowered.
- the fluorine-containing monomer may have a plurality of fluoropolyether sites per molecule.
- fluorine-containing compounds having a reactive group include, for example, a fluorine-based additive (product name: OPTOOL (registered trademark) DAC-HP) manufactured by Daikin Industries, Ltd., and a fluorine-based additive manufactured by Asahi Glass ( Product name: Afluid), DIC's fluorinated additive (Product name: MegaFac (registered trademark) RS-76-NS), DIC's fluorinated additive (Product name: MegaFac RS-90), Fluoro-based additive (product name: Footage (registered trademark) 601AD) manufactured by Neos Co., Ltd. Fluoro-based additive (product name: C10GACRY) manufactured by Yushi Co., Ltd.
- a fluorine-based additive product name: OPTOOL (registered trademark) DAC-HP
- a fluorine-based additive manufactured by Asahi Glass Product name: Afluid
- DIC's fluorinated additive Product name:
- the fluorine-containing compound may be composed of only one type of fluorine-containing compound, or may be composed of a combination of a plurality of types of fluorine-containing compounds.
- the concentration of fluorine atoms in the fluorine-containing compound having a reactive group is preferably 20% by weight or more and 50% by weight or less, more preferably 25% by weight or more and 45% by weight or less, and more preferably 30% by weight. As mentioned above, it is still more preferable that it is 40 weight% or less.
- concentration of fluorine atoms in the fluorine-containing compound is less than 20% by weight, the amount of fluorine atoms is small, and it becomes difficult for the fluorine atoms to orient on the surface of the polymer layer 3 opposite to the substrate 2, so moisture absorption As a result, there is a concern that the adhesion between the substrate 2 and the polymer layer 3 is lowered.
- Content of the fluorine-containing compound which has a reactive group is 0.1 weight part or more and 10 weight part or less.
- the content of the fluorine-containing compound is less than 0.1 parts by weight, the amount of fluorine atoms in the polymer layer 3 becomes too small and the hygroscopicity is increased. Adhesiveness with the layer 3 will fall.
- the content of the fluorine-containing compound is more than 10 parts by weight, the amount of fluorine atoms in the polymer layer 3 becomes too large. As a result, the fluorine atoms are opposite to the base material 2 of the polymer layer 3. Many orientations occur not only on the surface on the side, but also on the surface of the polymer layer 3 on the substrate 2 side.
- the content of the fluorine-containing compound is preferably 0.3 parts by weight or more and 8 parts by weight or less, More preferably, it is 0.5 parts by weight or more and 5 parts by weight or less.
- the fluorine-containing compound is composed of a combination of a plurality of fluorine-containing compounds, the total content of each fluorine-containing compound is defined as the content of the fluorine-containing compound.
- the polymerizable composition may appropriately contain additives such as a polymerization initiator in addition to the above-mentioned polyfunctional acrylate, monofunctional monomer, and fluorine-containing compound.
- a polymerization initiator examples include a photopolymerization initiator.
- the photopolymerization initiator is a compound that is active with respect to active energy rays and is added to initiate a polymerization reaction for polymerizing monomers.
- a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used.
- photopolymerization initiators examples include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; Ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.
- acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one
- Ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-
- photopolymerization initiators known ones include a photopolymerization initiator manufactured by BASF (product name: IRGACURE (registered trademark) 819) and a photopolymerization initiator manufactured by BASF (product name: LUCIRIN (registered trademark) TPO). ) And the like.
- the polymerizable composition preferably does not contain a solvent. That is, the polymerizable composition is preferably a solventless system.
- the polymerizable composition is a solventless system, it is possible to reduce the cost associated with the use of the solvent and the environmental load (odor during use, etc.). Furthermore, an apparatus for drying and removing the solvent is unnecessary, and the apparatus cost can be suppressed.
- the polymerizable composition contains a solvent, the fluorine-containing compound is excessively mixed, and there is a concern that the fluorine atoms are less likely to be oriented on the surface of the polymer layer 3 opposite to the substrate 2.
- drying of a solvent is inadequate, there exists a possibility that the adhesiveness of the base material 2 and the polymer layer 3 may fall.
- the thickness of the polymer layer 3 is not particularly limited, the thickness of the polymer layer 3 is preferably thin from the viewpoint of orienting fluorine atoms at a high concentration on the surface of the polymer layer 3 opposite to the substrate 2. Specifically, it is preferably 5.0 ⁇ m or more and 20.0 ⁇ m or less. In the present specification, the thickness of the polymer layer refers to the distance from the surface on the substrate side to the apex of the convex portion.
- the shape of the convex portion 4 provided on the surface of the polymer layer 3 is not particularly limited, and for example, a shape (bell shape) constituted by a columnar lower portion and a hemispherical upper portion, a cone shape (cone shape, conical shape) ) And the like (taper shape) that narrows toward the tip.
- the convex portion 4 may have a shape having a branch protrusion.
- the branch protrusion indicates a convex portion corresponding to a portion having an irregular interval, which has been formed in the process of anodizing and etching for producing a mold for forming a moth-eye structure.
- the bottom of the gap of the convex portion 4 has an inclined shape, but it may have a horizontal shape without being inclined.
- the pitch P of the protrusions 4 is not particularly limited as long as it is less than or equal to the wavelength of visible light (780 nm). However, from the viewpoint of sufficiently preventing optical phenomena such as moire and rainbow unevenness, it may be 100 nm or more and 400 nm or less. Preferably, it is 100 nm or more and 200 nm or less.
- the pitch of the convex portions is within a 1 ⁇ m square area read from a photographed plane photograph using a scanning electron microscope (product name: S-4700) manufactured by Hitachi High-Technologies Corporation as a measuring instrument. The average value of the distance between all the adjacent convex parts except branch protrusions is shown.
- the measurement of the pitch of a convex part measured the osmium oxide VIII (thickness: 5 nm) by Wako Pure Chemical Industries, Ltd. on an uneven structure using the osmium coater (product name: Neoc-ST) by Meiwaforsys. Performed in the applied state.
- the height of the convex portion 4 is not particularly limited, but is preferably 50 nm or more and 600 nm or less, and more preferably 100 nm or more and 300 nm or less from the viewpoint of achieving compatibility with a suitable aspect ratio of the convex portion 4 described later. .
- the height of the convex portion is a continuous value excluding branch protrusions read from a photographed cross-sectional photograph using a scanning electron microscope (product name: S-4700) manufactured by Hitachi High-Technologies Corporation as a measuring instrument. The average value of the height of 10 convex parts arranged side by side is shown.
- the convex portion having a defect or a deformed portion (such as a portion deformed when preparing a sample) is excluded.
- a sample sampled in a region where there is no specific defect of the optical member is used.
- the optical member is a roll produced continuously, a sample sampled near the center is used.
- the height of the convex portion was measured using an osmium coater (product name: Neoc-ST) manufactured by Meiwa Forsys Co., Ltd., and osmium oxide VIII (thickness: 5 nm) manufactured by Wako Pure Chemical Industries, Ltd. on the concavo-convex structure. Was carried out in a state of coating.
- the aspect ratio of the convex part 4 is not specifically limited, It is preferable that it is 0.8 or more and 1.5 or less. When the aspect ratio of the convex portion 4 is 1.5 or less, the workability of the moth-eye structure is sufficiently increased, sticking occurs, or the transfer condition when forming the moth-eye structure is deteriorated (the mold is clogged). Or concerns about it) When the aspect ratio of the convex portion 4 is 0.8 or more, optical phenomena such as moire and rainbow unevenness can be sufficiently prevented, and good reflection characteristics can be realized.
- the aspect ratio of the convex portion is the pitch of the convex portion measured by the method described above using a scanning electron microscope (product name: S-4700) manufactured by Hitachi High-Technologies Corporation as a measuring instrument. It is indicated by the ratio to the height (height / pitch).
- the arrangement of the protrusions 4 is not particularly limited, and may be arranged randomly or regularly. From the viewpoint of sufficiently preventing the occurrence of moiré, it is preferably arranged randomly.
- the polymerizable composition constituting the polymer layer 3 has a polyfunctional acrylate of 30 parts by weight or more and 75 parts by weight or less of a monofunctional monomer having a tertiary amide group. More than 60 parts by weight and less than 60 parts by weight and 0.1 to 10 parts by weight of the fluorine-containing compound having a reactive group, so the adhesion between the substrate 2 and the polymer layer 3 due to moisture absorption The optical member 1 in which the decrease in the thickness is suppressed is obtained. Moreover, the surface energy of the polymer layer 3 can be made low by containing the fluorine-containing compound which has a reactive group, and the optical member 1 excellent in water repellency is obtained. Furthermore, since the polymer layer 3 has a concavo-convex structure in which the plurality of convex portions 4 are provided at a pitch P equal to or less than the wavelength of visible light, the optical member 1 having excellent antireflection properties can be obtained.
- FIG. 2 is a schematic cross-sectional view for explaining a manufacturing process of the optical member of the embodiment (steps a to d).
- the polymerizable composition 5 is applied on the substrate 2 as shown in FIG. As a result, the polymerizable composition 5 is formed so as to be in direct contact with the substrate 2.
- the coating method of the polymerizable composition 5 is not particularly limited, and examples thereof include a method of coating by a spray method, a gravure method, a slot die method, or the like.
