JP6811337B2 - Transmission filter and immersion exposure equipment - Google Patents

Description

The present invention relates to a transmission filter and an immersion exposure apparatus.

Conventionally, in the manufacturing process of electronic components such as integrated circuits, an illumination optical system that illuminates a reticle with light from a light source and a projection optical system that projects a reticle pattern onto a substrate (wafer) on which a resist film is formed. By exposing the substrate on which the resist film is formed and then developing it using an exposure apparatus equipped with the above, fine processing for forming a pattern on the substrate is performed. In recent years, with the increasing integration of integrated circuits, the formation of ultrafine patterns in the submicron region or the micron region has been required. Along with this, there is a tendency for the exposure wavelength to be shortened from g-line to i-line, and further to KrF excimer laser and ArF excimer laser.
Further, an immersion exposure apparatus has been proposed in which the resolution is improved by filling the space between the lower surface of the projection optical system and the surface of the substrate with a liquid (immersion liquid) such as water.
In the exposure apparatus, a protective member for protecting the optical system may be used in order to prevent the optical system including the lens from coming into contact with the substrate or the immersion liquid and being damaged or contaminated (see Patent Document 1). ).

Further, Patent Document 2 describes an optical element having a silicon oxide film on the bottom surface of an optical member at the tip of a projection optical system and a superhydrophobic film made of an alkyl ketene dimer having a fractal structure on the side surface.

In Patent Document 3, the first fine particles bonded and fixed to the surface of the glass substrate and the second fine particles bonded and fixed to the surface of the first fine particles and having a particle size smaller than that of the first fine particles are described. A water-repellent oil-repellent antifouling glass having a water-repellent oil-repellent antifouling thin film formed on the surfaces of the first and second fine particles is described.

Japanese Unexamined Patent Publication No. 2006-24706 Japanese Unexamined Patent Publication No. 2010-118678 JP-A-2010-222199

As a protective member for protecting the optical system used in the immersion exposure apparatus, it is considered desirable to use a transmission filter having a high transmittance of ultraviolet rays, which are the main exposure rays. The high transmittance of ultraviolet rays of the transmissive filter (highly transmissive ultraviolet rays) means that the transmissive filter does not easily absorb ultraviolet rays, so that the exposure durability is excellent. Even if the transmission filter is a portion other than the translucent portion (for example, a portion around the translucent portion), the exposed light wraps around due to reflection or the like, so it is desirable that the transmissive filter has high ultraviolet transparency. Further, from the viewpoint of exposure durability, it is desirable to have excellent scratch resistance.
Conventional transmission filters do not have both water repellency and exposure durability, which are important performances especially when water is used as the immersion liquid, and the exposure device is operated for replacement after a certain period of use. The outage was mandatory and the productivity was significantly poor.

An object of the present invention is to provide a transmission filter having excellent ultraviolet transmission, water repellency and scratch resistance, and an immersion exposure apparatus provided with the transmission filter.

The present inventors have speculated that it is effective to apply a film having a moth-eye structure on the surface of a base material having a high ultraviolet transmittance to a transmission filter, and as a result of repeated studies, the above problems are solved by the following means. I found out what I could do.

<1>
A transmission filter having a base material having a light transmittance of 65% or more at a wavelength of 315 nm and a water-repellent layer arranged on the base material.
The water-repellent layer includes a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and containing no fluorine atom, and particles (a2) having an average primary particle size of 150 nm or less. And a reaction product of a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group.
The content of the reaction product of the fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group is 0.05% by mass or more in the total solid content of the water-repellent layer.
The surface of the water-repellent layer opposite to the base material side has a convex portion formed by the particles (a2) and a concave portion between the convex portions.
B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions of the water-repellent layer to the distance B between the center and the concave portion between the vertices of the adjacent convex portions, is larger than 0.50.
The distance A is 315 nm or less,
A transmission filter having a water contact angle of 120 ° or more on the surface of the water-repellent layer opposite to the base material side.
<2>
The compound (a1) is a compound having at least three alkoxy groups bonded to a silicon atom in the molecule.
The resin obtained by curing the compound (a1) is a resin having a siloxane bond.
The transmission filter according to <1>.
<3>
The transmission filter according to <1> or <2>, wherein the indentation hardness of the particles (a2) is 400 MPa or more.
<4>
The transmission filter according to any one of <1> to <3>, wherein the particles (a2) are unfired silica particles, fired silica particles, or synthetic quartz particles.
<5>
The transmission filter according to any one of <1> to <4>, wherein the sliding angle of water on the surface of the water-repellent layer opposite to that of the base material is 30 ° or less.
<6>
A layer (cae) containing a resin obtained by curing particles (a2e) having an average primary particle size smaller than the particles (a2) and a compound (a1e) having at least one (meth) acryloyl group on the convex portion. And have
The transmission according to any one of <1> to <5>, wherein the surface of the layer (cae) opposite to the particle (a2) side has a convex portion formed by the particles (a2e). filter.
<7>
The transmission filter according to <6>, wherein the average primary particle size of the particles (a2e) is 5 to 50 nm.
<8>
The transmission filter according to <6> or <7>, wherein the indentation hardness of the particles (a2e) is less than 400 MPa.
<9>
The transmission filter according to any one of <6> to <8>, wherein the particles (a2e) are unfired silica particles.
<10>
The transmission filter according to any one of <1> to <9>, wherein the contact angle of water on the surface of the water-repellent layer opposite to that of the base material is 130 ° or more.
<11>
The item according to any one of <1> to <10> used for protecting the optical system of the immersion exposure apparatus that exposes an exposure object with an exposure ray transmitted through an optical system through an immersion liquid. Transmission filter.
<12>
The transmission filter according to <11>, wherein the distance A is equal to or less than the wavelength of the exposed light beam.
<13>
The transmission filter according to <12>, wherein the average primary particle size of the particles (a2) is 9/14 or less of the wavelength of the exposed light beam, and the distance A is 5/7 or less of the wavelength of the exposed light beam.
<14>
The transmission filter according to <13>, wherein the average primary particle size of the particles (a2) is 9/19 or less of the wavelength of the exposed light beam, and the distance A is 1/2 or less of the wavelength of the exposed light beam.
<15>
The transmission filter according to <14>, wherein the average primary particle size of the particles (a2) is 7/19 or less of the wavelength of the exposed light beam, and the distance A is 15/38 or less of the wavelength of the exposed light beam.
<16>
Having a hydrophilic layer in the same plane as the water-repellent layer on the base material,
The water-repellent layer and the hydrophilic layer are alternately arranged in the in-plane direction.
The shapes of the water-repellent layer and the hydrophilic layer when viewed from a direction orthogonal to the in-plane direction are triangular.
The hydrophilic layer is a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and not containing a fluorine atom, and particles (a2) having an average primary particle size of 150 nm or less. Including and
The surface of the hydrophilic layer on the side opposite to the base material side has a convex portion formed by the particles (a2) and a concave portion between the convex portions.
B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions of the hydrophilic layer to the distance B between the center and the concave portion between the vertices of the adjacent convex portions, is larger than 0.50.
The distance A is 315 nm or less,
The contact angle of water on the side of the hydrophilic layer opposite to that of the base material is 20 ° or less.
The transmission filter according to any one of <1> to <15>.
<17>
An immersion exposure apparatus that exposes an object to be exposed with an exposure ray that has passed through an optical system through an immersion liquid, and is provided with a transmission filter according to any one of <1> to <16>. Immersion exposure equipment.

According to the present invention, it is possible to provide a transmission filter having excellent ultraviolet transmission, water repellency and scratch resistance, and an immersion exposure apparatus provided with the transmission filter.

It is sectional drawing which shows an example of the transmission filter of this invention. It is sectional drawing which shows an example of the transmission filter of this invention. It is a plane schematic diagram which shows an example of the transmission filter of this invention. It is a schematic diagram for demonstrating an example of the installation method of the transmission filter of this invention. It is a schematic diagram for demonstrating an example of the manufacturing method of the transmission filter of this invention. It is a schematic diagram for demonstrating an example of the manufacturing method of the transmission filter of this invention. It is a schematic diagram for demonstrating an example of the manufacturing method of the transmission filter of this invention.

In the present specification, "(meth) acrylate" represents at least one of acrylate and methacrylate, "(meth) acrylic" represents at least one of acrylic and methacrylic, and "(meth) acryloyl" represents at least one of acryloyl and methacryloyl. Represents a kind.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

[Transparent filter]
The transmission filter of the present invention
A transmission filter having a base material having a light transmittance of 65% or more at a wavelength of 315 nm and a water-repellent layer arranged on the base material.
The water-repellent layer includes a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and containing no fluorine atom, and particles (a2) having an average primary particle size of 150 nm or less. And a reaction product of a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group.
The content of the reaction product of the fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group is 0.05% by mass or more in the total solid content of the water-repellent layer.
The surface of the water-repellent layer opposite to the base material side has a convex portion formed by the particles (a2) and a concave portion between the convex portions.
B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions of the water-repellent layer to the distance B between the center and the concave portion between the vertices of the adjacent convex portions, is larger than 0.50.
The distance A is 315 nm or less,
A transmission filter having a water contact angle of 120 ° or more on the surface of the water-repellent layer opposite to the base material side.

The application of the transmission filter of the present invention is not limited, and it is preferably used to protect the optical system. In particular, the immersion liquid exposes the object to be exposed with an exposure ray transmitted through the optical system. It is preferably used to protect the optical system of the exposure apparatus.

An example of a preferred embodiment of the transmission filter of the present invention is shown in FIG.
The transmission filter 10 of FIG. 1 has a base material 9 and a water-repellent layer 2. The water-repellent layer 2 includes particles (a2) (reference numeral 3) and layer (ca) (reference numeral 4). The particles (a2) form convex portions on the surface of the layer (ca), and there are concave portions between the convex portions. B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions to the distance B between the center between the vertices of the adjacent convex portions and the concave portion, is larger than 0.50. The concave-convex shape composed of the convex portion and the concave portion preferably has a moth-eye structure.

(Moss eye structure)
The moth-eye structure is usually a processed surface of a substance (material) for suppressing light reflection, and refers to a structure having a periodic fine structure pattern. In the transmission filter of the present invention, in addition to using a base material having a high ultraviolet transmittance, by having a moth-eye structure on the surface of the water-repellent layer, reflection of exposure light is suppressed when used in an immersion exposure apparatus. It is considered that the transmittance can be increased by doing so. Further, the high transmittance means that it is difficult to absorb the energy of the exposure light beam, and there is an advantage that it is not easily damaged by the exposure light beam and has excellent exposure durability. Further, it is considered that water repellency due to the uneven shape of the surface can be imparted.

In the water-repellent layer of the transmission filter of the present invention, the distance A is 315 nm or less, but the distance A corresponds to the period in the moth-eye structure, and when the transmission filter is used in the immersion exposure apparatus, the exposure light beam From the viewpoint of suppressing the reflection of the particles and improving the transmittance, it is preferable that the average primary particle size of the particles (a2) is 150 nm or less and the distance A is not more than the wavelength of the exposed light beam.

From the viewpoint of improving the ultraviolet transmittance, the distance A is preferably 5/7 or less of the wavelength of the exposed light beam. In this case, the average primary particle size of the particles (a2) is preferably 9/14 or less of the wavelength of the exposed light beam.
The distance A is more preferably 1/2 or less of the wavelength of the exposed light beam. In this case, the average primary particle size of the particles (a2) is preferably 9/19 or less of the wavelength of the exposed light beam. Under the above conditions, the primary diffracted light of the exposure light can be suppressed, so that the ultraviolet transmittance can be further increased.
It is more preferable that the distance A is 15/38 or less of the wavelength of the exposed light beam. In this case, the average primary particle size of the particles (a2) is preferably 7/19 or less of the wavelength of the exposed light beam. Under the above conditions, the 0th-order diffracted light of the exposed light beam can also be suppressed, so that the ultraviolet transmittance can be further increased.

In the uneven shape of the water-repellent layer of the transmission filter of the present invention, B / A, which is the ratio of the distance A between the vertices of adjacent convex portions and the distance B between the center and the concave portion between the vertices of adjacent convex portions, is It is preferably 0.51 or more, and more preferably 0.55 or more.
B / A can be controlled by the volume ratio of the resin contained in the layer (ca) and the particles (a2). Therefore, it is preferable to appropriately design the blending ratio of the resin contained in the layer (ca) and the particles (a2).

Further, in order to realize low reflectance and suppress the occurrence of haze, it is preferable that the particles forming the convex portion are uniformly spread with an appropriate filling rate. From the above viewpoint, it is preferable that the content of the particles (a2) forming the convex portion is adjusted so as to be uniform over the entire transmission filter. The filling rate is measured as the area occupancy rate (particle occupancy rate) of the particles (a2) located on the most surface side when observing the inorganic particles forming the convex portion from the surface with a scanning electron microscope (SEM) or the like. 25% to 94% is preferable, 30 to 85% is more preferable, and 35 to 80% is further preferable.

The surface uniformity of the transmission filter can be evaluated by haze. The measurement can be performed on a film sample of 40 mm × 80 mm at 25 ° C. and a relative humidity of 60% with a haze meter NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to JIS-K7136 (2000). If the particles are agglomerated and non-uniform, the haze will be high. The lower the haze, the better. The haze value is preferably 0.0 to 3.0%, more preferably 0.0 to 2.5%, and even more preferably 0.0 to 2.0%.

The uneven shape of the water-repellent layer can be confirmed by observing the surface shape with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like.

Hereinafter, each element constituting the transmission filter of the present invention will be described in detail.

[Base material]
The substrate of the transmission filter of the present invention has a transmittance of light having a wavelength of 315 nm of 65% or more.
Since the base material has the above transmittance, when a transmission filter is used in an exposure apparatus, exposure using ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and i-line (365 nm) can be performed. It will be possible.
The transmittance of light having a wavelength of 315 nm of the base material is preferably 70% or more.
The component constituting the base material is not particularly limited as long as it is a base material having the above-mentioned transmittance, and low expansion glass, synthetic quartz, fluorite and the like are preferable. As the low expansion glass, Corning's Pyrex (registered trademark), Schott's Tempax Float (registered trademark), and the like can also be used.
The thickness of the base material is not particularly limited and can be usually about 300 μm to 20 mm, but 700 μm to 10 mm is preferable from the viewpoint of ease of production.

[Water repellent layer]
The water-repellent layer of the transmission filter of the present invention includes a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and not containing a fluorine atom, and an average primary particle size of 150 nm or less. (A2) and a reaction product of a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group. The content of the reactant of the fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group is 0.05% by mass or more in the total solid content of the water-repellent layer.

(Layer (ca))
The layer (ca) is a layer containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and containing no fluorine atom (also referred to as “compound (a1)”). The resin obtained by curing the compound (a1) is a polymer obtained by polymerizing the compound (a1) which is a monomer. The resin obtained by curing the compound (a1) may be a cured product of a composition containing the compound (a1) and other components (for example, other monomers, a polymerization initiator, a solvent, etc.). The resin obtained by curing the compound (a1) can function as a binder for binding the particles (a2) and the base material.

