JP6189377B2 - Optical member and polymerizable composition for nanoimprint - Google Patents

Description

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.

Various optical members having antireflection properties have been studied (for example, see Patent Documents 1 and 2). In particular, it is known that an optical member having a nanometer-sized uneven structure (nanostructure) has excellent antireflection properties (see, for example, Patent Document 3). 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.

JP 2007-291372 A JP 2008-106190 A International Publication No. 2013/005769

Examples of such an optical member include a configuration in which a polymer layer having antireflection properties is disposed on a base material. As 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. Moreover, in order to implement | achieve the display apparatus which has antireflection property, the base material of such an optical member and the polarizing plate of a display apparatus may be bonded together through the adhesive agent made from polyvinyl alcohol (PVA). However, when the present inventors examined, the adhesive made from polyvinyl alcohol is the surface of the base material containing triacetyl cellulose and the surface of the base material containing triacetyl cellulose subjected to primer treatment. It turns out that there is a problem that does not adhere. Therefore, with a protective film attached to the surface of the optical member on the polymer layer side, the surface on the base material side containing triacetyl cellulose is subjected to saponification treatment, thereby improving the adhesiveness with the polyvinyl alcohol adhesive. It was thought to increase.

However, in the method as described above, it is necessary to use a protective film to prevent the surface of the optical member on the polymer layer side from being subjected to saponification treatment. I understood. Moreover, since the protective film will be discarded later, it has been found that there is a problem that an environmental load is applied. For this reason, it is conceivable to improve the adhesiveness with an adhesive made of polyvinyl alcohol by using a base material containing triacetyl cellulose that has been subjected to saponification treatment in advance, instead of placing a protective film and performing saponification treatment. It was.

However, when saponification treatment is performed on a substrate containing triacetylcellulose, its polarity increases and the difference in solubility parameter from the polymerizable composition constituting the polymer layer increases, so that adhesion to the polymer layer is increased. It has been found that there is a problem that decreases. On the other hand, the present inventors examined increasing the polarity of the polymer layer in order to reduce the difference between the solubility parameters of the two. However, it has been found that when the polarity of the polymer layer becomes too high, white turbidity occurs due to moisture absorption, and the transparency of the optical member (polymer layer) decreases.

As described above, the conventional optical member having a base material containing triacetyl cellulose that has been previously saponified includes triacetyl cellulose that has been subjected to saponification while suppressing a decrease in transparency. There existed a subject of suppressing the fall of the adhesiveness of a base material and a polymer layer. However, no means for solving the above problem has been found.

For example, Patent Document 3 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 is no description relating to a decrease in adhesion when using a base material containing triacetylcellulose to which the above has been applied, and the above problem has not been solved. Similarly, the inventions described in Patent Documents 1 and 2 do not solve the above problem.

The present invention has been made in view of the above situation, and while suppressing the decrease in transparency, the decrease in the adhesion between the saponified triacetylcellulose-containing substrate and the polymer layer is suppressed. Another object is to provide an optical member. Also provided is a polymerizable composition for nanoimprint that constitutes a polymer layer that suppresses a decrease in adhesion to a substrate containing saponified triacetyl cellulose while suppressing a decrease in transparency. It is intended.

The inventors of the present invention have studied various optical members in which the decrease in the adhesion between the substrate containing the acetylated triacetyl cellulose and the polymer layer is suppressed while the decrease in transparency is suppressed. Attention was focused on a composition in which the polymerizable composition constituting the polymer layer contains a component having a strong cohesive force with triacetyl cellulose subjected to saponification treatment together with a polyfunctional acrylate. Further, according to the monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule, saponified triacetyl cellulose while suppressing a decrease in transparency of the optical member (polymer layer) It was found that the cohesive strength with As a result, the polymerizable composition contains a polyfunctional acrylate and a monofunctional monomer having at least one amide group and one hydroxyl group in a molecule at a predetermined ratio, so that an optical member (polymer layer) It was found that the decrease in the adhesion between the polymer layer and the base material containing triacetylcellulose subjected to the saponification treatment was suppressed while the decrease in transparency of the polymer was suppressed. As a result, the inventors have conceived that the above problems can be solved brilliantly and have reached the present invention.

That is, 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. A saponified triacetyl cellulose is present on at least the surface of the substrate 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 polymerizable composition is 40 parts by weight or more and 70 parts by weight or less of polyfunctional acrylate, and 30 parts by weight or more of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule, An optical member containing 60 parts by weight or less may be used.

Another embodiment of the present invention is a polyfunctional acrylate of 40 parts by weight or more and 70 parts by weight or less, and a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule, 30 parts by weight or more, It may be a polymerizable composition for nanoimprint, which is contained in an amount of at most parts by weight and polymerizes by irradiation with active energy rays.

ADVANTAGE OF THE INVENTION According to this invention, the optical member by which the fall of the adhesiveness of the base material and polymer layer containing the triacetyl cellulose which performed the saponification process was suppressed can be provided, the transparency fall being suppressed. . Also provided is a polymerizable composition for nanoimprint that constitutes a polymer layer that suppresses a decrease in adhesion to a substrate containing saponified triacetyl cellulose while suppressing a decrease in transparency. Can do.

It is a cross-sectional schematic diagram which shows the optical member of embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing process of the optical member of embodiment (process ad).

Embodiments will be described below, and the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited to these embodiments. Moreover, each structure of embodiment may be suitably combined in the range which does not deviate from the summary of this invention, and may be changed.

[Embodiment]
FIG. 1 is a schematic cross-sectional view illustrating an optical member according to an embodiment. As shown in FIG. 1, 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.

Saponified triacetyl cellulose (TAC) is present on at least the surface of the substrate 2 on the polymer layer 3 side. The saponification rate of the saponified triacetyl cellulose is preferably 80% or more, more preferably 90% or more, and particularly preferably 100%. The saponification rate can be known, for example, by FT-IR measurement using the ATR method (total reflection measurement method). The surface of the base material 2 on the polymer layer 3 side may not be subjected to surface treatment, and may be a surface such as a cleaning treatment as long as it does not change the chemical structure of the saponified triacetyl cellulose. Processing may be performed. On the other hand, the surface of the substrate 2 on the polymer layer 3 side is not subjected to surface treatment such as corona discharge treatment that changes the chemical structure of the saponified triacetyl cellulose. Moreover, since the base material 2 and the polymer layer 3 are in direct contact, a layer by surface treatment (for example, a primer layer by primer treatment) is formed on the surface of the base material 2 on the polymer layer 3 side. There is nothing. The substrate 2 may be a substrate composed of only triacetyl cellulose and at least a surface of the substrate 2 on the polymer layer 3 side subjected to saponification treatment. As long as the chemical structure of the existing triacetyl cellulose subjected to the saponification treatment does not change, an additive such as a plasticizer may be appropriately contained.

The shape of the substrate 2 is not particularly limited, and examples thereof include a film shape and a sheet shape. When the optical member 1 is formed into a film, a film-like substrate 2 may be used, and a saponified triacetyl cellulose film (TAC film) is preferably used. Moreover, the form in which the base material 2 comprises a part of polarizing plate is preferable.

Although 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. In this specification, 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 40 parts by weight or more and 70 parts by weight or less, and a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (hereinafter also simply referred to as a monofunctional monomer). .) Is contained in an amount of 30 to 60 parts by weight. According to such a structure, the polymeric composition for nanoimprint which comprises the polymer layer 3 which suppresses the fall of adhesiveness with the base material 2, suppressing the fall of transparency is obtained. As a result, it is possible to obtain the optical member 1 in which the decrease in the adhesion between the substrate 2 and the polymer layer 3 is suppressed while the decrease in transparency is suppressed.