- the polymerizable composition 5 on which the cured concavo-convex structure of the polymerizable composition is formed is cured by irradiation with an active energy ray (polymerized).
- an active energy ray polymerized
- a polymer layer 3 as shown in FIG. 2C is formed. Irradiation of active energy rays may be performed from the substrate 2 side or from the polymerizable composition 5 side.
- count of irradiation of the active energy ray with respect to the polymeric composition 5 is not specifically limited, One time may be sufficient and multiple times may be sufficient.
- (D) Mold release The mold 6 is released from the polymer layer 3.
- the concavo-convex structure formed on the surface of the polymer layer 3 corresponds to a structure in which the plurality of convex portions 4 are provided with a pitch P equal to or less than the wavelength of visible light, that is, a moth-eye structure.
- the mold 6 for example, one produced by the following method can be used. First, aluminum as a material for the mold 6 is formed on the support substrate by sputtering. Next, a female mold (mold 6) having a moth-eye structure can be produced by alternately repeating anodic oxidation and etching on the formed aluminum layer. At this time, the concavo-convex structure of the mold 6 can be changed by adjusting the time for performing anodic oxidation and the time for performing etching.
- the material of the support substrate is not particularly limited.
- glass metal material such as stainless steel and nickel; polypropylene, polymethylpentene, cyclic olefin polymer (typically, norbornene resin, manufactured by Nippon Zeon Co., Ltd.)
- Polyolefin resins such as polymers (product name: ZEONOR (registered trademark)) and polymers manufactured by JSR (product name: ARTON (registered trademark)); polycarbonate resins; polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose Resin materials, and the like.
- An aluminum substrate may be used instead of the aluminum film formed on the support substrate.
- the shape of the mold 6 is not particularly limited, and examples thereof include a flat plate shape and a roll shape.
- the mold 6 is preferably surface-treated with a release agent. That is, the mold 6 is preferably subjected to a mold release process.
- the mold 6 can be easily peeled from the polymer layer 3 in the step (d). Further, the surface energy of the mold 6 can be lowered, and when the mold 6 is pressed against the polymerizable composition 5 in the step (b), the fluorine atom is used as the base material 2 of the polymerizable composition 5. It can be suitably oriented on the opposite surface. Furthermore, before the polymerizable composition 5 is cured, it is possible to suitably prevent the fluorine atoms from separating from the surface of the polymerizable composition 5 on the side opposite to the substrate 2. As a result, in the optical member 1, fluorine atoms can be suitably oriented on the surface of the polymer layer 3 opposite to the substrate 2.
- the release agent examples include fluorine-based, silicon-based, and phosphate-based release agents, and fluorine-based release agents are preferable.
- fluorine-based mold release agent When a fluorine-based mold release agent is used, the interaction with the fluorine-containing compound in the polymerizable composition 5 becomes stronger, and the fluorine atoms are more suitably oriented on the surface of the polymerizable composition 5 opposite to the substrate 2. Can be made.
- the fluorine-type mold release agent product name: Optool AES4 by Daikin Industries, Ltd. etc. are mentioned, for example.
- the steps (a) to (d) can be performed continuously and efficiently.
- Example 1 The optical member of Example 1 was produced by the following manufacturing process.
- the polymerizable composition 5 was applied onto the substrate 2 with a bar coater (product name: No. 05) manufactured by Daiichi Rika Co., Ltd. As a result, the polymerizable composition 5 was formed so as to be in direct contact with the substrate 2.
- a triacetyl cellulose film (product name: TAC-TD80U) manufactured by FUJIFILM Corporation was used.
- the thickness of the base material 2 was 80 ⁇ m.
- the polymerizable composition 5 a mixture of a polyfunctional acrylate, a monofunctional monomer, a fluorine-containing compound, and a polymerization initiator as shown below was used. In addition, the numerical value attached
- the polymerizable composition 5 was a solventless system.
- Pentaerythritol triacrylate 38.4 parts by weight
- a polyfunctional acrylate product name: A-TMM-3LM-N
- Ethoxylated pentaerythritol tetraacrylate 25.6 parts by weight
- Polyfunctional acrylate product name: ATM-35E
- Shin-Nakamura Chemical Co., Ltd. was used as the ethoxylated pentaerythritol tetraacrylate.
- N-acryloylmorpholine 34 parts by weight
- ACMO monofunctional monomer manufactured by KJ Chemicals
- 2-Perfluorohexyl ethyl acrylate 50 parts by weight As 2-perfluorohexyl ethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-6) manufactured by Unimatec was used.
- -4-hydroxybutyl acrylate 40 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- N-acryloylmorpholine 10 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3500, and the concentration of fluorine atoms in the fluorine-containing compound was 37% by weight.
- the weight average molecular weight of the fluorine-containing compound and the concentration of fluorine atoms in the fluorine-containing compound were measured by the following methods. These measurements were performed after measuring the weight before and after the heat treatment described above.
- Weight average molecular weight of fluorine-containing compound The weight average molecular weight in terms of polystyrene of the fluorine-containing compound was calculated by gel permeation chromatography (GPC). The equipment used and the conditions were as follows. Molecular weight calibration curves were generated using standard polystyrene. Equipment used: Chromatography manufactured by Showa Denko KK (Product name: SHODEX GPC SYSTEM-11) Column: 3 columns manufactured by Tosoh Corporation (product name: TSKgel ⁇ MXL) Measurement temperature: 40 ° C Sample solution: 0.10% dimethylformamide solution of pigment surface treatment agent having a thermally decomposable polar group Injection amount: 100 ml Detector: Refractive index detector
- the above-mentioned cured product film (concentration of fluorine-containing compound: 50%) under the conditions of an acceleration voltage of 50 kV and a current of 60 mA using a scanning fluorescent X-ray analyzer (product name: ZSX Primus) manufactured by Rigaku Corporation.
- concentration of fluorine atoms in the fluorine-containing compound was determined by measuring the strength of fluorine atoms in the compound.
- a photopolymerization initiator manufactured by BASF product name: LUCIRIN TPO was used.
- the mold 6 one produced by the following method was used. First, aluminum as a material for the mold 6 was formed on a 10 cm square glass substrate by a sputtering method. The thickness of the formed aluminum layer was 1.0 ⁇ m. Next, by repeating anodization and etching alternately on the formed aluminum layer, a large number of minute holes (recesses) (the distance between the bottom points of adjacent holes is less than the wavelength of visible light) An anodized layer provided with was formed.
- anodization, etching, anodization, etching, anodization, etching, anodization, etching, and anodization are sequentially performed (anodization: 5 times, etching: 4 times), thereby forming the inside of aluminum.
- Anodization was performed using oxalic acid (concentration: 0.03% by weight) under conditions of a liquid temperature of 5 ° C. and an applied voltage of 80V. The time for one anodic oxidation was 25 seconds.
- Etching was performed using phosphoric acid (concentration: 1 mol / l) at a liquid temperature of 30 ° C.
- the time for performing one etching was set to 25 minutes.
- die 6 was observed with the scanning electron microscope, the height of a convex part was 290 nm.
- the mold 6 was subjected to a mold release treatment in advance with a fluorine-based mold release agent (product name: OPTOOL AES4) manufactured by Daikin Industries.
- the polymerizable composition 5 on which the cured concavo-convex structure of the polymerizable composition was formed was cured (polymerized) by irradiation with ultraviolet rays (irradiation amount: 1 J / cm 2 ) from the substrate 2 side. As a result, the polymer layer 3 was formed. The thickness of the polymer layer 3 was 11.0 ⁇ m.
- Example 2 An optical member was produced in the same manner as in Example 1 except that the type of monofunctional monomer was changed to N, N-dimethylacrylamide.
- N N-dimethylacrylamide
- a monofunctional monomer product name: DMAA
- DMAA monofunctional monomer manufactured by KJ Chemicals was used.
- a total of 35 parts by weight of a monofunctional monomer having a tertiary amide group 34 parts by weight of N, N-dimethylacrylamide contained as a monofunctional monomer and N in a solution of a fluorine-containing compound).
- -Sum of 1 part by weight of acryloylmorpholine 1 part by weight of acryloylmorpholine.
- Example 3 An optical member was produced in the same manner as in Example 1 except that the type of monofunctional monomer was changed to N, N-diethylacrylamide.
- N, N-diethylacrylamide a monofunctional monomer (product name: DEAA) manufactured by KJ Chemicals was used.
- DEAA a monofunctional monomer manufactured by KJ Chemicals
- a total of 35 parts by weight of a monofunctional monomer having a tertiary amide group 34 parts by weight of N, N-diethylacrylamide contained as a monofunctional monomer and N in a solution of a fluorine-containing compound).
