Antifouling member, display, touch panel and sensor using same, and method for manufacturing antifouling member

Abstract

In a first aspect of the present invention, provided is a method for manufacturing an antifouling member, the method comprising: a step in which a surface of one surface of a base material is provided with nanoscale irregularities; and a step in which an antifouling layer containing a silane compound containing a perfluoropolyether group is formed in at least a recessed portion of the irregularities.

Description

TECHNICAL FIELD

[0001] The present invention relates to an antifouling member, a display, a touch panel, a sensor using the antifouling member, and a method for manufacturing the antifouling member. BACKGROUND ART

[0002] It is known that a fluorine-based compound is used for surface treatment of a substrate to impart water / oil repellency and antifouling property to the substrate (for example, Patent Documents 1 and 2).

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-218639

[0004] [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-082194

[0005] In a first aspect of the present invention, there is provided a method for manufacturing an antifouling member. The manufacturing method includes a base formation stage and an antifouling layer formation stage. In the base formation stage, a base layer can be formed on the surface of one face of a substrate. In the antifouling layer formation stage, an antifouling layer containing a perfluoropolyether group-containing silane compound can be formed on the base layer.

[0006] Among the above, the base layer may have nano-scale irregularities. In the antifouling layer formation stage, the antifouling layer can be formed at least in the concave portions of the irregularities.

[0007] Among the above, the base formation stage may include a drying stage and an irregularity formation stage. In the drying stage, for the substrate, the base resin composition can be coated on the substrate and dried. In the irregularity formation stage, the irregularities can be formed from the dried base resin composition.

[0008] Among the above, the base resin composition may contain an organosilicon resin including a T unit structure and a Q unit structure. The stage of forming the irregularities from the dried base resin composition may include a pretreatment of the dried base resin composition to modify the T unit structure into silica.

[0009] Among the above, the pretreatment can be performed by exposure to light having a wavelength of 150 to 200 nm.

[0010] Among the above, the pretreatment can be performed by exposure in such a manner that the cumulative illuminance reaches a range of 200 to 6000 mJ / cm 2 2.

[0011] Among the above, the pretreatment can be performed by applying an Ar / O2 mixed gas plasma in an output range of 0.2 to 1.0 kW.

[0012] Among the above, the pretreatment can be carried out by applying an Ar / O2 mixed gas plasma at a flow rate of 2000 to 5000 sccm and an oxygen fraction of 0.03 to 0.4.

[0013] Among the above, for the substrate, the coating in the stage of coating the substrate with the base resin composition and drying can be carried out in such a way that the coating film thickness becomes 1 to 20 μm.

[0014] Among the above, for the substrate, the drying in the stage of coating the substrate with the base resin composition and drying can be carried out at a temperature of 100 to 150 °C for 10 to 120 minutes.

[0015] Among the above, before the stage of forming the base by coating the substrate with the base resin composition and drying for the substrate, the stage of coating the substrate with the primer composition can also be included.

[0016] Among the above, the substrate can be glass or resin.

[0017] Among the above, the average pitch width of the convex portions of the unevenness can be 5 to 18 nm.

[0018] Among the above, the surface roughness (Rz) of the unevenness can be 3 to 15 nm.

[0019] Among the above, the contact angle when one side contacts water can be 105 to 120°.

[0020] Among the above, the pencil hardness on one side can be HB or more.

[0021] Among the above, the antifouling member can be used to cover at least a part of the display portion of the display.

[0022] Among the above, the antifouling member can be used to cover at least a part of the touch portion of the touch panel.

[0023] Among the above, the antifouling member can be used to cover at least a part of the surface of the sensor.

[0024] In the second aspect of the present invention, an antifouling member is provided, which has a substrate, a base layer provided on the substrate, and an antifouling layer provided on the base layer. The Δ haze (ΔHaze) before and after the Taber abrasion test on the antifouling layer side of the antifouling member can be 8 or less. The contact angle of water after the Taber abrasion test on the antifouling layer side of the antifouling member can be 85° or more.

[0025] Among the above, the base layer can contain a silicone resin.

[0026] Among the above, the silicone resin can include a Q unit structure and a T unit structure.

[0027] Among them, the above summary of the invention does not list all the features of the present invention. In addition, sub - combinations of these feature groups can also constitute an invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Shows an example of the antifouling component 10 of the present embodiment.

[0029] Figure 2 Shows another example of the antifouling component 10 of the present embodiment.

[0030] Figure 3 Shows an example of the process flow of the manufacturing method of the antifouling component 10 of the present embodiment.

[0031] Figure 4 Shows when setting the base layer 120 Figure 3 An example of S100 of the process flow. DETAILED DESCRIPTION OF THE INVENTION

[0032] Hereinafter, the present invention will be described by way of embodiments of the invention. However, the following embodiments do not limit the invention covered by the scope of the claims. In addition, not all combinations of features described in the embodiments are essential in the solution of the invention.

[0033] Figure 1 and Figure 2 Shows an example of the antifouling component 10 of the present embodiment. The antifouling component 10 is a surface protection component that is not easily attached with dirt and other attachments, and the attached attachments are also easily removed. The antifouling component 10 is applicable to products (such as mobile terminals such as cars, smart phones, optical products such as cameras, measuring instruments such as sensors, other mechanical and electrical products, etc.) or components where dirt (such as dust, pollen, fingerprints, oil, etc.) is not desired to be attached. For example, the antifouling component 10 is used to cover at least a part of the display part of a display, to cover at least a part of the touch part of a touch panel, or to cover at least a part of the surface of a sensor. The antifouling component 10 has nano - scale irregularities on the surface of one side, and an antifouling layer 130 is provided in the concave portions of the irregularities.

[0034] In Figure 1 the antifouling component 10 has a base material 110, a base layer 120, and an antifouling layer 130, and nano - scale irregularities are provided on the surface of the base layer 120.

[0035] The base material 110 serves to carry the unevenness provided on the antifouling member 10 and the antifouling layer 130. The base material 110 can be selected from various materials according to the purpose of using the antifouling member 10. For example, the base material 110 can be formed of glass, resin, metal, ceramic, semiconductor, fiber material, fur, leather, wood, porcelain, stone, or any arbitrary material. When the antifouling member 10 is provided on an optical article such as a display and a touch panel or a component thereof, the base material 110 can be formed of a transparent material such as glass or resin. The base material 110 can have an arbitrary shape as long as there is a portion where unevenness can be provided, and for example, it can be plate-shaped.

[0036] The base layer 120 is provided on one surface of the base material 110 and is a layer that holds the antifouling layer 130. The base layer 120 can also function as a hard coat that imparts abrasion resistance to the antifouling member 10. The base layer 120 can be a material having abrasion resistance, and for example, it can be formed of an inorganic material such as silica or metal oxide, or a relatively hard organic material such as silicone resin, acrylic resin, melamine resin, or polyurethane resin.

[0037] In Figure 1 the example, unevenness is provided on the base layer 120. By providing unevenness on the base layer 120 which is the lower layer of the antifouling layer 130, the antifouling layer 130 is surrounded by the convex portions and is protected, and by embedding the antifouling layer 130 in the concave portions, the antifouling layer 130 is firmly joined to the base layer 120. Currently, due to friction such as wiping stains or long-term use, the antifouling layer on the surface of the antifouling member sometimes suffers wear, and the antifouling performance cannot be sustained. On the other hand, with the antifouling member 10 of the present embodiment, the antifouling layer 130 is firmly held by the unevenness, so that the antifouling performance can be sustained for a longer time. In addition, by making the unevenness nanoscale, the transparency of the antifouling member 10 can also be ensured.

[0038] As an example, the base layer 120 can be composed of a silicone resin having unevenness. The silicone resin can contain a Q unit structure and a T unit structure. The concave portions can contain more T unit structures than the convex portions of the unevenness. In this case, the base layer 120 does not become too hard, and when coated on the base material 110, the occurrence of cracks can be suppressed in deterioration tests such as a heat resistance test. The surfaces of the convex and concave portions (especially the surface of the concave portion) can also at least partially expose active silanol groups (Si-OH). Thereby, the bonding with the antifouling layer 130 can be made more firm. The method of forming the unevenness of the silicone resin will be described later.

[0039] The cross section of the convex portion of the unevenness can adopt various shapes. For example, the cross section of the convex portion can be a shape with a rectangular front end, a shape with a conical or inverted conical front end, a shape with a pointed front end, a shape with a curved surface such as a hemisphere at the front end, etc.

[0040] The average pitch width (average peak-to-peak length) of the convex portions of the unevenness can be 5 to 18 nm, preferably 7 to 15 nm. As long as the average pitch width is below a specified size, the transparency of the antifouling member 10 can be ensured. In addition, as long as the average pitch width is above a specified size, the antifouling layer 130 can be held more firmly.

[0041] The surface roughness (Rz) of the unevenness can be 3 to 15 nm, and can preferably be 5 to 15 nm. As long as the surface roughness (Rz) is below a specified size, the transparency of the antifouling member 10 can be ensured. In addition, as long as the surface roughness (Rz) is above a specified size, the antifouling layer 130 can be held more firmly.

[0042] The antifouling layer 130 is formed on the side of the base layer 120 opposite to the base material 110 (i.e., the outermost surface of the antifouling member 10), and prevents attachments such as stains from adhering to the surface of the antifouling member 10. The antifouling layer 130 can be formed at least in the concave portions of the base layer 120. For example Figure 1 As shown, the antifouling layer 130 can be formed only in the concave portions.

[0043] Alternatively, the antifouling layer 130 can be formed not only in the concave portions but also on the convex portions. In this case, due to handling, use, and wiping of attachments of the product, there is a possibility that the antifouling layer 130 on the convex portions may be partially or completely peeled off. Even in such a case, the antifouling layer 130 in the concave portion is held firmly. Therefore, the antifouling member 10 can maintain its antifouling performance.

[0044] The antifouling layer 130 only needs to be provided on at least the bottom surface of the concave portions and / or the upper surface of the convex portions. The antifouling layer 130 can be provided on all or part of the side faces of the concave portions and / or the convex portions, or can be not provided at all.

[0045] The height in the normal direction ( Figure 1 the up-and-down direction) of one surface of the antifouling layer 130 formed in the concave portions of the base layer 120 can not exceed the convex portions of the unevenness of the base layer 120. For example, it is desired that on at least about half of the concave portions, the height of the antifouling layer 130 in the concave portions does not exceed the convex portions. In Figure 1 the example, the height in the normal direction of one surface of the antifouling layer 130 formed in the concave portions is the same as the height of the convex portions of the base layer 120 (i.e., flush with the upper surface of the convex portions). In addition, the thickness of the antifouling layer 130 in the concave portions is preferably 1 to 10 nm.

[0046] The anti-fouling performance of the anti-fouling layer 130 is exhibited by the surface portion. When the film thickness of the anti-fouling layer 130 in the concave portion is too thick, it may cause the anti-fouling member to become cloudy (blurred). Thus, by ensuring that the film thickness of the anti-fouling layer 130 in the concave portion is not too thick, cloudiness (blurring) of the anti-fouling member can be prevented. In addition, the anti-fouling layer 130 on the convex portion is less likely to be damaged due to wiping or the like, so the problem of cloudiness (blurring) is less likely to occur.

[0047] The anti-fouling layer 130 can be formed of a material having oil-repellency and / or water-repellency. For example, the anti-fouling layer 130 can contain a fluorosilane compound. Examples of the fluorosilane compound include silane compounds containing perfluoropolyether groups, silane compounds containing perfluoroalkyl groups, silane compounds containing an isocyanuric acid skeleton, and the like. The details of the material of the anti-fouling layer 130 will be described later.

[0048] The contact angle of the anti-fouling member 10 when contacting water on one surface side (e.g., the anti-fouling layer 130 side) can be 105 to 120°. Thereby, the anti-fouling member 10 can exhibit water-repellency and exert anti-fouling performance. In addition, the contact angle of the anti-fouling member 10 after the following abrasion test 1 and / or abrasion test 2 can be 85° or more, preferably 90° or more. Thereby, the anti-fouling member 10 can exert anti-fouling performance for a long time.

[0049] The pencil hardness of one surface side (e.g., the anti-fouling layer 130 side) of the anti-fouling member 10 can be HB or more. Thereby, the anti-fouling member 10 can maintain sufficient abrasion resistance to keep the anti-fouling layer 130 for a longer time.

[0050] The Δ haze (increase in haze value before and after the test) of the anti-fouling member 10 in the Taber abrasion test based on the ASTM D1044 standard (or the following abrasion test 2) on one surface side (e.g., the anti-fouling layer 130 side) can be 10 or less, preferably 8 or less, more preferably 5 or less, and further preferably 2 or less. Thereby, the anti-fouling member 10 can keep the anti-fouling layer 130 for a longer time and maintain sufficient abrasion resistance to maintain transparency.

[0051] In Figure 2 the embodiment, the anti-fouling member 10 has a substrate 110 and an anti-fouling layer 130. In Figure 2 there is no base layer 120, and irregularities are provided on the surface of the substrate 110. Thus, the substrate 110 is in direct contact with the anti-fouling layer 130. In Figure 2 the embodiment, the anti-fouling layer 130 is also firmly held by the irregularities, so the same effect as in Figure 1 the embodiment can also be obtained. The materials, shapes of the substrate 110 and the anti-fouling layer 130, and the dimensions of the irregularities, contact angle, hardness, etc. are described in Figure 1 What is described in Figure 2The present invention is also applicable to the embodiment of the present invention, so the description is omitted.

[0052] exist Figures 1 - 2 In the example of the antifouling member 10, the antifouling layer 130 ( Figure 1 While the example of the antifouling member 10 further comprising a base layer 120 is described, other layers may be provided. For example, the antifouling member 10 may be provided with a primer layer, an antireflection layer, an antiglare layer, an insulating layer, an adhesive layer, a release layer, a polarizing layer, and / or a phase difference layer, as needed.

[0053] Figure 3 An example of a flow of a method for manufacturing the antifouling member 10 according to this embodiment is shown. The antifouling member 10 can be manufactured by performing at least a part of S100 to S200.

[0054] In S100, nano-scale concavities and convexities are provided on the surface of the substrate 110. The substrate 110 may be Figures 1 - 2 For example, by providing the base layer 120 provided with nano-scale concavities and convexities on the base material 110, concavities and convexities can be formed on the base material 110.