Examples of the polyfunctional acrylate include pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated (4 mol adduct) bisphenol A diacrylate, epoxy acrylate Etc. Known examples of pentaerythritol triacrylate include polyfunctional acrylate (product name: A-TMM-3LM-N) manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of known ethoxylated pentaerythritol tetraacrylate include polyfunctional acrylate (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. Examples of known tripropylene glycol diacrylate include polyfunctional acrylate (product name: APG-200) manufactured by Shin-Nakamura Chemical Co., Ltd. Known examples of ethoxylated (4 mol adduct) bisphenol A diacrylate include, for example, polyfunctional acrylate (product name: A-BPE-4) manufactured by Shin-Nakamura Chemical Co., Ltd. Known epoxy acrylates include, for example, Kyoeisha Chemical Co., Ltd. polyfunctional acrylate (product name: epoxy ester 70PA), Kyoeisha Chemical Co., Ltd. polyfunctional acrylate (product name: epoxy ester 80MFA), and the like. Of these, polyfunctional acrylates having a hydroxyl group, such as pentaerythritol triacrylate and epoxy acrylate, are preferable from the viewpoint of sufficiently improving the adhesion to saponified triacetyl cellulose. 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 40 parts by weight or more and 70 parts by weight or less. When the content of the polyfunctional acrylate is less than 40 parts by weight, the content of the monofunctional monomer is relatively increased. As a result, since the polarity of the polymer layer 3 becomes too high, white turbidity occurs due to moisture absorption, and the transparency of the optical member 1 (polymer layer 3) is lowered. When the content of the polyfunctional acrylate is more than 70 parts by weight, the content of the monofunctional monomer is relatively decreased. As a result, the amount of amide groups and hydroxyl groups in the polymer layer 3 becomes too small, and the adhesion between the substrate 2 and the polymer layer 3 decreases. When 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 at least one amide group and one hydroxyl group in one molecule. According to such a monofunctional monomer, the cohesive force with the saponified triacetyl cellulose is strengthened, so that the polymer layer 3 having high adhesion to the base material 2 while suppressing a decrease in transparency. A polymerizable composition for nanoimprinting is obtained. As a result, the optical member 1 having high adhesion between the base material 2 and the polymer layer 3 can be obtained while suppressing a decrease in transparency.

Examples of the monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule include N- (2-hydroxyethyl) acrylamide, N- (hydroxymethyl) acrylamide, and N- (4-hydroxyphenyl) methacryl. Amide, N-acryloylamide-ethoxyethanol, N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propenamide, N- (1-methyl-2-hydroxyethyl) acrylamide, N-methylene-3 -Hydroxyacrylamide etc. are mentioned. Known examples of N- (2-hydroxyethyl) acrylamide include a monofunctional monomer (product name: HEAA (registered trademark)) manufactured by KJ Chemicals. Known examples of N- (hydroxymethyl) acrylamide include a monofunctional monomer (product code: M0574) manufactured by Tokyo Chemical Industry Co., Ltd. Examples of known N- (4-hydroxyphenyl) methacrylamide include monofunctional monomers (product code: H1164) manufactured by Tokyo Chemical Industry Co., Ltd. Known examples of N-acryloylamide-ethoxyethanol include a monofunctional monomer (product code: 12059) manufactured by Sigma-Aldrich. Known examples of N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propenamide include, for example, a monofunctional monomer manufactured by BOC Sciences (product name: N- [Tris (hydroxymethyl)) Methyl] acrylamide) and the like. 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- (2-hydroxyethyl) acrylamide and N- (hydroxymethyl) acrylamide.

The content of the monofunctional monomer is 30 parts by weight or more and 60 parts by weight or less. When the content of the monofunctional monomer is less than 30 parts by weight, the amount of amide groups and hydroxyl groups in the polymer layer 3 becomes too small, and the adhesion between the substrate 2 and the polymer layer 3 decreases. End up. When 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 white turbidity occurs due to moisture absorption and the transparency of the optical member 1 (polymer layer 3) decreases. Resulting in. From the viewpoint of sufficiently suppressing the decrease in transparency of the optical member 1 (polymer layer 3) and the decrease in adhesion between the substrate 2 and the polymer layer 3, the content of the monofunctional monomer is 35 parts by weight. The content is preferably 55 parts by weight or less, more preferably 40 parts by weight or more and 50 parts by weight or less. When 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 polymerizable composition may further contain 0.1 to 10 parts by weight of a fluorine-containing compound having a reactive group (hereinafter also simply referred to as a fluorine-containing compound). 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.

In the present specification, 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.

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. For this reason, it is possible to suppress a decrease in the adhesion between the substrate 2 and the polymer layer 3 due to moisture absorption, particularly in an environment where moisture is easily absorbed, such as under high humidity. Furthermore, since 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 adhesion between the substrate 2 and the polymer layer 3 is improved. The decrease can be suppressed.

Further, according to the fluorine-containing compound having a reactive group, 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. As a result, 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. From the viewpoint of obtaining the optical member 1 having sufficiently high 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.

An example of the fluorine-containing monomer that is a constituent component of the fluorine-containing compound is represented by the following general formula (A).
R ^f1 -R ² -D ¹ (A)
In the general formula (A), 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. Represents. 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.

Examples of the fluorine-containing monomer represented by the general formula (A) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, and 2-perfluorobutyl. Ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexyl ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctyl ethyl acrylate, 3-perfluorooctyl-2 -Hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5 Methylhexylethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl Acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-par Fluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropylene Methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3 -Perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octa Fluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyl trifluoro Examples include ethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol, and the like.

Moreover, as a suitable material of a fluorine-containing monomer, the material which has a fluoro polyether part is mentioned, for example. 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).
_{CF n1 H (3-n1)} - (CF n2 H (2-n2)) k O- (CF n3 H (2-n3)) m O- (B)
_{- (CF n4 H (2-} n4)) p O- (CF n5 H (2-n5)) s O- (C)
In the general formulas (B) and (C), n1 is an integer of 1 to 3, n2 to n5 are 1 or 2, and 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, n3 and n5 are 1 or 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. When the number of carbon atoms is less than 4, there is a concern that the surface energy is reduced. When the number of carbon atoms is more than 12, there is a concern that the solubility in a solvent is lowered. In addition, the fluorine-containing monomer may have a plurality of fluoropolyether sites per molecule.

Known fluorine-containing compounds having a reactive group include, for example, a fluorine-based additive (product name: OPTOOL DAC-HP) manufactured by Daikin Industries, Ltd., and a fluorine-based additive (product name: Afluid) manufactured by Asahi Glass Co., Ltd. ), DIC's fluorinated additive (product name: MegaFac RS-76-NS), DIC's fluorinated additive (Product name: MegaFac RS-90), Neos' fluorinated additive (Product name: FERENTENT 601AD), fluorinated additive (product name: C10GACRY) manufactured by Yushi Co., Ltd., and fluorinated additive (product name: C8HGOL) manufactured by Yushi Co., Ltd. The fluorine-containing compound is preferably one that is polymerized by ultraviolet rays, and preferably has a —OCF ₂ — chain and / or a ═NCO— chain. 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 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 30% by weight or more and 40% by weight or less. More preferably, it is as follows. When the 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. Further, white turbidity due to moisture absorption is likely to occur, and there is a concern that the transparency of the optical member 1 (polymer layer 3) is lowered. When the concentration of fluorine atoms in the fluorine-containing compound is higher than 50% by weight, the polarity of the fluorine-containing compound becomes too low, the compatibility with the monofunctional monomer in the polymerizable composition deteriorates, and There is concern about uneven distribution. As a result, fluorine atoms are less likely to be oriented on the surface of the polymer layer 3 opposite to the substrate 2, so that there is a concern that the adhesion between the substrate 2 and the polymer layer 3 is reduced due to moisture absorption. Further, white turbidity due to moisture absorption is likely to occur, and there is a concern that the transparency of the optical member 1 (polymer layer 3) is lowered.

