JP2019171743A - Antifouling film - Google Patents

Abstract

To provide an antifouling film that has an antifouling layer excellent in antifouling property even after aging.SOLUTION: Provided is an antifouling film having an antifouling layer on one surface of the film substrate, and in which, when performing an aging at 40°C for 72 hours in a state in which the antifouling layer and the surface of the opposite side to the antifouling layer of the film substrate are in contact with each other, and then followed by peeling, the contact angle of water on the surface of the opposite side of the film substrate that was in contact with the antifouling layer is 90° to 115°. More preferably, the antifouling film in which the surface of the film substrate of the side opposite to the antifouling layer is a resin functional layer.SELECTED DRAWING: None

Description

  The present invention relates to an antifouling film having excellent antifouling properties.

  In recent years, with the widespread use of mobile terminal devices such as personal computers, mobile phones, and smartphones, there is an increasing demand for protecting these articles from dirt and scratches. In particular, it is essential to impart antifouling properties to display surfaces that require visibility, even though they are always touched surfaces such as touch panels. On the other hand, the technique for imparting antifouling properties has been applied to art works such as paintings, building materials such as wall surfaces, and articles such as furniture that are regarded as important in appearance.

  As a method of imparting antifouling property to an article, there is a method of directly applying to the article, but as a simple method, a method of applying an antifouling layer and attaching a laminated film material is generally used. As a method for forming the antifouling layer, a method of forming a silane coupling agent having a perfluoroalkyl group by heat treatment is simple, but damage to the film is a problem because it is a treatment at a relatively high temperature. It becomes. Therefore, in recent years, a technique in which a compound having a perfluoroalkyl group that is soluble in an organic solvent is crosslinked with a crosslinking agent at a low temperature (see Patent Document 1).

Japanese Patent No. 5989291

  A film excellent in antifouling property can be easily formed by crosslinking the fluorine-containing resin, but aging is necessary because the reaction rate is slow. It is efficient to perform the aging in a state in which the fluorine-containing resin is wound up, but there is a problem that the antifouling property is not sufficiently exhibited when the aging proceeds with the fluorine-containing resin in contact with the back surface thereof.

  An object of the present invention is to solve the above-described problems of the prior art and to provide an antifouling film having an antifouling layer excellent in antifouling properties even after aging.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an effect of obtaining an antifouling layer having excellent antifouling properties is exhibited even after aging. That is, the present invention comprises the following method and configuration.

1. An antifouling film having an antifouling layer on one surface on a film substrate, wherein the antifouling layer and the surface of the film substrate opposite to the antifouling layer are in contact with each other at 40 ° C. for 72 hours The antifouling film has a contact angle of water of 90 ° to 115 ° on the opposite surface of the film substrate that has been peeled off and then contacted with the antifouling layer.
2. The antifouling film as described in the above item 1, wherein the antifouling layer is mainly composed of a silicone resin and / or a fluorine resin.
3. The method for producing an antifouling film according to the first or second aspect, wherein the surface of the film base opposite to the antifouling layer satisfies Formula 1.
| A−b | ≦ 10 (°) Expression 1
a: Contact angle (°) of water before contacting the antifouling layer on the surface opposite to the antifouling layer of the film substrate
b: Aging was performed at 40 ° C. for 72 hours in a state where the antifouling layer of the film base material and the surface opposite to the antifouling layer of the film base material were in contact with each other, and the antifouling layer was peeled off after aging. Water contact angle on the surface of the film base opposite to the antifouling layer (°)
4). The antifouling film according to any one of the first to third aspects, wherein the surface of the film base opposite to the antifouling layer is a resin functional layer.
5. 5. The resin composition according to the fourth aspect, wherein a mass concentration of 60% or more of all resin components constituting the resin functional layer is at least one resin selected from silicone-based, cyclic olefin-based, acyclic olefin-based, and fluorine-based resin. Antifouling film.

  According to the present invention, by controlling the contact angle of water on the surface opposite to the antifouling layer of the film base that was in contact with the antifouling layer of the film base, the antifouling of the antifouling layer even after aging is controlled. It was possible to provide an antifouling film that can maximize its performance.