[0055] Figure 4 Indicates when the base layer 120 is set Figure 3 An example of S100 of the process. Figure 3 The S100 can be performed by Figure 4 The processing of S110 to S130 is implemented.

[0056] In S110, a base resin composition is applied to a substrate 110. The base resin composition may be an organosiloxane hard coating agent having a T unit structure and a Q unit structure. The base resin composition may further contain one or more of a UV absorbing material, a catalyst, and a solvent.

[0057] The Q unit structure is contained in the base resin composition in the form of silica gel particles (colloidal silica). The silica gel particles are substances that provide the shape of the concavo-convex portions later. The diameter is preferably 1 to 100 nm, preferably 10 to 50 nm, and more preferably 10 to 20 nm. The diameter can be the particle size at which the cumulative volume accounts for 50% by volume when the volume-based particle size distribution is measured using laser diffraction scattering particle size distribution measurement, i.e., the median particle size D50.

[0058] The T unit structure can be included in the base resin composition in the form of an organosilsesquioxane polymer. The Q unit structure can be uniformly dispersed in the matrix of the T unit structure. The Q unit structure can be included in an amount of 5 to 50% by weight, preferably 15 to 35% by weight, relative to the total weight of the T and Q units.

[0059] For example, regarding the resin composition for the substrate, by hydrolyzing colloidal silica and an alkyltrialkoxysilane (as an example, methyltrimethoxysilane) and then performing condensation, a resin composition for the substrate containing a T-unit structure and a Q-unit structure can be obtained.

[0060] A skeleton having an ultraviolet absorption function can be introduced at least partially into the T-unit structure and / or the Q-unit structure. As the skeleton having an ultraviolet absorption function, examples include 4,6-dibenzoyl-2-(3-trialkoxysilylalkyl)resorcinol (specifically, 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol, etc.) described in Japanese Patent Laid-Open No. 7-278525, and hydroxybenzophenone-based compounds described in Japanese Patent Laid-Open Nos. 57-21476 and 57-21432. As an example of the resin composition for the substrate, hard coat agents AS4700, AS4700F, PHC587C, PHC587C2, etc. manufactured by Momentive can be used.

[0061] As the organosilsesquioxane polymer forming the T-unit structure, Component A described in Japanese Patent Application Laid-Open No. 2021-531387 can be used. For example, as the organosilsesquioxane polymer, Component A represented by an organoalkoxysilane of the formula (R1)dSi(OR2)4-d can be used. Among them, R1 can be a C1-C3 monovalent hydrocarbon, preferably a C1-C3 alkyl radical, more preferably methyl or ethyl. R2 is a C1-C3 monovalent hydrocarbon or a hydrogen radical, and d can be 0, 1, or 2. As an example, Component A can be methyltrimethoxysilane.

[0062] Component A includes methyltrimethoxysilane, methyltriethoxysilane, or a mixture thereof, which can form a partial condensate. In addition, the organoalkoxysilane includes tetraethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, tetramethoxysilane, dimethyldimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, etc., but is not limited thereto.

[0063] Component A can be present in an amount of about 5 wt% to about 99.9 wt%, about 10 wt% to about 90 wt%, and about 20 wt% to about 80 wt% based on the total weight of the resin composition for the substrate.

[0064] The catalyst can be at least one or more selected from tetra-n-butylammonium acetate, tetra-n-butylammonium formate, tetra-n-butylammonium benzoate, tetra-n-butylammonium 2-ethylhexanoate, tetra-n-butylammonium p-ethylbenzoate, tetra-n-butylammonium propionate, and TBD-acetate (acetate of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)).

[0065] For a specific purpose or intended use, a catalyst can be added to the base resin composition as needed. Generally, the catalyst is in an amount that does not affect or impair the physical properties of the coating and can be added in a sufficient amount effective for the catalytic curing reaction. In one embodiment, the catalyst is provided in an amount in the range of 1 ppm to about 75 ppm, about 10 ppm to about 70 ppm, and about 20 ppm to about 60 ppm. Herein, ppm represents one millionth of the weight relative to the total weight of the base resin composition.

[0066] The catalyst can be added directly to the base resin composition or can be dissolved in a solvent or other suitable carrier. The solvent can be polar solvents such as methanol, ethanol, n-butanol, tert-butanol, n-octanol, n-decanol, 1-methoxy-2-propanol, isopropanol, ethylene glycol, tetrahydrofuran, dioxane, bis(2-methoxyethyl) ether, 1,2-dimethoxyethane, acetonitrile, benzonitrile, methyl ethyl ketone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and propylene carbonate.

[0067] The UV absorber can also be selected from a combination of inorganic UV absorbers and organic UV absorbers. Examples of suitable organic UV absorbers include compounds capable of co-condensing with silanes, but are not limited to these. Such UV absorbers are disclosed in U.S. Patent Nos. 4,863,520, 4,374,674, 4,680,232, and 5,391,795, which are incorporated herein by reference in their entirety. As specific examples, 4-[γ-(trimethoxysilyl)propoxy]-2-hydroxybenzophenone, 4-[γ-(triethoxysilyl)propoxy]-2-hydroxybenzophenone, and 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol can be cited. In the case of using a UV absorber capable of co-condensing with silanes, the UV absorber should be thoroughly mixed before applying the coating composition to the substrate, thereby co-condensing with other reactive species. By co-condensing (co-condensing) the UV absorber, a decrease in the coating performance caused by the leaching of free UV absorber into the environment during weathering is prevented.

[0068] The solvent may be selected from aliphatic alcohols, glycol ethers, cycloaliphatic alcohols, aliphatic esters, cycloaliphatic esters, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic compounds, halogenated cycloaliphatic compounds, halogenated aromatic compounds, aliphatic ethers, cycloaliphatic ethers, amide solvents, sulfoxide solvents, or a combination of two or more thereof. Examples of suitable solvents include alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, methoxypropanol, ethylene glycol, diethylene glycol butyl ether, or a combination thereof, but are not limited thereto. Other polar organic solvents such as acetone, methyl ethyl ketone, ethylene glycol monopropyl ether, 2-butoxyethanol, etc. may also be used. In one embodiment, the solvent used is one or more selected from 1-methoxy-2-propanol, diacetone alcohol (DAA), acetylacetone, cyclohexanone, methoxypropyl acetate, ketones, glycol ethers, or a mixture of two or more thereof. The amount of the solvent in the resin composition for the substrate is preferably in the range of about 25% by weight to about 85% by weight, more preferably about 40% by weight to about 80% by weight, and most preferably about 50% by weight to about 75% by weight based on the total weight of the entire composition. The composition may also contain a catalyst. The catalyst is not particularly limited, and any suitable catalyst for curing the resin composition for the substrate can be used.

[0069] For a specific purpose or intended use, in order to impart desired properties to the coating agent, the resin composition for the substrate may contain other materials or additives. The resin composition for the substrate of the present invention may also contain a surfactant as a leveling agent. Examples of suitable surfactants include organosilicon polyethers such as Silwet (registered trademark) and CoatOSil (registered trademark) available from Momentive Performance Materials, Inc., Albany, N.Y., and FLUORAD (trademark) named polyether-polysiloxane copolymers manufactured by 3M Company, St. Paul, Minn., and BYK (registered trademark)-331 manufactured by BYK (registered trademark)-Chemie., but are not limited thereto. Suitable antioxidants include hindered phenols (e.g., IRGANOX (registered trademark) 1010 manufactured by Ciba Specialty Chemicals), but are not limited thereto.

[0070] As a coating method, various coating methods such as dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, etc., or printing methods such as letterpress printing, gravure printing, lithographic printing, reverse printing, inkjet printing, etc. can be used for coating.

[0071] The film thickness of the resin composition for the substrate after coating can be 1 to 20 μm, preferably 3 to 10 μm.

[0072] Among them, in S110, before applying the resin composition for the coating substrate, a primer composition for improving the adhesion between the substrate 110 and the resin composition for the coating substrate may be applied to the substrate 110. For example, the primer composition may be an acrylic resin composition, a polyester resin composition, a polyurethane resin composition, an epoxy resin composition, a melamine resin composition, a polyolefin resin composition, or a polyurethane acrylate resin composition.

[0073] Next, in S120, the resin composition for the coating substrate applied in S110 is dried. For example, heating and curing may be performed at a temperature of 100 to 150 °C, preferably 120 to 130 °C, for a time of 10 to 120 minutes, preferably 30 to 60 minutes. Drying may be carried out using a hot air drying furnace, a heating plate, an infrared heater, or the like.

[0074] Next, in S130, unevenness is formed from the dried resin composition for the coating substrate. For example, unevenness is formed by pretreating the resin composition for the coating substrate. This is because volume shrinkage occurs when the T unit structure of the resin composition for the coating substrate is modified into silica (SiO2) by pretreatment. For example, the pretreatment may be exposure or plasma treatment. Specifically, by irradiating UV light for exposure, ozone and reactive oxygen radicals are generated from oxygen in the atmosphere, and they react with the Si-alkyl groups contained in the T unit structure. As a result, the Si-alkyl groups contained in the T unit structure are decomposed into silanol groups and aldehydes, and the 2 silanol groups are further condensed to form silica (SiO2). The aldehydes are further decomposed into water and CO2. Thus, when the T unit structure is modified into silica (SiO2), volume shrinkage occurs, and the portion where volume shrinkage occurs sinks to form a recess.

[0075] In addition, although it depends on the exposure conditions, it is considered that not all of the T unit structures are modified into silica (SiO2) as the Q unit structure, and there are components in which the T structural units still remain. Thus, the convex portions of the unevenness are composed of the Q unit structure, and the concave portions of the unevenness contain the Q unit structure and the T unit structure.

[0076] On the other hand, the Q unit structure (colloidal silica) does not undergo chemical changes due to exposure and does not undergo volume shrinkage. As a result, in the layer of the resin composition for the coating substrate, recesses are formed only in the portions where the T unit structure is abundant, and convex portions are formed in the portions where the Q unit structure is abundant. Thus, the base layer 120 having unevenness can be formed.

[0077] In the thus-formed base layer 120, silanol groups remain on the surface. Particularly in the concave portions, a part of the silanol groups obtained by the decomposition of the T-unit structure remains uncondensed. In addition, in the concave portions, a part of the Si-alkyl groups derived from the T-unit structure also remains. As a result, the composition ratio of carbon atoms contained in the concave portions is greater than that in the convex portions. Thus, as a result of a large amount of carbon atoms or silanol groups remaining in the concave portions, it is possible to more firmly bond with the antifouling layer 130 containing a silane compound having a perfluoropolyether group or the like, improving the durability of the antifouling layer 130. Among them, the molar concentration of carbon atoms can be measured using an X-ray photoelectron spectroscopy apparatus.

[0078] As the light source for exposure, as long as it can modify the T-unit structure into silica, for example, a light source with a wavelength of about 150 to 190 nm can be used. Specifically, an excimer lamp, an excimer laser, an F2 laser, etc. can be used for exposure.

[0079] Exposure can be carried out in such a way that the cumulative illuminance reaches 300 mJ / cm 2 or more. When the cumulative illuminance is less than 1000 mJ / cm 2 , the decomposition and condensation of the T-unit structure are insufficient, and it may not be possible to sufficiently form irregularities.

[0080] Exposure can be carried out in such a way that the cumulative illuminance reaches 6000 mJ / cm 2 or less. When it exceeds 6000 mJ / cm 2 , silanol groups may not sufficiently remain on the surface of the concave portions, and the adhesiveness with the antifouling layer 130 may be insufficient. However, even when the cumulative illuminance exceeds 6000 mJ / cm 2 , the base layer 120 itself can be formed, so it helps to sufficiently improve the durability of the antifouling layer. Therefore, it is not necessary to make the cumulative illuminance 6000 mJ / cm 2 or less.

[0081] Instead of exposure / in addition to exposure, plasma treatment using an Ar / O2 mixed gas plasma or the like can also be applied. In this case, the flow rate of the Ar / O2 mixed gas plasma can be 2000 sccm or more. When the flow rate is less than 2000 sccm, the decomposition and condensation of the T-unit structure are insufficient, and the formation of irregularities may be insufficient.

[0082] The flow rate of the Ar / O2 mixed gas plasma can be 5000 sccm or less. When the flow rate exceeds 5000 sccm, silanol groups may not sufficiently remain on the surface of the concave portions, and the adhesiveness with the antifouling layer 130 may be insufficient.

[0083] The output of the Ar / O2 mixed gas plasma can be 0.2 kW or more. When the output is less than 0.2 kW, the decomposition and condensation of the T-unit structure are insufficient, and the formation of irregularities may be insufficient.

[0084] It can be carried out in such a way that the output of the Ar / O2 mixed gas plasma is 1.0 kW or less. When it exceeds 1.0 kW, the silanol groups remaining on the surface of the concave portion are insufficient, and the adhesiveness to the antifouling layer 130 may be insufficient. The Ar / O2 mixed gas plasma can be applied in such a way that the oxygen fraction is 0.03 to 0.4.

[0085] In Figure 4 In the description involved, it is described that the base layer 120 is obtained by exposing an organosiloxane-based hard coat agent, but it is not limited to this method. Regarding the base layer 120, nano-level unevenness can also be formed by nanoimprinting, photolithography, plasma treatment, laser treatment, etc. on a thin film formed of a resin material or the like.

[0086] Instead of Figure 4 the processes of S110 to S130, S100 can also be carried out by forming unevenness on the substrate 110. For example, by etching, nanoimprinting, photolithography, plasma treatment, laser treatment, etc. on the substrate 110, the desired unevenness can also be formed. In this case, the antifouling member 10 as shown in Figure 2 can be formed. The process of S200 is carried out after S100.

[0087] In S200, the antifouling layer 130 is formed on the unevenness formed in S100. For example, by forming a layer of a fluorosilane compound having oil repellency and / or water repellency on the unevenness, the antifouling layer 130 can be formed. By coating a composition containing a fluorosilane compound on the unevenness and drying it, the antifouling layer 130 can be formed.

[0088] Examples of the fluorosilane compound include a silane compound containing a perfluoroalkyl group (especially a silane compound containing a perfluoropolyether group), a silane compound having an isocyanuric acid skeleton, and the like.

[0089] As an example of the silane compound containing a perfluoroalkyl group, the compound represented by the following formula (I) can be cited.