- -Sum of 1 part by weight of acryloylmorpholine a monofunctional monomer having a tertiary amide group
- Example 4 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 43.8 parts by weight Ethoxylated pentaerythritol tetraacrylate: 29.2 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 25 parts by weight Polymerizable composition 5 contains a total of 26 parts by weight of monofunctional monomers having tertiary amide groups (25 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 5 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 41.4 parts by weight Ethoxylated pentaerythritol tetraacrylate: 27.6 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 29 parts by weight Polymerizable composition 5 has a total of 30 parts by weight of monofunctional monomers having tertiary amide groups (29 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 6 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 24.0 parts by weight Ethoxylated pentaerythritol tetraacrylate: 16.0 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 58 parts by weight Polymerizable composition 5 contains 59 parts by weight of monofunctional monomers having tertiary amide groups in total (58 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 7 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 27.6 parts by weight Ethoxylated pentaerythritol tetraacrylate: 18.4 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 52 parts by weight Polymerizable composition 5 has a total of 53 parts by weight of monofunctional monomers having tertiary amide groups (52 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 8 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 38.9 parts by weight Ethoxylated pentaerythritol tetraacrylate: 26.0 parts by weight ⁇ fluorine-containing compound>: 0.1 part by weight In this example, 0.1 part by weight of the fluorine-containing compound Thus, a fluorine-containing compound solution to which 1 part by weight of N-acryloylmorpholine was added was prepared.
- the polymerizable composition 5 has a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 9 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 33.0 parts by weight Ethoxylated pentaerythritol tetraacrylate: 22.0 parts by weight ⁇ Fluorine-containing compound>: 10 parts by weight In this example, N-acryloyl with respect to 10 parts by weight of the fluorine-containing compound A solution of a fluorine-containing compound to which 1 part by weight of morpholine was added was prepared.
- the polymerizable composition 5 has a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 10 An optical member was produced in the same manner as in Example 1 except that 1 part by weight of a fluorine-based additive (product name: Megafac RS-90) manufactured by DIC was used as the fluorine-containing compound. The concentration of fluorine atoms in the fluorine-containing compound was 47% by weight.
- a total of 35 parts by weight of monofunctional monomers having a tertiary amide group 34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N-acryloyl in a solution of a fluorine-containing compound
- Sum of 1 part by weight of morpholine Sum of 1 part by weight of morpholine).
- Example 11 An optical member was produced in the same manner as in Example 1 except that 1 part by weight of a fluorine-based additive (product name: FERENTENT 601AD) manufactured by Neos was used as the fluorine-containing compound. The concentration of fluorine atoms in the fluorine-containing compound was 21% by weight.
- a total of 35 parts by weight of monofunctional monomers having a tertiary amide group 34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N-acryloyl in a solution of a fluorine-containing compound) Sum of 1 part by weight of morpholine).
- Example 12 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 44.4 parts by weight Ethoxylated pentaerythritol tetraacrylate: 29.6 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 24 parts by weight Polymerizable composition 5 contains a total of 25 parts by weight of monofunctional monomers having tertiary amide groups (24 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 13 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows.
- ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 23.4 parts by weight
- Ethoxylated pentaerythritol tetraacrylate 15.6 parts by weight
- N-acryloylmorpholine 59 parts by weight
- Polymerizable composition 5 has a total of 60 parts by weight of monofunctional monomers having tertiary amide groups (59 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 14 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate, the content of the monofunctional monomer, and the content of the fluorine-containing compound were changed as follows.
- ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 18.0 parts by weightEthoxylated pentaerythritol tetraacrylate: 12.0 parts by weight
- N-acryloylmorpholine 59 parts by weight
- a solution of a fluorine-containing compound was prepared by adding 1 part by weight of N-acryloylmorpholine to 10 parts by weight of the fluorine-containing compound.
- the polymerizable composition 5 has a total of 60 parts by weight of monofunctional monomers having a tertiary amide group (59 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 15 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate was changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 45.0 parts by weight Ethoxylated pentaerythritol tetraacrylate: 30.0 parts by weight In the polymerizable composition 5, a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (monofunctional) 34 parts by weight of N-acryloylmorpholine contained as a monomer and 1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 16 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows.
- ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 26.4 parts by weight
- Ethoxylated pentaerythritol tetraacrylate 17.6 parts by weight
- N-acryloylmorpholine 54 parts by weight
- Polymerizable composition 5 contains a total of 55 parts by weight of monofunctional monomers having tertiary amide groups (54 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 17 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 29.4 parts by weight Ethoxylated pentaerythritol tetraacrylate: 19.6 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 49 parts by weight Polymerizable composition 5 contains 50 parts by weight of monofunctional monomers having tertiary amide groups in total (49 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, fluorine Contained in the solution of the compound containing 1 part by weight of N-acryloylmorpholine).
- Example 18 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 38.8 parts by weight Ethoxylated pentaerythritol tetraacrylate: 25.9 parts by weight ⁇ Fluorine-containing compound>: 0.3 parts by weight In this example, the amount of fluorine-containing compound is 0.3 parts by weight. Thus, a fluorine-containing compound solution to which 1 part by weight of N-acryloylmorpholine was added was prepared.
- the polymerizable composition 5 contained 1.3 parts by weight of the obtained fluorine-containing compound solution, that is, 0.3 parts by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 has a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 19 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 34.2 parts by weight Ethoxylated pentaerythritol tetraacrylate: 22.8 parts by weight ⁇ Fluorine-containing compound>: 8 parts by weight In this example, N-acryloyl is used with respect to 8 parts by weight of the fluorine-containing compound. A solution of a fluorine-containing compound to which 1 part by weight of morpholine was added was prepared.
- the polymerizable composition 5 contained 9 parts by weight of the resulting solution of the fluorine-containing compound, that is, 8 parts by weight of the fluorine-containing compound when converted to solid content.
- the polymerizable composition 5 has a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 20 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 38.7 parts by weight Ethoxylated pentaerythritol tetraacrylate: 25.8 parts by weight ⁇ Fluorine-containing compound>: 0.5 part by weight In this example, 0.5 part by weight of the fluorine-containing compound was used. Thus, a fluorine-containing compound solution to which 1 part by weight of N-acryloylmorpholine was added was prepared.
- the polymerizable composition 5 has a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 21 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 36.0 parts by weight Ethoxylated pentaerythritol tetraacrylate: 24.0 parts by weight ⁇ fluorine-containing compound>: 5 parts by weight In this example, N-acryloyl is used with respect to 5 parts by weight of the fluorine-containing compound. A solution of a fluorine-containing compound to which 1 part by weight of morpholine was added was prepared.
- the polymerizable composition 5 has a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- Example 22 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- -4-hydroxybutyl acrylate 40 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- -Normal butyl methacrylate 27 parts by weight As normal butyl methacrylate, methacrylic acid ester (product name: BMA) manufactured by Mitsubishi Rayon Co., Ltd. was used.
- N-acryloylmorpholine 10 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 4050, and the concentration of fluorine atoms in the fluorine-containing compound was 18% by weight.
- Example 23 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- -4-hydroxybutyl acrylate 40 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- -Normal butyl methacrylate 23 parts by weight As normal butyl methacrylate, methacrylic acid ester (product name: BMA) manufactured by Mitsubishi Rayon Co., Ltd. was used.
- N-acryloylmorpholine 10 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3850, and the concentration of fluorine atoms in the fluorine-containing compound was 20% by weight.
- Example 24 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- 4-hydroxybutyl acrylate 10 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- N-acryloylmorpholine 5 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3150, and the concentration of fluorine atoms in the fluorine-containing compound was 52% by weight.
- Example 25 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- 4-hydroxybutyl acrylate 13 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- N-acryloylmorpholine 5 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3200, and the concentration of fluorine atoms in the fluorine-containing compound was 50% by weight.
- Example 26 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- -4-hydroxybutyl acrylate 40 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- -Normal butyl methacrylate 15 parts by weight As normal butyl methacrylate, methacrylic acid ester (product name: BMA) manufactured by Mitsubishi Rayon Co., Ltd. was used.
- N-acryloylmorpholine 10 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3740, and the concentration of fluorine atoms in the fluorine-containing compound was 25% by weight.
- Example 27 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- -4-hydroxybutyl acrylate 30 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- N-acryloylmorpholine 5 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3260, and the concentration of fluorine atoms in the fluorine-containing compound was 45% by weight.
- Example 28 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- 2-Perfluorobutyl ethyl acrylate 40 parts by weight As 2-perfluorobutyl ethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-4) manufactured by Unimatec was used.
- -Normal butyl methacrylate 10 parts by weight As normal butyl methacrylate, methacrylic acid ester (product name: BMA) manufactured by Mitsubishi Rayon Co., Ltd. was used.
- N-acryloylmorpholine 5 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3420, and the concentration of fluorine atoms in the fluorine-containing compound was 30% by weight.
- Example 29 An optical member was produced in the same manner as in Example 1 except that a fluorine-containing compound produced by the following method was used.
- -4-hydroxybutyl acrylate 37 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- N-acryloylmorpholine 10 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight
- a polymerization inhibitor product code: M0123 manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition 5 contained 2 parts by weight of the obtained solution of the fluorine-containing compound, that is, 1 part by weight of the fluorine-containing compound when converted to a solid content.
- the polymerizable composition 5 contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound. That is, the polymerizable composition 5 contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-containing compound). -Sum of 1 part by weight of acryloylmorpholine).
- the weight average molecular weight of the fluorine-containing compound was 3530, and the concentration of fluorine atoms in the fluorine-containing compound was 40% by weight.
- Example 1 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 59.4 parts by weight Ethoxylated pentaerythritol tetraacrylate: 39.6 parts by weight ⁇ Monofunctional monomer>: 0 part by weight
- the polymerizable composition contains a monofunctional monomer having a tertiary amide group. 1 part by weight (1 part by weight of N-acryloylmorpholine in the solution of the fluorine-containing compound) was contained.