Hereinafter, the present invention will be described in detail.
Usually, in many cases, the film is wound into a roll and conveyed. In the case of an antifouling film having an antifouling layer on the film substrate, the antifouling layer must be stored in contact with the surface of the film substrate opposite to the antifouling layer when wound up in a roll shape. become. Conventionally, while the antifouling film is stored in such a roll shape, the antifouling layer is in contact with the surface of the film base opposite to the antifouling layer, so that the antifouling layer has an antifouling property. Although there was a problem which was spoiled, it can be said that this invention solved the problem.

[Film substrate]
The film base material to which the antifouling layer is applied in the present invention is not particularly limited in terms of material, shape and the like.

  The film base material is polyolefin resin such as polyethylene, polypropylene, polybutene, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, 1,4-cyclohexanedimethanol copolymerized polyester, neopentyl glycol copolymer Polyester, polyester resins such as 5-sodium isophthalic acid copolyester, polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polycaprolactam polyurethane and other polyurethane resins, polycarbonate resins, acrylic resins, etc. Can be used without any particular restrictions.

  The film base material may use a single material, may be a mixed system such as a polymer alloy, or may have a structure in which a plurality of materials are laminated. As the shape of the film substrate, there is no particular problem whether it is a sheet shape or a roll shape, but the roll shape has a higher production efficiency and is generally used. A film substrate having a thickness of 9 to 250 μm is preferably used.

[Anti-fouling layer]
The antifouling layer in the present invention contains a silicone resin and / or a fluorine resin as a main component. Here, the antifouling layer of the antifouling film in the present invention includes a case where the antifouling layer is cross-linked and cured with a cross-linking agent, but the main component here is in the solid content mass of the coating liquid forming the antifouling layer. This means that a total of 50 mass% or more of the silicone resin and / or fluorine resin is contained.

  As the silicone-based antifouling agent, for example, organopolysiloxane mainly composed of dimethylpolysiloxane can be used, and a part of the methyl group is phenyl group, ethyl group, isopropyl group, hexyl group, cyclohexyl group, hydroxyl group, It may be substituted with a vinyl group or the like. In addition, it may be modified with an organic functional group such as polyether, polyester, acrylic, etc., and is not particularly limited.

  Examples of the fluorine-based antifouling agent include compounds containing a perfluoroalkyl group and a perfluoroalkylene ether group. What combined organic siloxanes, such as dimethyl silicone, can also be used.

  The silicone antifouling agent and the fluorine antifouling agent can be used alone or in combination of two or more antifouling agents.

  The antifouling layer may have a crosslinked structure. Examples of the antifouling layer crosslinking agent include aromatic diisocyanates such as tolylene diisocyanate, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, tetramethylene diisocyanate, Isocyanate-based crosslinking agents such as lower aliphatic diisocyanates such as hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, alicyclic isocyanates such as hydrogenated aromatic diisocyanates, and methyl etherified melamine Examples thereof include melamine-based crosslinking agents such as resins and butyl etherified melamine resins, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents.

  In addition, a known catalyst can be used for speeding up the formation of the crosslinked structure, and it can be diluted with a known organic solvent for the purpose of reducing the viscosity at the time of applying the antifouling layer.

[Application method of antifouling layer]
The method for applying the antifouling layer to the film substrate is not particularly limited, and can be applied by a known method. Specific examples include a direct gravure coater, a micro gravure coater, a reverse gravure coater, a direct kiss coater, a reverse kiss coater, a comma coater, a die coater, and a bar / lot type coating apparatus.

[Drying of antifouling layer]
The drying temperature after coating is preferably 80 ° C. or higher and lower than 180 ° C. When the temperature is 80 ° C. or higher, it is possible to prevent the solvent from being dried insufficiently, and due to the residual solvent, the adhesive force with the surface of the film base opposite to the antifouling layer is excessively increased during aging, resulting in a peeling force. Since it can prevent heavy peeling, 80 degreeC or more is preferable. Moreover, when it is less than 180 degreeC, since a film base material cannot raise | generate a shrinkage | contraction and a deformation | transformation with a heat | fever, and it can dry, maintaining flatness, it is preferable.