[0090] [A] b1 Q 2 [B] b2 (I)

[0091] [In the formula:

[0092] Q 2 is a linking group having a valence of (b1 + b2),

[0093] A is a group represented by R f3 -O-R f2 -,

[0094] Rf2 is a poly(oxyfluoroalkylene) chain,

[0095] R f3 is a perfluoroalkyl group,

[0096] B is a monovalent group having one -R 12 -(SiR 2 r X 2 3－r ) and containing no fluorine atoms,

[0097] R 12 is a hydrocarbon group having 2 to 10 carbon atoms which may have an etheric oxygen atom at the terminal on the side opposite to the terminal bonded to Si, or may have -NH- between carbon-carbon atoms,

[0098] R 2 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent,

[0099] X 2 are each independently a hydroxyl group or a group capable of hydrolysis,

[0100] r is an integer of 0 to 2,

[0101] Q 2 and B do not contain a cyclic siloxane structure,

[0102] b1 is an integer of 1 to 3,

[0103] b2 is an integer of 2 to 9,

[0104] wherein, when b1 is 2 or more, the b1 A's may be the same or different, and the b2 B's may be the same or different.]

[0105] In formula (I), A is a group represented by R f3 -O-R f2 -.

[0106] R f3 is a perfluoroalkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. R f3 may be linear or branched. Among them, from the aspect of ease of obtaining, a linear group: CF3(CF2) m3－1 (wherein, m3 is 1 to 20, preferably 1 to 6) is preferred, more preferably CF3- or CF3(CF2)2-, and particularly preferably CF3(CF2)2-.

[0107] R f2 is a poly(oxyfluoroalkylene) chain. R f2 For example, it is -(Cx F 2x O) y -(where x is an integer from 1 to 6, y is an integer of 2 or more, and each -C x F 2x O-unit can be the same or different). -C x F 2x O-units can be linear or branched. For example, -CF2CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-, -CF2CF2O-, -CF2O- can be listed. y can be appropriately adjusted according to the desired number average molecular weight. The preferred upper limit value of y is 200.

[0108] R f2 can also be a combination of multiple units. In this case, each unit can exist in any of the block, alternating, or random manners. For example, from the aspect of excellent light resistance, it is preferably to contain -CF2CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2O-. The larger the existence ratio of these structures, the more preferred. From the aspect of ease of synthesis, it is more preferably a unit formed by combining -CF2CF2CF2CF2O- and -CF2CF2O-, that is, -CF2CF2O-CF2CF2CF2CF2O-.

[0109] R f2 Specifically, - (CF2CF2CF2CF2CF2CF2O) n3 - (CF2CF2CF2CF2CF2O) n4 - (CF2CF2CF2CF2O) n5 - (CF2CF2CF2O) n6 - (CF(CF3)CF2O) n7 - (CF2CF2O) n8 - (CF2O) n9 - (wherein, n3, n4, n5, n6, n7, n8, and n9 are each independently an integer of 0 or more, the sum of n3, n4, n5, n6, n7, n8, and n9 is 2 or more, and each repeating unit can exist in any of the block, alternating, or random manners).

[0110] As R f2 , preferably {(CF2O) n11 (CF2CF2O) n12}、(CF2CF2O) n13 、(CF2CF2CF2O)n14 、(CF2CF2O-CF2CF2CF2CF2O) n15 , more preferably {(CF2O) n11 (CF2CF2O) n12}, (CF2CF2CF2O) n14 . Among them, n11 is an integer of 1 or more, n12 is an integer of 1 or more, n11 + n12 is an integer of 2 to 200, and the combination order of n11 CF2O and n12 CF2CF2O is not limited. n13 and n14 are integers of 2 to 200, and n15 is an integer of 1 to 100.

[0111] In formula (I), the number (b1) of the group A represented by R f3 -O-R f2 - is an integer of 1 to 3. In formula (I), when there are multiple groups A, the groups A may be the same or different. The group A and the perfluoroalkyl group in the fluoroalkylsilane compound are groups that contribute to the water repellency of the obtained surface treatment layer. When the silane compound containing a perfluoroalkyl group has multiple groups A, from the aspect of excellent abrasion resistance of the surface treatment layer, it is preferred that the density of the R f3 -O-R f2 - group is high.

[0112] In formula (I), the group B is a monovalent group having 1 - R 12 -(SiR 2 r X 2 3－r )(hereinafter also referred to as "group (B a )") at the end and containing no cyclic siloxane structure and fluorine atom.

[0113] The group B is specifically a group represented by -Y a -R 12 -(SiR 2 r X 2 3－r ). Through -Y a -, the group (B a ) and Q 2 are connected. Y a is a single bond or a divalent organic group containing no cyclic siloxane structure and fluorine atom. Y aFor example, it is an alkylene group having an arylene group such as a phenylene group having 6 to 8 carbon atoms at the end (such as an alkylene group or an arylene group having 8 to 16 carbon atoms), an alkylene group (such as having 1 to 20 carbon atoms) bonded to a silylene structure (such as having 1 to 10 carbon atoms and 2 to 10 Si atoms) or a silylarylene structure (such as having 1 to 10 carbon atoms and 2 to 10 Si atoms), and a divalent group formed, and the end on the group (B a ) side does not include an alkylene group. Y a The atom of Q to which it is bonded 2 is an atom constituting the main chain, and specifically, Si, C, and N can be cited. Y a Preferably a single bond.

[0114] R 12 is a hydrocarbon group having 2 to 10 carbon atoms that can have an etheric oxygen atom at the end on the opposite side of the carbon-carbon bond or with Si, or can have -NH- between carbon-carbon atoms. Specifically, groups selected from -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2-, -OCH2CH2CH2- are preferred (wherein the right side is bonded to Si). From the aspect of excellent light resistance of the water-repellent film, -CH2CH2- and -CH2CH2CH2- that do not have an etheric oxygen atom are particularly preferred. In the formula (I), the R of the plurality of groups B present 12 can all be the same group, or not all be the same group.

[0115] X 2 is a hydroxyl group or a hydrolyzable group. As the hydrolyzable group, the exemplified and preferred modes of the hydrolyzable group of X 1 are applicable. r is an integer from 0 to 2. From the aspect of excellent adhesion and durability, 0 or 1 is preferred, and 0 is more preferred. When there are a plurality of X 2 , X 2 can be the same or different. From the aspect of ease of obtaining, they are preferably the same.

[0116] R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may also have a substituent. As the hydrocarbon group, linear or branched alkyl groups can be cited. Among them, from the aspect of ease of obtaining, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and methyl or ethyl is more preferred. As the substituent, a halogen atom (such as a chlorine atom) can be cited. The number r of R 2 bonded to Si is an integer from 0 to 2. When there are a plurality of R 2 , R 2 can be the same or different. From the aspect of ease of obtaining, they are preferably the same. [[ID=z38]]

[0117] In formula (I), the number of group B represented by b2 is an integer of 2 to 9. Therefore, in the perfluoroalkyl group-containing silane compound, the number of group (B a ) is 2 to 9. Group (B a ) is a group that contributes to the light resistance and abrasion resistance of the obtained water-repellent film. Considering the excellent light resistance and abrasion resistance of the obtained water-repellent film, the number of group B in the perfluoroalkyl group-containing silane compound, that is, the number of group (B a ) is preferably 2 to 4.

[0118] Among them, the plurality of group Bs possessed by the perfluoroalkyl group-containing silane compound may be the same or different. Regarding group (B a ), they may be the same or different.

[0119] In formula (I), Q 2 is a linking group with a valence of (b1 + b2). Q 2 is, for example, a hydrocarbon group, and an ester bond, an ether bond, an amide bond, a urethane bond, a phenylene group, -S-, a divalent amino group, a silylene structure, a silylarylene structure, or a siloxane structure (excluding a cyclic siloxane structure) may be present at the terminal or between carbon atoms - carbon atoms. The hydrogen atoms of the hydrocarbon group may be substituted by fluorine atoms. The hydrogen atoms of the hydrocarbon group may be substituted by hydroxyl groups, and the number of the substituted hydroxyl groups is preferably 1 to 5. The hydrocarbon group may be linear or branched. The number of carbon atoms of Q 2 is preferably 1 to 20, more preferably 1 to 10.

[0120] Among them, in Q[[ID=2)4]] 2 , group A and group B may be bonded to the same atom, preferably bonded to different atoms, and more preferably the bonded atoms are as far apart from each other in the molecule as possible.

[0121] In addition, Q 2 may have -SiR 0 r1 X 4 3－r1 bonded directly to an atom other than the terminal of the molecular chain (R 0 , X 4 and r1 are the same as R a , X 2 and r of group (B 2 ) respectively.). As the perfluoroalkyl group-containing silane compound, it preferably does not have a hydrolyzable silyl group other than group (B a ). Among them, when the perfluoroalkyl group-containing silane compound has -SiR 0 r1 X 4 3－r1 bonded directly to an atom other than the terminal of the molecular chain, when calculating SiR 1p X 1 3－p With the molar ratio of the SiR of the perfluoroalkyl-containing silane compound 2 r X 2 3－r When it is, the -SiR 0 r1 X 4 3－r1 Is not included in SiR 2 r X 2 3－r Inside.

[0122] In one embodiment, the perfluoroalkyl-containing silane compound may be a compound represented by any of the following formulas (A1), (A2), (B1), (B2), (C1) and (C2):

[0123] (Rf-PFPE) β’ -X 5 -(SiR 21 n1 R 22 3-n1 ) β ···(A1)

[0124] (R 22 3-n1 R 21 n1 Si) β -X 5 -PFPE-X 5 -(SiR 21 n1 R 22 3-n1 ) β ·(A2)

[0125] (Rf-PFPE) γ’ -X 7 -(SiR a k1 R b 11 R c m1 ) γ ···(B1)

[0126] (R c m1 R b 11 R a k1 Si) γ -X 7 -PFPE-X7 -(SiR a k1 R b 11 R c m1 ) γ ···(B2)

[0127] (Rf-PFPE) δ -X 9 -(CR d k2 R e 12 R f m2 ) δ ···(C1)

[0128] (R f m2 R e 12 R d k2 C) δ -X 9 -PFPE-X 9 -(CR d k2 R e 12 R f m2 ) δ ···(C2)

[0129] [Where:

[0130] PFPE is independently represented at each occurrence by a group of the formula:

[0131] -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) d -

[0132] (wherein, a, b, c, and d are each independently an integer of 0 to 200, the sum of a, b, c, and d is at least 1, and the order of the repeating units marked with the subscript a, b, c, or d and enclosed in parentheses is arbitrary in the formula.);

[0133] Rf, when present, independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

[0134] R 21 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0135] R 22 Each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

[0136] n1 is independently an integer of 0 to 3 in each (-SiR 21 n1 R 22 3－n1 ) unit;

[0137] Wherein, in formula (A1) and (A2), at least one n1 is an integer of 1 to 3;

[0138] X 5 Each independently represents a single bond or an organic group having a valence of 2 to 10;

[0139] β is independently an integer of 1 to 9;

[0140] β' is independently an integer of 1 to 9;

[0141] X 7 Each independently represents a single bond or an organic group having a valence of 2 to 10;

[0142] γ is independently an integer of 1 to 9;

[0143] γ' is independently an integer of 1 to 9;

[0144] R a Each occurrence independently represents -Z 1 -SiR 71 p1 R 72 q1 R 73 r1 ;

[0145] Z 1 Each occurrence independently represents an oxygen atom or a divalent organic group;

[0146] R 71 Each occurrence independently represents R a' ;

[0147] R a' has the same meaning as R a ;

[0148] R a In, the maximum number of Si linearly connected through the Z 1 group is 5;

[0149] R 72 Each occurrence independently represents a hydroxyl group or a group capable of hydrolysis;

[0150] R73 each independently represents a hydrogen atom or a lower alkyl group each time it appears;

[0151] p1 is independently an integer of 0 to 3 each time it appears;

[0152] q1 is independently an integer of 0 to 3 each time it appears;

[0153] r1 is independently an integer of 0 to 3 each time it appears;

[0154] wherein, in formulas (B1) and (B2), at least one q1 is an integer of 1 to 3;

[0155] R b each independently represents a hydroxyl group or a hydrolyzable group each time it appears;

[0156] R c each independently represents a hydrogen atom or a lower alkyl group each time it appears;

[0157] k1 is independently an integer of 1 to 3 each time it appears;

[0158] l1 is independently an integer of 0 to 2 each time it appears;

[0159] m1 is independently an integer of 0 to 2 each time it appears;

[0160] wherein, in the unit marked with γ and enclosed in parentheses, the sum of k1, l1 and m1 is 3;

[0161] X 9 each independently represents a single bond or an organic group with a valence of 2 to 10;

[0162] δ is independently an integer of 1 to 9;

[0163] δ' is independently an integer of 1 to 9;

[0164] R d each independently represents -Z 2 -CR 81 p2 R 82 q2 R 83 r2 ;

[0165] Z 2 each independently represents an oxygen atom or a divalent organic group each time it appears;

[0166] R 81 each independently represents R d' ;

[0167] R d' The significance of R d same;

[0168] R d In, through Z 2 The maximum number of C atoms in a straight chain is 5.

[0169] R 82 Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 ;

[0170] Y each independently represents a divalent organic group;

[0171] R 85 Each occurrence independently represents a hydroxyl group or a group capable of hydrolyzing;

[0172] R 86 represents independently at each occurrence a hydrogen atom or a lower alkyl group;

[0173] n2 in each (-Y-SiR 85 n2 R 86 3－n2 ) units independently represent an integer from 0 to 3;

[0174] wherein, in formulas (C1) and (C2), at least one n2 is an integer from 1 to 3;

[0175] R 83 represents independently at each occurrence a hydrogen atom, a hydroxyl group or a lower alkyl group;

[0176] p2 is independently an integer from 0 to 3 at each occurrence;

[0177] q2 is independently an integer from 0 to 3 at each occurrence;

[0178] r2 is independently an integer from 0 to 3 at each occurrence;

[0179] R e Each occurrence represents -Y-SiR independently 85 n2 R 86 3－n2 ;

[0180] R f represents independently at each occurrence a hydrogen atom, a hydroxyl group or a lower alkyl group;

[0181] k2 is independently an integer from 0 to 3 at each occurrence;

[0182] l2 is independently an integer from 0 to 3 each time it appears;

[0183] m2 is independently an integer from 0 to 3 each time it appears;

[0184] Wherein, in formula (C1) and (C2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3.