The content of the fluorine-containing compound is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.3 parts by weight or more and 8 parts by weight or less, 0.5 parts by weight or more, More preferably, it is 5 parts by weight or less. When 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 is small, and it becomes easy to absorb moisture, so that the substrate 2 and the polymer layer 3 are adhered by moisture absorption. There is a concern that the sex will decline. Further, white turbidity due to moisture absorption is likely to occur, and there is a concern that the transparency of the optical member 1 (polymer layer 3) is lowered. When 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. Therefore, on the surface of the polymer layer 3 on the substrate 2 side, the amounts of amide groups and hydroxyl groups are relatively reduced, and the adhesion between the substrate 2 and the polymer layer 3 is reduced. When 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 further contain additives such as a polymerization initiator as appropriate. Examples of the polymerization initiator 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. As the photopolymerization initiator, for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used. Examples of such a photopolymerization initiator 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. And benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone. Known photopolymerization initiators include BASF photopolymerization initiator (product name: IRGACURE 819), BASF photopolymerization initiator (product name: LUCIRIN TPO), and the like.

The polymerizable composition preferably does not contain a solvent. That is, the polymerizable composition is preferably a solventless system. When 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. On the other hand, when the polymerizable composition contains a solvent, the fluorine-containing compound is excessively mixed even if the fluorine-containing compound is contained in order to reduce the hygroscopicity, and the fluorine atom becomes a group of the polymer layer 3. There is a concern that it is difficult to orient on the surface opposite to the material 2. As a result, there is a concern that the adhesion between the base material 2 and the polymer layer 3 is reduced due to moisture absorption. Moreover, when 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, but the thickness of the polymer layer 3 is preferably thin from the viewpoint of orienting amide groups and hydroxyl groups at a high concentration on the surface of the polymer layer 3 on the substrate 2 side. Specifically, it is preferably 5.0 μm or more and 20.0 μm 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. Further, 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. In FIG. 1, 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. In the present specification, the pitch of the convex portion is within a 1 μm 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. In addition, the measurement of the pitch of a convex part uses the osmium coater (product name: Neoc-ST) by Meiwaforsys, and the osmium oxide VIII (thickness: 5 nm) by Wako Pure Chemical Industries Ltd. on an uneven structure. 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. . In the present specification, 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. However, when selecting ten convex portions, the convex portion having a defect or a deformed portion (such as a portion deformed when preparing a sample) is excluded. As the sample, a sample sampled in a region where there is no specific defect of the optical member is used. For example, when the optical member is a roll produced continuously, a sample sampled near the center is used. . In addition, the measurement of the height of a convex part uses the osmium coater (product name: Neoc-ST) by Meiwaforsys, and the osmium oxide VIII (thickness: 5 nm) by Wako Pure Chemical Industries on an uneven structure. Was carried out in a state of coating.

Although 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. In this specification, the aspect ratio of a convex part is the pitch of the convex part measured by the method as mentioned above using the scanning electron microscope (product name: S-4700) by Hitachi High-Technologies Corporation as a measuring machine. 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.

From the above, according to the optical member of the embodiment, the polymerizable composition constituting the polymer layer 3 has a polyfunctional acrylate of 40 parts by weight or more and 70 parts by weight or less, and an amide group and a hydroxyl group in one molecule. Since the monofunctional monomer having one or more each of 30 parts by weight or more and 60 parts by weight or less is contained, the lowering of the adhesion between the base material 2 and the polymer layer 3 is suppressed while the lowering of the transparency is suppressed. The optical member 1 is obtained. Moreover, since the polymer layer 3 has the uneven structure in which the some convex part 4 is provided with the pitch P below the wavelength of visible light on the surface, the optical member 1 excellent in antireflection property is obtained.

Next, the manufacturing process of the optical member of the embodiment will be exemplified with reference to FIG. FIG. 2 is a schematic cross-sectional view for explaining a manufacturing process of the optical member of the embodiment (steps a to d).

(A) Application of polymerizable composition First, 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.

(B) Formation of concavo-convex structure As shown in FIG. 2 (b), the mold 6 is pressed against the applied polymerizable composition 5 from the side opposite to the substrate 2 and bonded to the polymerizable composition 5. An uneven structure is formed on the surface opposite to the substrate 2.

(C) 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). As a result, 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. Moreover, the frequency | 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. As a result, the optical member 1 as shown in FIG. 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.

As the substrate 2, for example, a triacetyl cellulose film that has been saponified by immersing it in an alkaline solution can be used.

Examples of the alkaline solution include a sodium hydroxide (NaOH) aqueous solution and a potassium hydroxide (KOH) aqueous solution. The normality of the alkaline solution is preferably 0.5 N or more and 4.0 N or less, more preferably 1.0 N or more and 3.0 N or less, from the viewpoint of efficiently performing the saponification treatment. The liquid temperature of the alkaline solution is preferably 30 ° C. or higher and 70 ° C. or lower, more preferably 40 ° C. or higher and 60 ° C. or lower, from the viewpoint of efficiently performing the saponification treatment. The immersion time is preferably 30 seconds or longer and 300 seconds or shorter, and more preferably 60 seconds or longer and 240 seconds or shorter from the viewpoint of efficiently performing the saponification treatment. In order to prevent the alkali component from remaining after the saponification treatment, the triacetylcellulose film is preferably washed with water or immersed in a dilute acid to neutralize the alkali component.

As 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. For example, 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. By performing the mold release treatment on the mold 6, the mold 6 can be easily peeled from the polymer layer 3 in the step (d). Further, when the surface energy of the mold 6 can be lowered and the polymerizable composition 5 contains a fluorine-containing compound, when the mold 6 is pressed against the polymerizable composition 5 in the step (b). The fluorine atoms can be suitably oriented on the surface of the polymerizable composition 5 opposite to the substrate 2. 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.

Examples of the release agent include fluorine-based, silicon-based, and phosphate-based release agents, and fluorine-based release agents are preferable. When the polymerizable composition 5 contains a fluorine-containing compound, if a fluorine-based mold release agent is used, the interaction with the fluorine-containing compound becomes strong, and the fluorine atom is opposite to the substrate 2 of the polymerizable composition 5. It can be more suitably oriented on the side surface. As a well-known thing among fluorine-type mold release agents, the fluorine-type mold release agent (product name: Optool AES4) by Daikin Industries, Ltd. etc. are mentioned, for example.

In the manufacturing process described above, for example, if the substrate 2 is formed into a roll, the steps (a) to (d) can be performed continuously and efficiently.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1
The optical member of Example 1 was produced by the following manufacturing process.

(A) Application of polymerizable composition First, 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.

As the base material 2, what was produced by the following method was used. First, it is immersed in an aqueous potassium hydroxide solution (normality: 2.0 N) at a liquid temperature of 50 ° C. for 2 minutes in a triacetyl cellulose film (product name: TAC-TD80U) manufactured by Fuji Film with a thickness of 80 μm. Saponification treatment was performed. Thereafter, it was washed with water and dried in an environment at a temperature of 23 ° C. to produce a saponified triacetyl cellulose film (base material 2).