- Example 2 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 48.0 parts by weight Ethoxylated pentaerythritol tetraacrylate: 32.0 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 19 parts by weight
- the polymerizable composition contains a total of 20 parts by weight of monofunctional monomers having tertiary amide groups (19 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and fluorine-containing) (Combined with 1 part by weight of N-acryloylmorpholine in the solution of the compound).
- Example 4 An optical member was produced in the same manner as in Example 1 except that 34 parts by weight of hydroxyethyl acrylamide having a secondary amide group was used instead of the monofunctional monomer.
- hydroxyethylacrylamide an amide group-containing monomer (product name: HEAA (registered trademark)) manufactured by KJ Chemicals was used.
- the polymerizable composition contained 1 part by weight of a monofunctional monomer having a tertiary amide group (1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 5 An optical member was produced in the same manner as in Example 1, except that 34 parts by weight of Nn-butoxymethylacrylamide having a secondary amide group was used instead of the monofunctional monomer.
- Nn-butoxymethylacrylamide an amide group-containing monomer (product name: NBMA) manufactured by MRC Unitech was used.
- the polymerizable composition contained 1 part by weight of a monofunctional monomer having a tertiary amide group (1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 6 An optical member was produced in the same manner as in Example 1 except that 34 parts by weight of N-isopropylacrylamide having a secondary amide group was used in place of the monofunctional monomer.
- N-isopropylacrylamide an amide group-containing monomer (product name: NIPAM (registered trademark)) manufactured by KJ Chemicals was used.
- the polymerizable composition contained 1 part by weight of a monofunctional monomer having a tertiary amide group (1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 7 An optical member was produced in the same manner as in Example 1 except that 34 parts by weight of acrylamide having a primary amide group was used instead of the monofunctional monomer.
- acrylamide an amide group-containing monomer (product code: A1132) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition contained 1 part by weight of a monofunctional monomer having a tertiary amide group (1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 8 An optical member was produced in the same manner as in Example 1 except that 34 parts by weight of 4-hydroxybutyl acrylate having a primary hydroxyl group was used instead of the monofunctional monomer.
- 4-hydroxybutyl acrylate an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- the polymerizable composition contained 1 part by weight of a monofunctional monomer having a tertiary amide group (1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 9 An optical member was produced in the same manner as in Example 1, except that 34 parts by weight of 1,4-cyclohexanedimethanol monoacrylate having a primary hydroxyl group was used instead of the monofunctional monomer.
- 1,4-cyclohexanedimethanol monoacrylate an ester group-containing monomer (product name: CHDMMA) manufactured by Mitsubishi Chemical Corporation was used.
- the polymerizable composition contained 1 part by weight of a monofunctional monomer having a tertiary amide group (1 part by weight of N-acryloylmorpholine in a solution of a fluorine-containing compound).
- Example 10 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate, the content of the monofunctional monomer, and the content of the fluorine-containing compound were changed as follows.
- ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 39.0 parts by weight
- Ethoxylated pentaerythritol tetraacrylate 26.0 parts by weight
- N-acryloylmorpholine 35 parts by weight
- the polymerizable composition contains 35 parts by weight of a monofunctional monomer having a tertiary amide group (N-acryloylmorpholine contained as a monofunctional monomer). 35 parts by weight) and a fluorine-containing compound having a reactive group was not contained.
- Example 11 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 30.0 parts by weight Ethoxylated pentaerythritol tetraacrylate: 20.0 parts by weight ⁇ Fluorine-containing compound>: 15 parts by weight In this comparative example, N-acryloyl is added to 15 parts by weight of the fluorine-containing compound. A solution of a fluorine-containing compound to which 1 part by weight of morpholine was added was prepared.
- the polymerizable composition contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N— in a solution of a fluorine-containing compound. (A sum of 1 part by weight of acryloylmorpholine).
- the content of the monofunctional monomer was changed to 35 parts by weight, and instead of the fluorine-containing compound, 1 weight of the silicon-based surface conditioner (product name: BYK-UV3500) manufactured by Big Chemie Japan, described in Patent Document 4 above.
- An optical member was produced in the same manner as in Example 1 except that the part was used.
- the polymerizable composition contains 35 parts by weight of a monofunctional monomer having a tertiary amide group (35 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer), and a fluorine-containing compound having a reactive group. It was not contained.
- -4-hydroxybutyl acrylate 40 parts by weight As 4-hydroxybutyl acrylate, an ester group-containing monomer (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd. was used.
- N-acryloylmorpholine 10 parts by weight As N-acryloylmorpholine, a monofunctional monomer (product name: ACMO) manufactured by KJ Chemicals was used.
- Radical polymerization initiator 3.5 parts by weight As a radical polymerization initiator, a polymerization initiator (product name: V-601) manufactured by Wako Pure Chemical Industries, Ltd. was used.
- 1,8-diazabicyclo [5.4.0] -7-undecene 0.3 parts by weight 1,8-diazabicyclo [5.4.0] -7-undecene is a catalyst manufactured by Tokyo Chemical Industry Co., Ltd.
- Product code: D1270 was used.
- 4-methoxyphenol 0.1 parts by weight As 4-methoxyphenol, a polymerization inhibitor (product code: M0123) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
- the polymerizable composition contained 1 part by weight of N-acryloylmorpholine in the solution of the fluorine-based additive. That is, the polymerizable composition contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N in a solution of a fluorine-based additive).
- the weight average molecular weight of the fluorine-based additive was 3200, and the concentration of fluorine atoms in the fluorine-based additive was 40% by weight.
- Example 15 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 45.6 parts by weight Ethoxylated pentaerythritol tetraacrylate: 30.4 parts by weight ⁇ Monofunctional monomer> N-acryloylmorpholine: 22 parts by weight
- the polymerizable composition contains a total of 23 parts by weight of monofunctional monomers having a tertiary amide group (22 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and fluorine-containing) (Combined with 1 part by weight of N-acryloylmorpholine in the solution of the compound).
- the polymerizable composition contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N— in a solution of a fluorine-containing compound. (A sum of 1 part by weight of acryloylmorpholine).
- Example 18 An optical member was produced in the same manner as in Example 1 except that the content of the polyfunctional acrylate and the content of the fluorine-containing compound were changed as follows. ⁇ Multifunctional acrylate> Pentaerythritol triacrylate: 31.8 parts by weight Ethoxylated pentaerythritol tetraacrylate: 21.2 parts by weight ⁇ Fluorine-containing compound>: 12 parts by weight In this comparative example, N-acryloyl is used with respect to 12 parts by weight of the fluorine-containing compound. A solution of a fluorine-containing compound to which 1 part by weight of morpholine was added was prepared.
- the polymerizable composition contains a total of 35 parts by weight of monofunctional monomers having a tertiary amide group (34 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N— in a solution of a fluorine-containing compound. (A sum of 1 part by weight of acryloylmorpholine).
- the polymerizable composition contains a total of 60 parts by weight of monofunctional monomers having a tertiary amide group (59 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer and N— in a solution of a fluorine-containing compound). (A sum of 1 part by weight of acryloylmorpholine).
- a solution of was prepared. And 1.1 weight part of fluorine-containing compounds were contained in the polymeric composition, when converted into 1.1 weight part, ie, solid content, of the obtained fluorine-containing compound solution.
- the polymerizable composition contains a total of 23 parts by weight of monofunctional monomers having a tertiary amide group (22 parts by weight of N-acryloylmorpholine contained as a monofunctional monomer, and N— (A sum of 1 part by weight of acryloylmorpholine).
- the adhesion under normal temperature and humidity was evaluated by the following method. First, the surface of the polymer layer opposite to the base material (surface of the concavo-convex structure) using a wipe made by Daio Paper Co., Ltd. (product name: Eliere Pro Wipe Soft Micro Wiper S220) for the optical member of each example ) For 100 round trips. Thereafter, the optical member of each example was left for 3 days in an environment of a temperature of 23 ° C. and a humidity of 50%. Next, with respect to the surface of the polymer layer opposite to the base material, with a cutter knife, 11 vertical and 11 horizontal cuts are made at 1 mm intervals to form 100 square squares. (1mm square) was chopped. Then, after a polyester adhesive tape (product name: No.
- the adhesion under high temperature and high humidity was evaluated by the following method. First, the surface of the polymer layer opposite to the base material (surface of the concavo-convex structure) using a wipe made by Daio Paper Co., Ltd. (product name: Eliere Pro Wipe Soft Micro Wiper S220) for the optical member of each example ) For 100 round trips. Thereafter, the optical members of each example were left for 3 days in an environment of a temperature of 60 ° C. and a humidity of 95%, and then returned to an environment of a temperature of 23 ° C. and a humidity of 50% and left for 1 day.
- X is the number of cells on which the polymer layer on the substrate was peeled off.
- the judgment criteria were as follows. Level a: None of the 100 pieces were peeled off (0/100). Level b: 1 to 2 out of 100 pieces were peeled off (1/100 to 2/100). Level c: 3 to 5 out of 100 pieces were peeled off (3/100 to 5/100). Level d: 6 or more and 99 or less of 100 pieces were peeled off (6/100 to 99/100). Level e: 100 pieces out of 100 pieces were peeled off (100/100).