[0185] Formulas (A1) and (A2):

[0186] (Rf - PFPE) β’ -X 5 -(SiR 21 n1 R 22 3-n1 ) β ···(A1)

[0187] (R 22 3-n1 R 21 n1 Si) β -X 5 -PFPE-X 5 -(SiR 21 n1 R 22 3-n1 ) β ···(A2)

[0188] In the above formulas (A1) and (A2), PFPE is independently each time it appears

[0189] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - the group shown.

[0190] In the formula, a, b, c, d, e and f are independently integers of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, more preferably 200 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

[0191] Preferably, a and b are each independently 0 or more and 30 or less, and may be 0.

[0192] In one embodiment, a, b, c, and d are each independently preferably an integer of 0 or more and 30 or less, more preferably an integer of 20 or less, particularly preferably an integer of 10 or less, and further preferably an integer of 5 or less, and may be 0.

[0193] In one embodiment, the sum of a, b, c, and d is preferably 30 or less, more preferably 20 or less, further preferably 10 or less, and particularly preferably 5 or less.

[0194] In one embodiment, the sum of e and f is preferably 30 or more, more preferably 40 or more, and further preferably 50 or more.

[0195] These repeating units may be linear or branched, preferably linear. For example, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc., preferably -(OCF2CF2CF2CF2CF2CF2)-. -(OC5F 10) - It can be - (OCF2CF2CF2CF2CF2)-, - (OCF(CF3)CF2CF2CF2)-, - (OCF2CF(CF3)CF2CF2)-, - (OCF2CF2CF(CF3)CF2)-, - (OCF2CF2CF2CF(CF3))-, etc., preferably - (OCF2CF2CF2CF2CF2)-. - (OC4F8)- can be any one of - (OCF2CF2CF2CF2)-, - (OCF(CF3)CF2CF2)-, - (OCF2CF(CF3)CF2)-, - (OCF2CF2CF(CF3))-, - (OC(CF3)2CF2)-, - (OCF2C(CF3)2)-, - (OCF(CF3)CF(CF3))-, - (OCF(C2F5)CF2)- and - (OCF2CF(C2F5))-, preferably - (OCF2CF2CF2CF2)-. - (OC3F6)- can be any one of - (OCF2CF2CF2)-, - (OCF(CF3)CF2)- and - (OCF2CF(CF3))-, preferably - (OCF2CF2CF2)-. In addition, - (OC2F4)- can be any one of - (OCF2CF2)- and - (OCF(CF3))-, preferably - (OCF2CF2)-.

[0196] In one embodiment, the above PFPE is - (OC3F6) d - (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). The preferred PFPE is - (OCF2CF2CF2) d - (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or - (OCF(CF3)CF2) d - (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). More preferably, the PFPE is - (OCF2CF2CF2) d - (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less).

[0197] In another embodiment, the PFPE is - (OC4F8) c - (OC3F6) d - (OC2F4) e - (OCF2) f-(wherein c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the sum of c, d, e, and f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit with a subscript c, d, e, or f and enclosed in parentheses is arbitrary in the formula). Preferably, PFPE is -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f -

[0198] In one embodiment, PFPE can be -(OC2F4) e -(OCF2) f -(wherein e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the order of presence of each repeating unit with a subscript e or f and enclosed in parentheses is arbitrary in the formula).

[0199] In addition, in another embodiment, PFPE is -(R 6 -R 7 ) j -the group shown. In the formula, R 6 is each independently OCF2 or OC2F4 at each occurrence, preferably OC2F4. In the formula, R 7 is each independently a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 , or a combination of 2 or 3 groups independently selected from these groups. Preferably, R 7 is a group selected from OC2F4, OC3F6, and OC4F8, and is selected from OC3F6, OC4F8, OC5F 10 and OC6F 12The groups in [it], or a combination of 2 or 3 groups independently selected from these groups. As a combination of 2 or 3 groups independently selected from OC2F4, OC3F6 and OC4F8, there is no particular limitation. For example, -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4- etc. can be listed. The above j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more and 100 or less, preferably 50 or less. In the above formula, OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 can be either straight-chain or branched-chain, preferably straight-chain. In this mode, PFPE is preferably -(OC2F4-OC3F6) j - or -(OC2F4-OC4F8) j -.

[0200] In PFPE, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, more preferably 0.2 or more and 2 or less, and further preferably 0.2 or more and 1.5 or less. By making the e / f ratio within the above range, the water repellency, oil repellency and chemical resistance (for example, durability against brine, acidic or alkaline aqueous solutions, acetone, oleic acid or hexane) of the surface treatment layer obtained from the surface treatment agent of the present invention can be further improved. The smaller the e / f ratio, the higher the water repellency, oil repellency and chemical resistance of the above surface treatment layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the higher the stability of the compound.

[0201] In the above formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted by 1 or more fluorine atoms.

[0202] The "alkyl group having 1 to 16 carbon atoms" in the above alkyl group having 1 to 16 carbon atoms which may be substituted by 1 or more fluorine atoms can be straight-chain or branched-chain, preferably a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, especially an alkyl group having 1 to 3 carbon atoms, and more preferably a straight-chain alkyl group having 1 to 3 carbon atoms.

[0203] The above Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably CF2H-C 1－15 fluorinated alkylene group, and further preferably a perfluoroalkyl group having 1 to 16 carbon atoms.

[0204] The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0205] In the above formula, R 21 each independently represents a hydroxyl group or a group capable of hydrolysis each time it appears.

[0206] In the above formula, R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms each time it appears, preferably an alkyl group having 1 to 4 carbon atoms.

[0207] In the above formula, n1 is independently an integer of 0 to 3 in each (-SiR 21 n1 R 22 3－n1 ) unit, preferably 1 to 3, and more preferably 3. Among them, in the formula, all n1 are not simultaneously 0. In other words, in the formula, there is at least one R 21 .

[0208] In the above formula, X 5 each independently represents a single bond or an organic group having a valence of 2 to 10. This X 5 in the compounds represented by formulas (A1) and (A2) can be understood as a linking group connecting the perfluoropolyether moiety (Rf-PFPE moiety or -PFPE-) mainly providing water repellency and surface smoothness and the silane moiety providing the binding energy to the substrate (specifically -SiR 21 n1 R 22 3－n1 ). Therefore, as long as the compounds represented by formulas (A1) and (A2) can stably exist, this X 5 can be any organic group.

[0209] β in the above formula is an integer of 1 to 9, and β' is an integer of 1 to 9. These β and β' are determined according to the valence of X 3 , and in formula (A1), the sum of β and β' is the same as the valence of X 5 . For example, in X 5When it is a 10-valent organic group, the sum of β and β' is 10. For example, β can be 9 and β' can be 1, β can be 5 and β' can be 5, or β can be 1 and β' can be 9. Additionally, when X 5 is a 2-valent organic group, β and β' are 1. In formula (A2), β is the value obtained by subtracting 1 from the valence number value of X 5 .

[0210] The above-mentioned X 5 is preferably an organic group with a valence of 2 to 7, more preferably 2 to 4, and further preferably 2.

[0211] In one embodiment, X 5 is an organic group with a valence of 2 to 4, β is 1 to 3, and β' is 1.

[0212] In another embodiment, X 5 is a 2-valent organic group, β is 1, and β' is 1. In this case, formulas (A1) and (A2) are represented by the following formulas (A1') and (A2').

[0213] Rf-PFPE-X 5 -SiR 21 n1 R 22 3-n1 …(A1')

[0214] R 22 31-n1 R 21 n1 si-X 5 -PFPE-X 5 -siR 21 n1 R 22 3-n1 …(A2')

[0215] Examples of the above-mentioned X 5 are not particularly limited. For example, a single bond or a 2-valent group represented by the following formula can be cited:

[0216] -(R 31 ) p' -(X a ) q' -

[0217] [In the formula:

[0218] R 31 each independently represents a single bond, -(CH2) s' -, or ortho-phenylene, meta-phenylene, or para-phenylene each time it appears, and is preferably -(CH2) s' -.

[0219] s' is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2,

[0220] X a each independently represents, at each occurrence, -(X b ) l' -,

[0221] X b each independently represents, at each occurrence, a group selected from -O-, -S-, o-phenylene, m-phenylene or p-phenylene, -C(O)O-, -Si(R 33 )2-, -(Si(R 33 )2O) m' -Si(R 33 )2-, -CONR 34 -, -O-CONR 34 -, -NR 34 - and -(CH2) n' - in the group,

[0222] R 33 each independently represents, at each occurrence, phenyl, C 1－6 alkyl or C 1－6 alkoxy, preferably phenyl or C 1－6 alkyl, more preferably methyl,

[0223] R 34 each independently represents, at each occurrence, a hydrogen atom, phenyl or C 1－6 alkyl (preferably methyl),

[0224] m' is an integer from 1 to 100 at each occurrence, preferably an integer from 1 to 20,

[0225] n' is an integer from 1 to 20 at each occurrence, preferably an integer from 1 to 6, more preferably an integer from 1 to 3,

[0226] l' is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3,

[0227] p' is 0, 1 or 2,

[0228] q' is 0 or 1,

[0229] wherein at least one of p' and q' is 1, and the order of occurrence of each repeating unit marked with p' or q' and enclosed in parentheses is arbitrary.

[0230] wherein R 31 and X a (typically R 31 and Xa The hydrogen atom) may be substituted with one or more substituents selected from a fluorine atom, C 1－3 alkyl, and C 1－3 fluoroalkyl.

[0231] In one embodiment, l' is 1.

[0232] Preferably, the above X 5 is -(R 31 ) p' -(X a ) q' -R 32 -. R 32 represents a single bond, -(CH2) t' -, or ortho-phenylene, meta-phenylene, or para-phenylene, preferably -(CH2) t' -. t' is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3. Among them, R 32 (typically the hydrogen atom of R 32 ) may be substituted with one or more substituents selected from a fluorine atom, C 1－3 alkyl, and C 1－3 fluoroalkyl.

[0233] Preferably, the above X 5 is a single bond or a group represented by -Rf'-X 12 -[wherein, X 12 is C 1－ 20 alkylene, -R 31 -X c -R 32 -, or -X d -R 32 -[wherein, the meanings of R 31 and R 32 are the same as above.], Rf' is a single bond or -(C l' F 2l' )-, and l' is an integer from 1 to 4.]. Among them, alkylene is a group having a -(C n H 2n )- structure, which may be substituted or unsubstituted, and may be linear or branched.

[0234] More preferably, the above X 5 is

[0235] -X f -,

[0236] -X f -C 1－20 alkylene,

[0237] -X f-(CH2) s' -X c -

[0238] -X f -(CH2) s' -X c -(CH2) t' -

[0239] -X f -X d -,or

[0240] -X f -X d -(CH2) t' -.

[0241] Wherein, s' and t' have the same meanings as above.

[0242] In the above formula, X f It is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, for example, a methylene group. f The hydrogen atoms in the 1－3 Alkyl and C 1－3 The fluoroalkyl group is substituted with one or more substituents, preferably substituted. f It may be linear or branched, and is preferably linear.

[0243] More preferably, the above X 5 Can be a single bond, or -Rf'-X 13 - the group shown,

[0244] [Where, X 13 for

[0245] C 1－20 Alkylene,

[0246] -(CH2) s' -X c -

[0247] -(CH2) s' -X c -(CH2) t' -

[0248] -X d -,or

[0249] -X d -(CH2) t' -

[0250] [In the formula, s' and t' have the same meanings as above.] group,

[0251] Rf' is a single bond or -(C l' F 2l' )-,

[0252] l' is an integer from 1 to 4. ].

[0253] In the above formula, X c express

[0254] -O-,

[0255] -S-,

[0256] -C(O)O-,

[0257] -CONR 34 -

[0258] -O-CONR 34 -

[0259] -Si(R 33 )2-、

[0260] -(Si(R 33 )2O) m' -Si(R 33 )2-、

[0261] -O-(CH2) u' -(Si(R 33 )2O) m' -Si(R 33 )2-、

[0262] -O-(CH2) u' -Si(R 33 )2-O-Si(R 33 )2-CH2CH2-Si(R 33 )2-O-Si(R 33 )2-、

[0263] -O-(CH2) u' -Si(OCH3)2OSi(OCH3)2-,

[0264] -CONR 34 -(CH2) u' -(Si(R 33 )2O) m' -Si(R 33 )2-、

[0265] -CONR 34 -(CH2) u' -N(R 34 )-,or

[0266] -CONR34 -(o-Phenylene, m-phenylene or p-phenylene)-Si(R 33 )2-

[0267] [wherein, the meanings of R 33 , R 34 and m' are the same as those described above,

[0268] u' is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3.].

[0269] X c is preferably -O-.

[0270] In the above formula, X d represents

[0271] -S-,

[0272] -C(O)O-,

[0273] -CONR 34 -,

[0274] -CONR 34 -(CH2) u' -(Si(R 33 )2O) m' -Si(R 33 )2-,

[0275] -CONR 34 -(CH2) u' -N(R 34 )-, or

[0276] -CONR 34 -(o-Phenylene, m-phenylene or p-phenylene)-Si(R 33 )2-

[0277] [wherein, the meanings of each symbol are the same as those described above.].

[0278] Particularly preferably, the above X 5 is

[0279] -X f -,

[0280] -X f -C 1－20 alkylene,

[0281] -X f -(CH2) s' -X c -,

[0282] -X f -(CH2) s'-X c -(CH2) t' -,

[0283] -X f -X d -, or

[0284] -X f -X d -(CH2) t' -represented groups,

[0285] [wherein, X f , s' and t' have the same meanings as described above.],

[0286] X c is -O-, or -CONR 34 -,

[0287] X d is -CONR 34 -,

[0288] R 34 each independently represents a hydrogen atom, a phenyl group or a C 1－6 alkyl group (preferably a methyl group).].

[0289] In one embodiment, the above X 5 is

[0290] -X f -(CH2) s' -X c -,

[0291] -X f -(CH2) s' -X c -(CH2) t' -,

[0292] -X f -X d -, or

[0293] -X f -X d -(CH2) t' -represented groups,

[0294] [wherein, X f , s' and t' have the same meanings as described above.],

[0295] X c is -CONR 34 -,

[0296] X d is -CONR 34 -,

[0297] R 34 each independently represents a hydrogen atom, a phenyl group or a C 1－6 alkyl group (preferably a methyl group) each time it appears.