As 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 | subjected to each material shows content of each material. The polymerizable composition 5 was a solventless system.

<Multifunctional acrylate>
Pentaerythritol triacrylate: 21.6 parts by weight As the pentaerythritol triacrylate, a polyfunctional acrylate (product name: A-TMM-3LM-N) manufactured by Shin-Nakamura Chemical Co., Ltd. was used.
Epoxy acrylate: 32.4 parts by weight As the epoxy acrylate, polyfunctional acrylate (product name: epoxy ester 80MFA) manufactured by Kyoeisha Chemical Co., Ltd. was used.

<Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 44 parts by weight As N- (2-hydroxyethyl) acrylamide, a monofunctional monomer (product name: HEAA) manufactured by KJ Chemicals was used.

<Fluorine-containing compound>
What was produced with the following method was used. First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
-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 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) by Nippon Kasei Co., Ltd. was used.
N-acryloylmorpholine: 10 parts by weight As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO (registered trademark)) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI (registered trademark)) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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. Here, 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 (product name: SHODEX GPC SYSTEM-11)
Column: 3 columns manufactured by Tosoh Corporation (product name: TSKgel αMXL) 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

(Concentration of fluorine atom in fluorine-containing compound)
To 100 parts by weight of the fluorine-containing compound solution, 0.5 part by weight of a photopolymerization initiator (product name: LUCIRIN TPO) manufactured by BASF was added and dissolved by stirring. Next, the obtained solution was poured into a polytetrafluoroethylene (PTFE) cylindrical frame (diameter: 30 mm, thickness: 1 mm), and then irradiated with ultraviolet rays (irradiation amount: 1 J / cm ² ) to form a cylindrical shape. A cured product film was prepared. Then, 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. The concentration of fluorine atoms in the fluorine-containing compound was determined by measuring the strength of fluorine atoms in the compound.

<Polymerization initiator>
-Photopolymerization initiator: 0.5 part by weight As the photopolymerization initiator, a photopolymerization initiator manufactured by BASF (product name: LUCIRIN TPO) was used.

(B) Formation of concavo-convex structure The polymerizable composition 5 is pressed and bonded to the coated polymerizable composition 5 from the side opposite to the base material 2 so that no air bubbles enter, and the base material 2 of the polymerizable composition 5 and Formed an uneven structure on the opposite surface.

As 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 μm. 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. Specifically, 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. A large number of minute holes (concave portions) having a shape (tapered shape) that narrows toward the surface are formed, and as a result, a mold 6 having an uneven structure is obtained. 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. When the metal mold | 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.

(C) The polymerizable composition 5 on which the cured concavo-convex structure of the polymerizable composition was formed was cured by being irradiated with ultraviolet rays from the substrate 2 side (polymerized). As a result, the polymer layer 3 was formed. Irradiation with ultraviolet rays has ^two specifications: when the irradiation amount is 1 J / cm ² (hereinafter also referred to as specification 1) and when it is 0.5 J / cm ² (hereinafter also referred to as specification 2). went. The thickness of the polymer layer 3 was 12.5 μm.

(D) Mold release The mold 6 was released from the polymer layer 3. As a result, the optical member 1 was completed. The surface specification of the optical member 1 was as follows.
Shape of convex portion 4: Pitch P of bell-shaped convex portion 4: 200 nm
Height of convex part 4: 200 nm
Convex part 4 aspect ratio: 1

(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- (hydroxymethyl) acrylamide. As N- (hydroxymethyl) acrylamide, a monofunctional monomer (product code: M0574) manufactured by Tokyo Chemical Industry Co., Ltd. was used. In the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (44 parts by weight of N- (hydroxymethyl) acrylamide contained as a monofunctional monomer) And 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(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- (4-hydroxyphenyl) methacrylamide. As N- (4-hydroxyphenyl) methacrylamide, a monofunctional monomer (product code: H1164) manufactured by Tokyo Chemical Industry Co., Ltd. was used. In the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (4-hydroxyphenyl) methacrylamide incorporated as monofunctional monomers) 44 parts by weight and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

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: 27.6 parts by weight Epoxy acrylate: 41.4 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 29 parts by weight The polymerizable composition 5 has a total of 30 parts by weight (monofunctional monomer) of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule. N- (2-hydroxyethyl) acrylamide 29 parts by weight and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the fluorine-containing compound solution.

(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: 23.6 parts by weight Epoxy acrylate: 35.4 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 39 parts by weight Polymerizable composition 5 contains 40 parts by weight (monofunctional monomer) of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule. N- (2-hydroxyethyl) acrylamide 39 parts by weight and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the fluorine-containing compound solution.

(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: 19.6 parts by weight Epoxy acrylate: 29.4 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 49 parts by weight The polymerizable composition 5 contains 50 parts by weight (monofunctional monomer) of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule. 49 parts by weight of N- (2-hydroxyethyl) acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound.

(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: 25.6 parts by weight Epoxy acrylate: 38.4 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 34 parts by weight The polymerizable composition 5 contains 35 parts by weight (monofunctional monomer) of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule. As a total of 34 parts by weight of N- (2-hydroxyethyl) acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound.

(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 monofunctional monomer were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 17.6 parts by weight Epoxy acrylate: 26.4 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 54 parts by weight The polymerizable composition 5 has a total of 55 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (monofunctional monomer) As a mixture of 54 parts by weight of N- (2-hydroxyethyl) acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound.

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 monofunctional monomer were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 16.0 parts by weight Epoxy acrylate: 24.0 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 59 parts by weight The polymerizable composition 5 contains 60 parts by weight (monofunctional monomer) of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule. N- (2-hydroxyethyl) acrylamide 59 parts by weight and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the fluorine-containing compound solution.

(Example 10)
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: 16.0 parts by weight Epoxy acrylate: 24.0 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 58 parts by weight The polymerizable composition 5 contains 59 parts by weight (monofunctional monomer) of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule. As a mixture of 58 parts by weight of N- (2-hydroxyethyl) acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the fluorine-containing compound solution.

(Example 11)
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: 28.0 parts by weight Epoxy acrylate: 42.0 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 30 parts by weight <fluorine-containing compound>: 0 parts by weight The polymerizable composition 5 has a monofunctional monomer having at least one amide group and one hydroxyl group in one molecule. 30 parts by weight (30 parts by weight of N- (2-hydroxyethyl) acrylamide contained as a monofunctional monomer) was contained, and no fluorine-containing compound having a reactive group was contained.