- the determination was level a, level b, or level c, it was determined that there was no problem in actual use (high adhesion under high temperature and high humidity).
- Adhesiveness under normal temperature and normal humidity was level C, and adhesiveness under high temperature and high humidity was level e.
- the case where the overall evaluation is ⁇ , ⁇ , or ⁇ was judged as a level at which there is no problem in actual use.
- the water repellency was evaluated by the contact angle of water with the surface of the polymer layer opposite to the base material (surface of the uneven structure) in each example optical member. Specifically, first, the surface of the polymer layer on the opposite side of the base material of the polymer layer by using a wipe made by Daio Paper Co., Ltd. (product name: Ellere Pro Wipe Soft Micro Wiper S220) for the optical members in each example. Was wiped for 100 round trips. Thereafter, a black acrylic plate was attached to the surface of the substrate opposite to the polymer layer, and 10 ⁇ l of water was dropped onto the surface of the polymer layer opposite to the substrate. . And after leaving for 20 seconds, the contact angle was measured at 10 points at intervals of 1 second.
- the first measurement point the central portion of the surface of the polymer layer opposite to the substrate was selected.
- the second and third measurement points two points that are 10 mm away from the first measurement point and are symmetrical with respect to the first measurement point are selected.
- a contact angle measuring device product name: DSA10-Mk2 manufactured by Kruss was used.
- Examples 1 to 29 As shown in Table 1, in each of Examples 1 to 29, the adhesion under normal temperature and normal humidity and the adhesion under high temperature and high humidity were both high. Among them, Examples 1 to 3, 5, 7, 9 to 11, 16 to 21, 23, 25 to 29 have higher adhesion under high temperature and high humidity, and Examples 1 to 3, 17, 20, 21, Nos. 28 and 29 had particularly high adhesion under high temperature and high humidity. Further, as can be seen from the adhesion evaluation method as described above, the adhesion of Examples 1 to 29 under high temperature and high humidity is that after the surface of the polymer layer opposite to the substrate is wiped with a wipe. I found it expensive.
- Example 1 Example 4, Example 5, and Example 12 in which the type of the monofunctional monomer having a tertiary amide group is the same (N-acryloylmorpholine) are compared, it is found that the monofunctional monomer is contained.
- Example 12 25 parts by weight
- Example 4 26 parts by weight
- Example 5 (30 parts by weight
- Example 1 35 parts by weight
- the adhesion under high temperature and high humidity is increased. Increased. This is because the amount of the tertiary amide group in the polymer layer increases in the order of Example 12, Example 4, Example 5, and Example 1.
- Example 1 Example 6, Example 7, Example 13, Example 16, and Example 17 in which the types of monofunctional monomers having a tertiary amide group are the same (N-acryloylmorpholine) are compared. Then, the content of the monofunctional monomer was Example 13 (60 parts by weight), Example 6 (59 parts by weight), Example 16 (55 parts by weight), Example 7 (53 parts by weight), Example 17 ( The adhesiveness under high temperature and high humidity was equal or increased with decreasing order of 50 parts by weight) and Example 1 (35 parts by weight). This is because the polarity of the polymer layer is the same or lower in the order of Example 13, Example 6, Example 16, Example 7, Example 17, and Example 1.
- the adhesiveness between the base material and the polymer layer can be controlled even in an environment where moisture is easily absorbed, such as under high temperature and high humidity, by optimally controlling the content of the monofunctional monomer having a tertiary amide group. It was found that the decrease in the resistance can be suppressed. Further, from the viewpoint of sufficiently increasing the adhesion under high temperature and high humidity, the content of the monofunctional monomer is preferably 30 parts by weight or more and 55 parts by weight or less, and 35 parts by weight or more and 50 parts by weight or less. It has also been found to be more preferable.
- Example 1 when Example 1, Example 8, Example 18, and Example 20 with the same kind of fluorine-containing compound which has a reactive group are compared, content of a fluorine-containing compound is Example 8 (0). .1 parts by weight), Example 18 (0.3 parts by weight), Example 20 (0.5 parts by weight), and Example 1 (1 part by weight) in that order, the adhesion at high temperature and high humidity increases. Equal or higher. This is because the amount of fluorine atoms in the polymer layer increases in the order of Example 8, Example 18, Example 20, and Example 1, and the hygroscopicity is equivalent or lowered.
- Example 1 Example 9, Example 19, and Example 21 in which the kind of fluorine-containing compound having a reactive group is the same are compared
- the content of the fluorine-containing compound is found in Example 9 (10 Parts by weight), Example 19 (8 parts by weight), Example 21 (5 parts by weight), and Example 1 (1 part by weight) decreased in this order, and the adhesion under high temperature and high humidity was equal or increased.
- the amount of fluorine atoms in the polymer layer decreases in the order of Example 9, Example 19, Example 21, and Example 1, and as a result, the fluorine atoms are present on the substrate side surface of the polymer layer. This is because the polymer layer is efficiently oriented on the surface opposite to the base material without being oriented in a large amount.
- Example 1 the amount of tertiary amide groups on the surface of the polymer layer on the substrate side is larger than that in Example 9.
- the content of the fluorine-containing compound having a reactive group is preferably 0.3 parts by weight or more and 8 parts by weight or less, and 0.5 parts by weight. It has also been found that the content is more preferably 5 parts by weight or less.
- Example 1 Example 22, Example 23, Example 26, and Example 28 in which the content of the fluorine-containing compound having a reactive group is the same (1 part by weight) are compared
- the fluorine-containing compound The concentration of fluorine atoms in Examples 22 (18% by weight), Example 23 (20% by weight), Example 26 (25% by weight), Example 28 (30% by weight), and Example 1 (37% by weight). %), The adhesiveness under high temperature and high humidity was equal or increased. This is because the amount of fluorine atoms in the polymer layer increases in the order of Example 22, Example 23, Example 26, Example 28, and Example 1, and the hygroscopicity is equivalent or lowered.
- Example 1 Example 24, Example 25, Example 27, and Example 29 in which the content of the fluorine-containing compound having a reactive group is the same (1 part by weight) are compared
- the fluorine-containing compound The concentration of fluorine atoms in Examples 24 (52% by weight), Example 25 (50% by weight), Example 27 (45% by weight), Example 29 (40% by weight), and Example 1 (37% by weight). %), The adhesion under high temperature and high humidity was equal or increased. This is because the amount of fluorine atoms in the polymer layer decreases in the order of Example 24, Example 25, Example 27, Example 29, and Example 1, and as a result, the fluorine atom becomes a group of the polymer layer.
- the polymer layer is efficiently oriented on the surface opposite to the base material without being oriented much on the material side surface.
- the concentration of fluorine atoms in the fluorine-containing compound having a reactive group is preferably 20% by weight or more and 50% by weight or less, preferably 25% by weight. As described above, it was found that the content was more preferably 45% by weight or less, and further preferably 30% by weight or more and 40% by weight or less.
- Examples 1 to 29 were also excellent in water repellency and excellent in antifouling properties against hydrophilic dirt. This is because the polymerizable composition constituting the polymer layer contains a fluorine-containing compound having a reactive group, and the surface energy of the polymer layer is reduced.
- Comparative Examples 1 to 20 had low adhesion under high temperature and high humidity.
- Comparative Examples 1, 4 to 9 since the content of the monofunctional monomer having a tertiary amide group is as very small as 1 part by weight, both adhesiveness at normal temperature and normal humidity and adhesiveness at high temperature and high humidity are obtained. It was low.
- Comparative Example 2 and Comparative Example 15 the content of the monofunctional monomer having a tertiary amide group is less than 25 parts by weight, and the amount of the tertiary amide group in the polymer layer becomes too small. The adhesion under high temperature and high humidity was low.
- Comparative Example 3 and Comparative Example 16 the content of the monofunctional monomer having a tertiary amide group is more than 60 parts by weight, and the polarity of the polymer layer becomes too high. The sex was low. Since Comparative Example 10, Comparative Example 12, Comparative Example 13, and Comparative Example 14 did not contain a fluorine-containing compound having a reactive group, the hygroscopic property was high and the adhesiveness under high temperature and high humidity was low. Further, Comparative Example 10, Comparative Example 12, Comparative Example 13, and Comparative Example 14 do not contain a fluorine-containing compound having a reactive group, so that the contact angle of water is smaller than in Examples 1 to 29, The water repellency was poor.
- Comparative Example 11 and Comparative Example 18 the content of the fluorine-containing compound having a reactive group is more than 10 parts by weight, and the amount of fluorine atoms in the polymer layer is excessively increased. Since the amount of the tertiary amide group is relatively reduced on the surface of the combined layer on the base material side, both the adhesion under normal temperature and normal humidity and the adhesion under high temperature and high humidity were low. In Comparative Example 17, the content of the fluorine-containing compound having a reactive group is less than 0.1 parts by weight, the amount of fluorine atoms in the polymer layer is too small, and the hygroscopicity is increased. The adhesion under high humidity was low.
- Comparative Example 17 had a smaller water contact angle and inferior water repellency than Examples 1 to 29.
- the content of the polyfunctional acrylate is less than 30 parts by weight, and the content of the fluorine-containing compound is relatively excessive.
- the surface of the polymer layer on the substrate side is 3 Since the amount of the primary amide group was relatively small, both the adhesion under normal temperature and normal humidity and the adhesion under high temperature and high humidity were low.