[0298] In one embodiment, the above X 5 can be

[0299] a single bond,

[0300] C 1－20 alkylene,

[0301] -(CH2) s' -X c -(CH2) t' -, or

[0302] -X d -(CH2) t' -

[0303] [wherein, the meanings of the symbols are the same as above.

[0304] Preferably, the above X 5 is a single bond or a group represented by -Rf'-X 14 -.

[0305] [wherein, X 14 is

[0306] C 1－20 alkylene,

[0307] -(CH2) s' -O-(CH2) t' -,

[0308] -(CH2) s' -(Si(R 33 ))2O) m' -Si(R 33 )2-(CH2) t' -,

[0309] -(CH2) s' -O-(CH2) u' -(Si(R 33 )2O) m' -Si(R 33 )2-(CH2) t' -, or

[0310] -(CH2) s' -O-(CH2) t' -Si(R 33 )2-(CH2) u'-Si(R 33 )2-(C v H 2v )-

[0311] [In the formula, the meanings of R 33 , m', s', t' and u' are the same as described above, v is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3.] group,

[0312] Rf' is a single bond or -(C l' F 2l' )-,

[0313] l' is an integer from 1 to 4.].

[0314] In the above formula, -(C v H 2v )- can be linear or branched, for example, it can be -CH2CH2-, -CH2CH2CH2-, -CH(CH3)-, -CH(CH3)CH2-.

[0315] The above X 5 group can be substituted by one or more substituents selected from a fluorine atom, C 1－3 alkyl and C 1－3 fluoroalkyl (preferably C 1－3 perfluoroalkyl).

[0316] In another embodiment, as the X 5 group, for example, the following groups can be listed:

[0317]

[0318]

[0319] [In the formula, R 41 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms or a C 1－6 alkoxy group, preferably a methyl group;

[0320] D is -Rf'-X 15 -

[0321] [In the formula, X 15 is selected from

[0322] -CH2O(CH2)2-,

[0323] -CH2O(CH2)3-,

[0324] -CF2O(CH2)e3-,

[0325] -(CH2)2-,

[0326] -(CH2)3-,

[0327] -(CH2)4-,

[0328] -CONH-(CH2)-、

[0329] -CONH-(CH2)2-、

[0330] -CONH-(CH2)3-,

[0331] -CON(CH3)-(CH2)3-,

[0332] -CON(Ph)-(CH2)3- (wherein Ph refers to phenyl), and

[0333]

[0334] (Where R 42 Each independently represents a hydrogen atom, C 1－6 Alkyl or C 1－6 The alkoxy group of , preferably represents a methyl group or a methoxy group, more preferably represents a methyl group.

[0335] Rf' is a single bond or -(C l' F 2l' )-,

[0336] l' is an integer from 1 to 4. ] represented by the group,

[0337] E is -(CH2) n - (n is an integer from 2 to 6),

[0338] D is bonded to the PFPE of the molecular main chain, and E is bonded to the group opposite to the PFPE. ].

[0339] As the above X 5 Specific examples include:

[0340] Single bond, or -Rf'-X 10 - the groups shown, etc.,

[0341] [Where, X 10 For selected

[0342] -CH2OCH2-,

[0343] -CH2O(CH2)2-,

[0344] -CH2O(CH2)3-,

[0345] -CH2O(CH2)6-,

[0346] <h2 style=";text-align:left;direction:ltr">CF2+CH2+O+CH2+<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0347] <h2 style=";text-align:left;direction:ltr"> -CF2-CH2-O-(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0348] <h2 style=";text-align:left;direction:ltr"> -CF2-CH2-O-(CH2)3-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0349] <h2 style=";text-align:left;direction:ltr"> -CF2-CH2-O-(CH2)6-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0350] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0351] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0352] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0353] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0354] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0355] <h2 style=";text-align:left;direction:ltr"> -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)<h2 style=";text-align:left;direction:ltr"> 20 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2(CH2)2-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0356] <h2 style=";text-align:left;direction:ltr"> CH2OCF2CHFOCF2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0357] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0358] <h2 style=";text-align:left;direction:ltr"> -CH2OCF2CHFOCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0359] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0360] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0361] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF2CF2CF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0362] <h2 style=";text-align:left;direction:ltr"> -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0363] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-,

[0364] -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-,

[0365] -CH2OCH2CHFCF2OCF2-,

[0366] -CH2OCH2CHFCF2OCF2CF2-,

[0367] -CH2OCH2CHFCF2OCF2CF2CF2-,

[0368] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-,

[0369] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-,

[0370] -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-,

[0371] -CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-,

[0372] -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-,

[0373] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-,

[0374] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-,

[0375] -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-,

[0376] -CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-,

[0377] -(CH2)2-Si(CH3)2-(CH2)2-,

[0378] -CH2-,

[0379] -(CH2)2-,

[0380] -(CH2)3-,

[0381] -(CH2)4-,

[0382] -(CH2)5-,

[0383] -(CH2)6-,

[0384] -CF2-,

[0385] -(CF2)2-,

[0386] -CF2-CH2-,

[0387] -CF2-(CH2)2-, -CF2-(CH2)3-, -CF2-(CH2)4-, -CF2-(CH2)5-, -CF2-(CH2)6-, -CO-

[0388] -CONH-

[0389] -CONH-CH2-, -CONH-(CH2)2-, -CONH-(CH2)3-, -CONH-(CH2)6-, -CF2CONH-,

[0390] -CF2CONHCH2-, -CF2CONH(CH2)2-, -CF2CONH(CH2)3-, -CF2CONH(CH2)6-, -CON(CH3)-(CH2)3-, -CON(Ph)-(CH2)3- (wherein Ph refers to a phenyl group), -CON(CH3)-(CH2)6-, -CON(Ph)-(CH2)6- (wherein Ph refers to a phenyl group), -CF2-CON(CH3)-(CH2)3-, -CF2-CON(Ph)-(CH2)3- (wherein Ph refers to a phenyl group), -CF2-CON(CH3)-(CH2)6-,

[0391] -CF2-CON(Ph)-(CH2)6- (where Ph refers to phenyl),

[0392] -CONH-(CH2)2NH(CH2)3-,

[0393] -CONH-(CH2)6NH(CH2)3-,

[0394] -CH2O-CONH-(CH2)3-、

[0395] -CH2O-CONH-(CH2)6-、

[0396] -S-(CH2)3-,

[0397] -(CH2)2S(CH2)3-、

[0398] -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、

[0399] -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、

[0400] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、

[0401] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、

[0402] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 10 Si(CH3)2(CH2)2-、

[0403] -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O) 20 Si(CH3)2(CH2)2-、

[0404] -C(O)O-(CH2)3-、

[0405] -C(O)O-(CH2)6-、

[0406] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、

[0407] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、

[0408] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、

[0409] -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、

[0410] -OCH2-、

[0411] -O(CH2)3-、

[0412] -OCFHCF2-、

[0413]

[0414] The group in

[0415] Rf' is a single bond or -(C l' F 2l' ).

[0416] l' is an integer from 1 to 4. ].

[0417] In a more preferred embodiment, X 5 represents X e' . X e' is a single bond, an alkylene group having 1 to 6 carbon atoms, -R 51 -C6H4-R 52 -, -R 51 -CONR 4 -R 52 -, -R 51 -CONR 4 -C6H4-R 52 -, -R 51 -CO-R 52 -, -R 51 -CO-C6H4-R 52 -, -R 51 -SO2NR 4 -R 52 -, -R 51 -SO2NR 4 -C6H4-R 52 -, -R 51 -SO2-R 52 - or -R 51 -SO2-C6H4-R 52 -. R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms. The meaning of R 4 is the same as above. The above alkylene group is substituted or unsubstituted, preferably unsubstituted. As substituents of the above alkylene group, for example, a halogen atom can be listed, and a fluorine atom is preferably listed. The above alkylene group is linear or branched, preferably linear.

[0418] In a further preferred embodiment, X e' can be

[0419] a single bond,

[0420] -X f -,

[0421] an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

[0422] -Xf -C 1－6 Alkylene, preferably -X f -C 1－3 Alkylene, more preferably -X f -C 1－2 Alkylene

[0423] -C6H4-R 52' -

[0424] -CONR 4' -R 52' -

[0425] -CONR 4' -C6H4-R 52' -

[0426] -X f -CONR 4' -R 52' -

[0427] -X f -CONR 4' -C6H4-R 52' -

[0428] -CO-R 52' -

[0429] -CO-C6H4-R 52' -

[0430] -SO2NR 4' -R 52' -

[0431] -SO2NR[[ID=6C]] 4' -C6H4-R 52' -

[0432] -SO2-R 52' -[[ID=7B]]

[0433] -SO2-C6H4-R 52' -

[0434] -R 51' -C6H4-

[0435] -R 51' -CONR 4' -

[0436] -R 51' -CONR 4' -C6H4-

[0437] -R 51' -CO-

[0438] -R 51' -CO-C6H4-、

[0439] -R 51' -SO2NR 4' -、

[0440] -R 51' -SO2NR 4' -C6H4-、

[0441] -R 51' -SO2-、

[0442] -R 51' -SO2-C6H4-、

[0443] -C6H4-、

[0444] -CONR 4' -、

[0445] -CONR 4' -C6H4-、

[0446] -X f -CONR 4' -、

[0447] -X f -CONR 4' -C6H4-、

[0448] -CO-、

[0449] -CO-C6H4-、

[0450] -SO2NR 4' -、

[0451] -SO2NR<L 4' -C6H4-

[0452] -SO2-、 or

[0453] -SO2-C6H4-

[0454] (In the formula, R 51' and R 52' are each independently a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. As described above, the alkylene group is substituted or unsubstituted. Examples of the substituent of the alkylene group include a halogen atom, preferably a fluorine atom.)

[0455] R 4' is a hydrogen atom or a methyl group.).

[0456] Among the above, X e' can preferably be

[0457] -X f -,

[0458] an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

[0459] -X f -C 1－6 an alkylene group, preferably -X f -C 1－3 an alkylene group, more preferably -X f -C 1－2 an alkylene group,

[0460] -CONR 4' -R 52' -,

[0461] -CONR 4' -C6H4-R 52' -,

[0462] -X f -CONR 4' -R 52' -,

[0463] -X f -CONR 4' -C6H4-R 52' -,

[0464] -R 51' -CONR 4' -,

[0465] -R 51' -CONR 4' -C6H4-,

[0466] -CONR 4' -,

[0467] -CONR 4' -C6H4-,

[0468] -X f -CONR 4' -,

[0469] -X f -CONR 4' -C6H4-,

[0470] -R 51' -CONR 4' -、or

[0471] -R 51' -CONR 4' -C6H4-.

[0472] Where, X f 、R 4' 、R 51' and R 52' The meanings are the same as above.

[0473] Among the above, X e' It can be more preferably

[0474] -CONR 4' -R 52' -

[0475] -CONR 4' -C6H4-R 52' -

[0476] -X f -CONR 4' -R 52' -

[0477] -X f -CONR 4' -C6H4-R 52' -

[0478] -R 51' -CONR 4' -

[0479] -R 51' -CONR 4' -C6H4-,

[0480] -CONR 4' -

[0481] -CONR 4' -C6H4-,

[0482] -X f -CONR 4' -,or

[0483] -X f -CONR 4' -C6H4-.

[0484] In this method, as X e' Specific examples include, for example,

[0485] single bond,

[0486] Perfluoroalkylene groups having 1 to 6 carbon atoms (e.g., -CF2-, -(CF2)2-, etc.), alkylene groups having 1 to 6 carbon atoms,

[0487] -CF2-C 1－6 Alkylene,

[0488] -CONH-、

[0489] -CONH-CH2-、-CONH-(CH2)2-、-CONH-(CH2)3-、-CF2-CONH-、 -CF2CONHCH2-、-CF2CONH(CH2)2-、-CF2CONH(CH2)3-、-CON( CH3)-、-CON(CH3)-CH2-、-CON(CH3)-(CH2)2-、-CON(CH3)-( CH2)3-、-CF2-CON(CH3)-、-CF2-CON(CH3)CH2-、-CF2-CON(CH 3)-(CH2)2-、-CF2-CON(CH3)-(CH2)3-、-CH2-CONH-、-CH2-C ONH-CH2-、-CH2-CONH-(CH2)2-、-CH2-CONH-(CH2)3-、-CF2- CH2-CONH-、-CF2-CH2-CONH-CH2-、-CF2-CH2-CONH-(CH2)2- 、-CF2-CH2-CONH-(CH2)3-、-CONH-C6H4-、-CON(CH3)-C6H4-、

[0490] -CH2-CON(CH3)-CH2-、-CH2-CON(CH3)-(CH2)2-、-CH2-CON(CH3)-(CH2)3-、-CON(CH3)-C6H4-、

[0491] -CF2-CONH-C6H4-、-CF2-CON(CH3)-C6H4-、

[0492] -CF2-CH2-CON(CH3)-CH2-、

[0493] -CF2-CH2-CON(CH3)-(CH2)2-、

[0494] -CF2-CH2-CON(CH3)-(CH2)3-、

[0495] -CF2-CON(CH3)-C6H4-、

[0496] -CO-、

[0497] -CO-C6H4-、

[0498] -C6H4-、

[0499] -SO2NH-、

[0500] -SO2NH-CH2-、

[0501] -SO2NH-(CH2)2-、

[0502] -SO2NH-(CH2)3-、

[0503] -SO2NH-C6H4-、

[0504] -SO2N(CH3)-、

[0505] -SO2N(CH3)-CH2-、

[0506] -SO2N(CH3)-(CH2)2-、

[0507] -SO2N(CH3)-(CH2)3-、

[0508] -SO2N(CH3)-C6H4-、

[0509] -SO2-、

[0510] -SO2-CH2-、

[0511] -SO2-(CH2)2-、

[0512] -SO2-(CH2)3-、 or

[0513] -SO2-C6H4- etc.