  The drying time is preferably 1 second or more and less than 180 seconds. If it is longer than 1 second, it is possible to prevent the solvent from becoming insufficiently dried, and the residual solvent increases the adhesion between the antifouling layer and the surface opposite to the antifouling layer of the film base during aging. Therefore, it is preferable because the peeling force can be prevented from becoming heavy peeling. From the standpoint of productivity, if less than 180 seconds, the cost can be suppressed, so less than 180 seconds is preferable.

  The thickness of the antifouling layer after drying is preferably 0.01 μm or more and 20 μm or less. A thickness of 0.01 μm or more is preferable because durability against friction is improved. In the case of 20 μm or less, the residual solvent is unlikely to remain in the antifouling layer drying step, and the peeling force after aging is difficult to cause heavy peeling, which is preferable.

[Lamination process]
After drying, the antifouling layer is laminated with the opposite surface. The process of laminating includes the method of laminating the antifouling layer on a film substrate, drying it and then cutting it to a certain size in a single wafer state, laminating it in a roll state, etc. In order to improve productivity, it is preferable to laminate the opposite surface by winding. As temperature at the time of winding, 20 degreeC or more and 60 degrees C or less are preferable. If it is 20 degreeC or more, since the adhesiveness of the surface and antifouling layer on the opposite side to the surface which apply | coated and formed the antifouling layer is good, it is preferable. If it is less than 80 degreeC, since it can prevent that the adhesiveness of the surface and antifouling layer on the opposite side to the surface which apply | coated and formed the antifouling layer can be prevented, it is preferable. More preferably, they are 30 degreeC or more and 55 degrees C or less, More preferably, they are 35 degreeC or more and 52 degrees C or less.

[aging]
After the antifouling layer is applied on the film substrate and dried, the film is aged in contact with the surface opposite to the antifouling layer of the substrate film, but can be applied regardless of the sheet state or the roll state. The method of aging in a roll state after winding into a roll is superior in productivity and is a simple method.

  The state in which the antifouling layer is in contact with the opposite surface is, in detail, the state in which it is in direct contact, and the air between the antifouling layer and the opposite surface is almost completely expelled, causing bubbles. It is in a state of being in close contact.

  The aging is preferably performed at 30 ° C. or more and 60 ° C. or less. A temperature of 30 ° C. or higher is preferable because it can promote the crosslinking reaction of the antifouling layer and enhance the curability. When the temperature is 60 ° C. or lower, it is preferable that the antifouling layer is softened and the adhesion of the surface in contact with the antifouling layer becomes too strong to prevent peeling. More preferably, it is 35 degreeC or more and 55 degrees C or less, More preferably, it is 38 degreeC or more and 52 degrees C or less.

  The aging time is preferably 1 day or more and less than 10 days. In the case of 1 day or more, it is preferable because it is a sufficient time until heat is sufficiently transmitted to the center of the roll body, and the antifouling layer near the winding core is cured without being insufficiently crosslinked. If it is less than 10 days, the crosslinking reaction is completed even if the aging temperature is low, and the productivity does not decrease, which is preferable.

  The antifouling film of the present invention is in contact with the surface opposite to the antifouling layer and the antifouling layer of the film base, and is on the side opposite to the antifouling layer when peeled after aging at 40 ° C. for 72 hours. Excellent antifouling property is exhibited when the contact angle of water on the surface is 90 ° to 115 °. The contact angle of water is more preferably 90 ° to 110 °, and most preferably 95 ° to 105 °. When the contact angle of water is 90 ° or more, the component of the part in contact with the antifouling layer on the surface opposite to the antifouling layer of the film base described later is transferred to inhibit the antifouling property of the antifouling layer It is preferable without fear. Moreover, it is preferable that the contact angle of water is 115 ° or less because there is no possibility that the antifouling component of the antifouling layer is transferred to the functional layer side of the protective film and inhibits the antifouling property.

Moreover, it is preferable that the antifouling film of this invention satisfy | fills following formula 1.
| A−b | ≦ 10 Equation 1
a: Contact angle (°) of water before contacting the antifouling layer on the surface opposite to the antifouling layer of the film substrate
b: Aging was performed at 40 ° C. for 72 hours in a state where the antifouling layer of the film base material and the surface opposite to the antifouling layer of the film base material were in contact with each other, and the antifouling layer was peeled off after aging. Water contact angle on the surface of the film base opposite to the antifouling layer (°)
It is preferable that | a−b | ≦ 10 because the antifouling property of the antifouling layer after the two sample films are peeled off after aging can be prevented.