- the polyfunctional acrylate content is more than 75 parts by weight, and the monofunctional monomer content is relatively too low. As a result, the amount of the tertiary amide group in the polymer layer is small. Since it decreased too much, the adhesiveness under high temperature and high humidity was low.
- the monofunctional monomer may include at least one monomer selected from the group consisting of N-acryloylmorpholine, N, N-dimethylacrylamide, and N, N-diethylacrylamide. Thereby, the said monofunctional monomer can be utilized effectively.
- the concentration of fluorine atoms in the fluorine-containing compound may be 20% by weight or more and 50% by weight or less.
- the said fluorine atom can be orientated suitably on the surface on the opposite side to the said base material of the said polymer layer. As a result, it is possible to further suppress a decrease in adhesion between the substrate and the polymer layer due to moisture absorption.
- the concentration of fluorine atoms in the fluorine-containing compound may be 25% by weight or more and 45% by weight or less. Thereby, the fall of the adhesiveness of the said base material and the said polymer layer by moisture absorption can further be suppressed.
- the concentration of fluorine atoms in the fluorine-containing compound may be 30% by weight or more and 40% by weight or less. Thereby, especially the fall of the adhesiveness of the said base material and the said polymer layer by moisture absorption can be suppressed.
- the content of the monofunctional monomer may be not less than 30 parts by weight and not more than 55 parts by weight. Thereby, the fall of the adhesiveness of the said base material and the said polymer layer by moisture absorption can be suppressed more.
- the content of the monofunctional monomer may be not less than 35 parts by weight and not more than 50 parts by weight. Thereby, the fall of the adhesiveness of the said base material and the said polymer layer by moisture absorption can further be suppressed.
- the content of the fluorine-containing compound may be 0.3 parts by weight or more and 8 parts by weight or less. Thereby, the fall of the adhesiveness of the said base material and the said polymer layer by moisture absorption can be suppressed more.
- the content of the fluorine-containing compound may be 0.5 parts by weight or more and 5 parts by weight or less.
- Optical member 2 Base material 3: Polymer layer 4: Convex part 5: Polymerizable composition 6: Mold P: Pitch
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Abstract
Description
図1は、実施形態の光学部材を示す断面模式図である。図1に示すように、光学部材1は、基材2と、基材2と直に接する重合体層3とを備えている。重合体層3は、複数の凸部(突起)4が可視光の波長以下のピッチ(隣接する凸部4の頂点間の距離)Pで設けられる凹凸構造を表面に有している。よって、光学部材1は、モスアイ構造(蛾の目状の構造)を有する反射防止部材に相当する。これにより、光学部材1は、モスアイ構造による優れた反射防止性(低反射性)を示すことができる。
Rf1-R2-D1 (A)
上記一般式(A)中、Rf1は、フルオロアルキル基、フルオロオキシアルキル基、フルオロアルケニル基、フルオロアルカンジイル基、及び、フルオロオキシアルカンジイル基からなる群より選択される少なくとも1つを含む部位を表す。R2は、アルカンジイル基、アルカントリイル基、又は、それらから導出されるエステル構造、ウレタン構造、エーテル構造、トリアジン構造を表す。D1は、反応性基を表す。
CFn1H(3-n1)-(CFn2H(2-n2))kO-(CFn3H(2-n3))mO- (B)
-(CFn4H(2-n4))pO-(CFn5H(2-n5))sO- (C)
上記一般式(B)及び(C)中、n1は1~3の整数であり、n2~n5は1又は2であり、k、m、p、及び、sは0以上の整数である。n1~n5の好ましい組み合わせとしては、n1が2又は3、n2~n5が1又は2である組み合わせであり、より好ましい組み合わせとしては、n1が3、n2及びn4が2、n3及びn5が1又は2である組み合わせである。
まず、図2(a)に示すように、重合性組成物5を基材2上に塗布する。その結果、重合性組成物5は、基材2と直に接するように形成される。重合性組成物5の塗布方法としては特に限定されず、例えば、スプレー方式、グラビア方式、スロットダイ方式等で塗布する方法が挙げられる。
図2(b)に示すように、塗布された重合性組成物5に、金型6を基材2とは反対側から押し付けて貼り合わせ、重合性組成物5の基材2とは反対側の表面に凹凸構造を形成する。
凹凸構造が形成された重合性組成物5に、活性エネルギー線を照射して硬化させる(重合させる)。その結果、図2(c)に示すような重合体層3が形成される。活性エネルギー線の照射は、基材2側から行ってもよく、重合性組成物5側から行ってもよい。また、重合性組成物5に対する活性エネルギー線の照射回数は特に限定されず、1回のみであってもよいし、複数回であってもよい。
金型6を重合体層3から剥離する。その結果、図2(d)に示すような光学部材1が完成する。重合体層3の表面に形成された凹凸構造は、複数の凸部4が可視光の波長以下のピッチPで設けられる構造、すなわち、モスアイ構造に相当する。
実施例1の光学部材を、以下の製造プロセスによって作製した。
まず、重合性組成物5を基材2上に、第一理化社製のバーコーター(製品名:No.05)で塗布した。その結果、重合性組成物5は、基材2と直に接するように形成された。
・ペンタエリスリトールトリアクリレート:38.4重量部
ペンタエリスリトールトリアクリレートとしては、新中村化学工業社製の多官能アクリレート(製品名:A-TMM-3LM-N)を用いた。
・エトキシ化ペンタエリスリトールテトラアクリレート:25.6重量部
エトキシ化ペンタエリスリトールテトラアクリレートとしては、新中村化学工業社製の多官能アクリレート(製品名:ATM-35E)を用いた。
・N-アクリロイルモルホリン:34重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
以下の方法で作製したものを用いた。まず、攪拌装置、温度計、窒素導入口、及び、冷却管を備えるセパラブルフラスコ(容量:300ml)に、酢酸ブチルを100重量部投入した。次に、セパラブルフラスコを窒素雰囲気下で加熱して、その内部空間の温度を110℃に保った状態で、下記材料の混合物を、セパラブルフラスコ内に3時間かけて滴下した。
・2-パーフルオロヘキシルエチルアクリレート:50重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・4-ヒドロキシブチルアクリレート:40重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・N-アクリロイルモルホリン:10重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI(登録商標))を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
ゲルパーミエーションクロマトグラフィー(GPC)によって、フッ素含有化合物のポリスチレン換算の重量平均分子量を算出した。使用装置及び条件は、下記の通りとした。分子量較正曲線は、標準ポリスチレンを用いて作成した。
使用装置:昭和電工社製のクロマトグラフィー(製品名:SHODEX GPC SYSTEM-11)
カラム:東ソー社製のカラム(製品名:TSKgelαMXL)3本
測定温度:40℃
試料溶液:熱分解性極性基を有する顔料表面処理剤の0.10%ジメチルホルムアミド溶液
注入量:100ml
検出器:屈折率検出器
フッ素含有化合物の溶液100重量部に、BASF社製の光重合開始剤(製品名:LUCIRIN TPO)0.5重量部を添加し、撹拌することによって溶解させた。次に、得られた溶液を、ポリテトラフルオロエチレン(PTFE)製の円筒枠(直径:30mm、厚み:1mm)に流し込んだ後、紫外線(照射量:1J/cm2)を照射して円筒形の硬化物フィルムを作製した。その後、リガク社製の走査型蛍光X線分析装置(製品名:ZSX Primus)を用いて、加速電圧50kV、電流60mAの条件下で、上述した硬化物フィルム(フッ素含有化合物の濃度:50%)中のフッ素原子の強度を測定することによって、フッ素含有化合物中のフッ素原子の濃度を決定した。
・光重合開始剤:0.5重量部
光重合開始剤としては、BASF社製の光重合開始剤(製品名:LUCIRIN TPO)を用いた。
塗布された重合性組成物5に、金型6を基材2とは反対側から気泡が入らないように押し付けて貼り合わせ、重合性組成物5の基材2とは反対側の表面に凹凸構造を形成した。
凹凸構造が形成された重合性組成物5に、基材2側から紫外線(照射量:1J/cm2)を照射して硬化させた(重合させた)。その結果、重合体層3が形成された。重合体層3の厚みは、11.0μmであった。
金型6を重合体層3から剥離した。その結果、光学部材1が完成した。光学部材1の表面仕様は、以下の通りであった。
凸部4の形状:釣鐘状
凸部4のピッチP:200nm
凸部4の高さ:200nm
凸部4のアスペクト比:1
単官能モノマーの種類を、N,N-ジメチルアクリルアミドに変更したこと以外、実施例1と同様にして、光学部材を作製した。N,N-ジメチルアクリルアミドとしては、KJケミカルズ社製の単官能モノマー(製品名:DMAA)を用いた。重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN,N-ジメチルアクリルアミド34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
単官能モノマーの種類を、N,N-ジエチルアクリルアミドに変更したこと以外、実施例1と同様にして、光学部材を作製した。N,N-ジエチルアクリルアミドとしては、KJケミカルズ社製の単官能モノマー(製品名:DEAA)を用いた。重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN,N-ジエチルアクリルアミド34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:43.8重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:29.2重量部
<単官能モノマー>
・N-アクリロイルモルホリン:25重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で26重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン25重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:41.4重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:27.6重量部
<単官能モノマー>
・N-アクリロイルモルホリン:29重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で30重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン29重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:24.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:16.0重量部
<単官能モノマー>
・N-アクリロイルモルホリン:58重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で59重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン58重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:27.6重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:18.4重量部
<単官能モノマー>
・N-アクリロイルモルホリン:52重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で53重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン52重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:38.9重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:26.0重量部
<フッ素含有化合物>:0.1重量部