<Compound (a1) having at least one (meth) acryloyl group and not containing a fluorine atom>
By using the compound (a1) having at least one (meth) acryloyl group and not containing a fluorine atom, the compound (a1) can be partially cured and immobilized while the particles (a2) are separated from each other. In the concave-convex shape including the convex portion including (a2) and the concave portion between the convex portions, the distance A between the vertices of the adjacent convex portions and the distance B between the center and the concave portion between the apex of the adjacent convex portions B / A, which is the ratio with, can be made larger than 0.50.
The compound (a1) is a compound having a (meth) acryloyl group as a photopolymerizable functional group, and various monomers, oligomers or polymers can be used.

Specific examples of the compound (a1) include (meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate;
(Meta) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meta) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
Ethylene oxides such as 2,2-bis {4- (acryloxy diethoxy) phenyl} propane, 2-2-bis {4- (acryloxy polypropoxy) phenyl} propane, or (meth) acrylic acid diesters with propylene oxide adducts ; Etc. can be mentioned.

Further, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the compound (a1).

Among them, esters of a polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, one molecule contains at least one polyfunctional monomer having three or more (meth) acryloyl groups.
For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO (ethylene oxide) modified trimethylolpropane tri (meth) acrylate, PO (propylene oxide) modified trimethylol Propanetri (meth) acrylate, EO-modified tri (meth) phosphate, trimethylolethanetri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, dipentaerythritol hex (meth) acrylate, pentaerythritol hex (meth) acrylate, 1,2,3-clohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, caprolactone-modified trics (acryloxyethyl) isocyanurate, etc. Can be mentioned.

Specific compounds of polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA-manufactured by Nippon Kayaku Co., Ltd. 330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, V # 3PA, V manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples thereof include esterified compounds of polyols such as # 400, V # 36095D, V # 1000, V # 1080 and (meth) acrylic acid. In addition, purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B. , UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA. , UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306I, UA-306T, UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (Dainippon Ink and Chemicals) EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (manufactured by Daicel UCB Co., Ltd.), U-4HA, U-6HA, U-10HA, U-15HA (manufactured by Daicel UCB Co., Ltd.) Shin-Nakamura Chemical Industry Co., Ltd.), Hicorp AU-2010, AU-2020 (Tokushiki Co., Ltd.), Aronix M-1960 (Toa Synthetic Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, Trifunctional or higher urethane acrylate compounds such as UN-3320HS, UN-904, HDP-4T, Aronix M-8100, M-8030, M-9050 (manufactured by Toa Synthetic Co., Ltd., KRM-8307) (Dicel Cytec Co., Ltd.) A trifunctional or higher functional polyester compound such as (manufactured by) can also be preferably used.

Furthermore, resins having three or more (meth) acryloyl groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, and polythiol polyene resins. , Oligomers such as polyfunctional compounds such as polyhydric alcohols, prepolymers and the like.

Further, the compounds described in JP-A-2005-76005 and JP-A-2005-36105, dendrimers such as SIRIUS-501 and SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), JP-A-2005-60425. Norbornene ring-containing monomers and alkoxy oligomers (KR-513, acrylic / methyl group-containing, Shin-Etsu Chemical Industry Co., Ltd.) as described in the publication can also be used.

In the present invention, in order to bond the particles (a2) and the layer (ca) to form a strong water-repellent layer, a compound (a1) having an alkoxy group further bonded to a silicon atom (silane coupling agent). It is more preferable that the compound has three or more alkoxy groups bonded to a silicon atom.
Since the alkoxy group bonded to the silicon atom of such a silane coupling agent is hydrolyzed and then subjected to a condensation reaction to form a siloxane bond, the compound (a1) contains a (meth) acryloyl group and a silicon atom. The resin obtained by curing the compound having an alkoxy group bonded to is preferably having a siloxane bond.
The compound (a1) is preferably a compound represented by the following general formula (1) or (2).

Formula ^{(1): R 1 -Si-} OR 2 3

In the general formula (1), R ¹ represents an organic group having a (meth) acryloyl group.
R ² represents an alkyl group. The plurality of R ^2s may be the same or different.

General formula (2):

In the general formula (2), R ³ represents an organic group having a (meth) acryloyl group, an alkyl group, or a hydroxyl group, and the alkyl group may further have a substituent.
R ⁴ represents an alkyl group or a hydrogen atom.
m represents an integer of 3 to 22.
The plurality of R ³ may be the same or different, but at least one represents an organic group having a (meth) acryloyl groups.
A plurality of R ⁴ may be the same or different, respectively, but at least three represents an alkyl group.

When R ² and R ^{4 in the} general formula (1) or (2) each represent an alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.

When R ³ in the general formula (2) represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of reactivity. Alkyl groups are more preferred. These may further have a substituent, and may have an atom other than a carbon atom (for example, a halogen atom other than a fluorine atom, S, N, O, Si, etc.) in the substituent. Examples of the substituent include a halogen atom other than the fluorine atom, a mercapto group, an amino group, an oxylan ring-containing group, and other functional groups.

Specific examples of the silane coupling agent that can be used as the compound (a1) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth). Acryloxypropyl dimethylmethoxysilane, 3- (meth) acryloxipropylmethyldiethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 2- (meth) acryloxiethyltrimethoxysilane, 2- (meth) acry Examples thereof include loxyethyltriethoxysilane, 4- (meth) acryloxibutyltrimethoxysilane, 4- (meth) acryloxibutyltriethoxysilane, and the like. Specifically, KBM-503, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), silane coupling agents X-12-1048, X-12-1049, X- described in JP-A-2014-123091. Examples thereof include 12-1050 (manufactured by Shin-Etsu Chemical Co., Ltd.) and compound C3 represented by the following structural formula.

As the compound (a1), only one type may be used, or two or more types may be used in combination. The polymerization of these compounds (a1) can be carried out by irradiation with ionizing radiation or heating in the presence of a photoradical initiator or a thermal radical initiator.

The layer (ca) can further contain a compound other than the resin obtained by curing the compound (a1).
In the present invention, as the compound (a1), a compound having two or less (meth) acryloyl groups in one molecule may be used, but in particular, it has three or more (meth) acryloyl groups in one molecule. It is preferable to use the compound in combination with a compound having two or less (meth) acryloyl groups in one molecule, or a compound having no (meth) acryloyl group as a compound other than the compound (a1).
As a compound having two or less (meth) acryloyl groups in one molecule or a compound having no (meth) acryloyl group, the weight average molecular weight Mw is preferably 40 <Mw <500.
The compound having two or less (meth) acryloyl groups in one molecule is preferably a compound having one (meth) acryloyl group in one molecule.

Further, the compound having two or less (meth) acryloyl groups in one molecule or the compound having no (meth) acryloyl group preferably has a viscosity at 25 ° C. of 100 mPas or less, more preferably 1 to 50 mPas. preferable. The compound in such a viscosity range is preferable because it works to suppress the aggregation of the particles (a2) and improves the ultraviolet transmittance and the water repellency, respectively.

As the compound having no (meth) acryloyl group, an ester compound, an amine compound, an ether compound, an aliphatic alcohol compound, a hydrocarbon compound and the like can be preferably used, and an ester compound is particularly preferable. More specifically, dimethyl succinate (viscosity 2.6 mPas), diethyl succinate (viscosity 2.6 mPas), dimethyl adipate (viscosity 2.8 mPas), dibutyl succinate (viscosity 3.9 mPas), bis adipate (viscosity 3.9 mPas). 2-Butoxyethyl) (viscosity 10.8 mPas), dimethyl sverate (viscosity 3.7 mPas), diethyl phthalate (viscosity 9.8 mPas), dibutyl phthalate (viscosity 13.7 mPas), triethyl citrate (viscosity 22.6 mPas) ), Acetyltriethyl citrate (viscosity 29.7 mPas), diphenyl ether (viscosity 3.8 mPas) and the like.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are values measured by gel permeation chromatography (GPC) under the following conditions.
[Solvent] Tetrahydrofuran [Device name] TOSOH HLC-8220GPC
[Column] TOSOH TSKgel Super HZM-H
Use by connecting 3 (4.6 mm x 15 cm).
[Column temperature] 25 ° C
[Sample concentration] 0.1% by mass
[Flow velocity] 0.35 ml / min
[Calibration curve] TOSOH TSK standard polystyrene Mw = 2800000-1050 7 samples calibration curve is used.

The layer (ca) may contain, for example, a dispersant for the particles (a2), a metal chelate catalyst, or the like, in addition to the above-mentioned components.
Details of the components that can be contained in the layer (ca) will be described later in the description of the layer (a) (layer before curing (ca)).

(Particles with an average primary particle size of 150 nm or less (a2))
The particles (a2) form protrusions on the surface of the layer (ca) in the transmission filter.
Examples of the particles (a2) include metal oxide particles, resin particles, and organic-inorganic hybrid particles having a core of metal oxide particles and a resin shell, and metal oxide particles are preferable from the viewpoint of excellent strength.
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, antimony pentoxide particles, etc., but since the refractive index is close to that of many binders, haze is unlikely to occur and a desired uneven shape is easily formed. From the viewpoint, silica particles are preferable. In the present specification, "silica particles" are used in the sense of including both "uncalcined silica particles (uncalcined silica particles)" and "calcined silica particles (calcined silica particles)".
Examples of the resin particles include polymethyl methacrylate particles, polystyrene particles, melamine particles and the like.

The average primary particle size of the particles (a2) is 150 nm or less from the viewpoint that the particles can be arranged side by side to form a desired uneven shape and the ultraviolet transparency is enhanced.
When the transmission filter of the present invention is used in an exposure apparatus, the average primary particle size of the particles (a2) is 9/14 or less of the exposure wavelength from the viewpoint of suppressing diffraction of the exposure light and further enhancing the transparency. It is more preferably 9/19 or less, and even more preferably 7/19 or less.
For example, when an ArF excimer laser (wavelength 193 nm) is used as the exposure light, the average primary particle size of the particles (a2) is preferably 124 nm or less, more preferably 91 nm or less, and more preferably 72 nm or less. More preferred.
From the viewpoint of particle dispersibility, the average primary particle size of the particles is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more.

As the particles (a2), only one kind may be used, two or more kinds of particles having different average primary particle sizes may be used, or two or more kinds of particles having different constituent components may be used. Good.

The average primary particle size of the particles (a2) refers to a cumulative 50% particle size of the volume average particle size. A scanning electron microscope (SEM) can be used to measure the particle size. Observe the powder particles (in the case of a dispersion, dried and volatilized the solvent) at an appropriate magnification (about 5000 times) by SEM observation, measure the diameter of each of the 100 primary particles, and measure the volume thereof. Can be calculated and the cumulative 50% particle size can be used as the average primary particle size. If the particle is not spherical, the average of the major and minor diameters is considered to be the diameter of the primary particle. When measuring the particles contained in the transmission filter, the transmission filter is observed from the surface side by SEM in the same manner as described above and calculated. At this time, the sample may be appropriately subjected to carbon vapor deposition, etching treatment, or the like for easy observation.

The shape of the particles (a2) is most preferably spherical, but there is no problem even if the particles (a2) are not spherical such as indeterminate.
The particles (a2) may be solid particles or hollow particles, but are preferably solid particles.
Further, the silica particles may be either crystalline or amorphous.

As the particles (a2), it is preferable to use surface-treated inorganic fine particles in order to improve dispersibility in the coating liquid, improve strength, and prevent aggregation in the production process. Specific examples of the surface treatment method and preferable examples thereof are the same as those described in <0119> to <0147> of JP-A-2007-298974.
In particular, from the viewpoint of imparting the binding property of the binder compound (a1) to the cured resin and improving the strength, the compound having an unsaturated double bond on the particle surface and a functional group having reactivity with the particle surface. It is preferable to modify the surface with (1) to impart an unsaturated double bond to the particle surface. As the compound used for surface modification, the above-mentioned silane coupling agent having a (meth) acryloyl group as the compound (a1) can be preferably used.

Specific examples of particles having an average primary particle size of 150 nm or less include Seahoster KE-P10 (average primary particle size of 100 nm, amorphous silica manufactured by Nippon Shokubai Co., Ltd.) and stuffyloid (multilayer organic structure manufactured by Aica Kogyo Co., Ltd.). Fine particles), Ganzpearl (polymethylmethacrylate, polystyrene particles manufactured by Aica Kogyo Co., Ltd.) and the like can be preferably used.

The particles (a2) are preferably unfired silica particles, fired silica particles, synthetic quartz particles, or fluorite particles from the viewpoint of ultraviolet transmission, particle strength, binding to compound (a1), and the like. From the viewpoint of particle strength, calcined silica particles or synthetic quartz particles are more preferable, and calcined silica particles are particularly preferable because the amount of hydroxyl groups on the surface is moderately large and the particles are hard. ..
The calcined silica particles are produced by a known technique of calcining silica particles after hydrolyzing and condensing a hydrolyzable silicon compound in an organic solvent containing water and a catalyst. For example, JP-A-2003-176121 and JP-A-2008-137854 can be referred to.
The silicon compound as a raw material for producing calcined silica particles is not particularly limited, and chlorosilanes such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, trimethylchlorosilane, and methyldiphenylchlorosilane. Compounds; tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 3-glycidoxypropyltrimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycid Alkoxysilanes such as xypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethoxydiethoxysilane, trimethylmethoxysilane, and trimethylethoxysilane. Compounds; Asyloxysilane compounds such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, and trimethylacetoxysilane; silanol compounds such as dimethylsilanediol, diphenylsilanediol, and trimethylsilanol. ; Etc. can be mentioned. Among the above-exemplified silane compounds, the alkoxysilane compound is particularly preferable because it is more easily available and the obtained calcined silica particles do not contain halogen atoms as impurities. As a preferable form of the calcined silica particles according to the present invention, it is preferable that the content of halogen atoms is substantially 0% and no halogen atoms are detected.
The firing temperature is not particularly limited, and is preferably 800 to 1300 ° C, more preferably 1000 ° C to 1200 ° C.

As the particles (a2), only one type of monodisperse silica fine particles having an average primary particle size of 150 nm or less and a particle size dispersion (CV value) of less than 5% is contained in the unevenness of the moth-eye structure. It is preferable because the height becomes uniform and the transmittance becomes higher. The CV value is usually measured using a laser diffraction type particle size measuring device, but other particle size measuring methods may be used, and the particle size distribution is calculated by image analysis from the surface SEM image of the water-repellent layer of the present invention. You can also do it. More preferably, the CV value is less than 4%.

The indentation hardness of the particles (a2) is preferably 400 MPa or more, more preferably 500 MPa or more, and even more preferably 600 MPa or more. It is preferable that the indentation hardness of the particles (a2) is 400 MPa or more because the durability of the moth-eye structure against pressure in the thickness direction is high. Further, if the indentation hardness is too high, the particles (a2) tend to be brittle and easily cracked, so that the indentation hardness of the particles (a2) is preferably 1000 MPa or less.
The indentation hardness of the particle (a2) can be measured by a nano indenter or the like. In the sample, the particles (a2) were arranged on a substrate (glass plate, quartz plate, etc.) harder than itself so as not to overlap in the thickness direction of the substrate, and fixed with resin or the like with the particle surface exposed. You can prepare a sample and push it with a diamond indenter to measure it. It is even better to specify the pushing position with a tribo indenter.
As the particles having an indentation hardness of 400 MPa or more, calcined silica particles, synthetic quartz particles and the like can be preferably mentioned.