  In the present invention, a resin functional layer having a composition different from that of the film substrate may be provided on the surface of the film substrate opposite to the antifouling layer. Examples of the composition of the resin functional layer include silicone-based, cyclic olefin-based, acyclic olefin-based, and fluorine-based resins. These resins may be used as a main resin or may be used as an additive for a binder resin. The binder resin is not particularly limited. For example, a UV curable resin obtained by curing a functional group such as an acrylic group, a vinyl group, or an epoxy group by UV irradiation, an ester type, a urethane type, an olefin type, an acrylic type, or the like. Thermoplastic resins such as epoxy resins, and thermosetting resins such as epoxy resins and melamine resins can also be used.

  It is preferable that a mass concentration of 60% or more of all the resin components forming the resin functional layer is selected from at least one resin selected from the aforementioned silicone-based, cyclic olefin-based, acyclic olefin-based, and fluorine-based resins. A mass concentration of 60% or more is preferred because the contact angle difference | ab− before and after lamination with the antifouling layer is effectively 10 ° or less. More preferably, it is 80 mass% or more. The upper limit may be 100% by mass or 98% by mass or less.

  The silicone-based resin is a resin having a silicone structure in the molecule, and examples thereof include reactive curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl modification.

As the reactive curable silicone resin, an addition reaction type, a condensation reaction type, an ultraviolet ray or an electron beam curable type can be used.
Examples of the addition reaction type silicone resin include those obtained by reacting and curing polydimethylsiloxane having a vinyl group introduced into the terminal or side chain thereof with hydrodienesiloxane using a platinum catalyst. At this time, it is more preferable to use a resin that can be cured at 120 ° C. within 30 seconds because processing at a low temperature is possible. Examples include low temperature addition curing type (LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC75A, LTC75A, LTC75A, LTC75A, LTC75A, LTC75A, LTC75A, LTC7A50 Mold (LTC851, BY24-510, BY24-561, BY24-562, etc.), Shinetsu Chemical's solvent addition type (KS-774, KS-882, X62-2825, etc.) Solvent addition + UV curing type (X62-5040, X62-5065, X62-5072T, KS5508, etc.), dual cure curing type (X62-2835, X62-2834, X62-1980, etc.) and the like. As a silicone resin of the condensation reaction system, for example, a polydimethylsiloxane having an OH group at the end and a polydimethylsiloxane having an H group at the end are subjected to a condensation reaction using an organotin catalyst to form a three-dimensional crosslinked structure. Can be mentioned. Examples of UV curable silicone resins include those that use the same radical reaction as ordinary silicone rubber crosslinks as the most basic types, those that introduce photopolymerization by introducing unsaturated groups, and those that decompose onium salts with UV light. Examples include those that generate a strong acid and then cleave the epoxy group to crosslink, and those that crosslink by the addition reaction of thiol to vinylsiloxane. Further, an electron beam can be used instead of the ultraviolet rays. Electron beams have stronger energy than ultraviolet rays, and can use a radical crosslinking reaction without using an initiator as in the case of ultraviolet curing. Examples of the resin to be used include UV-curable silicones (X62-7028A / B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance UV curable silicones manufactured by Materials (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.), UV curable silicones manufactured by Arakawa Chemical (Silicolys UV POLY200, POLY215, POLY201, KF-UV265AM, etc.) ).

  As the ultraviolet curable silicone resin, polydimethylsiloxane modified with acrylate or glycidoxy may be used. These modified polydimethylsiloxanes can be mixed with a polyfunctional acrylate resin or epoxy resin and used in the presence of an initiator.

The cyclic olefin-based resin contains a cyclic olefin as a polymerization component. The cyclic olefin is a polymerizable cyclic olefin having an ethylenic double bond in the ring, and can be classified into a monocyclic olefin, a bicyclic olefin, a tricyclic or higher polycyclic olefin, and the like.
Examples of monocyclic olefins include cyclic C4-12 cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.
Examples of the bicyclic olefin include 2-norbornene; alkyl groups such as 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, and 5-butyl-2-norbornene. Norbornenes having (C1-4 alkyl group); norbornenes having an alkenyl group such as 5-ethylidene-2-norbornene; 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, etc. Norbornenes having an alkoxycarbonyl group; norbornenes having a cyano group such as 5-cyano-2-norbornene; having an aryl group such as 5-phenyl-2-norbornene and 5-phenyl-5-methyl-2-norbornene Norbornenes; octaline; 6-ethyl-oct Such -octalin having an alkyl group such as tetrahydronaphthalene can be exemplified.