[0514] In the above-listed examples, as the preferred X e' , the following can be listed

[0515] an alkylene group having 1 to 6 carbon atoms,

[0516] a perfluoroalkylene group having 1 to 6 carbon atoms (e.g., -CF2-, -(CF2)2-, etc.),

[0517] -CF2-C 1－6 alkylene group,

[0518] -CONH-,

[0519] -CONH-CH2-,

[0520] -CONH-(CH2)2-,

[0521] -CONH-(CH2)3-,

[0522] -CF2CONH-,

[0523] -CF2CONHCH2-, -CF2CONH(CH2)2-, -CF2CONH(CH2)3-, -CON(CH3)-, -CON(CH3)-CH2-, -CON(CH3)-(CH2)2-, -CON(CH3)-(CH2)3-, -CF2-CON(CH3)-, -CF2-CON(CH3)CH2-, -CF2-CON(CH3)-(CH2)2-, -CF2-CON(CH3)-(CH2)3-, -CH2-CONH-, -CH2-CONH-CH2-, -CH2-CONH-(CH2)2-, -CH2-CONH-(CH2)3-, -CF2-CH2-CONH-, -CF2-CH2-CONH-CH2-, -CF2-CH2-CONH-(CH2)2-, -CF2-CH2-CONH-(CH2)3-, -CONH-C6H4-, -CON(CH3)-C6H4-, -CH2-CON(CH3)-CH2-, -CH2-CON(CH3)-(CH2)2-, -CH2-CON(CH3)-(CH2)3-, -CON(CH3)-C6H4-, -CF2-CONH-C6H4-, -CF2-CON(CH3)-C6H4-

[0524] -CF2-CH2-CON(CH3)-CH2-, -CF2-CH2-CON(CH3)-(CH2)2-, -CF2-CH2-CON(CH3)-(CH2)3-, -CF2-CON(CH3)-C6H4-, etc.

[0525] In the above-listed examples, as a more preferred X e' , -CONH- can be listed,

[0526] -CONH-CH2-,

[0527] -CONH-(CH2)2-,

[0528] -CONH-(CH2)3-,

[0529] -CF2CONH-,

[0530] -CF2CONHCH2-,

[0531] -CF2CONH(CH2)2-,

[0532] -CF2CONH(CH2)3-,

[0533] -CON(CH3)-,

[0534] -CON(CH3)-CH2-、

[0535] -CON(CH3)-(CH2)2-、

[0536] -CON(CH3)-(CH2)3-、

[0537] -CF2-CON(CH3)-、

[0538] -CF2-CON(CH3)CH2-、

[0539] -CF2-CON(CH3)-(CH2)2-、

[0540] -CF2-CON(CH3)-(CH2)3-、

[0541] -CH2-CONH-、

[0542] -CH2-CONH-CH2-、

[0543] -CH2-CONH-(CH2)2-、

[0544] -CH2-CONH-(CH2)3-、

[0545] -CF2-CH2-CONH-、

[0546] -CF2-CH2-CONH-CH2-、

[0547] -CF2-CH2-CONH-(CH2)2-、

[0548] -CF2-CH2-CONH-(CH2)3-、

[0549] -CONH-C6H4-、

[0550] -CON(CH3)-C6H4-、

[0551] -CH2-CON(CH3)-CH2-、

[0552] -CH2-CON(CH3)-(CH2)2-、

[0553] -CH2-CON(CH3)-(CH2)3-、

[0554] -CON(CH3)-C6H4-、

[0555] -CF2-CONH-C6H4-、

[0556] -CF2-CON(CH3)-C6H4-、

[0557] -CF2-CH2-CON(CH3)-CH2-、

[0558] -CF2-CH2-CON(CH3)-(CH2)2-、

[0559] -CF2-CH2-CON(CH3)-(CH2)3-、or

[0560] -CF2-CON(CH3)-C6H4-etc.

[0561] The compounds represented by the above formulas (A1) and (A2) can be produced by known methods, such as the method described in Patent Document 1 or its modified method.

[0562] Formulas (B1) and (B2):

[0563] (Rf-PFPE) γ ’-X 7 -(SiR a k1 R b l1 R c m1 ) γ ···(B1)

[0564] (R c m1 R b 11 R a k1 Si) γ -X 7 -PFPE-X 7 -(SiR a k1 R b l1 R c m1 ) γ ·(B2)

[0565] In the above formulas (B1) and (B2), the meanings of Rf and PFPE are the same as those described for the above formulas (A1) and (A2).

[0566] In the above formulas, X 7 independently represents a single bond or an organic group having a valence of 2 to 10. This X 7 in the compounds represented by formulas (B1) and (B2) can be understood as connecting the perfluoropolyether moiety (Rf-PFPE moiety or -PFPE- moiety) that mainly provides water repellency and surface smoothness, etc., and the silane moiety that provides the binding energy to the substrate (specifically, -SiR a k1 Rb l1 R c m1 a linking group of (a radical). Thus, as long as the compounds represented by formulas (B1) and (B2) can exist stably, this X 7 can be any organic group.

[0567] In the above formulas, γ is an integer from 1 to 9, and γ' is an integer from 1 to 9. These γ and γ' are determined according to the valence of X 7 and, in formula (B1), the sum of γ and γ' is the same as the valence of X 7 . For example, when X 7 is a 10-valent organic group, the sum of γ and γ' is 10. For example, γ can be 9 and γ' can be 1, γ can be 5 and γ' can be 5, or γ can be 1 and γ' can be 9. Additionally, when X 7 is a 2-valent organic group, γ and γ' are 1. In formula (B2), γ is the value obtained by subtracting 1 from the valence value of X 7 .

[0568] The above X 7 is preferably an organic group with a valence of 2 to 7, more preferably 2 to 4, and even more preferably 2.

[0569] In one embodiment, X 7 is an organic group with a valence of 2 to 4, γ is from 1 to 3, and γ' is 1.

[0570] In another embodiment, X 7 is a 2-valent organic group, γ is 1, and γ' is 1. In this case, formulas (B1) and (B2) are represented by the following formulas (B1') and (B2').

[0571] Rf-PFPE-X 7 -SiR a k1 R b l1 R c m1 ···(B1')

[0572] R c m1 R b l1 R a k1 Si-X 7 -PFPE-X 7 -SiR a k1 R b l1 R c m1 ···(B2')

[0573] As the above X 7 For example, without particular limitation, groups the same as those described for X 5 can be cited.

[0574] In the above formula, R a independently represents -Z 1 -SiR 71 p1 R 72 q1 R 73 r1 .

[0575] In the formula, Z 1 independently represents an oxygen atom or a divalent organic group each time it appears.

[0576] The above Z 1 is preferably a divalent organic group and does not contain a group that forms a siloxane bond with the Si atom (the Si atom bonded to R a ) at the end of the main chain of the molecule in formula (B1) or formula (B2).

[0577] The above Z 1 is preferably C 1－6 alkylene, -(CH2) g -O-(CH2) h -(where g is an integer from 1 to 6 and h is an integer from 1 to 6), or -phenylene-(CH2) i -(where i is an integer from 0 to 6), and more preferably C 1－3 alkylene. These groups can be substituted, for example, by one or more substituents selected from a fluorine atom, C 1－6 alkyl, C 2－6 alkenyl, and C 2－6 alkynyl.

[0578] In the formula, R 71 independently represents R a' . The meaning of R a' is the same as that of R a .

[0579] In R a , the maximum number of Si atoms linearly connected through the Z 1 group is 5. That is, in the above R a , in the case where there is at least one R 71 , there are two or more Si atoms linearly connected through the Z a group in R 1 , but such Si atoms linearly connected through the Z 1The maximum number of Si atoms linearly connected by the group is 5. Among them, "R a The number of Si atoms linearly connected through Z 1 in the group" is equal to the repetition number of -Z a linearly connected in R 1 -Si-.

[0580] For example, the following shows an example of connecting Si atoms through the Z a group (hereinafter simply referred to as "Z") in R 1 group.

[0581]

[0582] In the above formula, * refers to the bonding site with the main chain Si, and... refers to the end position of the ZSi repetition when all three bonds of the specified group other than ZSi bonded to the Si atom are... In addition, the number in the upper right corner of Si refers to the number of appearances of Si linearly connected through the Z group counted from *. That is, in the chain ending with Si 2 for the ZSi repetition, "the number of Si atoms linearly connected through the Z a group in R 1 " is 2. Similarly, in the chains ending with Si 3 Si 4 and Si 5 for the ZSi repetition, "the number of Si atoms linearly connected through the Z a group in R 1 " are 3, 4, and 5 respectively. In addition, it can be clarified from the above formula that in R a there are multiple ZSi chains, but they do not have to be all of the same length, and each can be of any length.

[0583] In a preferred embodiment, as described below, "the number of Si atoms linearly connected through the Z a group in R 1 " is 1 (left formula) or 2 (right formula) in all chains.

[0584]

[0585] In one embodiment, the number of Si atoms linearly connected through the Z group in R a is 1 or 2, preferably 1.

[0586] In the formula, R 72 independently represents a hydroxyl group or a hydrolyzable group each time it appears.

[0587] As used in this specification, the above-mentioned "hydrolyzable group" refers to a group capable of undergoing a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -O-N=C(R)2, -N(R)2, -NHR, and halogen (in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., and -OR (alkoxy group) is preferred. Examples of R include: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, unsubstituted alkyl groups are particularly preferred, and methyl or ethyl is more preferred. The hydroxyl group is not particularly limited and may be a hydroxyl group generated by hydrolysis of the hydrolyzable group.

[0588] Preferably, R 72 is -OR (wherein R represents a substituted or unsubstituted C 1－3 alkyl group, and more preferably represents methyl).

[0589] In the formula, R 73 independently represents a hydrogen atom or a lower alkyl group each time it appears. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably methyl.

[0590] In the formula, p1 is independently an integer of 0 to 3 each time it appears; q1 is independently an integer of 0 to 3 each time it appears; r1 is independently an integer of 0 to 3 each time it appears. Among them, the sum of p1, q1, and r1 is 3.

[0591] In a preferred embodiment, in R a at the end (when R a' does not exist, it is R a' ), the above-mentioned q1 is preferably 2 or more, for example, 2 or 3, and more preferably 3. a )

[0592] In a preferred embodiment, at least one of the terminal portions of R a can be -Si(-Z 1 -SiR 72 q R 73 r )2 or -Si(-Z 1 -SiR 72 q R 73 r )3, and preferably -Si(-Z 1 -SiR 72 q R 73 r )3. In the formula, (-Z 1 -SiR 72q R 73 r ) The unit of () is preferably (-Z 1 -SiR 72 3). In a further preferred embodiment, R a The terminal portions of all can be -Si(-Z 1 -SiR 72 q R 73 r )3, preferably -Si(-Z 1 -SiR 72 3)3.

[0593] In the above formulas (B1) and (B2), there is at least one R 72 .

[0594] In the above formulas, R b Each independently represents a hydroxyl group or a hydrolyzable group each time it appears.

[0595] The above R b Is preferably a hydroxyl group, -OR, -OCOR, -O-N = C(R)2, -N(R)2, -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), preferably -OR. R includes: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, unsubstituted alkyl groups are particularly preferred, and methyl or ethyl is more preferred. The hydroxyl group is not particularly limited and can be a hydroxyl group generated by hydrolysis of a hydrolyzable group. More preferably, R b Is -OR (in the formula, R represents a substituted or unsubstituted C 1－3 Alkyl group, more preferably represents methyl).

[0596] In the above formulas, R c Each independently represents a hydrogen atom or a lower alkyl group each time it appears. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably methyl.

[0597] In the formula, k1 is independently an integer from 0 to 3 each time it appears; l1 is independently an integer from 0 to 3 each time it appears; m1 is independently an integer from 0 to 3 each time it appears. Among them, the sum of k1, l1, and m1 is 3.

[0598] In a preferred embodiment, k1 is independently an integer from 1 to 3 each time it appears; l1 is independently an integer from 0 to 2 each time it appears; m1 is independently an integer from 0 to 2 each time it appears.

[0599] For example, using a perfluoropolyether derivative corresponding to the Rf-PFPE moiety as a raw material, after introducing a hydroxyl group to the terminal, a group having an unsaturated bond is introduced to the terminal, and the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom. Then, a hydroxyl group is introduced to the terminal of the silyl group, and the introduced group having an unsaturated bond is reacted with the silyl derivative, whereby the compounds represented by the above formulas (B1) and (B2) can be obtained.

[0600] Formulas (C1) and (C2):

[0601] (Rf-PFPE) δ -X 9 -(CR d k2 R e l2 R f m2 ) δ ···(C1)

[0602] (R f m2 R e l2 R d 2C) δ -X 9 -PFPE-X 9 -(CR d k2 R e l2 R f m2 ) δ ···(C2)

[0603] In the above formulas (C1) and (C2), the meanings of Rf and PFPE are the same as those described for the above formulas (A1) and (A2).

[0604] In the above formulas, X 9 each independently represents a single bond or a divalent to decavalent organic group. In the compounds represented by formulas (C1) and (C2), X can be understood as a linking group that connects the perfluoropolyether moiety (i.e., the Rf-PFPE moiety or the -PFPE- moiety) that mainly provides water repellency and surface smoothness, etc., and the part that provides the binding energy to the substrate (i.e., the group marked with δ and enclosed in parentheses). Therefore, as long as the compounds represented by formulas (C1) and (C2) can exist stably, X can be any organic group.

[0605] In the above formulae, δ is an integer from 1 to 9, and δ' is an integer from 1 to 9. These δ and δ' vary according to the valence of X. In formula (C1), the sum of δ and δ' is the same as the valence of X. For example, when X is a 10-valent organic group, the sum of δ and δ' is 10. For example, δ can be 9 and δ' can be 1, δ can be 5 and δ' can be 5, or δ can be 1 and δ' can be 9. Additionally, when X 9 is a 2-valent organic group, δ and δ' are 1. In formula (C2), δ is the value obtained by subtracting 1 from the valence of X 9 .

[0606] The above X 9 is preferably an organic group with a valence of 2 to 7, more preferably 2 to 4, and even more preferably 2.

[0607] In one embodiment, X 9 is an organic group with a valence of 2 to 4, δ is from 1 to 3, and δ' is 1.

[0608] In another embodiment, X 9 is a 2-valent organic group, δ is 1, and δ' is 1. In this case, formulae (C1) and (C2) are represented by the following formulae (C1') and (C2').

[0609] Rf-PFPE-X 9 -CR d k2 R e l2 R f m2 ···(C1')

[0610] R f m2 R e l2 R d k2 C-X 9 -PFPE-X 9 -CR d k2 R e l2 R f m2 ···(C2’)

[0611] Examples of the above X 9 are not particularly limited. For example, groups the same as those described for X 5 can be listed.

[0612] In the above formulae, R d independently represents -Z 2 -CR 81p2 R 82 q2 R 83 r2 。

[0613] In the formula, Z 2 independently represents an oxygen atom or a divalent organic group each time it appears.