(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 fluorine-containing compound were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 22.0 parts by weight Epoxy acrylate: 33.0 parts by weight <fluorine-containing compound>: 0.07 part by weight In this example, N- ( A solution of a fluorine-containing compound to which 1 part by weight of 2-hydroxyethyl) acrylamide was added was prepared. Then, 1.07 parts by weight of the obtained fluorine-containing compound solution was converted into the polymerizable composition 5, that is, 0.07 parts by weight of the fluorine-containing compound when converted to solid content. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(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 fluorine-containing compound were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 22.0 parts by weight Epoxy acrylate: 32.9 parts by weight <fluorine-containing compound>: 0.1 part by weight In this example, N- ( A solution of a fluorine-containing compound to which 1 part by weight of 2-hydroxyethyl) acrylamide was added was prepared. And 1.1 parts by weight of the fluorine-containing compound was contained in the polymerizable composition 5 when converted to 1.1 parts by weight of the resulting solution of the fluorine-containing compound, that is, the solid content. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(Example 14)
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: 17.2 parts by weight Epoxy acrylate: 25.8 parts by weight <Fluorine-containing compound>: 12 parts by weight In this example, N- (2-hydroxyethyl) was added to 12 parts by weight of the fluorine-containing compound. ) A solution of a fluorine-containing compound to which 1 part by weight of acrylamide was added was prepared. Then, 13 parts by weight of the resulting fluorine-containing compound solution, that is, 12 parts by weight of the fluorine-containing compound was converted into the solid content in the polymerizable composition 5. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(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 fluorine-containing compound were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 18.0 parts by weight Epoxy acrylate: 27.0 parts by weight <Fluorine-containing compound>: 10 parts by weight In this example, N- (2-hydroxyethyl) was added to 10 parts by weight of the fluorine-containing compound. ) A solution of a fluorine-containing compound to which 1 part by weight of acrylamide was added was prepared. Then, 11 parts by weight of the obtained fluorine-containing compound solution, that is, 10 parts by weight of the fluorine-containing compound was converted into the solid content in the polymerizable composition 5. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the 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 fluorine-containing compound were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 21.9 parts by weight Epoxy acrylate: 32.8 parts by weight <Fluorine-containing compound>: 0.3 part by weight In this example, N- ( A solution of a fluorine-containing compound to which 1 part by weight of 2-hydroxyethyl) acrylamide was added was prepared. Then, 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. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(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 fluorine-containing compound were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 18.8 parts by weight Epoxy acrylate: 28.2 parts by weight <Fluorine-containing compound>: 8 parts by weight In this example, N- (2-hydroxyethyl) was added to 8 parts by weight of the fluorine-containing compound. ) A solution of a fluorine-containing compound to which 1 part by weight of acrylamide was added was prepared. Then, 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. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(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: 21.8 parts by weight Epoxy acrylate: 32.7 parts by weight <Fluorine-containing compound>: 0.5 part by weight In this example, N- ( A solution of a fluorine-containing compound to which 1 part by weight of 2-hydroxyethyl) acrylamide was added was prepared. And 1.5 parts by weight of the obtained fluorine-containing compound solution was converted into the polymerizable composition 5, that is, 0.5 parts by weight of the fluorine-containing compound was converted into the solid content. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(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: 20.0 parts by weight Epoxy acrylate: 30.0 parts by weight <Fluorine-containing compound>: 5 parts by weight In this example, N- (2-hydroxyethyl) was added to 5 parts by weight of the fluorine-containing compound. ) A solution of a fluorine-containing compound to which 1 part by weight of acrylamide was added was prepared. And 6 parts by weight of the solution of the obtained fluorine-containing compound was converted into the polymerizable composition 5, that is, 5 parts by weight of the fluorine-containing compound was converted into the solid content. In addition, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(Example 20)
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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
2-Perfluorobutylethyl acrylate: 23 parts by weight As 2-perfluorobutylethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-4) manufactured by Unimatec was used.
-4-hydroxybutyl acrylate: 40 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) 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, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 21)
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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
-2-perfluorobutyl ethyl acrylate: 27 parts by weight As 2-perfluorobutyl ethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-4) manufactured by Unimatec was used.
-4-hydroxybutyl acrylate: 40 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) 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, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
2-perfluorohexyl ethyl acrylate: 85 parts by weight As 2-perfluorohexyl ethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-6) manufactured by Unimatec Co., Ltd. was used.
-4-hydroxybutyl acrylate: 10 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) by Nippon Kasei Co., Ltd. was used.
N-acryloylmorpholine: 5 parts by weight As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
-2-perfluorohexyl ethyl acrylate: 82 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: 13 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) by Nippon Kasei Co., Ltd. was used.
N-acryloylmorpholine: 5 parts by weight As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
2-Perfluorobutyl ethyl acrylate: 35 parts by weight As 2-perfluorobutyl ethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-4) manufactured by Unimatec was used.
-4-hydroxybutyl acrylate: 40 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) 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, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
2-Perfluorohexyl ethyl acrylate: 65 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: 30 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) by Nippon Kasei Co., Ltd. was used.
N-acryloylmorpholine: 5 parts by weight As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
-2-perfluorohexyl ethyl acrylate: 45 parts by weight As 2-perfluorohexyl ethyl acrylate, a fluorine-containing monomer (product name: CHEMINOX FAAC-6) manufactured by Unimatec 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, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 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.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
-2-perfluorohexyl ethyl acrylate: 53 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: 37 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) by Nippon Kasei Co., Ltd. was used.
N-acryloylmorpholine: 10 parts by weight As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-2-isocyanatoethyl acrylate: 5 parts by weight As 2-isocyanatoethyl acrylate, a monomer (product name: Karenz AOI) manufactured by Showa Denko KK was used.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine-containing compound solution) in which the solid content (fluorine-containing compound) concentration was adjusted to 50%.

In this example, 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. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound). 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 28)
An optical member was produced in the same manner as in Example 1 except that a fluorine-based additive having no reactive group was used instead of the fluorine-containing compound.

First, 100 parts by weight of butyl acetate was charged into a separable flask (volume: 300 ml) equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. Next, the separable flask was heated in a nitrogen atmosphere, and a mixture of the following materials was dropped into the separable flask over 3 hours while maintaining the temperature of the internal space at 110 ° C.
-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 weight part As 4-hydroxybutyl acrylate, the monofunctional monomer (product name: 4HBA) by Nippon Kasei Co., Ltd. was used.
N-acryloylmorpholine: 10 parts by weight As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used.
-Radical polymerization initiator: As a 3.5 weight part radical polymerization initiator, the polymerization initiator (product name: V-601) by Wako Pure Chemical Industries Ltd. was used.

After the dropping, 0.1 parts by weight of the same radical polymerization initiator as described above was further added to the obtained reaction solution, and the reaction was allowed to proceed for 5 hours. Thereafter, the following materials were added to the obtained molten resin and reacted for 2 hours in an environment at a temperature of 70 ° C.
-1,8-diazabicyclo [5.4.0] -7-undecene: 0.3 parts by weight As 1,8-diazabicyclo [5.4.0] -7-undecene, a catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) Product code: D1270) was used.
-4-methoxyphenol: 0.1 weight part As 4-methoxyphenol, the polymerization inhibitor (product code: M0123) by Tokyo Chemical Industry Co., Ltd. was used.

After the reaction, solvent substitution of butyl acetate and N-acryloylmorpholine was performed using a rotary evaporator (product name: N-1110 type) manufactured by Tokyo Rika Kikai Co., Ltd. Then, heat treatment was performed at a temperature of 180 ° C. for 5 hours using a mini jet oven (product name: MD-92) manufactured by Toyama Sangyo Co., Ltd. After the heat treatment, N- (2-hydroxyethyl) acrylamide was added to prepare a solution (fluorine additive solution) in which the solid content (fluorine additive) concentration was adjusted to 50%.