(Reactant of fluorine-containing copolymer having fluoroalkyl group and cross-linking group)
In the water-repellent layer of the transmission filter of the present invention, a reaction product of a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group (hereinafter, also referred to as “fluorine-containing copolymer (c)”) is completely solidified in the water-repellent layer. Contains 0.05% by mass or more in minutes. Examples of the cross-linking group include a radical-reactive group and a reactive group other than the radical-reactive group, and a radical-reactive group is preferable.
Examples of the radically reactive group include a group having an unsaturated bond capable of addition polymerization (for example, (meth) acryloyl group, (meth) acrylamide group, (meth) acrylonitrile group, allyl group, vinyl group, styrene structure, vinyl ether structure, acetylene. Structure, etc.), -SH, -PH, SiH, -GeH, disulfide structure, etc., and polymerizable functional groups (polymerizable carbon-carbon non-polymeric groups) such as (meth) acryloyl group, vinyl group, styryl group, allyl group, etc. A group having a saturated double bond) is preferable, among them, a (meth) acryloyl group and −C (O) OCH = CH ₂ are preferable, and a (meth) acryloyl group is most preferable.
Examples of the reactive group other than the radically reactive group include an epoxy group, an amino group, a boronic acid group, a boronic acid ester group, an oxylanyl group, an oxetanyl group, a hydroxyl group, a carboxyl group and an isocyanate group.
The reaction product of the fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group is a cross-linked polymer obtained by reacting the cross-linking groups of the fluoroalkyl-containing copolymer having a fluoroalkyl group and a cross-linking group.
From the viewpoint of uneven distribution in the water-repellent layer, the fluorine-containing copolymer (c) may be a polymer having a low friction site and a cross-linking group in the side chain and having a weight average molecular weight of 6,000 or more. preferable. The weight average molecular weight of the fluorine-containing copolymer (c) is preferably 6,000 to 100,000, more preferably 8,000 to 80,000. The weight average molecular weight of the fluorine-containing copolymer (c) is determined by the same method as the weight average molecular weight of the compound (a1) described above.
Further, from the viewpoint of chemical resistance and durability, the fluorine-containing copolymer (c) preferably has a cross-linking group linked to the main chain by a CC bond or a CO bond.

The fluorine-containing copolymer (c) is preferably, for example, a resin having a repeating unit represented by the following general formula (3), but the present invention is not limited thereto. In the present invention, the hydrocarbon chain may be described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted in the chemical formula.

General formula (3)

In the general formula (3), R represents a hydrogen atom or a fluorine atom.

The content of the reactant of the fluorine-containing copolymer (c) is 0.05% by mass or more in the total solid content of the water-repellent layer in order to give water repellency to all the uneven structures, and is 0.1. Mass% or more is preferable, and 0.2% by mass or more is more preferable. From the viewpoint of durability, the content of the reactant of the fluorine-containing copolymer (c) is preferably 10% by mass or less, more preferably 7% by mass or less, and 5% by mass in the total solid content of the water-repellent layer. % Or less is more preferable.

From the viewpoint of further improving the water repellency, the transmission filter of the present invention has an average primary particle size smaller than that of the particles (a2) on the convex portion formed in the layer (ca) by the particles (a2) of the water repellent layer. Particles (a2e) and a layer (cae) containing a resin obtained by curing a compound (a1e) having at least one (meth) acryloyl group, and the particles (a2e) are particles of the layer (cae). It is preferable that a convex portion is formed on the surface opposite to the a2) side.
Hereinafter, the transmission filter having the above configuration is also referred to as a “transmission filter of the second aspect”.

FIG. 2 shows an example of a preferred embodiment of the transmission filter of the second aspect.
The transmission filter 11 of FIG. 2 has a base material 9 and a water-repellent layer 2. The water-repellent layer 2 includes particles (a2) (reference numeral 3) and layer (ca) (reference numeral 4). The particles (a2) form convex portions on the surface of the layer (ca). Further, on the surface of the convex particles (a2), particles (a2e) (reference numeral 3e) having an average primary particle size smaller than those of the particles (a2) and layers (cae) (reference numeral 4e) are provided. The particles (a2e) form convex portions on the surface of the layer (cae) opposite to the particles (a2) side.
Similarly to the transmission filter 10 of FIG. 1, the transmission filter of the second aspect also includes a convex portion containing the particles (a2) and a concave portion between the convex portions, and has adjacent convex portions. B / A, which is the ratio of the distance A between the vertices and the distance B between the center between the vertices of the adjacent convex portions and the concave portion, is larger than 0.50. Further, the preferable range of this uneven shape is the same as that described above.
The apex of the convex portion is the point farthest from the substrate in the direction orthogonal to the in-plane direction of the substrate, and the convex portion is the particle (a2) and the particles arranged on the particle (a2) as shown in FIG. When a2e) is included, the apex of the convex portion exists on the particle (a2e).

It is presumed that the transmission filter of the present invention is further improved in water repellency because the region where water droplets can exist is further limited and the water droplets are brought into contact with only the water repellent portion by the configuration of the second aspect. Will be done.

<Layer (cae)>
The layer (cae) is a layer containing a resin obtained by curing a compound (a1e) having at least one (meth) acryloyl group (also referred to as “compound (a1e)”).
The compound (a1e) is the same as the above-mentioned compound (a1).

The layer (cae) can further contain components other than the resin obtained by curing the compound (a1e), and specific examples thereof include components that can be contained in the above-mentioned layer (ca).

<Particle (a2e)>
The particles (a2e) are particles having an average primary particle size smaller than that of the particles (a2).
From the viewpoint of water repellency, the average primary particle size of the particles (a2e) is preferably 5 to 50 nm, more preferably 10 to 45 nm, and even more preferably 15 to 40 nm.
Examples of the particles (a2e) include metal oxide particles, resin particles, and organic-inorganic hybrid particles having a core of metal oxide particles and a resin shell, and metal oxide particles are preferable from the viewpoint of excellent film strength.
Examples of the metal oxide particles include silica particles, titania particles, zirconia particles, antimony pentoxide particles, etc., but silica particles are preferable from the viewpoint of dispersibility and precipitation, and unfired silica particles are preferable.
Examples of the resin particles include polymethyl methacrylate particles, polystyrene particles, melamine particles and the like.

As the particles (a2e), only one type may be used, two or more types of particles having different average primary particle sizes may be used, or two or more types of particles having different constituent components may be used. Good.

The average primary particle size of the particles (a2e) refers to a cumulative 50% particle size of the volume average particle size. The particle size can be measured in the same manner as the above particles (a2).

The shape of the particles (a2e) is most preferably spherical, but there is no problem even if the shape is other than spherical such as indeterminate form.
The particles (a2e) may be solid particles or hollow particles, but are preferably solid particles.
Further, the silica particles may be either crystalline or amorphous.

As the particles (a2e), it is preferable to use surface-treated inorganic fine particles in order to improve dispersibility in the coating liquid, improve strength, and prevent aggregation in the production process. Specific examples of the surface treatment method and preferable examples thereof are the same as those described in <0119> to <0147> of JP-A-2007-298974.
In particular, from the viewpoint of imparting the binding property of the binder compound (a1e) to the cured resin and improving the strength, the compound having an unsaturated double bond on the particle surface and a functional group having reactivity with the particle surface. It is preferable to modify the surface with (1) to impart an unsaturated double bond to the particle surface. As the compound used for surface modification, the above-mentioned silane coupling agent having a (meth) acryloyl group as the compound (a1e) can be preferably used.

Specific examples of the particles (a2e) include MEK-ST (coloidal silica, average primary particle size 15 nm), MEK-AC-2140Z (acrylic modified colloidal silica, average primary particle size 15 nm), MEK-ST-L ( Colloidal silica with an average primary particle size of 45 nm) and MEK-AC-4130Y (acrylic modified colloidal silica with an average primary particle size of 45 nm) can preferably be manufactured by Nissan Chemical Industries, Ltd. or the like.

As the particles (a2e), it is preferable that only one type of monodisperse silica fine particles having a particle size dispersion (CV value) of less than 5% is contained. The CV value can be measured by the same method as that of the particle (a2).

From the viewpoint of particle monodispersity, the indentation hardness of the particles (a2e) is preferably less than 400 MPa, more preferably 10 to 350 MPa, and even more preferably 50 to 300 MPa.
The indentation hardness of the particles (a2e) can be measured in the same manner as the indentation hardness of the particles (a2).

(Water contact angle)
In the transmission filter of the present invention, the contact angle of water on the surface of the water-repellent layer opposite to the substrate side is 120 ° or more. The present inventors speculate that the water-repellent layer of the transmission filter of the present invention can impart excellent water repellency by having a specific uneven shape on the surface.
The water contact angle of the water-repellent layer of the transmission filter of the present invention is preferably 125 ° or more, more preferably 130 ° or more, and even more preferably 135 ° or more.

(Water sliding angle)
In the transmission filter of the present invention, it is preferable that the sliding angle of water on the surface of the water-repellent layer opposite to the base material side is 30 ° or less.
In the operation of the immersion exposure apparatus, the operation of applying water as an immersion liquid between the lower surface of the projection optical system and the surface of the wafer before exposure and sucking and removing water after exposure is repeated. The shorter the time required for the immersion, the higher the productivity, which is preferable. Further, if water remains between the lower surface of the lens of the optical system and the surface of the wafer for a long time, the lens may be contaminated by the components derived from the wafer eluted in the water.
It is preferable to set the sliding angle of water to 30 ° or less to improve the water removability because the time required for water application and suction removal can be shortened, so that productivity can be improved and contamination of the lens of the optical system can be prevented.
It is more preferable that the sliding angle of water on the surface of the water-repellent layer of the transmission filter of the present invention opposite to the base material side is 20 ° or less.

The transmission filter of the present invention is used from the viewpoint of increasing the water removal rate in order to improve the productivity of the exposure apparatus.
Having a hydrophilic layer in the same plane as the water-repellent layer on the substrate,
The water-repellent layer and the hydrophilic layer are alternately arranged in the in-plane direction.
The shape of the water-repellent layer and the hydrophilic layer when viewed from the direction orthogonal to the in-plane direction is triangular.
The hydrophilic layer includes a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and containing no fluorine atom, and particles (a2) having an average primary particle size of 150 nm or less. Including
The surface of the hydrophilic layer on the side opposite to the base material side has a convex portion formed by the particles (a2) and a concave portion between the convex portions.
B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions of the hydrophilic layer to the distance B between the center and the concave portion between the vertices of the adjacent convex portions, is larger than 0.50.
The distance A is 315 nm or less,
It is preferable that the contact angle of water on the side opposite to the base material side of the hydrophilic layer is 20 ° or less.

The constitution of the hydrophilic layer is the same as that of the water-repellent layer except that it does not contain the reactant of the fluorine-containing copolymer (c), and the water-repellent layer except that the fluorine-containing copolymer (c) is not used. It can be formed in the same manner as above.

A transmission filter having the above configuration is also referred to as a "transmission filter having a water-repellent / hydrophilic pattern".

FIG. 3 shows an example of a preferred embodiment of a transmission filter having a water repellent / hydrophilic pattern.

As described above, the transmission filter of the present invention is preferably applied to an immersion exposure apparatus.
FIG. 4 is a schematic view showing a state in which the transmission filter of the present invention is applied to the lens of the optical system of the immersion exposure apparatus. In FIG. 4, the transmission filter 55 of the present invention is applied to the surface 54A and the side surface 54B on the immersion side (the portion through which the exposure light is transmitted) of the lens 54, and the surface opposite to the side having the water-repellent layer of the base material. However, it is installed so as to make optical contact.
When the transmission filter of the present invention is a transmission filter having no hydrophilic layer as shown in FIG. 1 or 2, the side far from the lens of the portion optically in contact with the side surface 54B of the lens of FIG. 4 A water-repellent layer is preferably provided on the surface, and in this case, a hydrophilic layer may be provided on the surface of the portion of the lens that is in optical contact with the surface 54A on the side far from the lens. Moreover, the above-mentioned water-repellent / hydrophilic pattern may be provided.
When the transmission filter of the present invention is a transmission filter having a water-repellent / hydrophilic pattern, the surface of the portion optically in contact with the surface 54A of the lens of FIG. 4 is water-repellent / hydrophilic on the surface far from the lens. It is preferable that a pattern is provided, and in this case, a water-repellent layer is preferably provided on the surface of the portion that is optically in contact with the side surface 54B of the lens on the side far from the lens.

[Manufacturing method of transmission filter]
The method for producing the transmission filter of the present invention is not particularly limited.
The temporary support has particles (a2) having an average primary particle size of 150 nm or less, a compound (a1) having at least one (meth) acryloyl group and not containing a fluorine atom, and a fluoroalkyl group and a bridging group. Step (1) of providing the fluorine-containing copolymer with a thickness at which the particles (a2) are embedded in the layer (a) containing the compound (a1).
Step (2) of obtaining a layer (ca) by curing a part of the layer (a).
Step (3) of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (ca).
The layer (ca) is buried in the combined layer of the layer (ca) and the layer (b), and the particles (a2) protrude from the interface of the layer (ca) on the support side. ), The step (4) of bringing the position of the interface on the support side closer to the temporary support side.
Step (5) of peeling off the temporary support,
Step (6) of bonding the above layer (ca) and the base material,
A step (7) of curing the layer (ca) in a state where the particles (a2) are buried in a layer in which the layer (ca) and the layer (b) are combined.
Step (8) of peeling the adhesive film,
Is preferably produced by a production method having the above in this order.

In the above-mentioned manufacturing method, the above-mentioned particles (a2) are buried in a layer in which the above-mentioned layer (ca) and the above-mentioned layer (b) are combined between the above-mentioned step (4) and the above-mentioned step (5). It is preferable to have a step (4-2) of curing a part of the layer (ca).

Further, after the step (8), the step of curing the layer (ca) in a state where the particles (a2) protrude from the interface on the side opposite to the interface on the base material side of the layer (ca) (ca). 9),
Step of cleaning with solvent (10)
Is more preferable to have in this order.

In the present invention, "the particles (a2) are buried in the layer (a)" means that the thickness of the layer (a) is 0.8 times or more the average primary particle size of the particles (a2). It is a thing.
Further, in the present invention, "the particles (a2) are buried in the layer in which the layer (ca) and the layer (b) are combined" means that the thickness of the layer in which the layer (ca) and the layer (b) are combined is used. Indicates that is 0.8 times or more the average primary particle size of the particles (a2).

In the present invention, in the step (1), the layer (a) is formed with a thickness in which the particles (a2) are buried. Therefore, in the step (4) and thereafter, the surface protruding from the layer (ca) of the particles (a2) is layered. A thin layer of (ca) may cover. The particles (a2) coated with the thin layer are also referred to as particles (a2) for convenience.

First, an outline of the method for manufacturing a transmission filter of the present invention will be described with reference to FIGS. 5 and 6.
5 and 6 are schematic views showing an example of a preferred embodiment of the method for manufacturing a transmission filter of the present invention.
FIG. 5 (1) shows particles having an average primary particle size of 150 nm or less in the layer (a) (reference numeral 4 in FIG. 5) containing the compound (a1) on the temporary support 1 in the step (1). A state in which (a2) (reference numeral 3 in FIG. 5) is provided with a thickness to be buried is schematically shown.