  Examples of the polycyclic olefin include dicyclopentadiene; 2,3-dihydrodicyclopentadiene, methanooctahydrofluorene, dimethanooctahydronaphthalene, dimethanocyclopentadienonaphthalene, methanooctahydrocyclopentadienaphthalene, and the like. Derivatives having substituents such as 6-ethyl-octahydronaphthalene; adducts of cyclopentadiene and tetrahydroindene, 3-pentamers of cyclopentadiene, and the like.

  The acyclic olefin-based resin contains an acyclic olefin as a polymerization component. Examples of the acyclic olefin include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, Examples include alkenes such as 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene.

  Rubber can also be used as a resin for surface treatment. Examples thereof include copolymers such as butadiene and isoprene. Regardless of the cyclic olefin or the non-cyclic olefin, the olefin resin may be used alone or two or more kinds thereof may be copolymerized. The cyclic olefin resin and the non-cyclic olefin resin may be partially modified with a hydroxyl group or an acid. You may make it crosslink with those functional groups using a crosslinking agent. The crosslinking agent may be appropriately selected according to the modifying group. For example, aromatic diisocyanates such as tolylene diisocyanate, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, and the like. , Cross-linked isocyanates such as lower aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, and alicyclic isocyanates such as hydrogenated aromatic diisocyanates In addition to the agent, melamine-based crosslinking agents such as methyl etherified melamine resin and butyl etherified melamine resin, and epoxy-based crosslinking agents.

The fluorine-based compound is not particularly limited as long as it is a compound having at least one of a perfluoroalkyl group and a perfluoroalkyl ether group. The fluorine-based compound may be partially modified with an acid, a hydroxyl group, an acrylate group, or the like. A crosslinking agent may be added to crosslink at the modification site. Alternatively, a compound having at least one of a perfluoroalkyl group and a perfluoroalkyl ether group may be added to the UV curable resin for polymerization. Alternatively, it may be used in the form of a small amount of a compound having a perfluoroalkyl group having no reactive functional group added to the binder resin.
The above resins may be used alone or in combination of two or more.

  The resin used for the resin functional layer provided on the surface opposite to the antifouling layer of the base film may be crosslinked using an arbitrary crosslinking agent.

  Examples of the crosslinking agent include aromatic diisocyanates such as tolylene diisocyanate, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate. In addition to isocyanate-based crosslinking agents such as lower aliphatic diisocyanates, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, alicyclic isocyanates such as hydrogenated aromatic diisocyanates, methyl etherified melamine Examples thereof include melamine crosslinking agents such as resins and butyl etherified melamine resins, and epoxy crosslinking agents.

  In the resin functional layer provided on the surface opposite to the antifouling layer of the base film described above, a known additive such as an antioxidant, light, and the like can be used as long as the effect of the film of the present invention is not impaired. Stabilizers, ultraviolet absorbers, crystallization agents and the like may be added.

  Examples of the method of applying a coating solution containing a resin include direct gravure coater, micro gravure coater, reverse gravure coater, direct kiss coater, reverse kiss coater, comma coater, die coater, and bar / lot type coater. It is done. The thickness of the resin functional layer after drying is preferably 10 nm or more and 1000 nm or less, more preferably 20 nm or more and 800 nm or less, and most preferably 20 nm or more and 500 nm or less. When the thickness is 10 nm or more, durability during pressurization is maintained, which is preferable. When the thickness is 1000 nm or less, the peel strength from the antifouling layer is not excessively decreased, which is preferable.