[0614] The above-mentioned Z 2 is preferably C 1－6 alkylene, -(CH2) g -O-(CH2) h -(wherein, g is an integer from 0 to 6, for example an integer from 1 to 6, h is an integer from 0 to 6, for example an integer from 1 to 6), or -phenylene-(CH2) i -(wherein, i is an integer from 0 to 6), more preferably C 1－3 alkylene. These groups may be substituted by one or more substituents selected from a fluorine atom, C 1－6 alkyl, C 2－6 1]]alkenyl and C 2－6 alkynyl.

[0615] In the formula, R 81 independently represents R d' . R d' has the same meaning as R d 4]]].

[0616] In R d , the maximum number of C atoms linearly connected by the Z 2 group is 5. That is, in the above R d , when there is at least one R 81 , there are 2 or more C atoms linearly connected by the Z d group in R 2 , but the number of such C atoms linearly connected by the Z 2 group is at most 5. Among them, "the number of C atoms linearly connected by the Z d group in R 2 " is equal to the repetition number of -Z d -C- linearly connected in R 2 . This is the same as the description of R a in formulas (B1) and (B2).

[0617] In a preferred embodiment, "the number of C atoms linearly connected by the Z d group in R 2 " is 1 (left formula) or 2 (right formula) in all chains.

[0618] In one embodiment, R d The number of C atoms linearly linked through the Z 2 group is 1 or 2, preferably 1.

[0619] In the formula, R 82 represents -Y-SiR 85 n2 R 86 3－2n .

[0620] Y, each occurrence being independent of one another, represents a divalent organic group.

[0621] In a preferred embodiment, Y is C 1－6 alkylene, -(CH2) g' -O-(CH2) h' -(wherein g' is an integer from 0 to 6, for example an integer from 1 to 6, h' is an integer from 0 to 6, for example an integer from 1 to 6), or -phenylene-(CH2) i' -(wherein i' is an integer from 0 to 6). These groups may be substituted, for example, with one or more substituents selected from a fluorine atom, C 1－6 alkyl, C 2－6 alkenyl and C 2－6 alkynyl.

[0622] In one embodiment, Y may be C 1－6 alkylene, -O-(CH2) h' - or -phenylene-(CH2) i' -. When Y is the above-mentioned group, the light resistance, especially the ultraviolet resistance, can be further improved.

[0623] Each occurrence of the above R 85 independently represents a hydroxyl group or a hydrolyzable group.

[0624] As used in this specification, the above-mentioned "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, -O-N=C(R)2, -N(R)2, -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., preferably -OR (alkoxy). Examples of R include: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl; substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, unsubstituted alkyl groups are particularly preferred, and methyl or ethyl is more preferred. The hydroxyl group is not particularly limited and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group.

[0625] Preferably, R 85-OR (where R represents a substituted or unsubstituted C 1－3 Alkyl, more preferably means ethyl or methyl, especially means methyl).

[0626] The above R 86 Each occurrence of ' represents independently a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0627] n2 in each (-Y-SiR 85 n2 R 86 3－n2 ) units independently represent an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0628] The above R 83 Each occurrence of is independently a hydrogen atom, a hydroxyl group or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group. In one embodiment, R 83 Each occurrence independently represents a hydrogen atom or a lower alkyl group.

[0629] In the formula, p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently an integer from 0 to 3 at each occurrence. The sum of p2, q2, and r2 is 3.

[0630] In a preferred embodiment, in R d The terminal R d' (There is no R d' When R d ), the above q2 is preferably greater than 2, for example, 2 or 3, more preferably 3.

[0631] In a preferred embodiment, R d At least one of the terminal portions may be -C(-Y-SiR 85 q2 R 86 r2 )2 or -C(-Y-SiR 85 q2 R 86 r2 )3, preferably -C(-Y-SiR 85 q2 R 86 r2 )3. In the formula, (-Y-SiR 85 q2 R 86r2 ) The unit is preferably (-Y-SiR 85 3). In a further preferred embodiment, R d The terminal portions of all can be -C(-Y-SiR 85 q2 R 86 r2 )3, preferably -C(-Y-SiR 85 3)3.

[0632] In the above formula, R e Each occurrence independently represents -Y-SiR 85 n2 R 86 3－n2 . Among them, the meanings of Y, R 85 , R 86 and n2 are the same as those described for R 82 above.

[0633] In the above formula, R f Each occurrence independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group. In one embodiment, R f Each occurrence independently represents a hydrogen atom or a lower alkyl group.

[0634] In the formula, k2 is independently an integer from 0 to 3 each occurrence; l2 is independently an integer from 0 to 3 each occurrence; m2 is independently an integer from 0 to 3 each occurrence. Among them, the sum of k2, l2 and m2 is 3.

[0635] In one embodiment, at least one k2 is 2 or 3, preferably 3.

[0636] In one embodiment, k2 is 2 or 3, preferably 3.

[0637] In one embodiment, l2 is 2 or 3, preferably 3.

[0638] In the above formulas (C1) and (C2), at least one q2 is 2 or 3, or at least one l is 2 or 3. That is, in the formula, there are at least two -Y-SiR 85 n2 R 86 3－n2 groups.

[0639] The perfluoro(poly)ether group-containing silane compound represented by formula (C1) or formula (C2) can be produced by combining known methods. For example, the compound represented by formula (C1') in which X is divalent is not limited, and can be produced according to the following operations.

[0640] In one mode, Rf' in each of the above modes is a single bond in formulas (A1), (B1), and (C1), and in formulas (A2), (B2), and (C2), in X located on the left side of PFPE 5 it is (C l' F 2l' ), and in X located on the right side of PFPE 5 it is (C l' F 2l' ).

[0641] In one mode, Rf' in each of the above modes can be a single bond.

[0642] The perfluoro(poly)ether group-containing silane compound represented by the above formulas (A1), (A2), (B1), (B2), (C1), and (C2) is not particularly limited and may have a number average molecular weight of 5×10 2 to 1×10 5 . The above number average molecular weight can be preferably 2,000 to 30,000, more preferably 3,000 to 10,000, and further preferably 3,000 to 8,000. This "number average molecular weight" can be measured by GPC (gel permeation chromatography) analysis.

[0643] In the surface treatment agent of the present invention, relative to the total of the compounds represented by formulas (A1), (B1), and (C1) (hereinafter also referred to as "single-terminal compounds") and the compounds represented by formulas (A2), (B2), or (C2) (hereinafter also referred to as "double-terminal compounds"), the double-terminal compound is preferably 0.1 mol% or more and 35 mol% or less. Relative to the total of the single-terminal compound and the double-terminal compound, the lower limit of the content of the double-terminal compound is preferably 0.1 mol%, more preferably 0.2 mol%, further preferably 0.5 mol%, further more preferably 1 mol%, particularly preferably 2 mol%, and particularly may be 5 mol%. Relative to the total of the single-terminal compound and the double-terminal compound, the upper limit of the content of the double-terminal compound can be preferably 35 mol%, more preferably 30 mol%, further preferably 20 mol%, further more preferably 15 mol% or 10 mol%. Relative to the total of the single-terminal compound and the double-terminal compound, the double-terminal compound is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, further preferably 0.2 mol% or more and 10 mol% or less, further more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less, for example, 2 mol% or more and 10 mol% or less or 5 mol% or more and 10 mol% or less. By making the double-terminal compound within this range, the friction durability can be further improved.

[0644] As other examples of the perfluoroalkyl group-containing silane compound, the following (1) and (2) described in WO2020 / 019653 can be cited.

[0645] R F1 α X A -R Si β (1)

[0646] R Si γ -X A -R F2 -X A -R Si γ (2)

[0647] R F1 is independently Rf at each occurrence 1 -R F -O q -;

[0648] R F2 is -Rf 2 p -R F -O q -;

[0649] Rf 1 is independently a C alkyl group that may be substituted with one or more fluorine atoms at each occurrence 1－16 alkyl;

[0650] Rf 2 is a C alkylene group that may be substituted with one or more fluorine atoms 1－6 alkylene;

[0651] R F is independently a divalent fluorinated polyether group at each occurrence;

[0652] p is 0 or 1;

[0653] q is independently 0 or 1 at each occurrence;

[0654] R Si is independently a monovalent group containing a Si atom bonded to a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group at each occurrence;

[0655] At least one R Si is a monovalent group containing a Si atom bonded to a hydroxyl group or a hydrolyzable group;

[0656] X AEach is independently a single bond or an organic group with a valence of 2 to 10;

[0657] α is an integer from 1 to 9;

[0658] β is an integer from 1 to 9;

[0659] γ is independently an integer from 1 to 9.

[0660] As the silane compound having an isocyanuric acid skeleton, for example, the following compound having an isocyanuric acid skeleton described in WO2018 / 056413 can be used.

[0661]

[0662] (In the formula, R 1 represents a monovalent organic group containing a polyether chain, X 1 and X 2 independently represent monovalent groups, and the above polyether chain is of the formula: -(OC6F 12 ) m11 -(OC5F 10 ) m12 -(OC4F8) m13 -(OC3X 10 6) m14 -(OC2F4) m15 -(OCF2) m16 -(wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or more, and X 10 is independently H, F or Cl, and the existence order of each repeating unit is arbitrary) the chain shown).

[0663] The antifouling layer 130 can form a film of the fluorosilane compound on the unevenness by PVD such as vacuum evaporation, sputtering, resistance heating evaporation, or CVD and other evaporation processes.

[0664] In addition, the antifouling layer 130 can also be formed by dissolving a fluorosilane compound in an organic solvent, coating it on the unevenness, and drying it. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butanediol diacetate, cyclohexyl acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, chloroform, HFC141b, HCHC225, hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. One or more of these can be selected.

[0665] As the coating method, various coating methods such as dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, etc., or printing methods such as letterpress printing, inkjet printing, etc. can be used for coating.

[0666] Drying can be carried out under conditions where the organic solvent evaporates and a solid film of the antifouling layer 130 can be formed. For example, it can be carried out by heating under the conditions of 100 to 200 °C for 1 to 60 minutes. In addition, even at a low temperature, the condensation reaction itself proceeds, so drying can also be carried out under milder conditions (heating at a temperature below 100 °C for more than 60 minutes). For example, drying can be carried out by leaving it at room temperature for a long time.

[0667] In addition to the fluorosilane compound, monomers, oligomers, polymers, fillers such as silica, and other additives (catalysts, surfactants, inhibitors, sensitizers, etc.) can also be used to form the antifouling layer 130.

[0668] For example, when a silane compound containing an isocyanuric acid skeleton is used as the fluorosilane compound, in addition, the following can also be used:

[0669] (A) Polymerizable coating agent monomers such as monofunctional and / or polyfunctional acrylates and methacrylates (hereinafter, acrylates and methacrylates will also be collectively referred to as “(meth)acrylates”), monofunctional and / or polyfunctional polyurethane (meth)acrylates, monofunctional and / or polyfunctional epoxy (meth)acrylates; or

[0670] (B) (b-1) Thermosetting resins such as acrylic polymers, polycarbonate polymers, polyester polymers, polyamide polymers, polyimide polymers, polyethersulfone polymers, cyclic polyolefin polymers, fluorinated polyolefin polymers (PTFE, etc.), and fluorinated cyclic amorphous polymers (CYTOP (registered trademark), Teflon (registered trademark) AF, etc.); and (b-2) curable monomers such as polyurethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, silicon-containing (meth)acrylates, and (meth)acrylate monomers.

[0671] When a perfluoroalkyl group-containing silane compound is used as the fluorine-containing silane compound, a fluoroalkyl silane oligomer mixture may be used in addition to the fluorine-containing silane compound to form the antifouling layer 130 .

[0672] The fluoroalkylsilane oligomer mixture may contain a partial hydrolysis-condensation product of a fluoroalkylsilane compound represented by the following formula (II).

[0673] Rf1-Q1-SiR1pX13-p(II)

[0674] [Where:

[0675] Rf1 is ClF2l+1,

[0676] l is an integer from 1 to 10,

[0677] Q1 is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms,

[0678] R1 is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms,

[0679] X1 is independently a hydroxyl group or a hydrolyzable group,

[0680] p is an integer from 0 to 2.]

[0681] In formula (II), R f1 C l F 2l+1 , l is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, for example an integer of 2 to 6 or an integer of 3 to 6.

[0682] In formula (II), Q 1 It is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group include a linear or branched alkylene group, a linear or branched alkylene group having 2 to 6 carbon atoms and a group having an amide group or an ethereal oxygen atom between carbon atoms, etc. Among them, a linear alkylene group having 1 to 6 carbon atoms is preferred from the perspective of excellent weather resistance: -(CH2) t-(wherein, t is an integer from 1 to 6), more preferably -(CH2)2 -, -(CH2)3 - or -(CH2)4 -, particularly preferably -(CH2)2 -.

[0683] In formula (II), R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include linear or branched alkyl groups. Among them, from the aspect of ease of obtaining, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, and more preferably methyl or ethyl. When there are a plurality of them, R 1 can be the same or different, and from the aspect of ease of obtaining, it is preferably the same.

[0684] In formula (II), X 1 is a hydroxyl group or a group capable of hydrolysis. Among them, the above-mentioned "group capable of hydrolysis" as used in this specification refers to a group that can be detached from the main skeleton of the compound through a hydrolysis reaction. Examples of the group capable of hydrolysis include -OR, -OCOR, -O-N=CR2, -NR2, -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), etc., and -OR (i.e., alkoxy) is preferred. Examples of R include: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, particularly preferably unsubstituted alkyl groups, and more preferably methyl or ethyl. The hydroxyl group is not particularly limited and can be a hydroxyl group generated by hydrolysis of a group capable of hydrolysis.

[0685] When X 1 is a chlorine atom, the reactivity is high, and the hydrolysis reaction proceeds sufficiently even without adding an acid catalyst. Depending on the use, it is preferable to use a compound in which X 1 is a chlorine atom.

[0686] In formula (II), p is an integer from 0 to 2, and from the aspect of excellent adhesion and durability, 0 or 1 is preferred, and more preferably 0.

[0687] As the compound represented by formula (II), for example, the following can be cited. In the formula, the exemplification and preferred modes of l, t, X 1 , R 1 are as described above.