(2) of FIG. 5 schematically shows a part of the layer (a) being cured in a state where the particles (a2) are buried in the layer (a) in the step (2). As a result, a part of the layer (a) is cured to obtain the layer (ca). In FIGS. 5 and 6, for convenience, both the layer (a) and the layer (ca) are represented by the same reference numerals 4. In addition, "UV" indicates ultraviolet rays.

FIG. 5 (3) shows the layer (b) of the pressure-sensitive adhesive film 7 having the support 5 and the layer (b) containing the pressure-sensitive adhesive (reference numeral 6 in FIG. 5) on the support 5 and the support 5 in the step (3). Is schematically shown in a state in which is bonded to the layer (ca) (reference numeral 4 in FIG. 5).

In FIG. 5 (4), in the step (4), the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b), and the interface of the layer (ca) on the support side ( The state in which the position of the interface on the support side of the layer (ca) is brought closer to the temporary support side so as to project from the interface between the layer (ca) and the layer (b)) is schematically shown. As will be described later, as a method of bringing the interface of the layer (ca) on the support side closer to the temporary support side, a part of the compound (a1) permeates the temporary support (the temporary support has a functional layer). In this case, it may permeate the functional layer), or a method of permeating a part of the compound (a1) into the layer (b) containing the adhesive.

In FIG. 5 (4-2), a part of the layer (ca) is formed in a state where the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) in the step (4-2). The part that is further cured is schematically shown.

FIG. 5 (5) shows a state (laminated body 8) after the temporary support 1 is peeled off in the step (5) of peeling the temporary support 1.
Since the step (4-2) is not essential, the step (5) may be performed after the step (4) without performing the step (4-2).

FIG. 6 (6) schematically shows a state in which the base material 9 is bonded to the layer (ca) (reference numeral 4 in FIG. 6) in the laminated body 8 in the step (6).

FIG. 6 (7) shows that the layer (ca) is further cured in the step (7) with the particles (a2) buried in the combined layer of the layer (ca) and the layer (b). It is represented schematically.

FIG. 6 (8) schematically shows a state after the adhesive film 7 is peeled off in the step (8) of peeling the adhesive film 7. The step (8) peels off the adhesive film 7 from the laminated body 8 and includes the particles (a2) (reference numeral 3 in FIG. 6) and the layer (ca) (reference numeral 4 in FIG. 6) in the laminated body 8. This is a step of transferring the portion (reference numeral 2 in FIG. 6) onto the base material 9. In the portion containing the particles (a2) and the layer (ca), the particles (a2) protrude from one surface of the layer (ca) to form a desired uneven shape (preferably a moth-eye structure). That is, the portion containing the particles (a2) and the layer (ca) is a water-repellent layer. By the step (8), a transmission filter 10 having a water-repellent layer having a concavo-convex shape composed of particles (a2) and a layer (ca) is obtained on the base material. Although the transmission filter 10 can be obtained when the step (8) is completed, it is preferable to further perform the steps (9) and (10).

In FIG. 6 (9), the layer (ca) is further cured in the step (9) with the particles (a2) protruding from the interface on the side opposite to the interface on the substrate side of the layer (ca). However, it is schematically represented.

FIG. 6 (10) shows the permeation filter 10 in the state after solvent cleaning in the step (10).

Hereinafter, each step of the preferable manufacturing method of the transmission filter of the present invention will be described in more detail.

[Step (1)]
In the step (1), 0.05% by mass or more of the compound (a1), particles (a2) having an average primary particle size of 150 nm or less, and a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group are placed on the temporary support. This is a step of providing the particles (a2) with a thickness of being buried in the layer (a) containing the compound (a1).
As described above, in the present invention, the "thickness in which the particles (a2) are buried in the layer (a)" means a thickness of 0.8 times or more the average primary particle size of the particles (a2). ..

In the step (1), the method of providing the layer (a) on the temporary support is not particularly limited, and it is preferable to provide the layer (a) by applying the layer (a) on the temporary support. In this case, the layer (a) contains 0.05% by mass or more of the compound (a1), particles (a2) having an average primary particle size of 150 nm or less, and a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group. (A) A layer formed by applying a forming composition. The coating method is not particularly limited, and a known method can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.

In the layer (a) provided on the temporary support in the step (1), it is preferable that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (a). Here, the fact that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (a) means that 10 μm × 10 μm in the plane of the layer (a) was observed in three fields with a scanning electron microscope (SEM). At that time, the ratio of the number of particles (a2) in a state in which a plurality of particles (a2) are not present in a direction orthogonal to the surface is 80% or more, and is preferably 95% or more.

(Temporary support)
The temporary support is not particularly limited as long as it has a smooth surface. The temporary support preferably has a surface roughness of about 30 nm or less and does not interfere with the application of the composition for forming the layer (a), and is a temporary support made of various materials. Although it can be used, for example, a polyethylene terephthalate (PET) film or a cycloolefin resin film is preferably used.
In the present invention, the surface roughness is measured by using SPA-400 (manufactured by Hitachi High-TechnoScience) under the measurement conditions of a measurement range of 5 μm × 5 μm, a measurement mode: DFM, and a measurement frequency: 2 Hz.

(Layer (a))
The layer (a) is a layer containing the compound (a1).
The compound (a1) contained in the layer (a) can become a resin (binder resin) in the water-repellent layer by being cured.
The film thickness of the layer (a) in the step (1) is preferably 0.8 times or more and 2.0 times or less, and 0.8 times or more and 1.5 times or less the average primary particle size of the particles (a2). It is more preferable that it is 0.9 times or more and 1.2 times or less.

Layer coating amount of the compound contained in (a) (a1) is ^preferably from ^{100mg / m 2 ~800mg / m 2} , more preferably ^{100mg / m 2 ~600mg / m 2} , 100mg / m 2 ~400mg / m ² is the most preferable.
When the compound (a1) and the compound having no polymerizable functional group are used in combination, the total coating amount of these compounds is preferably in the above range.

The coating amount of the particles (a2) is ^preferably from ^{50mg / m 2 ~200mg / m 2} , more preferably ^{100mg / m 2 ~180mg / m 2} , 130mg / m 2 ~170mg / m 2 is most preferred. Above the lower limit, many convex portions of the moth-eye structure can be formed, so that light transmission and water repellency are more likely to be improved. When the value is lower than the upper limit, aggregation in the liquid is less likely to occur, and a good moth-eye structure is easily formed.

The layer (a) contains a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group (fluorine-containing copolymer (c)) in addition to the compound (a1) and the particles (a2). The fluorine-containing copolymer (c) is as described above.

The layer (a) may contain components other than these in addition to the compound (a1), the particles (a2) and the fluorine-containing copolymer (c), and has, for example, the above-mentioned polymerizable functional group. It may contain a compound, a solvent, a polymerization initiator, a dispersant for particles (a2), a leveling agent, an antifouling agent, a metal chelate catalyst, and the like.

<Solvent>
As the solvent, it is preferable to select a solvent having a polarity close to that of the particles (a2) from the viewpoint of improving dispersibility. Specifically, for example, when the particles (a2) are metal oxide particles, an alcohol-based solvent is preferable, and methanol, ethanol, 2-propanol, 1-propanol, butanol, and the like can be mentioned. Further, for example, when the particles (a2) are hydrophobic surface-modified metal resin particles, a solvent such as a ketone type, an ester type, a carbonate type, an alkane, or an aromatic type solvent is preferable, and methyl ethyl ketone (MEK) or dimethyl carbonate , Methyl acetate, acetone, methylene chloride, cyclohexanone and the like. A plurality of these solvents may be mixed and used as long as the dispersibility is not significantly deteriorated.

<Dispersant for particles (a2)>
The dispersant of the particles (a2) can facilitate uniform arrangement of the particles (a2) by reducing the cohesive force between the particles. The dispersant is not particularly limited, and anionic compounds such as sulfates and phosphates, cationic compounds such as aliphatic amine salts and quaternary ammonium salts, nonionic compounds and polymer compounds are preferable, and adsorbing groups are preferable. A polymer compound is more preferable because the degree of freedom in selecting each of the steric repulsive groups is high. A commercially available product can also be used as the dispersant. For example, BYK Japan made of (stock) DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK164, DISPERBYK166, DISPERBYK167, DISPERBYK171, DISPERBYK180, DISPERBYK182, DISPERBYK2000, DISPERBYK2001, DISPERBYK2164, Bykumen, BYK-2009, BYK-P104, BYK-P104S, BYK-220S, Anti-Terra203, Anti-Terra204, Anti-Terra205 (hereinafter referred to as trade names) and the like can be mentioned.

<Leveling agent>
By lowering the surface tension of the composition for forming the layer (a), the leveling agent can stabilize the liquid after coating and facilitate the uniform arrangement of the compound (a1) and the particles (a2). For example, the compounds described in JP-A-2004-331812 and JP-A-2004-163610 can be used.

The leveling agent is preferably contained in an amount of 0.05 to 5.0% by mass, more preferably 0.05 to 3.0% by mass, in the total solid content of the composition for forming the layer (a). It is preferably contained in an amount of 0.05 to 2.0% by mass, most preferably.

<Anti-fouling agent>
The antifouling agent can suppress the adhesion of dirt by imparting water and oil repellency to the uneven structure. For example, the compounds described in JP2012-88699A can be used.

The antifouling agent is preferably contained in an amount of 0.05 to 15.0% by mass, more preferably 0.05 to 12.0% by mass, and 0, based on the total solid content in the layer (a). Most preferably, it is contained in an amount of .05 to 9.0% by mass.

<Polymerization initiator>
The layer (a) may contain a polymerization initiator.
When the compound (a1) is a photopolymerizable compound, it preferably contains a photopolymerization initiator.
Photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, etc. Fluoroamine compounds, aromatic sulfoniums, loffin dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like can be mentioned. Specific examples of the photopolymerization initiator, preferred embodiments, commercially available products, and the like are described in paragraphs <0133> to <0151> of JP-A-2009-098658, and they can also be preferably used in the present invention. it can.

"Latest UV Curing Technology" {Technical Information Association, Inc.} (1991), p. 159 and "Ultraviolet Curing System" by Kiyomi Kato (published by General Technology Center in 1989), p. Various examples are also described in 65 to 148, which are useful for the present invention.

The content of the polymerization initiator in the layer (a) is sufficient for polymerizing the polymerizable compound contained in the layer (a), and the starting point is set so as not to increase too much. , 0.1 to 8% by mass, more preferably 0.5 to 5% by mass, based on the total solid content in the layer (a).

In the layer (a), a compound that generates an acid or a base by light or heat in order to react the above-mentioned silane coupling agent (hereinafter, a photoacid generator, a photobase generator, a thermoacid generator, a thermobase generator). It may be referred to as an agent).

<Photoacid generator>
Examples of the photoacid generator include onium salts such as diazonium salt, ammonium salt, phosphonium salt, iodonium salt, sulfonium salt, selenium salt, and arsonium salt, organic halogen compounds, organic metals / organic halides, and o-nitrobenzyl type. Examples thereof include photoacid generators having a protective group, compounds that photodecompose to generate sulfonic acid, such as iminosulfonet, disulfone compounds, diazoketosulfone, and diazodisulfone compounds. In addition, triazines (for example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc.), quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, oximes. Sulfonate compounds can also be mentioned.
Further, a group in which an acid is generated by light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.
In addition, V. N. R. Pilrai, Synthesis, (1), 1 (1980), A.I. Abad et al. , Tetrahedron Lett. , (47) 4555 (1971), D.I. H. R. Barton et al. , J. Chem. Soc. , (C), 329 (1970), US Pat. No. 3,779,778, European Patent No. 126,712, etc., which generate acid by light can also be used.

<Thermal acid generator>
Examples of the thermoacid generator include salts composed of acids and organic bases.
Examples of the above-mentioned acids include organic acids such as sulfonic acid, phosphonic acid and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the compound (a1), an organic acid is more preferable, a sulfonic acid and a phosphonic acid are further preferable, and a sulfonic acid is the most preferable. Preferred sulfonic acids include p-toluene sulfonic acid (PTS), benzene sulfonic acid (BS), p-dodecylbenzene sulfonic acid (DBS), p-chlorobenzene sulfonic acid (CBS), 1,4-naphthalenedi sulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS) and the like.

As a specific example of the acid generator, those described in JP-A-2016-803 can be preferably used.

<Photobase generator>
Examples of the photobase generator include substances that generate a base by the action of active energy rays. More specifically, (1) salts of organic acids and bases that are decarbonated and decomposed by irradiation with ultraviolet rays, visible light, or infrared rays, and (2) amines that are decomposed by intramolecular nucleophilic substitution reaction or rearrangement reaction. A compound that emits a kind, or (3) a compound that causes some chemical reaction by irradiation with ultraviolet rays, visible light, or infrared rays to release a base can be used.
The photobase generator used in the present invention is not particularly limited as long as it is a substance that generates a base by the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays and visible rays.
Specifically, those described in JP-A-2010-243773 can be preferably used.

The content of the compound that generates an acid or a base by light or heat in the layer (a) is an amount sufficient to polymerize the polymerizable compound contained in the layer (a), and the starting point is increased. 0.1 to 8% by mass is preferable, and 0.1 to 5% by mass is more preferable, based on the total solid content in the layer (a), because the setting is not too much.

<Metal chelate catalyst>
The layer (a) may contain a metal chelate catalyst.
The metal chelate catalyst preferably acts as a catalyst for the condensation reaction of the above-mentioned silane coupling agent. The metal chelate catalyst also has an effect of enhancing the binding force between the particles (a2) and the binder resin.

The metal chelate catalyst includes metal elements selected from Group 2, Group 4, Group 5, and Group 13 of the periodic table, β-diketone, ketoester, hydroxycarboxylic acid or its ester, aminoalcohol, and enol. It is preferably a metal complex composed of an oxo or hydroxyoxygen-containing compound selected from the active hydrogen compounds.
Among the constituent metal elements, Group 2 elements such as Mg, Ca, Sr and Ba, Group 4 elements such as Ti and Zr, Group 5 elements such as V, Nb and Ta, and 13th elements such as Al and Ga. Group elements are preferable, and each forms a complex having an excellent catalytic effect. Among them, metal complexes obtained from Zr, Al and Ti are preferable.

The oxo or hydroxy oxygen-containing compounds constituting the ligand of the metal complex include β-diketones such as acetylacetone (2,4-pentandione) and 2,4-heptandione, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate and the like. Ketoesters, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartrate acid, methyl tartrate and other hydroxycarboxylic acids and their esters, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2- Keto alcohols such as pentanone, 4-hydroxy-4-methyl-2-heptanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-monoethanolamine, diethanolamine, tri Amino alcohols such as ethanolamine, enol active compounds such as methylol melamine, methylol urea, methylol acrylamide, malonic acid diethyl ester, methyl group of acetylacetone (2,4-pentandione), methylene group or carbonyl carbon substituent Examples include compounds having.

A preferred ligand is an acetylacetone derivative, which refers to a compound having a substituent on the methyl, methylene or carbonyl carbon of acetylacetone. The substituents to be substituted with the methyl group of acetylacetone are linear or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups and alkoxyalkyl groups, all of which are acetylacetones. The substituent substituting the methylene group of acetylacetone is a carboxyl group, both of which are linear or branched carboxyalkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms, and the substituent substituting the carbonyl carbon of acetylacetone has the number of carbon atoms. Is an alkyl group of 1 to 3, and in this case, a hydrogen atom is added to the carbonyl oxygen to form a hydroxyl group.