The area surface average roughness (Sa) of the resin functional layer provided on the surface opposite to the antifouling layer of the base film is preferably 50 nm or less, more preferably 20 nm or less, and still more preferably 10 nm or less. is there. When the area surface average roughness is 50 nm or less, irregularities are transferred when the protective film and the antifouling layer are pasted, and the appearance of the antifouling film after peeling off the protective film is not preferred. In addition, the said area | region surface roughness (Sa) is shown by the value measured on condition of the following using the non-contact surface shape measurement system (Ryoka System company make, VertScan R550H-M100).
(Measurement condition)
・ Measurement mode: WAVE mode ・ Objective lens: 10 times ・ 0.5 × Tube lens ・ Measurement area: 936 μm × 702 μm
(Analysis conditions)
・ Surface correction: 4th order correction ・ Interpolation processing: Complete interpolation

  In this invention, you may provide an easily bonding layer between a film base material and a resin functional layer for the purpose of improving the adhesiveness of a resin functional layer. The resin used for the easy-adhesion layer is not particularly limited, but preferably contains one, two, or three compositions of acrylic, polyester, and urethane compositions. If necessary, the coating composition for the easy-adhesion layer may contain a crosslinking agent. A method for providing the easy-adhesion layer may be an in-line coating method provided during film base film formation or an off-line coating method provided after base film formation, but the in-line coating method is preferred from the viewpoint of cost and the like.

There are various methods for forming the resin functional layer and various kinds of materials. For the antifouling property of the antifouling layer, the antifouling layer of the film substrate that has been in contact with the antifouling layer after aging at 40 ° C. for 72 hours is used. The contact angle of water on the opposite surface is 90 ° to 115 °, and the condition of Formula 1 is preferably satisfied, and the method and material are not particularly limited.
| A−b | ≦ 10 Equation 1
a: Contact angle (°) of water before contacting the antifouling layer on the surface opposite to the antifouling layer of the film substrate
b: Aging was performed at 40 ° C. for 72 hours in a state where the antifouling layer of the film base material and the surface opposite to the antifouling layer of the film base material were in contact with each other, and the antifouling layer was peeled off after aging. Water contact angle on the surface of the film base opposite to the antifouling layer (°)

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to a following example.

[Evaluation methods]
(1) Initial contact angle Water contact angle is measured using a contact angle meter ("FACE contact angle meter CA-X" manufactured by Kyowa Interface Science Co., Ltd.) under the conditions of 22 ° C and 60% RH. The surface opposite to the antifouling layer of the substrate was placed horizontally, and the contact angle measured with water for each N = 5 times was defined as the contact angle. In addition, when calculating | requiring the contact angle of water, the dripping amount was 1.8 microliters and the contact angle after standing still for 1 minute was read.

(2) Contact angle after peeling For the contact angle after peeling, prepare two antifouling film samples of appropriate size for contact angle measurement, and the opposite side of the antifouling layer of the film substrate of one sample The film that was in contact with the antifouling layer when the film bases were peeled off after adhering so that air did not enter between the surface and the antifouling layer of the other sample and aging at 40 ° C. for 72 hours The contact angle of water on the surface opposite to the antifouling layer of the substrate is defined as the contact angle after peeling. The method for measuring the contact angle was the same as that for the initial contact angle. The contact angle of the antifouling layer after peeling is also shown in Table 1 together with the measurement data.

(3) Antifouling The antifouling property is that after drying the antifouling resin, the surface opposite to the antifouling layer of the film substrate is brought into close contact with the antifouling layer so that air does not enter, and is directly maintained at 40 ° C. for 72 hours. After aging, the antifouling layer was judged from the ink repellency of the antifouling layer magic ink (M500-T1 manufactured by Teranishi Chemical Co., Ltd.) after peeling from the opposite surface of the film substrate. Good repellency. If the drawing line is 1 mm or less within 1 second, the antifouling property is ○. If the drawing line is 1 mm or less but less than 5 seconds, the antifouling property is Δ. No antifouling was observed when the drawing line width was 1 mm or more.

[Preparation of Resin Solution A for Antifouling Layer]
As the antifouling layer, a fluorine resin crosslinked with an isocyanate crosslinking agent was used.
Fluororesin solution (solid content 30% by mass, F-clear KD270R, manufactured by Kanto Denka Kogyo Co., Ltd.) 100 parts by weight, isocyanate-based crosslinking agent (solid content 100% by mass, Duranate TPA-100, manufactured by Asahi Kasei) 8.1 weight A part was diluted with methyl isobutyl ketone to prepare a resin solution A having a solid content of 20%.