In this example, 2 parts by weight of the resulting solution of the fluorine-based additive, that is, 1 part by weight of the fluorine-based additive was converted into the solid content in the polymerizable composition 5. Further, as apparent from the above-described contents, the polymerizable composition 5 contained 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-based additive. That is, in the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) contained as a monofunctional monomer). 44 parts by weight of acrylamide and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-based additive) were contained, and no fluorine-containing compound having a reactive group was contained. 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 29)
As a fluorine-containing compound, 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. The concentration of fluorine atoms in the fluorine-containing compound was 47% by weight. In the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) acrylamide 44 contained as a monofunctional monomer). Part by weight and the sum of 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(Example 30)
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. In the polymerizable composition 5, a total of 45 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule (N- (2-hydroxyethyl) acrylamide 44 contained as a monofunctional monomer). Part by weight and the sum of 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(Comparative Example 1)
An optical member was produced in the same manner as in Example 1 except that 44 parts by weight of N-acryloylmorpholine not having one or more amide groups and hydroxyl groups in one molecule was used instead of the monofunctional monomer. . As N-acryloylmorpholine, an amide group-containing monomer (product name: ACMO) manufactured by KJ Chemicals was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 2)
An optical member was produced in the same manner as in Example 1 except that 44 parts by weight of N-methoxymethylacrylamide not having one or more amide groups and hydroxyl groups in each molecule was used instead of the monofunctional monomer. did. As N-methoxymethylacrylamide, a monofunctional monomer (product name: NMMA) manufactured by MRC Unitech was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 3)
An optical member was prepared in the same manner as in Example 1 except that 44 parts by weight of N, N-dimethylacrylamide not having one or more amide groups and hydroxyl groups in each molecule was used instead of the monofunctional monomer. Produced. As N, N-dimethylacrylamide, an amide group-containing monomer (product name: DMAA (registered trademark)) manufactured by KJ Chemicals was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 4)
In the same manner as in Example 1, except that 44 parts by weight of Nn-butoxymethylacrylamide not having one or more amide groups and hydroxyl groups in each molecule was used instead of the monofunctional monomer, an optical member was used. Was made. As Nn-butoxymethylacrylamide, an amide group-containing monomer (product name: NBMA) manufactured by MRC Unitech Co., Ltd. was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 5)
An optical member was prepared in the same manner as in Example 1 except that 44 parts by weight of N, N-diethylacrylamide which does not have one or more amide groups and hydroxyl groups in each molecule was used instead of the monofunctional monomer. Produced. As N, N-diethylacrylamide, an amide group-containing monomer (product name: DEAA (registered trademark)) manufactured by KJ Chemicals was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 6)
An optical member was produced in the same manner as in Example 1, except that 44 parts by weight of 2-hydroxyethyl acrylate each having one or more amide groups and hydroxyl groups in one molecule was used instead of the monofunctional monomer. did. As 2-hydroxyethyl acrylate, an ester group-containing monomer (product name: HEA) manufactured by Osaka Organic Chemical Industry Co., Ltd. was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 7)
In the same manner as in Example 1 except that 44 parts by weight of 1,4-cyclohexanedimethanol monoacrylate having no more than one amide group and one hydroxyl group in each molecule was used instead of the monofunctional monomer, An optical member was produced. As 1,4-cyclohexanedimethanol monoacrylate, an ester group-containing monomer (product name: CHDMMA) manufactured by Nippon Kasei Co., Ltd. was used. In the polymerizable composition, 1 part by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (1 part by weight of N- (2-hydroxyethyl) acrylamide in a solution of a fluorine-containing compound) Contained.

(Comparative Example 8)
The composition of the polyfunctional acrylate, the monofunctional monomer, and the polymerization initiator was changed as follows, and instead of the fluorine-containing compound, a phosphoric acid ester-based additive (product of Nikko Chemicals Co., Ltd.) described in Patent Document 3 above An optical member was produced in the same manner as in Example 1 except that 0.1 part by weight of name: NIKKOL (registered trademark) TDP-2) was used. This comparative example corresponds to Example 1-14 of Patent Document 3.

<Multifunctional acrylate>
Dipentaerythritol penta (hexa) acrylate: 20.0 parts by weight As dipentaerythritol penta (hexa) acrylate, a polyfunctional acrylate (product name: A-DPH) manufactured by Shin-Nakamura Chemical Co., Ltd. was used.
Pentaerythritol (tetra) acrylate: 20.0 parts by weight As the pentaerythritol (tetra) acrylate, polyfunctional acrylate (product name: A-TMMT) manufactured by Shin-Nakamura Chemical Co., Ltd. was used.
・ Polyethylene glycol diacrylate (EO≈4 mol): 35.0 parts by weight Polyfunctional glycol acrylate (product name: A-200) manufactured by Shin-Nakamura Chemical Co., Ltd. is used as polyethylene glycol diacrylate (EO≈4 mol) It was.

<Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 25 parts by weight As N- (2-hydroxyethyl) acrylamide, a monofunctional monomer (product name: HEAA) manufactured by KJ Chemicals was used.
The polymerizable composition contains 25 parts by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (25 parts by weight of N- (2-hydroxyethyl) acrylamide contained as a monofunctional monomer). It was contained, and no fluorine-containing compound having a reactive group was contained.

<Polymerization initiator>
-Photoinitiator: 0.5 weight part As a photoinitiator, the photoinitiator (product name: IRGACURE819) by BASF Corporation was used.

(Comparative Example 9)
The content of the polyfunctional acrylate and the content of the monofunctional monomer were changed as follows, and instead of the fluorine-containing compound, a silicon surface conditioner (product of Big Chemie Japan Co., Ltd.) described in Patent Document 3 above An optical member was produced in the same manner as in Example 1 except that 1 part by weight of name: BYK-UV3500) was used.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 29.6 parts by weight Epoxy acrylate: 44.4 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 25 parts by weight of the polymerizable composition contains 25 parts by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule (as a monofunctional monomer). N- (2-hydroxyethyl) acrylamide (25 parts by weight) was contained, and no fluorine-containing compound having a reactive group was contained.

(Comparative Example 10)
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: 39.6 parts by weight Epoxy acrylate: 59.4 parts by weight <Monofunctional monomer>: 0 parts by weight In the polymerizable composition, one or more amide groups and hydroxyl groups in each molecule 1 part by weight of monofunctional monomer (1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound) was contained.

(Comparative 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 monofunctional monomer were changed as follows.
<Multifunctional acrylate>
Pentaerythritol triacrylate: 28.4 parts by weight Epoxy acrylate: 42.6 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 27 parts by weight The polymerizable composition contains a total of 28 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups per molecule (as monofunctional monomers) 27 parts by weight of N- (2-hydroxyethyl) acrylamide contained and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

(Comparative 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: 14.8 parts by weight Epoxy acrylate: 22.2 parts by weight <Monofunctional monomer>
N- (2-hydroxyethyl) acrylamide: 61 parts by weight The polymerizable composition contains a total of 62 parts by weight of monofunctional monomers each having one or more amide groups and hydroxyl groups per molecule (as monofunctional monomers) 61 parts by weight of N- (2-hydroxyethyl) acrylamide contained, and 1 part by weight of N- (2-hydroxyethyl) acrylamide in the solution of the fluorine-containing compound).

[Evaluation of optical members]
Tables 1 and 2 show evaluation results of adhesion between the base material and the polymer layer, transparency, and water repellency for the optical members of Examples 1 to 30 and Comparative Examples 1 to 12.