Specific examples of preferable acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, and acetoacetic acid. , Acetpropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol. Of these, acetylacetone and diacetylacetone are particularly preferable. The complex of the acetylacetone derivative and the metal element is a mononuclear complex in which 1 to 4 molecules of the acetylacetone derivative are coordinated per metal element, and the coordinable hand of the metal element is the coordinable bond of the acetylacetone derivative. If the total number of hands is larger than the total number of hands, a ligand generally used for a normal complex such as a water molecule, a halogen ion, a nitro group, and an ammonio group may be coordinated.

Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum-acco complex, mono (acetylacetonato) aluminum-chloro complex, di (diacetylacetonato) aluminum complex, ethylacet. Aluminum diisopropirate acetate, aluminum tris (ethylacetacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex salt, di (acetylacetonato) titanium complex salt, tris (acetylacetonato) titanium complex salt, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethylacetacetate), zirconium tris (benzoic acid) complex salt, and the like. These are excellent in stability in an aqueous coating solution and gelation promoting effect in a sol-gel reaction during heating and drying. Among them, ethylacetate acetate aluminum diisopropylate, aluminum tris (ethylacetate acetate), and di (di (ethylacetate acetate)) Acetylacetonato) titanium complex salt and zirconium tris (ethylacetacetate) are preferable.

Although the description of the salt of the metal complex described above is omitted in the present specification, the type of salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, for example, nitrate. Salt forms such as halides, sulfates and phosphates that ensure chemical neutrality are used.
Regarding the behavior of the metal complex in the silica solgel reaction, refer to J. Sol-Gel. Sci. and Tec. There is a detailed description in 16.209 (1999).

The above-mentioned metal chelate catalyst is easily available as a commercially available product, and can also be obtained by a known synthetic method, for example, a reaction between each metal chloride and an alcohol.

The content of the metal chelate catalyst in the layer (a) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, based on the compound (a1). More preferably, it is 1% by mass or more and 3% by mass or less. If it is 0.1% by mass or more, the hardness of the film is sufficient, and if it is 10% by mass or less, the condensation of the binder resin does not proceed too much. Therefore, the bond between the metal oxide particles and the binder resin is sufficient, and the metal Oxide particles are less likely to fall off.

[Step (2)]
The step (2) is a step of curing a part of the layer (a) of the step (1) to obtain the layer (ca), and specifically, the compound (specifically, the compound in the layer (a) of the step (1)). This is a step of curing a part of a1) to obtain a layer (ca) containing the cured compound (a1c).
By curing a part of the compound (a1) in the step (2), the particles (a2) can be made difficult to move and the agglomeration of the particles (a2) can be suppressed.
Curing a part of compound (a1) means curing only a part of compound (a1), not all of it. Only a part of the compound (a1) is cured in the step (2), and a part of the uncured compound (a1) is permeated into the temporary support in the step (4) (function when the temporary support has a functional layer). The thickness of the layer (ca) is reduced by a method of permeating the layer (b) or a method of permeating the layer (b) so that the particles (a2) protrude from the interface of the layer (ca) on the support side. It is possible to form a good uneven shape (moss eye structure).

Curing can be performed by irradiating with ionizing radiation. The type of ionizing radiation is not particularly limited and includes X-rays, electron beams, ultraviolet rays, visible light, infrared rays and the like. However, the compound (a1) is a photocurable compound and the light is emitted in the step (2). It is preferable to cure a part of the compound (a1) by irradiating (preferably ultraviolet rays).
The condition for curing a part of the compound (a1) in the step (2) is that the composition obtained by removing the particles (a2) from the composition for forming the layer (a) is applied onto the temporary support to a thickness of 2 μm. When cured, it is preferable that the curing rate is 2 to 20%, more preferably the curing rate is 3 to 15%, and the curing rate is 5 to 12%. It is more preferable to have.

Curing rate is
(1-Number of residual polymerizable functional groups after curing / Number of polymerizable functional groups before curing) × 100%, which is measured by the following method.
The polymerizable functional group is a group having a polymerizable carbon-carbon unsaturated double bond.
More specifically, the curable compound itself before curing was measured by KBr-IR using the NICOLET 6700 FT-IR (Fourier transform infrared spectrophotometer) of Thermo electron corporation, and the peak of the carbonyl group (1660-1800 cm ^-1). ) Area and the peak height (808 cm ^-1 ) of the polymerizable carbon-carbon unsaturated double bond were obtained, and the IR (infrared spectroscopy) measurement of the single reflection after curing showed that the carbonyl group peak area was similarly polymerizable. The peak of the carbon-carbon unsaturated double bond was determined, and the curing rate was calculated by comparing before and after irradiation with ultraviolet rays. When calculating hardening rate here is normalized measurement depth at 808cm ^-1 821nm, a depth of 1660-1800Cm ^-1 as 384 nm.

In step (2), it is preferable to irradiate the irradiation amount of ultraviolet 1~90mJ / cm ^2, it is more preferable to irradiate the irradiation amount of 1.2~40mJ / cm ^2, 1.5~10mJ / cm It is more preferable to irradiate with an irradiation amount of ² . Since the optimum value of the irradiation amount differs depending on the composition of the layer (a) forming composition, it can be appropriately adjusted.

In the step (2), it is preferable in terms of manufacturing suitability that a part of the compound (a1) is cured by irradiating ultraviolet rays from the side of the layer (a) opposite to the temporary support side.

It is preferable to carry out the step (2) in an environment having an oxygen concentration of 0.1 to 5.0% by volume, and more preferably to carry out the step (2) in an environment having an oxygen concentration of 0.5 to 1.0% by volume. .. By setting the oxygen concentration in the above range, it is possible to cure the region of the layer (a) on the temporary support side in particular.

Compound (a1c) is a cured product of compound (a1).
The molecular weight of compound (a1c) is not particularly limited. Further, the compound (a1c) may have an unreacted polymerizable functional group.
The layer (ca) obtained in the step (2) is a layer containing the compound (a1) and the compound (a1c) in the layer.
In the present invention, the layer (ca) can be further cured in the steps (4-2), (7), and (9) after the step (2), and before the curing in each step. Although the components contained in each layer after curing and their compositions (composition ratio of compound (a1) and its cured product (a1c), etc.) are different, in the present invention, the layer (ca) is conveniently used at any stage. It shall be called.

[Step (3)]
The step (3) is a step of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (ca).
The method of bonding the layer (ca) and the layer (b) of the adhesive film is not particularly limited, and a known method can be used, and examples thereof include a laminating method.
It is preferable to attach the adhesive film so that the layer (ca) and the layer (b) are in contact with each other.
Prior to step (3), there may be a step of drying the layer (ca). When the step of drying the layer (ca) is provided, the drying temperature of the layer (ca) is preferably 20 to 60 ° C, more preferably 20 to 40 ° C. The drying time is preferably 0.1 to 120 seconds, more preferably 1 to 30 seconds.

In the present invention, the layer (b) and the layer (ca) of the adhesive film are bonded together in the step (3), and the particles (a2) are combined with each other in the step (4) described later, and the layer (ca) and the layer (b) are combined. By burying it in the layer and projecting it from the interface of the layer (ca) on the support side, and more preferably, in the step (4-2), the particles (a2) are formed in the layer (ca) and the layer (b). By further curing a part of the layer (ca) while being buried in the combined layer, the particles (a2) are not exposed to the air interface before the layer (ca) is cured, and aggregation is suppressed. , A good uneven shape formed by the particles (a2) can be produced.

(Adhesive film)
The pressure-sensitive adhesive film has a support and a layer (b) containing a pressure-sensitive adhesive.

<Layer (b)>
The layer (b) is a layer containing a pressure-sensitive adhesive, and the pressure-sensitive adhesive is preferably a pressure-sensitive adhesive having a gel fraction of 95.0% or more.
When the gel content of the pressure-sensitive adhesive is 95.0% or more, in the production of the transmission filter of the present invention, when the pressure-sensitive adhesive film is peeled off, the pressure-sensitive adhesive component is less likely to remain on the surface of the transmission filter, and the pressure-sensitive adhesive component becomes It is highly effective in suppressing the decrease in transmittance caused by filling the gaps between the irregularities of the particles.
The gel fraction of the pressure-sensitive adhesive is preferably 95.0% or more and 99.9% or less, more preferably 97.0% or more and 99.9% or less, and 98.0% or more and 99.9%. The following is more preferable.
The gel fraction of the pressure-sensitive adhesive is the ratio of the insoluble content after immersing the pressure-sensitive adhesive in tetrahydrofuran (THF) at 25 ° C. for 12 hours, and is calculated from the following formula.
Gel fraction = (mass of adhesive insoluble in THF) / (total mass of adhesive) x 100 (%)

The weight average molecular weight of the sol component in the pressure-sensitive adhesive is preferably 10,000 or less, more preferably 7,000 or less, and most preferably 5,000 or less. By setting the weight average molecular weight of the sol component in the above range, it is possible to prevent the pressure-sensitive adhesive component from remaining on the surface of the transmission filter when the pressure-sensitive adhesive film is peeled off in the production of the transmission filter of the present invention.
The sol component of the pressure-sensitive adhesive represents the dissolved content in THF after the pressure-sensitive adhesive is immersed in tetrahydrofuran (THF) for 12 hours at 25 ° C. The weight average molecular weight can be analyzed by gel permeation chromatography (GPC).

It is also preferable that the storage elastic modulus (G') of the pressure-sensitive adhesive at 30 ° C. and 1 Hz is 1.3 GPa or less, and the weight average molecular weight of the sol component in the pressure-sensitive adhesive is 10,000 or less.
30 ° C. of the adhesive, and the storage modulus (G ') 1.3 × ¹⁰ 5 Pa or less at 1 Hz, and it is also preferable weight average molecular weight of sol component in the adhesive is less than or equal to 10000.
30 ° C. of the adhesive, the storage elastic modulus at 1 Hz (G ') is more preferably 0.1 × ¹⁰ 5 Pa or more 1.3 × ¹⁰ 5 Pa or less, 0.1 × ¹⁰ 5 Pa or more 1.2 × 10 ^It is more preferably ⁵ Pa or less. When the storage elastic modulus is 0.1 × 10 5 ^Pa or more, hardly causes cohesive failure of the pressure-sensitive adhesive, it is easy to handle. When the storage elastic modulus is 1.3 × 10 ⁵ Pa or less, the adhesive easily enters the gaps between the particles, so that the effect of suppressing the aggregation of the particles can be easily obtained, and at 1.2 × 10 ⁵ Pa or less. If there is, a transmission filter having a particularly good transmittance can be obtained.
Further, the preferable range of the weight average molecular weight of the sol component in the pressure-sensitive adhesive in this case is also the same as that described above.

The film thickness of the layer (b) is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 30 μm or less, and further preferably 1 μm or more and 20 μm or less.

The pressure-sensitive adhesive preferably contains a polymer, and more preferably contains a (meth) acrylic polymer. In particular, a polymer of at least one type of (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms (a copolymer in the case of two or more types of monomers) is preferable. The weight average molecular weight of the (meth) acrylic polymer is preferably 200,000 to 2,000,000.

Examples of the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate , Decyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isomyristyl (meth) acrylate, isosetyl (meth) acrylate, isostearyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate , Stearyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate and other alkyl (meth) acrylate monomers. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic. Two or more kinds of the above-mentioned monomers may be used in combination.

Preferable examples of the (meth) acrylate monomer having an aliphatic ring include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, isobornyl (meth) acrylate and the like. Of these, cyclohexyl (meth) acrylate is particularly preferable.

The (meth) acrylic polymer is a copolymer composed of at least one (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms and at least one other copolymerizable monomer. You may. In this case, as the other copolymerizable monomer, a copolymerizable vinyl monomer containing at least one group selected from a hydroxyl group, a carboxyl group, and an amino group, a copolymerizable vinyl monomer having a vinyl group, and an aromatic type Examples include monomers.

Examples of the copolymerizable vinyl monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Hydroxyl-containing (meth) acrylic acid esters such as hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate, and N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl. Examples thereof include hydroxyl group-containing (meth) acrylamides such as (meth) acrylamide, and at least one selected from these compound groups is preferable.

It is preferable that 0.1 to 15 parts by mass of a copolymerizable vinyl monomer containing a hydroxyl group is contained with respect to 100 parts by mass of the (meth) acrylic polymer.

Examples of the copolymerizable vinyl monomer containing a carboxyl group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. It is preferably at least one selected from these compound groups.

It is preferable that 0.1 to 2 parts by mass of a copolymerizable vinyl monomer containing a carboxyl group is contained with respect to 100 parts by mass of the (meth) acrylic copolymer.

Examples of the copolymerizable vinyl monomer containing an amino group include monoalkyls such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. Aminoalkyl (meth) acrylate and the like can be mentioned.

Examples of the aromatic monomer include aromatic group-containing (meth) acrylic acid esters such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, as well as styrene and the like.

Examples of copolymerizable vinyl monomers other than the above include various vinyl monomers such as acrylamide, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, and vinyl chloride.

The pressure-sensitive adhesive may contain a cured product of a composition for forming the pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive composition).
The pressure-sensitive adhesive composition preferably contains the above polymer and a cross-linking agent, and may be cross-linked using heat, ultraviolet rays (UV), or the like. As the cross-linking agent, one or more cross-linking agents selected from the compound group consisting of a bifunctional or higher functional isocyanate-based cross-linking agent, a bifunctional or higher functional epoxy-based cross-linking agent, and an aluminum chelate-based cross-linking agent are preferable. When a cross-linking agent is used, in the production of the transmission filter of the present invention, 0 is obtained with respect to 100 parts by mass of the polymer from the viewpoint of making it difficult for the pressure-sensitive adhesive component to remain on the surface of the transmission filter when the pressure-sensitive adhesive film is peeled off. .1 to 15 parts by mass is preferable, 3.5 to 15 parts by mass is more preferable, more than 3.5 parts by mass and less than 15 parts by mass is further preferable, and 5.1 to 10 parts by mass is contained. Is particularly preferable.

The bifunctional or higher functional isocyanate compound may be a polyisocyanate compound having at least two or more isocyanate (NCO) groups in one molecule, and may be hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, or xylylene. Bullet-modified products of diisocyanates (compounds having two NCO groups in one molecule) such as isocyanates, and trivalent or higher polyols such as isocyanurate-modified products, trimethylolpropane or glycerin (at least three in one molecule). Examples thereof include an adduct form (polypolymodified form) with the above compound having an OH group.
Further, the trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, particularly an isocyanurate form of a hexamethylene diisocyanate compound and an isocyanurate form of an isophorone diisocyanate compound. It is preferably at least one selected from the compound group consisting of an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a bullet body of a hexamethylene diisocyanate compound, and a bullet body of an isophorone diisocyanate compound.
The bifunctional or higher functional isocyanate-based cross-linking agent is preferably contained in an amount of 0.01 to 5.0 parts by mass, more preferably 0.02 to 3.0 parts by mass with respect to 100 parts by mass of the polymer.