[Preparation of Resin Solution B for Antifouling Layer]
As the antifouling layer, a silicone resin containing a fluorine component was used.
100 parts by mass of a fluorine component-containing silicone resin solution (solid content: 100% by mass, KR-400F, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with methyl isobutyl ketone to prepare a resin solution B having a solid content of 20%.

Example 1
Heat added silicone (solid content 30% by weight, LTC752 manufactured by Toray Dow Corning) 100 parts by weight, curing catalyst (SRX212 manufactured by Toray Dow Corning) 0.5 parts by weight, adhesion improver (SD7200 Toray Dow Corning) (Made) 0.5 parts by mass is diluted with a mixed solvent in which methyl ethyl ketone, toluene, and normal heptane are mixed at a mass ratio of 1: 1: 1 to prepare a coating solution for a resin functional layer having a solid content of 1% by mass. did. Resin functional layer so that the thickness of the coating layer after drying on a 125 μm thick film base material (biaxially stretched polyester film with a single-sided easy-adhesion layer [Cosmo Shine (registered trademark) A4100, manufactured by Toyobo Co., Ltd.)] is 50 nm. Was applied and dried at 130 ° C. for 60 seconds.
A separately prepared antifouling layer resin solution A was applied to the opposite side of the film base to which the resin functional layer was applied so that the thickness of the antifouling layer after drying would be 10 μm, and then 90 ° C. for 90 seconds. It dried and obtained the antifouling film. The antifouling film was aged in a roll state at 40 ° C. for 72 hours.

(Example 2)
Fluororesin (solid content 30% by mass, Fclear KD270R, manufactured by Kanto Denka) 100 parts by mass, curing agent (solid content 100% by mass, MR-400 manufactured by Tosoh Corporation), curing catalyst (solid content concentration 100% by mass) , Neostan U-860, manufactured by Nitto Kasei Co., Ltd.) 0.15 parts by weight is diluted with a mixed solvent in which methyl ethyl ketone and toluene are mixed at a mass ratio of 1: 1 to obtain a resin functional layer having a solid content of 1% by mass. A coating solution was prepared. Otherwise, an antifouling film was prepared in the same manner as in Example 1.

(Example 3)
Cyclic olefin resin (solid content 100% by mass, TOPAS 6017S, manufactured by Polyplastics Co., Ltd.) is diluted with a mixed solvent in which toluene and tetrahydrofuran are mixed at a mass ratio of 4: 1, and a resin functional layer having a solid content of 1% by mass. A coating solution was prepared. Otherwise, an antifouling film was prepared in the same manner as in Example 1.

(Example 4)
Acyclic olefin resin (solid content 100% by mass, GI-1000 manufactured by Nippon Soda Co., Ltd.) 100 parts by mass, curing agent (solid content 100%, MR-400 manufactured by Tosoh Corporation), 17.6 parts by mass, curing catalyst (solid content Resin having a solid content of 1% by mass, 0.6 parts by weight of 100% by mass, Neostan U-860 manufactured by Nitto Kasei Co., Ltd.) was diluted with a mixed solvent in which methyl ethyl ketone and toluene were mixed at a mass ratio of 1: 1. A functional layer coating solution was prepared. Otherwise, an antifouling film was prepared in the same manner as in Example 1.

(Example 5)
The resin functional layer was applied to the film base with the same formulation as in Example 1 so that the thickness of the coating layer after drying was 50 nm, and dried at 130 ° C. for 60 seconds. Thereafter, the resin solution B for the antifouling layer was applied to the surface opposite to the surface of the film base coated with the resin functional layer so that the thickness of the antifouling layer after drying was 10 μm, and dried at 100 ° C. for 90 seconds. An antifouling film was obtained. The antifouling film was aged in a roll state at 40 ° C. for 72 hours.

(Comparative Example 1)
Polyester urethane resin (solid content 33% by mass, Byron (registered trademark) UR-1350, manufactured by Toyobo Co., Ltd.) 100 parts by mass, additive (solid content mass 40%, MegaFac (registered trademark) RS-75, manufactured by DIC) 3 parts by mass was diluted with a mixed solvent in which methyl ethyl ketone and toluene were mixed at a mass ratio of 1: 1 to prepare a resin functional layer coating solution having a solid content of 1% by mass. The film was coated on a film substrate to a thickness of 50 nm, dried at 130 ° C. for 60 seconds, and then an antifouling film was prepared in the same manner as in Example 1.