The adhesion between the base material and the polymer layer was evaluated by the following method when the ultraviolet irradiation in the step (c) was performed according to the specification 1 and the specification 2 described above. Here, the specification 2 (UV irradiation amount: 0.5 J / cm ² ) is a condition assuming that the adhesion is more likely to be lower than the specification 1 (UV irradiation amount: 1 J / cm ² ). First, in an environment of a temperature of 23 ° C. and a humidity of 50%, on the surface opposite to the base material of the polymer layer, a cutter knife is used to cut 11 vertical and 11 horizontal cuts at 1 mm intervals. 100 square squares (1 mm square) were carved. Then, after a polyester adhesive tape (product name: No. 31B) manufactured by Nitto Denko Corporation was crimped to the mesh portion, the adhesive tape was peeled off at a rate of 100 mm / s in a direction of 90 ° with respect to the surface of the mesh portion. . Thereafter, the peeled state of the polymer layer on the substrate was visually observed, and the number of squares from which the polymer layer on the substrate was peeled was counted. The result was indicated by “X / 100” (X is the number of cells on which the polymer layer on the substrate was peeled off). The judgment criteria were as follows.
<Adhesion in specification 1>
Level A: None of the 100 pieces peeled off (0/100).
Level B: 1 or more and 99 or less of 100 pieces were peeled off (1/100 to 99/100).
Level C: 100 pieces out of 100 pieces were peeled off (100/100).
Here, when the determination was level A, it was determined that there was no problem in actual use (high adhesion in specification 1).
<Adhesion in specification 2>
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 or more and 5 or less 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).
Here, when the determination was level a, level b, or level c, it was determined that there was no problem in actual use (high adhesion in the specification 2).

Based on the evaluation results of the adhesion in the specification 1 and the adhesion in the specification 2 by the method described above, a comprehensive evaluation on the adhesion was performed as follows.
(Double-circle): The adhesiveness in the specification 1 was level A, and the adhesiveness in the specification 2 was level a.
○: Adhesion in specification 1 was level A, and adhesion in specification 2 was level b.
(Triangle | delta): The adhesiveness in the specification 1 was the level A, and the adhesiveness in the specification 2 was the level c.
X: Adhesion in specification 1 was level A or level B, and adhesion in specification 2 was level d or level e.
XX: The adhesion in the specification 1 was level C, and the adhesion in the specification 2 was level e.
Here, the case where the overall evaluation is ◎, ○, or △ was judged as a level at which there is no problem in actual use.

Transparency evaluated the haze (diffusivity) of the optical member of each example in the specification 1. Specifically, first, haze was measured in an environment of a temperature of 23 ° C. and a humidity of 50% with respect to the optical member of each example. Next, the optical member of each example was left for 3 days in an environment of 60 ° C. and 95% humidity, and after returning to an environment of 23 ° C. and 50% humidity for 1 day, the haze was measured. did. Haze uses a haze / transmittance meter (product name: HM-150) manufactured by Murakami Color Research Laboratory Co., Ltd. with the surface opposite to the base material of the polymer layer (surface of the concavo-convex structure) facing the light source. Measured in accordance with JISK7361. As an evaluation index, change in haze before and after being left (%) = (haze before being left) − (haze after being left) was used, and the criteria were as follows.
A: Haze change was less than 0.1%.
○: Haze change was 0.1% or more and less than 0.5%.
Δ: Haze change was 0.5% or more and less than 1.0%.
X: The haze change was 1.0% or more and less than 5.0%.
Xx: The haze change was 5.0% or more.
Here, when the judgment was ◎, ○, or Δ, it was judged as a level that has no problem in actual use (high transparency).

The water repellency was evaluated by the contact angle of water with respect to the surface of the polymer layer opposite to the substrate (surface of the concavo-convex structure) in each example of the optical member in the specification 1. Specifically, first, with respect to the optical member of each example, a black acrylic plate is attached to the surface of the base material opposite to the polymer layer, and 10 μl is applied to the surface of the polymer layer opposite to the base material. Of water was added dropwise. And after leaving for 20 seconds, the contact angle was measured at 10 points at intervals of 1 second. The procedure as described above was performed at a total of three locations by changing the position where water was dropped, and the average value of the measured contact angles (10 points × 3 locations = total 30 points) was calculated. Here, as the first measurement point, the central portion of the surface of the polymer layer opposite to the substrate was selected. As 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. For the measurement of the contact angle, a contact angle measurement device (product name: DSA10-Mk2) manufactured by Kruss was used.

As shown in Table 1, all of Examples 1 to 30 had high adhesion and transparency. Among them, Examples 1-3, 5-8, 13, 16-19, 24-29 have higher adhesion and transparency, and Examples 1, 2, 5, 6, 18, 19, 26, 27 are The adhesion and transparency were particularly high.

Here, Example 1, Example 4, Example 5 in which the types of monofunctional monomers having one or more amide groups and hydroxyl groups in one molecule are the same (N- (2-hydroxyethyl) acrylamide), And comparing Example 7, the content of the monofunctional monomer was Example 4 (30 parts by weight), Example 7 (35 parts by weight), Example 5 (40 parts by weight), and Example 1 (45 parts by weight). As the number increases in the order of (part), the adhesion in the specification 2 is equal or increased. This is because the amounts of amide groups and hydroxyl groups in the polymer layer increase in the order of Example 4, Example 7, Example 5, and Example 1. On the other hand, Example 1, Example 6, Example 8, wherein the types of monofunctional monomers each having one or more amide groups and hydroxyl groups in one molecule are the same (N- (2-hydroxyethyl) acrylamide), and In comparison with Example 9, the content of the monofunctional monomer was as follows: Example 9 (60 parts by weight), Example 8 (55 parts by weight), Example 6 (50 parts by weight), Example 1 (45 parts by weight). ), The transparency was the same or increased as the order decreased. This is because the polarity of the polymer layer decreases in the order of Example 9, Example 8, Example 6, and Example 1. As described above, by optimally controlling the content of the monofunctional monomer having at least one amide group and one hydroxyl group in one molecule, it is possible to suppress a decrease in transparency. It was also found that the decrease in adhesion between the substrate and the polymer layer can be suppressed even under conditions where the adhesion is more likely to decrease. Further, from the viewpoint of sufficiently improving the transparency of the optical member (polymer layer) and the adhesion between the substrate and the polymer layer, the content of the monofunctional monomer is 35 parts by weight or more and 55 parts by weight or less. It has also been found that it is preferably 40 parts by weight or more and 50 parts by weight or less.

Moreover, when Example 1, Example 12, Example 13, Example 16, and Example 18 which are the same kind of fluorine-containing compound which has a reactive group are compared, content of a fluorine-containing compound is implemented. Example 12 (0.07 parts by weight), Example 13 (0.1 parts by weight), Example 16 (0.3 parts by weight), Example 18 (0.5 parts by weight), Example 1 (1 part by weight) ), The transparency increased or increased in order. This is because the amount of fluorine atoms in the polymer layer increases in the order of Example 12, Example 13, Example 16, Example 18, and Example 1, and the hygroscopicity is equivalent or lowered. On the other hand, when Example 1, Example 14, Example 15, Example 17, and Example 19 in which the types of fluorine-containing compounds having reactive groups are the same are compared, the content of fluorine-containing compounds is As Example 14 (12 parts by weight), Example 15 (10 parts by weight), Example 17 (8 parts by weight), Example 19 (5 parts by weight), and Example 1 (1 part by weight) decrease in order. The adhesion in 2 was equal or increased. This is because the amount of fluorine atoms in the polymer layer decreases in the order of Example 14, Example 15, Example 17, Example 19, and Example 1, and as a result, the fluorine atoms are converted into the group of the polymer layer. This is because the polymer layer is efficiently oriented on the surface opposite to the base material without being oriented much on the material side surface. That is, the amount of amide groups and hydroxyl groups on the surface of the polymer layer on the substrate side is larger in Example 1 than in Example 14. From the above, it is possible to suppress a decrease in transparency by optimally controlling the content of the fluorine-containing compound having a reactive group, and further, under the condition that the adhesiveness is more likely to decrease as in specification 2. It was also found that the decrease in adhesion between the substrate and the polymer layer can be suppressed. Further, from the viewpoint of sufficiently improving the transparency of the optical member (polymer layer) and the adhesion between the substrate and the polymer layer, the content of the fluorine-containing compound is 0.1 parts by weight or more and 10 parts by weight. It was also found that the content was preferably 0.3 parts by weight or more and 8 parts by weight or less, more preferably 0.5 parts by weight or more and 5 parts by weight or less.