The pressure-sensitive adhesive composition may contain an antistatic agent in order to impart antistatic performance. The antistatic agent is preferably an ionic compound, more preferably a quaternary onium salt.

Examples of the antistatic agent which is a quaternary onium salt include an alkyldimethylbenzylammonium salt having an alkyl group having 8 to 18 carbon atoms, a dialkylmethylbenzylammonium salt having an alkyl group having 8 to 18 carbon atoms, and an alkyl methylbenzylammonium salt having 8 to 18 carbon atoms. A trialkylbenzylammonium salt having 18 alkyl groups, a tetraalkylammonium salt having an alkyl group having 8 to 18 carbon atoms, an alkyldimethylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, an alkyl having 8 to 18 carbon atoms. A dialkylmethylbenzylphosphonium salt having a group, a trialkylbenzylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, a tetraalkylphosphonium salt having an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 14 to 20 carbon atoms. Alkyltrimethylammonium salts, alkyldimethylethylammonium salts having an alkyl group having 14 to 20 carbon atoms, and the like can be used. These alkyl groups may be alkenyl groups having an unsaturated bond.

Other antistatic agents include nonionic, cationic, anionic, and amphoteric surfactants, ionic liquids, alkali metal salts, metal oxides, metal fine particles, conductive polymers, carbon, carbon nanotubes, and the like. be able to.

Examples of the alkali metal salt include a metal salt composed of lithium, sodium, and potassium, and a compound containing a polyoxyalkylene structure may be added to stabilize the ionic substance.

The antistatic agent is preferably contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer.

The pressure-sensitive adhesive composition may further contain a polyether-modified siloxane compound having an HLB of 7 to 15 as an antistatic auxiliary agent.
HLB is a hydrophilic lipophilic balance (hydrophilic lipophilic ratio) defined by, for example, JIS (Japanese Industrial Standards) K3211 (surfactant term).

The pressure-sensitive adhesive composition may further contain a cross-linking accelerator. The cross-linking accelerator may be a substance that functions as a catalyst for the reaction between the copolymer and the cross-linking agent (cross-linking reaction) when the polyisocyanate compound is used as the cross-linking agent, and is an amine-based substance such as a tertiary amine. Examples thereof include organic metal compounds such as compounds, metal chelate compounds, organotin compounds, organolead compounds, and organozinc compounds. In the present invention, a metal chelate compound or an organic tin compound is preferable as the cross-linking accelerator.

The cross-linking accelerator is preferably contained in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the copolymer.

The laminate 8 shown in FIG. 5 (5) has three or more cross-linking groups in one molecule on the surface of the layer (b) on the layer (ca) side, has a cross-linking group equivalent of 450 or less, and is made of fluorine or silicone. It is preferable that a slip agent having a low friction portion (hereinafter, also referred to as “slip agent a”) is present.
Due to the presence of the slip agent a on the surface of the layer (b) on the layer (ca) side, the pressure-sensitive adhesive in the layer (b) is a transmission filter when the pressure-sensitive adhesive film is peeled off in the production of the transmission filter of the present invention. It can be effectively prevented from remaining (transferred) on the surface of the film.

<Support>
The support in the adhesive film will be described.
As the support, a plastic film made of a transparent and flexible resin is preferably used. Suitable plastic films for the support include polyester films such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polybutylene terephthalate, (meth) acrylic resin, polycarbonate resin, polystyrene resin, and polyolefin resin. Examples thereof include a film made of a resin, a cyclic polyolefin resin, a polyethylene resin such as cellulose acylate, and the like. However, the (meth) acrylic resin includes a polymer having a lactone ring structure, a polymer having a glutaric anhydride ring structure, and a polymer having a glutarimide ring structure.
In addition, other plastic films can be used as long as they have the required strength and optical suitability. The support may be a non-stretched film, uniaxially or biaxially stretched, or may be a plastic film in which the stretching ratio or the angle of the axial method formed by the crystallization of stretching is controlled.

As the support, one having ultraviolet transparency is preferable. Having ultraviolet transparency enables ultraviolet irradiation from the support side when the layer (ca) is cured in steps (4-2) and (7), which is preferable in terms of production suitability.
Specifically, the maximum transmittance of the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and most preferably 60% or more. When the maximum transmittance at a wavelength of 250 nm to 300 nm is 20% or more, it is preferable that the layer (ca) is easily cured by irradiating ultraviolet rays from the support side.
Further, the maximum transmittance of the pressure-sensitive adhesive film having the layer (b) formed on the support at a wavelength of 250 nm to 300 nm is preferably 20% or more, more preferably 40% or more, and more preferably 60% or more. Is the most preferable.

The film thickness of the support is not particularly limited, and is preferably 10 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less, and further preferably 10 μm or more and 40 μm or less.

As the adhesive film having the layer (b) formed on the support, a commercially available protective film can be preferably used. Specifically, AS3-304, AS3-305, AS3-306, AS3-307, AS3-310, AS3-0421, AS3-0520, AS3-0620, LBO-307, NBO- manufactured by Fujimori Kogyo Co., Ltd. 0424, ZBO-0421, S-362, TFB-4T3-367AS and the like can be mentioned.

In steps (4-2) and (7), the particles (a2) are cured while maintaining the state of being buried in the combined layer of the layer (ca) and the layer (b), but the step (ca) is performed. In the step before step 4-2) (that is, after the completion of step (4)), it is preferable to have an uneven shape formed by particles (a2) protruding from the interface on the support side of the layer (ca). .. By doing so, when the layer (ca) is cured in the step (7) and then the layer (b) is peeled off in the step (8), the transmission filter in a state where the particles (a2) protrude from the surface of the layer (a). Can be obtained.
In order to have the uneven shape formed by the particles (a2) protruding from the interface on the support side of the layer (ca) in the step before the step (4-2), the step (4) Therefore, it is preferable to allow a part of the compound (a1) to penetrate into the layer (b).

[Step (4)]
In step (4), the layer (ca) is such that the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) and protrude from the interface on the support side of the layer (ca). ) Is a step of bringing the position of the interface on the support side (preferably the interface between the layer (ca) and the layer (b)) closer to the temporary support side.
In other words, "the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) and protrude from the interface on the support side of the layer (ca)". , "Particles (a2) are not exposed from the combined layer of layer (ca) and layer (b), and are present across both layers (ca) and layer (b) ( Particles (a2) exist across the interface between the layer (ca) and the layer (b)) ".
The step (4) is preferably carried out by infiltrating a part of the compound (a1) into the layer (b).
When a part of the compound (a1) is permeated into the layer (b) in the step (4), the laminate after the completion of the step (3) is preferably kept below 60 ° C., and kept at 40 ° C. or lower. Is more preferable. By keeping the temperature below 40 ° C., the viscosities of the compound (a1), the compound (a1c), and the pressure-sensitive adhesive can be kept high, and the thermal motion of the particles (a2) can be suppressed. The effect of preventing the deterioration of the light transmission performance and the water repellency performance due to the aggregation of a2) is great. The lower limit of the temperature at which the laminate is maintained is not particularly limited, and may be room temperature or a temperature lower than room temperature.

[Step (4-2)]
The step (4-2) is a step of curing a part of the layer (ca) in a state where the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b), specifically. , A step of curing a part of the compound selected from the group consisting of the compound (a1) and the compound (a1c) in the layer (ca).
Curing a part of the layer (ca) means curing only a part of the compound (a1) and the compound (a1c) in the layer (ca), not all of them. This makes it possible to form a binder resin in the water-repellent layer of the transmission filter. Further, by leaving the uncured compound (a1) in the layer (ca) after the completion of the step (4-2), the layer (ca) and the base material are bonded to each other in the step (6) described later. Alternatively, it can be bonded.
By maintaining the state in which the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) in the step (4-2), the aggregation of the particles (a2) is suppressed and the moth-eye structure is formed. can do.
After the layer (b) is provided, the particles (a2) are buried in the combined layer of the layer (ca) and the layer (b) due to volatilization of the layer (b) or the components of the layer (ca). If it is considered that the layer (b) cannot be maintained, an operation such as thickening the layer (b) in advance can be performed.

Curing in step (4-2) can be performed by irradiating ionizing radiation. The type of ionizing radiation is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are widely used. For example, if the coating film is UV curable, it is to cure a portion of the ultraviolet lamp and an irradiation amount of 10mJ ^/ cm ² ~1000mJ ^/ cm 2 layer (ca) compounds in (a1) preferable. When the irradiation amount of ultraviolet rays is 10 mJ / cm ² or more, the adhesion between the layer (b) and the portion containing the particles (a2) and the layer (ca) becomes moderately strong, and the step of peeling off the temporary support (5). ), The particles (a2) and the layer (ca) are less likely to remain on the temporary support, and defects (regions in which water repellency does not increase) are less likely to occur in the obtained transmission filter. Further, when the irradiation amount of ultraviolet rays is 1000 mJ / cm ² or less, the residual amount of the compound (a1) in the layer (ca) after the completion of the step (4-2) does not decrease too much, and in the step (6). An appropriate adhesive force between the layer (ca) and the base material can be obtained. The irradiation amount in the step (4-2) is not particularly limited, and the adhesion between the layer (b) to be used and the portion containing the particles (a2) and the layer (ca) and the adhesion between the layer (ca) and the base material It can be adjusted appropriately in consideration of the force. At the time of irradiation, the above energy may be applied all at once, or may be divided and irradiated. As the ultraviolet lamp type, a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.

The oxygen concentration at the time of curing in the step (4-2) is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and 0 to 0.05% by volume. Is the most preferable. By making the oxygen concentration at the time of curing smaller than 1.0% by volume, the film is less susceptible to the inhibition of curing by oxygen, and a strong film is formed.

In step (4-2), when a part of the compound selected from the group consisting of the compound (a1) and the compound (a1c) in the layer (ca) is cured, it is opposite to the layer (ca) side of the support. Ultraviolet rays may be irradiated from the side, or ultraviolet rays may be irradiated from the temporary support side.

[Step (5)]
The step (5) is a step of peeling the temporary support from the laminated body after the completion of the step (4) or (4-2).
In order for the temporary support to be peeled off from the laminated body after the completion of the step (4) or (4-2), an appropriate adhesive force is provided between the layer (ca) and the temporary support. , A portion including a layer (ca) and particles (a2) (a portion composed of a particle (a2) indicated by reference numeral 3 in FIG. 5 and a layer (ca) indicated by reference numeral 4 and the water-repellent layer 2 in FIG. It is preferable that the portion corresponding to) can be transferred to the adhesive film. For example, during bending or transport tension of the laminate during the manufacturing process, the portion containing the layer (ca) and the particles (a2) does not separate from the temporary support, but when it is brought into contact with the layer (b) or the layer (b). ), And the portion containing the layer (ca) and the particles (a2) is preferably in a desorbed state when irradiated with ultraviolet rays.

In steps (2), (3), (4), (4-2), and (5), it is preferable that a plurality of particles (a2) do not exist in the direction orthogonal to the surface of the layer (ca).
Here, the fact that there are no plurality of particles (a2) in the direction orthogonal to the surface of the layer (ca) means that 10 μm × 10 μm in the plane of the layer (ca) was observed in three fields with a scanning electron microscope (SEM). At that time, the ratio of the number of particles (a2) in a state in which a plurality of particles (a2) are not present in a direction orthogonal to the surface is 80% or more, and is preferably 95% or more.

In steps (4), (4-2), and (5), the total film thickness of the film thickness of the layer (ca) and the film thickness of the layer (b) is larger than the average primary particle size of the particles (a2). Is preferable.
When the total film thickness of the film thickness of the layer (ca) and the film thickness of the layer (b) is larger than the average primary particle size of the particles (a2), the particles (a2) form the layer (ca) and the layer (b). It is preferable because it can be buried in the combined layers.

Further, in steps (4), (4-2) and (5), the film thickness of the layer (ca) is preferably 5 to 70% of the average primary particle size of the particles (a2), and is preferably 20 to 40%. More preferably. When the film thickness of the layer (ca) is 5% or more of the average primary particle size of the particles (a2), the adhesive film is peeled off in the step (8) described later to include the layer (ca) and the particles (a2). It is preferable because the particles (a2) are hard to fall off from the transmission filter obtained after the portion is transferred to the substrate and the scratch resistance is improved. Further, when the film thickness of the layer (ca) is 70% or less of the average primary particle size of the particles (a2), the inclination of the refractive index becomes sufficient and sufficient light transmission performance can be obtained. It is preferable that the film thickness of the layer (ca) is 20 to 40% of the average primary particle size of the particles (a2) because sufficient scratch resistance and light transmission performance can be achieved at the same time. The same applies to the steps (6) to (10) described later.
The film thickness of the layer (ca) after the completion of the step (5) is obtained by observing the film cross section of the layer (ca) with a scanning electron microscope (SEM) and arbitrarily measuring the film thickness at 100 points and averaging the film thickness. When the value is determined, it is preferable to adjust the value to 10 nm to 100 nm (more preferably 20 nm to 90 nm, further preferably 30 nm to 70 nm).

It is preferable that the particles (a2) do not protrude from the surface of the layer (ca) obtained by completing the step (5) on the side opposite to the layer (b) side.
The surface roughness of the surface of the layer (ca) on the side opposite to the layer (b) side of the laminate obtained by completing the step (5) is preferably 30 nm or less, more preferably 10 nm or less.
When the surface roughness of the surface of the layer (ca) opposite to the layer (b) side is 30 nm or less, the particles (a2) protrude from the surface of the layer (ca) opposite to the layer (b) side. It is not easily transferred when the adhesive film is peeled off in the step (8) described later and the portion (water-repellent layer) containing the layer (ca) and the particles (a2) is transferred to the base material. The water-repellent layer is less likely to be defective later. Further, if the surface roughness of the surface of the layer (ca) opposite to the layer (b) side is 10 nm or less, good adhesion is obtained when the layer (ca) and the base material are bonded together in the step (6). It is preferable because it can be secured and the generation of voids between the transfer layer (the portion containing the particles (a2) and the layer (ca)) and the base material that causes an increase in the haze of the transmission filter can be suppressed.
In the present invention, the surface roughness was measured using SPA-400 (manufactured by Hitachi High-TechnoScience) under the measurement conditions of a measurement range of 5 μm × 5 μm, a measurement mode: DFM, and a measurement frequency: 2 Hz.