(Comparative Example 2)
100 parts by mass of acrylic acid ester (solid content: 100% by mass, NK ester A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 part by mass of fluorine compound (solid content: 100%, OPTOOL DAC-HP, manufactured by Daikin Industries, Ltd.), initiator 10 parts by weight (solid content concentration: 100% by mass, manufactured by OMNIRAD127 BASF) was diluted with a mixed solvent in which methyl ethyl ketone and toluene were mixed at a mass ratio of 1: 1, and a resin functional layer having a solid content of 10% was applied. A liquid was created. Thereafter, the film was coated on the film substrate so as to have a thickness of 1000 nm, dried at 90 ° C. for 30 seconds, and then irradiated with ultraviolet rays so as to be 150 mJ / cm ² using a high-pressure mercury lamp, thereby forming a resin functional layer. Thereafter, in the same manner as in Example 1, an antifouling layer was formed on the surface of the film base opposite to the resin functional layer to prepare an antifouling film.

(Comparative Example 3)
100 parts by mass of melamine resin (solid content 30% by mass, Super Becamine L-109-65, manufactured by DIC), additive (solid content 5%, Megafac F444, manufactured by DIC) 3 parts by mass, additive ( SD7200 Toray Dow Corning Co., Ltd.) 1 part by mass, catalyst (solid content 5%, Becamine P-198, manufactured by DIC) 3 parts by mass, methyl ethyl ketone, toluene mixed in a mass ratio of 1: 1 It diluted with the solvent and the coating liquid of the resin functional layer of 1 mass% of solid content was created. The film was coated on the film base so that the thickness was 50 nm, dried at 130 ° C. for 60 seconds, and then subjected to aging in the same manner as in Example 1.

(Comparative Example 4)
A resin functional layer was formed on one surface of the film substrate with the same formulation as Comparative Example 1. Thereafter, an antifouling film 8 was prepared in the same manner as in Example 1 except that the resin solution B for the antifouling layer was used.

[Evaluation results]
In Examples 1 to 5, the contact angle of water in the resin functional layer after peeling was 90 ° to 115 °, and the antifouling layer exhibited excellent antifouling properties even after aging. In Comparative Examples 1 to 4, since the contact angle of water after peeling was less than 90 °, part of the components of the resin functional layer was transferred to the antifouling layer, or the antifouling property of the antifouling layer was lowered.

  According to the antifouling film of the present invention, the antifouling property of the antifouling layer can be exhibited to the maximum after aging, and can be suitably used for protecting displays, building materials, home appliances, furniture and the like. .

Claims (5)

  An antifouling film having an antifouling layer on one surface on a film substrate, wherein the antifouling layer and the surface of the film substrate opposite to the antifouling layer are in contact with each other at 40 ° C. for 72 hours The antifouling film has a contact angle of water of 90 ° to 115 ° on the opposite surface of the film substrate that has been peeled off and then contacted with the antifouling layer.   The antifouling film according to claim 1, wherein the antifouling layer comprises a silicone resin and / or a fluorine resin as a main component. The method for producing an antifouling film according to claim 1 or 2, wherein the surface of the film base opposite to the antifouling layer satisfies Formula 1.
| A−b | ≦ 10 (°) Expression 1
a: Contact angle (°) of water before contacting the antifouling layer on the surface opposite to the antifouling layer of the film substrate
b: Aging was performed at 40 ° C. for 72 hours in a state where the antifouling layer of the film base material and the surface opposite to the antifouling layer of the film base material were in contact with each other, and the antifouling layer was peeled off after aging. Water contact angle on the surface of the film base opposite to the antifouling layer (°)   The antifouling film according to any one of claims 1 to 3, wherein the surface of the film base opposite to the antifouling layer is a resin functional layer.   5. The resin according to claim 4, wherein 60% or more of the total resin content constituting the resin functional layer is at least one resin selected from silicone-based, cyclic olefin-based, acyclic olefin-based, and fluorine-based resin. Antifouling film.