本実施例では、フッ素含有化合物0.1重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を1.1重量部、すなわち、固形分に換算すると、フッ素含有化合物を0.1重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:33.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:22.0重量部
<フッ素含有化合物>:10重量部
本実施例では、フッ素含有化合物10重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を11重量部、すなわち、固形分に換算すると、フッ素含有化合物を10重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
フッ素含有化合物として、DIC社製のフッ素系添加剤(製品名:メガファックRS-90)を1重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。フッ素含有化合物中のフッ素原子の濃度は47重量%であった。重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
フッ素含有化合物として、ネオス社製のフッ素系添加剤(製品名:フタージェント601AD)を1重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。フッ素含有化合物中のフッ素原子の濃度は21重量%であった。重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:44.4重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:29.6重量部
<単官能モノマー>
・N-アクリロイルモルホリン:24重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で25重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン24重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:23.4重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:15.6重量部
<単官能モノマー>
・N-アクリロイルモルホリン:59重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で60重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン59重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、単官能モノマーの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:18.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:12.0重量部
<単官能モノマー>
・N-アクリロイルモルホリン:59重量部
<フッ素含有化合物>:10重量部
本実施例では、フッ素含有化合物10重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を11重量部、すなわち、固形分に換算すると、フッ素含有化合物を10重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で60重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン59重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:45.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:30.0重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:26.4重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:17.6重量部
<単官能モノマー>
・N-アクリロイルモルホリン:54重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で55重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン54重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:29.4重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:19.6重量部
<単官能モノマー>
・N-アクリロイルモルホリン:49重量部
重合性組成物5には、3級アミド基を有する単官能モノマーが合計で50重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン49重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:38.8重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:25.9重量部
<フッ素含有化合物>:0.3重量部
本実施例では、フッ素含有化合物0.3重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を1.3重量部、すなわち、固形分に換算すると、フッ素含有化合物を0.3重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:34.2重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:22.8重量部
<フッ素含有化合物>:8重量部
本実施例では、フッ素含有化合物8重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を9重量部、すなわち、固形分に換算すると、フッ素含有化合物を8重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:38.7重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:25.8重量部
<フッ素含有化合物>:0.5重量部
本実施例では、フッ素含有化合物0.5重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を1.5重量部、すなわち、固形分に換算すると、フッ素含有化合物を0.5重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:36.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:24.0重量部
<フッ素含有化合物>:5重量部
本実施例では、フッ素含有化合物5重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物5に、得られたフッ素含有化合物の溶液を6重量部、すなわち、固形分に換算すると、フッ素含有化合物を5重量部含有させた。また、重合性組成物5には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロブチルエチルアクリレート:23重量部
2-パーフルオロブチルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-4)を用いた。
・4-ヒドロキシブチルアクリレート:40重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・メタクリル酸ノルマルブチル:27重量部
メタクリル酸ノルマルブチルとしては、三菱レイヨン社製のメタクリル酸エステル(製品名:BMA)を用いた。
・N-アクリロイルモルホリン:10重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロブチルエチルアクリレート:27重量部
2-パーフルオロブチルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-4)を用いた。
・4-ヒドロキシブチルアクリレート:40重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・メタクリル酸ノルマルブチル:23重量部
メタクリル酸ノルマルブチルとしては、三菱レイヨン社製のメタクリル酸エステル(製品名:BMA)を用いた。
・N-アクリロイルモルホリン:10重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロヘキシルエチルアクリレート:85重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・4-ヒドロキシブチルアクリレート:10重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・N-アクリロイルモルホリン:5重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロヘキシルエチルアクリレート:82重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・4-ヒドロキシブチルアクリレート:13重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・N-アクリロイルモルホリン:5重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロブチルエチルアクリレート:35重量部
2-パーフルオロブチルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-4)を用いた。
・4-ヒドロキシブチルアクリレート:40重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・メタクリル酸ノルマルブチル:15重量部
メタクリル酸ノルマルブチルとしては、三菱レイヨン社製のメタクリル酸エステル(製品名:BMA)を用いた。
・N-アクリロイルモルホリン:10重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロヘキシルエチルアクリレート:65重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・4-ヒドロキシブチルアクリレート:30重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・N-アクリロイルモルホリン:5重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロヘキシルエチルアクリレート:45重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・2-パーフルオロブチルエチルアクリレート:40重量部
2-パーフルオロブチルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-4)を用いた。
・メタクリル酸ノルマルブチル:10重量部
メタクリル酸ノルマルブチルとしては、三菱レイヨン社製のメタクリル酸エステル(製品名:BMA)を用いた。
・N-アクリロイルモルホリン:5重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
フッ素含有化合物として、以下の方法で作製したものを用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロヘキシルエチルアクリレート:53重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・4-ヒドロキシブチルアクリレート:37重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・N-アクリロイルモルホリン:10重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・2-イソシアナトエチルアクリレート:5重量部
2-イソシアナトエチルアクリレートとしては、昭和電工社製のモノマー(製品名:カレンズAOI)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:59.4重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:39.6重量部
<単官能モノマー>:0重量部
重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:48.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:32.0重量部
<単官能モノマー>
・N-アクリロイルモルホリン:19重量部
重合性組成物には、3級アミド基を有する単官能モノマーが合計で20重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン19重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:21.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:14.0重量部
<単官能モノマー>
・N-アクリロイルモルホリン:64重量部
重合性組成物には、3級アミド基を有する単官能モノマーが合計で65重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン64重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
単官能モノマーの代わりに、2級アミド基を有するヒドロキシエチルアクリルアミドを34重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。ヒドロキシエチルアクリルアミドとしては、KJケミカルズ社製のアミド基含有モノマー(製品名:HEAA(登録商標))を用いた。重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
単官能モノマーの代わりに、2級アミド基を有するN-n-ブトキシメチルアクリルアミドを34重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。N-n-ブトキシメチルアクリルアミドとしては、MRCユニテック社製のアミド基含有モノマー(製品名:NBMA)を用いた。重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
単官能モノマーの代わりに、2級アミド基を有するN-イソプロピルアクリルアミドを34重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。N-イソプロピルアクリルアミドとしては、KJケミカルズ社製のアミド基含有モノマー(製品名:NIPAM(登録商標))を用いた。重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
単官能モノマーの代わりに、1級アミド基を有するアクリルアミドを34重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。アクリルアミドとしては、東京化成工業社製のアミド基含有モノマー(製品コード:A1132)を用いた。重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
単官能モノマーの代わりに、1級水酸基を有する4-ヒドロキシブチルアクリレートを34重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