Further, when Example 1, Example 20, Example 21, Example 24, and Example 26 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 20 (18% by weight), Example 21 (20% by weight), Example 24 (25% by weight), Example 26 (30% by weight), and Example 1 (37% by weight). %), The transparency was equivalent or increased. This is because the amount of fluorine atoms in the polymer layer increases in the order of Example 20, Example 21, Example 24, Example 26, and Example 1, and the hygroscopicity is equivalent or lowered. On the other hand, when Example 1, Example 22, Example 23, Example 25, and Example 27 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 (52% by weight), Example 23 (50% by weight), Example 25 (45% by weight), Example 27 (40% by weight), and Example 1 (37% by weight). %), The adhesion and transparency in the specification 2 were equal or increased. This is because the amount of fluorine atoms in the polymer layer decreases in the order of Example 22, Example 23, Example 25, Example 27, and Example 1, and as a result, the fluorine atom becomes a group of the polymer layer. This is because the polymer layer is efficiently oriented on the surface opposite to the base material without being oriented much on the material side surface. From the above, by optimally controlling the concentration of fluorine atoms in the fluorine-containing compound having a reactive group, it is possible to suppress a decrease in transparency, and the adhesion as in specification 2 is further reduced. It was found that even under easy conditions, a decrease in adhesion between the substrate and the polymer layer can be suppressed. Further, from the viewpoint of sufficiently improving the transparency of the optical member (polymer layer) and the adhesion between the substrate and the polymer layer, the concentration of fluorine atoms in the fluorine-containing compound having a reactive group is 20 wt. It was also found that the content is preferably not less than 50% by weight and not more than 50% by weight, more preferably not less than 25% by weight and not more than 45% by weight, and further preferably not less than 30% by weight and not more than 40% by weight.

Examples 1 to 10, 12 to 19, and 21 to 30 were excellent in water repellency and excellent in antifouling properties against hydrophilic dirt. On the other hand, Example 11 and Example 20 had a smaller water contact angle than the other examples. This is because the polymerizable composition constituting the polymer layer does not contain a fluorine-containing compound having a reactive group (Example 11), or the concentration of fluorine atoms in the fluorine-containing compound is too low (implementation). Example 20).

On the other hand, as shown in Table 2, all of Comparative Examples 1 to 12 had low adhesion or transparency. Comparative Examples 1 to 7 and 10 have a content of monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule as very small as 1 part by weight, and are compared with saponified triacetyl cellulose. Since the cohesive force was reduced, the adhesion was low. In Comparative Example 8 and Comparative Example 9, the content of the monofunctional monomer having one or more amide groups and hydroxyl groups in each molecule is less than 30 parts by weight, and the amide groups and hydroxyl groups in the polymer layer Since the amount was too small, the adhesion was low. Moreover, since the comparative example 8 and the comparative example 9 did not contain the fluorine-containing compound which has a reactive group, the contact angle of water was smaller than the other comparative examples, and the water repellency was inferior. In Comparative Example 11, the content of the polyfunctional acrylate is more than 70 parts by weight, and the content of the monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule is less than 30 parts by weight. As a result, the amount of amide groups and hydroxyl groups in the polymer layer was too small, and the adhesion was low. In Comparative Example 12, the content of the polyfunctional acrylate is less than 40 parts by weight, and the content of the monofunctional monomer having one or more amide groups and hydroxyl groups in each molecule is more than 60 parts by weight. As a result, since the polarity of the polymer layer becomes too high, white turbidity occurs due to moisture absorption, and the transparency is low.

[Appendix]
The example of the preferable aspect of the optical member of this invention is given to the following. Each example may be appropriately combined without departing from the scope of the present invention.

The monofunctional monomer may include at least one monomer selected from the group consisting of N- (2-hydroxyethyl) acrylamide and N- (hydroxymethyl) acrylamide. Thereby, the said monofunctional monomer can be utilized effectively.

The polymerizable composition may further contain 0.1 to 10 parts by weight of a fluorine-containing compound having a reactive group. Thereby, since a fluorine atom is orientated and fixed to the surface on the opposite side to the said base material of the said polymer layer, hygroscopicity can be reduced. For this reason, it is possible to suppress a decrease in adhesion between the base material and the polymer layer due to moisture absorption, particularly in an environment where moisture absorption is easy, such as under high humidity. Moreover, according to the said fluorine-containing compound, the surface energy of the said polymer layer can be made low, and the said optical member excellent in water repellency is obtained by combining with the said uneven structure (moth eye structure).

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. 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 20% by weight or more and 50% by weight or less. Thereby, 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 35 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 can be suppressed more, suppressing the fall of the transparency of the said optical member (the said polymer layer) more.

The content of the monofunctional monomer may be 40 parts by weight or more and 50 parts by weight or less. Thereby, the fall of the adhesiveness of the said base material and the said polymer layer can further be suppressed, further suppressing the fall of the transparency of the said optical member (the said polymer layer).

As mentioned above, although the example of the preferable aspect of the optical member of this invention was given, what is related to the characteristic of polymerizable composition in those examples is the preferable aspect of the polymerizable composition for nanoimprint of this invention. It is also an example.

1: Optical member 2: Base material 3: Polymer layer 4: Convex part 5: Polymerizable composition 6: Mold P: Pitch

Claims (9)

A substrate;
A polymer layer having a concavo-convex structure on the surface, in which a plurality of convex portions are provided in a pitch equal to or smaller than the wavelength of visible light, in direct contact with the base material,
On the surface of at least the polymer layer side of the substrate, saponified triacetyl cellulose exists,
The polymer layer is formed from a polymerizable composition that is polymerized by irradiation with active energy rays,
The polymerizable composition includes 40 to 70 parts by weight of a polyfunctional acrylate, and 35 to 55 parts by weight of a monofunctional monomer having one or more amide groups and hydroxyl groups in one molecule. An optical member comprising: The optical system according to claim 1, wherein the monofunctional monomer includes at least one monomer selected from the group consisting of N- (2-hydroxyethyl) acrylamide and N- (hydroxymethyl) acrylamide. Element. The optical member according to claim 1, wherein the polymerizable composition further contains 0.1 to 10 parts by weight of a fluorine-containing compound having a reactive group. The optical member according to claim 3, wherein the content of the fluorine-containing compound is 0.3 parts by weight or more and 8 parts by weight or less. The optical member according to claim 4, wherein the content of the fluorine-containing compound is 0.5 parts by weight or more and 5 parts by weight or less. The optical member according to any one of claims 3 to 5, wherein the concentration of fluorine atoms in the fluorine-containing compound is 20 wt% or more and 50 wt% or less. The optical member according to claim 6, wherein the concentration of fluorine atoms in the fluorine-containing compound is 25 wt% or more and 45 wt% or less. The optical member according to claim 7, wherein the concentration of fluorine atoms in the fluorine-containing compound is 30% by weight or more and 40% by weight or less. The optical member according to any one of claims 1 to 8, wherein the content of the monofunctional monomer is 40 parts by weight or more and 50 parts by weight or less.

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