The portion of the laminate obtained by completing the step (5) containing the particles (a2) and the layer (ca) can be peeled off from the layer (b) of the adhesive film.
The part containing the particles (a2) and the layer (ca) can be peeled off from the layer (b) of the adhesive film between the part containing the particles (a2) and the layer (ca) and the layer (b) of the adhesive film. By imparting an appropriate adhesive force, in the transfer step (step (8)) described later, the portion containing the particles (a2) and the layer (ca) is separated from the surface of the layer (b) and becomes the surface of the base material. Indicates that the film is ready for transfer. The portion (water-repellent layer) containing the particles (a2) and the layer (ca) can be transferred to the surface of the base material, that is, the transferability is defined as the transfer surface (the surface having the water-repellent layer) of the transmission filter after transfer. When a black polyethylene terephthalate sheet with adhesive (manufactured by Tomagawa Paper Co., Ltd .; "Clear Mieru") was attached to the opposite side and visually observed, the water repellency was improved compared to before the water repellent layer was transferred. It means that the ratio of the area of the region is 80% or more with respect to the area to be transferred. The adhesive strength between the portion containing the particles (a2) and the layer (ca) and the layer (b) is not particularly limited, and for example, particles of a transfer member having a width of 25 mm (a laminate obtained by completing step (5)). The portion containing the particles (a2) and the layer (ca) is fixed to a glass substrate having a thickness of 1.1 mm using an adhesive, and the portion containing the particles (a2) and the layer (ca) and the layer (b) are oriented in the 90 ° direction. It can be measured by the peeling force when peeling at a speed of 1000 mm / min. The peeling force measured by the above method is preferably 0.2 N / 25 mm to 4.0 N / 25 mm, and more preferably 0.6 N / 25 mm to 4.0 N / 25 mm. If the peeling force is 0.6 N / 25 mm or more, part of the particles (a2) and the layer (ca) is unlikely to remain on the temporary support when the temporary support is peeled in the step (5). , The water repellency of the finally obtained transmission filter is improved. When the peeling force is 4.0 N / 25 mm or less, when the adhesive film is peeled off in the step (8), a part of the particles (a2) is unlikely to remain in the layer (b), so that the final transmission is obtained. The water repellency of the filter is improved.

[Step (6)]
The step (6) is a step of laminating the layer (ca) and the base material in the laminated body obtained by completing the above-mentioned step (5).
The method of bonding the layer (ca) and the base material is not particularly limited, and a known method can be used, and examples thereof include a roll laminating method.
It is preferable to attach the adhesive film so that the layer (ca) and the base material are in contact with each other.

[Step (7)]
The step (7) is a step of curing the layer (ca) in a state where the particles (a2) are buried in the combined layer of the layer (b) and the layer (ca), and specifically, the layer (ca). ) Is a step of curing a part or all of the compound selected from the group consisting of the compound (a1) and the compound (a1c). It should be noted that curing all of the compounds selected from the group consisting of the compound (a1) and the compound (a1c) in the layer (ca) means that the compounds that could not be completely cured when cured by a usual method It also includes cases where it remains. The curing rate in the step (7) is not particularly limited, but from the viewpoint of film strength, the curing rate is preferably 60% or more, and more preferably 80% or more.
By the step (7), the base material bonded in the above step (6) and the layer (ca) can be adhered to each other.

The curing in the step (7) is preferably performed under the same conditions as those described in the above step (4-2).

[Step (8)]
The step (8) is a step of peeling the adhesive film from the laminate obtained in the step (7).
In order to peel off the adhesive film in the step (8), an index of the adhesive force between the portion containing the particles (a2) and the layer (ca) and the layer (b) in the laminate obtained by completing the step (5). As a result, the peeling force measured by the above measuring method is preferably 0.2 N / 25 mm to 4.0 N / 25 mm or less.

After the step (8) is completed, a transmission filter having a moth-eye structure having a concavo-convex shape formed by particles (a2) on the surface of the layer (ca) is obtained, and then further steps (9) and (10) are obtained. ) May be performed.

[Step (9)]
The step (9) is a step of curing the layer (ca) in a state where the particles (a2) protrude from the interface on the side opposite to the interface on the base material side of the layer (ca). This is a step of curing all the compound (a1) and the compound (a1c) in the layer (ca). When all the compounds (a1) and the compound (a1c) in the layer (ca) are cured in the above-mentioned step (7), the step (9) does not have to be performed.

The curing in the step (9) is preferably performed under the same conditions as those described in the above step (4-2).
In the step (9), it is preferable in terms of production suitability that the compound (a1) and the compound (a1c) in the layer (ca) are cured by irradiating ultraviolet rays from the side opposite to the base material side of the layer (ca).

The layer (ca) after the completion of the step (9) is a layer containing the compound (a1c) in the layer. However, as described above, when the compound is cured by a usual method, the compound that has not been completely cured may remain.

[Step (10)]
The step (10) is a step of cleaning the laminate after the completion of the step (9) with a solvent.
In the above-mentioned method for producing a transmission filter of the present invention, the adhesive does not easily remain on the layer (ca) side even when the support and the layer (b) are peeled off, but the base material and the layer (10) are subjected to the step (10). Ca) may not be dissolved and may be washed with a solvent (methyl isobutyl ketone, methyl ethyl ketone, acetone, etc.) that dissolves the pressure-sensitive adhesive.

The transmission filter of the second aspect described above can be manufactured by using the laminated body 8 after the completion of the above steps (8), (9) or (10) and the laminated body 20 described later.

The laminated body 20 can be manufactured by a manufacturing method including the following steps (1e) to (5e).
On the temporary support, particles (a2e) having an average primary particle size smaller than the particles (a2) and a compound (a1e) having at least one (meth) acryloyl group are formed on a layer (ae) containing the compound (a1e). ), The step (1e) of providing the particles (a2e) with a thickness of burying them.
Step (2e) of obtaining a layer (cae) by curing a part of the layer (ae).
Step (3e) of laminating the layer (b) of the adhesive film having the support and the layer (b) containing the adhesive on the support with the layer (cae).
The layer (cae) is buried in the combined layer of the layer (cae) and the layer (b), and the particles (a2e) protrude from the interface of the layer (cae) on the support side. ), The step (4e) of bringing the position of the interface on the support side closer to the temporary support side.
Step of peeling off the temporary support (5e)

In the above-mentioned manufacturing method, the above-mentioned particles (a2e) are buried in a layer in which the above-mentioned layer (cae) and the above-mentioned layer (b) are combined between the above-mentioned step (4e) and the above-mentioned step (5e). It is preferable to have a step (4-2e) of curing a part of the layer (cae).

The method for manufacturing the transmission filter of the second aspect described above by using the laminated body 20 obtained at the stage where the step (5e) is completed and the laminated body 8 described above will be described below.
The transmission filter of the second aspect described above uses the laminated body 8 after the completion of the above steps (8), (9) or (10) and the above-mentioned laminated body 20, and the following steps (6e) to ( It can be produced by a production method including 8e).

A step of laminating the layer (cae) of the laminated body 20 and the surface (surface having an uneven shape) of the particles (a2) of the laminated body 8 on the side opposite to the base material side of the layer (ca). 6e),
A step (7e) of curing the layer (cae) in a state where the particles (a2e) are buried in a layer in which the layer (cae) and the layer (b) are combined.
Step of peeling the adhesive film (8e),
Is preferably produced by a production method having the above in this order.

Further, after the step (8e), the layer (cae) is cured in a state where the particles (a2e) protrude from the interface on the side opposite to the interface on the particle (a2) side of the layer (cae). Step (9e),
Step of cleaning with solvent (10e)
Is more preferable to have in this order.

For details of the above steps (1e) to (10e), the above steps (1) to (10) can be referred to. However, the "particles (a2)", "compound (a1)", "layer (a)", "layer (ca)", and "base material" in the steps (1) to (10) are referred to as "particles (a2e)". ) ”,“ Compound (a1e) ”,“ Layer (ae) ”,“ Layer (cae) ”, and“ Particle (a2) has a surface (having an uneven shape) opposite to the substrate side of the layer (ca). It shall be read as "surface)".

FIG. 7 shows a schematic diagram for explaining the above step (6e). In the laminated body 20 of FIG. 7, the particles (a2e) (reference numeral 13) are embedded in the combined layer of the layer (cae) (reference numeral 14) and the layer (b) (reference numeral 16), and the above-mentioned It exists across the layer (cae) (reference numeral 14) and the layer (b) (reference numeral 16), and crosses the interface between the layer (cae) (reference numeral 14) and the layer (b) (reference numeral 16). Existing. The support 15 is laminated on the surface of the layer (b) (reference numeral 16) opposite to the layer (cae) (reference numeral 14) side.
The transmission filter 10 obtained in any of the above steps (8) to (10) and the laminate 20 obtained in the above step (5e) are bonded together. At this time, it is preferable to adjust so that the particles (a2e) are arranged on the particles (a2) as in the optical system protection member 11 shown in FIG.

Further, in the step (1e), the coating amount of the compound contained in the layer (ae) (a1e) is ^preferably from ^{5mg / m 2 ~75mg / m 2} , more preferably ^{10mg / m 2 ~70mg / m 2} , 15mg ^{/ m 2} ~65mg ^/ m 2 is most preferred.

The coating amount of the particles (a2e) is ^preferably from ^{1mg / m 2 ~23mg / m 2} , more preferably ^{2mg / m 2 ~21mg / m 2} , 3mg / m 2 ~19mg / m 2 is most preferred.

[Immersion exposure device]
The transmission filter of the present invention can be applied to an immersion exposure apparatus. The immersion exposure apparatus of the present invention includes the transmission filter of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, reagents, amounts of substances and their ratios, operations, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[Synthesis of silica particles P1]
67.54 kg of methyl alcohol and 26.33 kg of 28% by mass aqueous ammonia (water and catalyst) were charged into a 200 L reactor equipped with a stirrer, a dropping device and a thermometer, and the liquid temperature was adjusted to 33 ° C. while stirring. Adjusted to. On the other hand, a solution prepared by dissolving 12.70 kg of tetramethoxysilane in 5.59 kg of methyl alcohol was charged into the dropping device. While maintaining the liquid temperature in the reactor at 33 ° C., the above solution was added dropwise from the dropping device over 44 minutes, and after the completion of the dropping, stirring was performed for another 21 minutes while maintaining the liquid temperature at the above temperature to tetra. Hydrolysis and condensation of methoxysilane were carried out to obtain a dispersion containing a silica particle precursor. Silica particles are dried by airflow using an instantaneous vacuum evaporator ((Cracks System CVX-8B type manufactured by Hosokawa Micron Co., Ltd.) at a heating tube temperature of 175 ° C. and a reduced pressure of 200 torr (27 kPa). Obtained P1.
The average primary particle size of the silica particles P1 was 80 nm, the dispersion degree (CV value) of the particle size was 4.8%, and the indentation hardness was 340 MPa.

[Preparation of calcined silica particles P2]
5 kg of silica particles P1 were placed in a crucible and calcined at 900 ° C. for 2 hours using an electric furnace, cooled, and then pulverized using a crusher to obtain preclassified calcined silica particles. Further, calcined silica particles P2 were obtained by crushing and classifying using a jet crushing classifier (IDS-2 type manufactured by Nippon Pneumatic Co., Ltd.).

[Preparation of Silane Coupling Agent-treated Silane Particles P3]
5 kg of calcined silica particles P2 were charged into a 20 L Henschel mixer (FM20J type manufactured by Mitsui Mining Co., Ltd.) equipped with a heating jacket. While stirring the calcined silica particles P2, 45 g of 3-acryloxypropyltrimethoxysilane (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise by dissolving a solution in 90 g of methyl alcohol and mixed. Then, the temperature was raised to 150 ° C. over about 1 hour while mixing and stirring, and the temperature was maintained at 150 ° C. for 12 hours for heat treatment. In the heat treatment, the scraping device was constantly rotated in the direction opposite to that of the stirring blade to scrape off the deposits on the wall surface. In addition, a spatula was used to scrape off the wall deposits as appropriate. After heating, it was cooled and crushed and classified using a jet pulverization classifier to obtain silane coupling agent-treated silica particles P3.
The average primary particle size of the silane coupling agent-treated silica particles P3 was 72 nm, the particle size dispersion (CV value) was 4.9%, and the indentation hardness was 470 MPa.

[Preparation of silica particle dispersion PA-1]
50 g of silica particles P1, 200 g of methyl ethyl ketone (MEK), and 600 g of zirconia beads having a diameter of 0.05 mm were placed in a 1 L bottle container having a diameter of 12 cm, set in a ball mill V-2M (Irie Shokai), and dispersed at 250 rpm for 10 hours. .. In this way, the silica particle dispersion liquid PA-1 (solid content concentration 20% by mass) was prepared.

[Preparation of silica particle dispersion PA-2]
50 g of silane coupling agent-treated silica particles P3, 200 g of MEK, and 600 g of zirconia beads with a diameter of 0.05 mm are placed in a 1 L bottle container with a diameter of 12 cm, set in a ball mill V-2M (Irie Shokai), and dispersed at 250 rpm for 10 hours. did. In this way, a silica particle dispersion liquid PA-2 (solid content concentration 20% by mass) was prepared.

<Example 1>
[Preparation of composition for forming layer (a)]
Each component was put into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to prepare a coating liquid. In this way, the composition (A-1), which is the composition for forming the layer (a), was prepared.

Composition (A-1)
SIRIUS-501: 1.4 parts by mass Compound C3: 1.5 parts by mass A-TMPT: 1.7 parts by mass Triethyl citrate: 4.1 parts by mass Irgacure 127: 0.2 parts by mass Compound P: 0.1 parts by mass Part Compound E: 0.1 part by mass Silica particle dispersion PA-1: 32.3 parts by mass Ethanol: 12.7 parts by mass Methyl ethyl ketone: 33.2 parts by mass Acetone: 12.7 parts by mass

The ingredients used are shown below.
SIRIUS-501: Dendrimer type polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

A-TMPT: Polyfunctional acrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Irgacure 127: Photopolymerization Initiator (manufactured by BASF Japan Ltd.)
Compound P: Photoacid generator represented by the following structural formula (manufactured by Wako Pure Chemical Industries, Ltd.)

Compound E: MEK solution formula (13) having a solid content concentration of 40% by mass of a fluorine-containing copolymer (weight average molecular weight 17,000) having a structure represented by the following formula (13).

In the composition (A-1), SIRIUS-501, compound C3, and A-TMPT are compounds (a1) having at least one (meth) acryloyl group and containing no fluorine atom.

<Manufacturing of transmission filter 1>
(Process (1) Coating of layer (a))
The composition (A-1) was applied 2.8 ml / m ² using a die coater on a 100 μm polyethylene terephthalate film (FD100M, manufactured by FUJIFILM Corporation) as a temporary support, and dried at 30 ° C. for 90 seconds. It was.

(Step (2) Pre-exposure of layer (a))
A layer (a) using a high-pressure mercury lamp (Dr. honle AG model: 33351N part number: LAMP-HOZ 200 D24 U 450 E) while purging nitrogen so that the oxygen concentration becomes an atmosphere of 1.4% by volume. ) Side was irradiated with light at an irradiation volume of 2.4 mJ / cm ² and an illuminance of 0.60 mW, and a part of the compound (a1) was cured to obtain a layer (ca). The irradiation amount was measured in a measurement range of 0.00 by attaching a HEAD SENSER PD-365 to the UV METER UVPF-A1 eye ultraviolet integrated illuminance meter manufactured by Eye Graphic.

(Step (3) Adhesive film bonding)
Next, an adhesive film obtained by peeling the release film from the protective film (Musstack TFB AS3-304) manufactured by Fujimori Kogyo Co., Ltd. is formed on the layer (ca), and the adhesive layer (layer (b)) is layered ( It was pasted so that it was on the ca) side. For bonding, a commercial laminator Bio330 (manufactured by DAE-EL Co.) was used, and the bonding was performed at a speed of 1.
The protective film here refers to a laminate composed of a support / adhesive layer / release film, and a laminate composed of a support / adhesive layer obtained by peeling the release film from the protective film. It is an adhesive film.