単官能モノマーの代わりに、1級水酸基を有する1,4-シクロヘキサンジメタノールモノアクリレートを34重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。1,4-シクロヘキサンジメタノールモノアクリレートとしては、三菱化学社製のエステル基含有モノマー(製品名:CHDMMA)を用いた。重合性組成物には、3級アミド基を有する単官能モノマーが1重量部(フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部)含有されていた。
多官能アクリレートの含有量、単官能モノマーの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:39.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:26.0重量部
<単官能モノマー>
・N-アクリロイルモルホリン:35重量部
<フッ素含有化合物>:0重量部
重合性組成物には、3級アミド基を有する単官能モノマーが35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン35重量部)含有されており、反応性基を有するフッ素含有化合物が含有されていなかった。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:30.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:20.0重量部
<フッ素含有化合物>:15重量部
本比較例では、フッ素含有化合物15重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物に、得られたフッ素含有化合物の溶液を16重量部、すなわち、固形分に換算すると、フッ素含有化合物を15重量部含有させた。また、重合性組成物には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
単官能モノマーの含有量を35重量部に変更し、フッ素含有化合物の代わりに、上記特許文献4に記載のビックケミー・ジャパン社製のシリコン系表面調整剤(製品名:BYK-UV3500)を1重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。重合性組成物には、3級アミド基を有する単官能モノマーが35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン35重量部)含有されており、反応性基を有するフッ素含有化合物が含有されていなかった。
単官能モノマーの含有量を35重量部に変更し、フッ素含有化合物の代わりに、上記特許文献8に記載のDIC社製の反応性基を有さないフッ素系界面活性剤(製品名:メガファックR-08)を1重量部用いたこと以外、実施例1と同様にして、光学部材を作製した。上記フッ素系界面活性剤中のフッ素原子の濃度は31重量%であった。重合性組成物には、3級アミド基を有する単官能モノマーが35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン35重量部)含有されており、反応性基を有するフッ素含有化合物が含有されていなかった。
フッ素含有化合物の代わりに、以下の方法で作製した、反応性基を有さないフッ素系添加剤を用いたこと以外、実施例1と同様にして、光学部材を作製した。
・2-パーフルオロヘキシルエチルアクリレート:50重量部
2-パーフルオロヘキシルエチルアクリレートとしては、ユニマテック社製のフッ素含有モノマー(製品名:CHEMINOX FAAC-6)を用いた。
・4-ヒドロキシブチルアクリレート:40重量部
4-ヒドロキシブチルアクリレートとしては、日本化成社製のエステル基含有モノマー(製品名:4HBA)を用いた。
・N-アクリロイルモルホリン:10重量部
N-アクリロイルモルホリンとしては、KJケミカルズ社製の単官能モノマー(製品名:ACMO)を用いた。
・ラジカル重合開始剤:3.5重量部
ラジカル重合開始剤としては、和光純薬工業社製の重合開始剤(製品名:V-601)を用いた。
・1,8-ジアザビシクロ[5.4.0]-7-ウンデセン:0.3重量部
1,8-ジアザビシクロ[5.4.0]-7-ウンデセンとしては、東京化成工業社製の触媒(製品コード:D1270)を用いた。
・4-メトキシフェノール:0.1重量部
4-メトキシフェノールとしては、東京化成工業社製の重合禁止剤(製品コード:M0123)を用いた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:45.6重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:30.4重量部
<単官能モノマー>
・N-アクリロイルモルホリン:22重量部
重合性組成物には、3級アミド基を有する単官能モノマーが合計で23重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン22重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、単官能モノマーの含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:21.6重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:14.4重量部
<単官能モノマー>
・N-アクリロイルモルホリン:62重量部
重合性組成物には、3級アミド基を有する単官能モノマーが合計で63重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン62重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:39.0重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:26.0重量部
<フッ素含有化合物>:0.07重量部
本比較例では、フッ素含有化合物0.07重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物に、得られたフッ素含有化合物の溶液を1.07重量部、すなわち、固形分に換算すると、フッ素含有化合物を0.07重量部含有させた。また、重合性組成物には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:31.8重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:21.2重量部
<フッ素含有化合物>:12重量部
本比較例では、フッ素含有化合物12重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物に、得られたフッ素含有化合物の溶液を13重量部、すなわち、固形分に換算すると、フッ素含有化合物を12重量部含有させた。また、重合性組成物には、3級アミド基を有する単官能モノマーが合計で35重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン34重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、単官能モノマーの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:16.8重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:11.2重量部
<単官能モノマー>
・N-アクリロイルモルホリン:59重量部
<フッ素含有化合物>:12重量部
本比較例では、フッ素含有化合物12重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物に、得られたフッ素含有化合物の溶液を13重量部、すなわち、固形分に換算すると、フッ素含有化合物を12重量部含有させた。また、重合性組成物には、3級アミド基を有する単官能モノマーが合計で60重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン59重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
多官能アクリレートの含有量、単官能モノマーの含有量、及び、フッ素含有化合物の含有量を下記のように変更したこと以外、実施例1と同様にして、光学部材を作製した。
<多官能アクリレート>
・ペンタエリスリトールトリアクリレート:46.14重量部
・エトキシ化ペンタエリスリトールテトラアクリレート:30.76重量部
<単官能モノマー>
・N-アクリロイルモルホリン:22重量部
<フッ素含有化合物>:0.1重量部
本比較例では、フッ素含有化合物0.1重量部に対してN-アクリロイルモルホリンが1重量部添加されたフッ素含有化合物の溶液を作製した。そして、重合性組成物に、得られたフッ素含有化合物の溶液を1.1重量部、すなわち、固形分に換算すると、フッ素含有化合物を0.1重量部含有させた。また、重合性組成物には、3級アミド基を有する単官能モノマーが合計で23重量部(単官能モノマーとして含有させたN-アクリロイルモルホリン22重量部と、フッ素含有化合物の溶液中のN-アクリロイルモルホリン1重量部との和)含有されていた。
実施例1~29、及び、比較例1~20の光学部材について、基材と重合体層との、常温常湿下における密着性、及び、高温高湿下における密着性、並びに、撥水性の評価結果を、表1及び表2に示す。ここで、高温高湿下における密着性の評価は、より吸湿しやすい環境を想定して行ったものである。
レベルA:100個のうち、1個も剥がれなかった(0/100)。
レベルB:100個のうち、1個以上、99個以下剥がれた(1/100~99/100)。
レベルC:100個のうち、100個とも剥がれた(100/100)。
ここで、判定がレベルAである場合を、実使用上問題ないレベル(常温常湿下における密着性が高い)と判断した。
レベルa:100個のうち、1個も剥がれなかった(0/100)。
レベルb:100個のうち、1個以上、2個以下剥がれた(1/100~2/100)。
レベルc:100個のうち、3個以上、5個以下剥がれた(3/100~5/100)。
レベルd:100個のうち、6個以上、99個以下剥がれた(6/100~99/100)。
レベルe:100個のうち、100個とも剥がれた(100/100)。
ここで、判定がレベルa、レベルb、又は、レベルcである場合を、実使用上問題ないレベル(高温高湿下における密着性が高い)と判断した。
◎:常温常湿下における密着性がレベルAであり、かつ、高温高湿下における密着性がレベルaであった。
○:常温常湿下における密着性がレベルAであり、かつ、高温高湿下における密着性がレベルbであった。
△:常温常湿下における密着性がレベルAであり、かつ、高温高湿下における密着性がレベルcであった。
×:常温常湿下における密着性がレベルA又はレベルBであり、かつ、高温高湿下における密着性がレベルd又はレベルeであった。
××:常温常湿下における密着性がレベルCであり、かつ、高温高湿下における密着性がレベルeであった。
ここで、総合評価が◎、○、又は、△である場合を、実使用上問題ないレベルと判断した。
以下に、本発明の光学部材の好ましい態様の例を挙げる。各例は、本発明の要旨を逸脱しない範囲において適宜組み合わされてもよい。
2:基材
3:重合体層
4:凸部
5:重合性組成物
6:金型
P:ピッチ
Claims (10)
- 基材と、
前記基材と直に接する、複数の凸部が可視光の波長以下のピッチで設けられる凹凸構造を表面に有する重合体層とを備え、
前記基材の少なくとも前記重合体層側の表面には、トリアセチルセルロースが存在し、
前記重合体層は、活性エネルギー線の照射によって重合する重合性組成物から形成されるものであり、
前記重合性組成物は、多官能アクリレートを30重量部以上、75重量部以下、3級アミド基を有する単官能モノマーを25重量部以上、60重量部以下、及び、反応性基を有するフッ素含有化合物を0.1重量部以上、10重量部以下含有することを特徴とする光学部材。 - 前記単官能モノマーは、N-アクリロイルモルホリン、N,N-ジメチルアクリルアミド、及び、N,N-ジエチルアクリルアミドからなる群より選択される少なくとも1つのモノマーを含むことを特徴とする請求項1に記載の光学部材。
- 前記フッ素含有化合物中のフッ素原子の濃度は、20重量%以上、50重量%以下であることを特徴とする請求項1又は2に記載の光学部材。
- 前記フッ素含有化合物中のフッ素原子の濃度は、25重量%以上、45重量%以下であることを特徴とする請求項3に記載の光学部材。
- 前記フッ素含有化合物中のフッ素原子の濃度は、30重量%以上、40重量%以下であることを特徴とする請求項4に記載の光学部材。
- 前記単官能モノマーの含有量は、30重量部以上、55重量部以下であることを特徴とする請求項1~5のいずれかに記載の光学部材。
- 前記単官能モノマーの含有量は、35重量部以上、50重量部以下であることを特徴とする請求項6に記載の光学部材。
- 前記フッ素含有化合物の含有量は、0.3重量部以上、8重量部以下であることを特徴とする請求項1~7のいずれかに記載の光学部材。
- 前記フッ素含有化合物の含有量は、0.5重量部以上、5重量部以下であることを特徴とする請求項8に記載の光学部材。
- 多官能アクリレートを30重量部以上、75重量部以下、3級アミド基を有する単官能モノマーを25重量部以上、60重量部以下、及び、反応性基を有するフッ素含有化合物を0.1重量部以上、10重量部以下含有し、
活性エネルギー線の照射によって重合することを特徴とするナノインプリント用の重合性組成物。
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| JP2017532591A JP6543344B2 (ja) | 2015-08-06 | 2016-08-01 | 光学部材、及び、ナノインプリント用の重合性組成物 |
| US15/743,373 US10471692B2 (en) | 2015-08-06 | 2016-08-01 | Optical member and polymerizable composition for nanoimprinting |
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| WO2018012340A1 (ja) * | 2016-07-12 | 2018-01-18 | シャープ株式会社 | 防汚性フィルム |
| WO2018151060A1 (ja) * | 2017-02-17 | 2018-08-23 | シャープ株式会社 | 防汚性フィルム |
| WO2018155317A1 (ja) * | 2017-02-23 | 2018-08-30 | シャープ株式会社 | 防汚性フィルム |
| WO2018173867A1 (ja) * | 2017-03-21 | 2018-09-27 | シャープ株式会社 | 防汚性フィルム |
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| JP7666513B2 (ja) | 2020-08-07 | 2025-04-22 | Agc株式会社 | 光学素子、及びその製造方法 |
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| Publication number | Publication date |
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| JP6543344B2 (ja) | 2019-07-10 |
| US10471692B2 (en) | 2019-11-12 |
| JPWO2017022701A1 (ja) | 2018-05-24 |
| US20180201001A1 (en) | 2018-07-19 |
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