The protective film used is shown below.
Massac TFB AS3-304 (Optical protective film with antistatic function manufactured by Fujimori Kogyo Co., Ltd.) (hereinafter also referred to as "AS3-304")
Support: Polyester film (thickness 38 μm)
Adhesive layer thickness: 20 μm
Maximum transmittance at wavelengths of 250 nm to 300 nm with the release film peeled off: less than 0.1%

The transmittance was measured using an ultraviolet-visible near-infrared spectrophotometer UV3150 manufactured by Shimadzu Corporation.

(Step (4) Penetration of compound (a1) into layer (b))
After the adhesive film was attached, the mixture was allowed to stand in an environment of 25 ° C. for 5 minutes to allow the compound (a1) to penetrate into the layer (b).

(Partial curing of step (4-2) layer (ca))
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the oxygen concentration became 0.01% by volume or less, and the layer (ca) side of the support was used. A part of the layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation amount of 600 mJ / cm ² from the opposite side.

(Step (5) Peeling of temporary support Preparation of laminated body)
The FD100M, which is a temporary support, was peeled from the laminated body in the 180 ° direction at a speed of 30 m / min. In this way, the laminated body 1 was produced.

(Step (6) Lamination of base materials)
The layer (ca) side of the laminate 1 from which the temporary support was removed in the step (5) was bonded to the CONTURAN Tempax float (thickness 2 mm, light transmittance of 315 nm, 72%, manufactured by SCHOOTT Co., Ltd.). For bonding, commercial laminator Bio330 (DAE-EL)
Co. Was carried out at a speed of 1.

(Step (7) Partial curing of layer (ca))
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the oxygen concentration became 0.01% by volume or less, and the layer (ca) side of the support was used. A part of the layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation amount of 600 mJ / cm ² from the opposite side.

(Step (8) Peeling of adhesive film)
The adhesive film (the release film was peeled off from Massac TFB AS3-304) was peeled off from the above-mentioned laminated body.

(Step (9) Curing of layer (ca))
Subsequently, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less, and the base material of the layer (ca) was used. The layer (ca) was cured by irradiating ultraviolet rays having an illuminance of 150 mW / cm ² and an irradiation volume of 600 mJ / cm ² from the opposite side.

(Step (10) Cleaning)
Subsequently, methyl isobutyl ketone was poured over the surface to which the adhesive film was bonded to wash away the residue of the adhesive layer. Then, it was dried at 25 degreeC for 10 minutes to obtain a transmission filter 1.

<Example 2>
The laminate 2 and the transmission filter 2 were produced in the same manner as in the production of the laminate 1 and the transmission filter 1 except that the types of the particles (a2) in the layer (a) forming composition were changed as shown in Table 1.
<Examples 6 to 9>
Laminated body 1 and permeation except that the types of particles (a2), compound (a1) and fluorine-containing copolymer (C) in the layer (a) forming composition and the type of base material were changed as shown in Table 1. Laminates 6 to 9 and transmission filters 6 to 9 were produced in the same manner as in the production of the filter 1. In Examples 6 to 9, 2.2 parts by mass of KR-513 and 2.4 parts by mass of compound C3 were used in the composition for forming the layer (a).

<Example 3>
[Preparation of composition for layer (ae) formation]
Each component was put into a mixing tank so as to have the following composition, stirred for 60 minutes, and dispersed by an ultrasonic disperser for 30 minutes to prepare a coating liquid. In this way, the composition (B-1), which is a composition for forming a layer (ae), was prepared.

Composition (B-1)
SIRIUS-501: 1.4 parts by mass Compound C3: 1.5 parts by mass A-TMPT: 1.7 parts by mass Triethyl citrate: 4.1 parts by mass Irgacure 127: 0.2 parts by mass Compound P: 0.1 parts by mass Part Compound E: 0.1 parts by mass MEK-AC-4130Y: 32.3 parts by mass Ethanol: 12.7 parts by mass Methyl ethyl ketone: 33.2 parts by mass acetone: 12.7 parts by mass

The components used other than those mentioned above are shown below.
MEK-AC-4130Y: Acrylic modified colloidal silica, average primary particle size 45 nm, manufactured by Nissan Chemical Industry Co., Ltd. MEK-AC-2140Z: Acrylic modified colloidal silica, average primary particle size 15 nm, manufactured by Nissan Chemical Industry Co., Ltd.

<Preparation of transmission filter 3>
(Coating of process (1e) layer (ae))
The composition (B-1) was applied to a polyethylene terephthalate film (FD100M, manufactured by FUJIFILM Corporation) of 100 μm as a temporary support at 2.8 ml / m ² using a die coater, and dried at 30 ° C. for 90 seconds. It was.

(Steps (2e) to (5e))
In the steps (2) to (5) for producing the transmission filter 1 described above, the laminate 3 containing the layer (ae) is formed in the same manner except that the layer (ae) is used instead of the layer (a). Was produced.

(Step (6e) Lamination of base materials)
The layer (ae) side of the laminated body 3 and the layer (ca) side (side having an uneven shape) of the transmission filter 1 produced above were bonded together. For bonding, a commercial laminator Bio330 (manufactured by DAE-EL Co.) was used, and the bonding was performed at a speed of 1.

(Steps (7e) to (10e))
The steps (7) to (10) for producing the transmission filter 1 described above were carried out in the same manner to produce the transmission filter 3.

<Example 4>
In the production of the transmission filter 3, the transmission filter 4 was produced in the same manner except that the transmission filter 2 was used instead of the transmission filter 1.
<Example 5>
A transmission filter 5 was produced in the same manner as the transmission filter 4 except that the types of particles (a2e) in the layer (ae) forming composition were changed as shown in Table 1.

The components other than those mentioned above used in the examples are as follows.
Synthetic quartz AQT; Grade synthetic quartz for deep ultraviolet excimer laser (manufactured by Asahi Glass Co., Ltd., thickness 2 mm, wavelength 315 nm, light transmittance 92%)
Synthetic quartz particles PA-3; Products with different particle sizes (average primary particle size 72 nm) produced in the same manner as the synthetic quartz particles described in Example 3 of JP-A-2003-12331.
RS-90; Perfluoro group-containing acrylate polymer (manufactured by DIC Corporation)
KR-513; Acryloyl group and methyl group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Comparative Examples 1, 2, 4, 5>
Laminated body 1 and permeation except that the types of particles (a2), compound (a1) and fluorine-containing copolymer (C) in the layer (a) forming composition and the type of base material were changed as shown in Table 1. Laminates 101, 102, 104, 105 and transmission filters 101, 102, 104, 105 were produced in the same manner as in the production of the filter 1.

The components other than those described above used in the comparative example are as follows.
TU2661; UV curable hollow silica-containing fluorine-containing low refractive index material (manufactured by JSR Corporation)
ZF-14: Cycloolefin resin film with a thickness of 100 μm (0.1 mm) (ZEONOR ZF-14, ZEON Corporation, light transmittance of 315 nm wavelength 87%)
Soda lime glass # 0050: Made by Matsunami Glass Co., Ltd., thickness 2 mm, wavelength 315 nm, light transmittance 55%

<Comparative example 3>
It is composed of an ultrafine silica compound plasma-treated using TMCTS (tetramethylcyclotetrasiloxane) as a raw material in the same manner except that the glass substrate is replaced with CONTURAN Tempax Float in the first embodiment of the embodiment of Japanese Patent No. 6142562. A superhydrophobic material was produced.

Table 1 also shows the distances A and B / A measured and calculated by the following measurement methods.
After scratching the transmission filter with a diamond cutter, a cross section was obtained by breaking along the scratch, and the cross section was etched for 10 minutes after carbon vapor deposition. A scanning electron microscope (SEM) was used to observe and photograph 20 fields of view at 5000 times. In the obtained image, at the interface between the air and the sample, the distance A between the vertices of the adjacent convex portions and the distance B between the center and the concave portion between the vertices of the adjacent convex portions are measured at 100 points, and A and , B / A was calculated as an average value.
When adjacent particles come into contact with each other and the distance A between the vertices of the convex portion becomes non-uniform and the size becomes bipolar, or when the distance B becomes non-uniform and the size becomes bipolar. It was evaluated as "unmeasurable".

(Evaluation method of transmission filter)
Various characteristics of the transmission filter were evaluated by the following method. The results are shown in Table 2.

(Water contact angle)
The contact angle of water refers to the contact angle of water obtained by tangential method by dropping pure water on the surface of a permeation filter (the surface opposite to the base material side). The contact angle was measured using a contact angle measuring device DM-700 manufactured by Kyowa Interface Science.

(Ultraviolet transmittance: UV-A transmittance)
The UV-A transmittance, which is an index of ultraviolet transmittance, was measured in the range of 190 nm to 780 nm using a spectrophotometer: UV3150 (manufactured by Shimadzu Corporation) in an atmosphere of 25 ° C. and 55% relative humidity. Of these, the transmittance at a wavelength of 315 nm was defined as the UV-A transmittance.

(Scratch resistance)
A non-woven fabric (Bencot M-3, manufactured by Asahi Kasei Corporation) is attached to the friction element of a device (Gakushin type friction fastness tester AB-301, manufactured by Tester Sangyo Co., Ltd.) that reciprocates at a speed of 6 m / min for testing. The transmission filter of the present invention was installed on one stand, and after reciprocating and rubbing with a load of 4.9 N / cm ² , the evaluation was performed according to the following criteria.
A: No change in appearance was observed in the transmission filter even after 30 round trips.
B: The whiteness of the transmission filter increased slightly between 21 and 30 round trips.
C: The whiteness of the transmission filter increased slightly between 11 and 20 round trips.
D: The whiteness of the transmission filter increased slightly between 1 and 10 round trips.
E: The whiteness of the transmission filter increased significantly between 1 and 9 round trips.

(Water sliding angle)
The water sliding angle refers to the angle at which water droplets start to move when pure water is dropped on the surface of the transmission filter (the surface opposite to the base material side) and the transmission filter is tilted. The sliding angle was measured by attaching the sliding method kit (DM-SA) to the contact angle measuring device DM-700 manufactured by Kyowa Interface Science.

As can be seen from the results in Table 2, it was found that the transmission filter of the example had a water contact angle of 120 ° or more and was excellent in water repellency. In particular, it was found that the water repellency was particularly high in Examples 3 to 5 having the configuration of the second aspect. Further, it was found that the transmission filter of the example was also excellent in repeated exposure durability because it had good UV-A transmittance and scratch resistance.
From the above, the transmission filter of the present invention is an optical member having excellent water repellency and repeated exposure durability, particularly as a transmission filter in an immersion exposure apparatus.

1 Temporary support 2 Water repellent layer 3 Particles (a2)
4 layer (a) or layer (ca)
5 Support 6 layers (b)
7 Adhesive film 8 Laminated body 9 Base material 10, 11, 23, 55 Transmission filter 3e Particles (a2e)
4e layer (ae) or layer (cae)
A Distance between the vertices of adjacent convex parts B Distance between the center and concave part between the vertices of adjacent convex parts 21 Water-repellent layer 22 Hydrophilic layer 54 Lens 54A Lens surface 54B Lens side surface UV UV

Claims (17)

A transmission filter having a base material having a light transmittance of 65% or more at a wavelength of 315 nm and a water-repellent layer arranged on the base material.
The water-repellent layer includes a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and containing no fluorine atom, and particles (a2) having an average primary particle size of 150 nm or less. And a reaction product of a fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group.
The content of the reactant of the fluorine-containing copolymer having a fluoroalkyl group and a cross-linking group is 0.05% by mass or more in the total solid content of the water-repellent layer.
The surface of the water-repellent layer opposite to the base material side has a convex portion formed by the particles (a2) and a concave portion between the convex portions.
B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions of the water-repellent layer to the distance B between the center and the concave portion between the vertices of the adjacent convex portions, is larger than 0.50.
The distance A is 315 nm or less,
A transmission filter having a water contact angle of 120 ° or more on the surface of the water-repellent layer opposite to the base material side. The compound (a1) is a compound having at least three alkoxy groups bonded to a silicon atom in the molecule.
The resin obtained by curing the compound (a1) is a resin having a siloxane bond.
The transmission filter according to claim 1. The transmission filter according to claim 1 or 2, wherein the indentation hardness of the particles (a2) is 400 MPa or more. The transmission filter according to any one of claims 1 to 3, wherein the particles (a2) are unfired silica particles, fired silica particles, or synthetic quartz particles. The transmission filter according to any one of claims 1 to 4, wherein the sliding angle of water on the surface of the water-repellent layer opposite to that of the base material is 30 ° or less. A layer (cae) containing a resin obtained by curing particles (a2e) having an average primary particle size smaller than the particles (a2) and a compound (a1e) having at least one (meth) acryloyl group on the convex portion. And have
The transmission filter according to any one of claims 1 to 5, wherein the surface of the layer (cae) opposite to the particle (a2) side has a convex portion formed by the particles (a2e). The transmission filter according to claim 6, wherein the average primary particle size of the particles (a2e) is 5 to 50 nm. The transmission filter according to claim 6 or 7, wherein the indentation hardness of the particles (a2e) is less than 400 MPa. The transmission filter according to any one of claims 6 to 8, wherein the particles (a2e) are unfired silica particles. The transmission filter according to any one of claims 1 to 9, wherein the contact angle of water on the surface of the water-repellent layer opposite to that of the base material is 130 ° or more. The transmission according to any one of claims 1 to 10, which is used to protect the optical system of the immersion exposure apparatus that exposes an exposure object with an exposure ray transmitted through the optical system through the immersion liquid. filter. The transmission filter according to claim 11, wherein the distance A is equal to or less than the wavelength of the exposed light beam. The transmission filter according to claim 12, wherein the average primary particle size of the particles (a2) is 9/14 or less of the wavelength of the exposed light beam, and the distance A is 5/7 or less of the wavelength of the exposed light beam. The transmission filter according to claim 13, wherein the average primary particle size of the particles (a2) is 9/19 or less of the wavelength of the exposed light beam, and the distance A is 1/2 or less of the wavelength of the exposed light beam. The transmission filter according to claim 14, wherein the average primary particle size of the particles (a2) is 7/19 or less of the wavelength of the exposed light beam, and the distance A is 15/38 or less of the wavelength of the exposed light beam. Having a hydrophilic layer in the same plane as the water-repellent layer on the substrate,
The water-repellent layer and the hydrophilic layer are alternately arranged in the in-plane direction.
The shape of the water-repellent layer and the hydrophilic layer when viewed from a direction orthogonal to the in-plane direction is triangular.
The hydrophilic layer is a layer (ca) containing a resin obtained by curing a compound (a1) having at least one (meth) acryloyl group and containing no fluorine atom, and particles (a2) having an average primary particle size of 150 nm or less. Including and
The surface of the hydrophilic layer opposite to the base material side has a convex portion formed by the particles (a2) and a concave portion between the convex portions.
B / A, which is the ratio of the distance A between the vertices of the adjacent convex portions of the hydrophilic layer to the distance B between the center and the concave portion between the vertices of the adjacent convex portions, is larger than 0.50.
The distance A is 315 nm or less,
The contact angle of water on the side of the hydrophilic layer opposite to that of the base material is 20 ° or less.
The transmission filter according to any one of claims 1 to 15. An immersion exposure apparatus for exposing an object to be exposed with an exposure ray transmitted through an optical system through an immersion liquid, the immersion exposure device including the transmission filter according to any one of claims 1 to 16. apparatus.