[0688] Formula (I-1): CF3(CF2) l－1 -(CH2) t -SiX 1 3

[0689] Formula (I-2): CF3(CF2) l－1 -(CH2) t -SiR 1 X 1 2

[0690] The fluoroalkylsilane compound represented by the formula (II) can be used alone or in combination of two or more. The fluoroalkylsilane compound represented by the formula (II) can be produced by a conventional production method and is also commercially available.

[0691] The above-mentioned fluoroalkylsilane oligomer is formed by hydrolysis and condensation of the (SiX 1 ) moieties of two or more of the fluoroalkylsilane compounds represented by the formula (II). The fluoroalkylsilane oligomer can generally be a mixture of polymers mainly containing 2 to 14-mers.

[0692] The degree of oligomerization / condensation can be measured by 29 Si-NMR and is represented by the integral values of T0 species ( 29 40 - 48 ppm in Si-NMR), T1 species (48 - 54 ppm), T2 species (54 - 63 ppm), and T3 species (63 - 75 ppm), respectively. The 29 Si-NMR of the fluoroalkylene oligomer mixture shows 0 to 10%, more preferably 0 to 5%, further preferably 0 to 3% of T0 species (40 - 48 ppm), 0 to 40%, more preferably 1 to 30%, further preferably 10 to 25% of T1 species (48 - 54 ppm), and 20 to 80%, more preferably 25 to 75%, further preferably 30 to 70% of T2 species (54 - 63 ppm). Among them, the explanations of T0, T1, T2, and T3 are described in "Tatsuya Miyazaki, et al., 'Structural Analysis of Silicon-Containing Materials by Si NMR Method', [online], Asahi Glass Research Report 66 (2016), pp. 32 - 36, URL <URL:https: / / www.agc.com / innovation / library / pdf / 66-07.pdf>". 29 Si NMR method for structural analysis of silicon-containing materials", [online], Asahi Glass Research Report 66 (2016), pp. 32 - 36, URL <URL:https: / / www.agc.com / innovation / library / pdf / 66-07.pdf>".

[0693] The oligomer is formed by hydrolysis of the compound represented by the formula (II). The oligomer can be formed by hydrolysis of the same or different compounds represented by the formula (II). The hydrolysis reaction of the compound represented by the formula (II) and water can be carried out in the presence of a catalyst or in the absence of a catalyst. As suitable catalysts, there is no particular limitation, and examples include acid catalysts, base catalysts, organic amine catalysts, or metal catalysts. In a specific example, the catalyst can be selected from hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, ammonia, triethylamine, titanium isopropoxide, or dibutyltin dilaurate. It should be understood that water can be provided as part of an aqueous catalyst composition.

[0694] The degree of oligomerization (based on 29 Si-NMR analysis) and / or the size of the oligomers (based on the number average molecular weight) can be adjusted by adjusting the amount of water in the reaction system, by selecting a suitable catalyst, and / or by selecting appropriate reaction conditions. In particular, the molar ratio of water to silicon is controlled when providing the oligomers according to the present invention. In a specific example, the molar ratio of water to silicon (water:silicon) can be about 2.5 or less:1, about 2 or less:1, about 1.5 or less:1, about 1.25 or less:1, about 1 or less:1, about 0.75 or less:1, or about 0.5 or less:1. In a specific example, the molar ratio of water to silicon (water:silicon) can be 0.5:1 to 2.5:1, 0.75:1 to 2:1, 1:1 to 1.5:1, or 1:1 to 1.25:1. Additionally, even for ranges other than the above, it can also be other ranges formed by combining the upper and lower limits described above.

[0695] For the above-mentioned fluoroalkylsilane oligomers, through 1 H-NMR, 29 Si-NMR, GC (gas chromatography), LC (liquid chromatography) analysis, structural analysis and compositional analysis can be carried out, the composition or ratio of a mixture of polymers containing 2 to 14 mers, the ratio or residual rate of hydrolyzable groups, the degree of condensation, etc. can be determined.

[0696] The number average molecular weight of the above-mentioned fluoroalkylsilane oligomer mixture can preferably be 300 or more, preferably 400 or more, more preferably 500 or more, and further preferably 800 or more.

[0697] The number average molecular weight of the above-mentioned fluoroalkylsilane oligomer mixture can preferably be 4500 or less, more preferably 4000 or less, further preferably 3500 or less, and further more preferably 3000 or less.

[0698] In addition, in the present invention, the "number average molecular weight" can be measured by GPC (gel permeation chromatography) analysis.

[0699] In the above-mentioned fluoroalkylsilane oligomer mixture, the content ratio (OCH3 / Si, molar ratio) of methoxy (OCH3) to silicon (Si) can preferably be 1.5 or more, more preferably 2.0 or more, and further preferably 2.2 or more. By making this ratio 1.5 or more, the friction durability is further improved. Additionally, the content ratio of methoxy to silicon is preferably 2.8 or less, more preferably 2.7 or less, and further preferably 2.5 or less. By making this ratio 2.8 or less, the wear durability is further improved.

[0700] The above-mentioned content ratio of methoxy to silicon can be measured using 29 Si-NMR.

[0701] The above fluorinated alkylsilane oligomer mixture can preferably be 20% by mass or less, more preferably 10% by mass or less, relative to the total amount of the above fluorinated alkylsilane oligomer mixture and the perfluoroalkyl group-containing silane compound.

[0702] The above fluorinated alkylsilane oligomer mixture can preferably be 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total amount of the above fluorinated alkylsilane oligomer mixture and the perfluoroalkyl group-containing silane compound.

[0703] As described above, by implementing S100 to S200 according to this embodiment, an antifouling layer 130 is formed on the unevenness (the unevenness of the base material 110 or the base layer 120). Thereby, the antifouling layer 130 is firmly bonded to the unevenness, and thus the abrasion resistance and durability of the antifouling layer 130 can be improved.

[0704] [Examples]

[0705] Hereinafter, examples of this embodiment will be described using examples.

[0706] [Example 1]

[0707] [Production of Resin Composition for Substrate]

[0708] Acetic acid (2.71 g) and methyltrimethoxysilane (MTMS, 35.21 g) were added to a small glass bottle, and then the mixture was cooled in an ice bath. Then, a mixture of silica (LUDOX (registered trademark) AS-40, 14.16 g) and water was added to the cooled mixture of silane and acetic acid over about 20 minutes. Due to the exothermic reaction of silane hydrolysis, the mixture was slightly heated and stirred for several hours while cooling to room temperature. Then, a mixture of IPA (isopropyl alcohol) and n-BuOH (n-butanol) was added and mixed for about 30 minutes. Then, 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol (SDBR) was added to the hydrolysis mixture (2.82 g, 32% SDBR in a 1-methoxy-2-propanol solution), and stirring was continued until SDBR was dispersed. The reaction mixture was further stirred for 1 day to mix. A 40% solution of tetrabutylammonium acetate (TBAA) in water (0.1 g) and BYK (registered trademark) 302 (0.05 g) were added. Then, the complex was fully cured to produce a resin composition for the substrate.

[0709] [Production of Primer Composition]

[0710] The undercoat composition is prepared by mixing polymethyl methacrylate (PMMA), a solvent, and a flow control agent. An PMMA solution was prepared by dissolving PMMA resin (7 gm) in 93 g of a mixture of 1-methoxy-2-propanol (85 wt%) and diacetone alcohol (15 wt%) at 50 °C in a glass bottle for more than 17 hours. The BYK (registered trademark) 331 (0.03%) flow additive was added to the above mixture to produce the undercoat composition.

[0711] As the substrate, a polycarbonate substrate was used. The undercoat composition was coated on the substrate and dried at 120 °C for 30 minutes. Then, the base resin composition was coated to a thickness of 8 μm on the surface of the substrate coated with the undercoat composition by dip coating. Then, it was dried at 120 °C for 60 minutes using a hot air drying oven.

[0712] In the exposure process, for the dried base resin composition, irradiation with a cumulative illuminance of 300 mJ / cm 2 was performed using a Xe excimer lamp (wavelength 172 nm, illuminance 100 mW / cm 2 ). Thus, the base layer 120 was formed. The component thus obtained was used as Example Component 1.

[0713] [Formation of the antifouling layer 130]

[0714] For Example Component 1 and Comparative Example Component 1, using a fluorine-based solvent HFE7200, OPTOOL UD120 (manufactured by Daikin Industries, Ltd.) containing a fluorosilane compound (a perfluoroalkyl-containing silane compound) was diluted to 0.5 wt%, and then the antifouling layer 130 was formed by flow coating. The antifouling component obtained from Example Component 1 was used as Antifouling Component A1.

[0715] [Example 2]

[0716] In the exposure process, the cumulative illuminance was made 2100 mJ / cm 2 , and except for this, the same treatment as in Example 1 was performed to obtain Example Component 2 and Antifouling Component A2.

[0717] [Example 3]

[0718] In the exposure process, the cumulative illuminance was made 2100 mJ / cm 2 , and the drying conditions of UD120 were made 25 °C for 164 hours. Except for this, the same treatment as in Example 1 was performed to obtain Example Component 3 and Antifouling Component A3.

[0719] [Example 4]

[0720] After applying the resin composition for coating the substrate, instead of the exposure process, Ar / O2 mixed gas plasma irradiation was performed at a flow rate of 3000 scccm, an oxygen fraction of 0.1, and an output of 0.5 kW. Otherwise, the same treatment as in Example 1 was carried out. The components thus obtained were used as Example Component 4 and Antifouling Component A4.

[0721] [Comparative Example 1]

[0722] After applying the resin composition for coating the substrate, no exposure was performed and no antifouling layer was provided. Otherwise, the same treatment as in Example 1 was carried out. The component thus obtained was used as Comparative Example Component 1.

[0723] [Comparative Example 2]

[0724] No antifouling layer was provided. Otherwise, the same treatment as in Example 2 was carried out. The component thus obtained was used as Comparative Example Component 2.

[0725] [Comparative Example 3]

[0726] The exposure process was omitted. Otherwise, the same treatment as in Example 1 was carried out. The components thus obtained were used as Comparative Example Component 3 and Antifouling Component B3.

[0727] [Comparative Example 4]

[0728] After applying and drying the resin composition for coating the substrate, no exposure was performed, but silica evaporation was carried out, and UD120 was provided by evaporation instead of flow coating. Otherwise, the same treatment as in Example 1 was carried out. The components thus obtained were used as Comparative Example Component 4 and Antifouling Component B4.

[0729] [Evaluation of unevenness]

[0730] [Surface roughness Rz]

[0731] The surface roughness (Rz) of Example Component 1 and Comparative Example Component 1 was measured by atomic force microscopy. As a result, the Rz of Example Component 1 was 6.62 nm, and the Rz of Comparative Example Component 1 was 2.07 nm.

[0732] [Evaluation of antifouling components]

[0733] [Pencil hardness]

[0734] After measuring the pencil hardness of Antifouling Component A1 and Antifouling Component B1, both were HB.

[0735] Among them, regarding the anti-fouling components A1 to A4 and the anti-fouling components B1 to B4, evaluations of TT, haze, water contact angle, and wiping property with a magic marker are carried out in the initial state after manufacturing, after wear test 1, after wear test 2, and after the weather resistance test. The content of wear test 1, etc. and various evaluation methods are as described below.

[0736] [Wear Test 1]

[0737] Wear test 1 is carried out according to the following key points. A 2×2 cm steel wool sheet is fixed to a weight of a cylindrical body (cylindrical, d = 4 cm, height = 7 cm) using double-sided adhesive tape. The weight is selected to achieve a load of 500 g / cm 2 . The steel wool sheet used is steel wool of type #0000 (microfibers of Rakso company, Lahr, Germany). For the 10 cm long coated surface of the anti-fouling component, the weight is reciprocated horizontally 500 times.

[0738] [Wear Test 2]

[0739] Wear test 2 is a Taber wear test and is carried out according to the following key points. Using a wear testing machine (Toyosha, TS type), a wear test of the anti-fouling component is carried out under the conditions of a wear wheel: CS-10F type, a load of 500 g, and a rotational speed of 1000 cycles. In addition, wear test 2 can also be carried out according to JIS K 7204.

[0740] [Weather Resistance Test]

[0741] Using a xenon lamp weather resistance testing machine, model SX75 (Suga Test Instruments Co., Ltd.), it is irradiated with a 7.5 kw water-cooled xenon lamp for 50,000 hours. The irradiation conditions are a wavelength of 300 nm to 400 nm, a radiation irradiance of 62 W / m 2 , the blackboard temperature of the anti-fouling component is 55 degrees, and the distance between the lamp and the surface of the anti-fouling component is 29 cm.

[0742] [Haze Measurement]

[0743] Using a haze meter (Nippon Denshoku, NDH-4000), the degree of light scattering (haze) on the surface of the specimen is measured.

[0744] [Total Transmittance (TT)]

[0745] Using a haze meter (Nippon Denshoku, NDH-4000), it is measured together with the haze.

[0746] [Contact Angle]

[0747] Drop 2 μL of pure water droplets onto the surface of the antifouling component, and use a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: Automatic Contact Angle Meter DropMaster 701) to measure the contact angle with water at 5 positions and calculate the average value.

[0748] [Universal pen wipeability]

[0749] Apply oil-based ink (ZEBRA Co., Ltd.: Mckee extra-fine black) to the surface of the antifouling component. After drying, wipe it with KimWipe (wiping paper) in a state without any wetting, and observe the appearance. Record as OK if the oil-based ink is completely wiped off, and record as NG if the ink remains.

[0750] The results of the initial state are shown below. As shown in the table, in antifouling components B1 - B2, sufficient antifouling performance cannot be achieved, and compared with antifouling components A1 - A4, the haze deteriorates in antifouling components B3 - B4.

[0751] [Table 1]

[0752]

[0753] The results after wear test 1 on the initial state are shown below. As shown in the table, in antifouling components A1 - A4, the antifouling performance is maintained after wear. In contrast, in antifouling components B1 - B4, the antifouling performance is lost after wear, and the haze also deteriorates significantly.

[0754] [Table 2]

[0755]

[0756] The results after wear test 2 on the initial state are shown below. As shown in the table, in antifouling components A1 - A4, the antifouling performance is maintained after wear. In contrast, in antifouling components B1 - B4, the antifouling performance is lost after wear.

[0757] [Table 3]

[0758]

[0759] The results after the weather resistance test on the initial state are shown below. As shown in the table, in antifouling components A1 - A4, the antifouling performance is maintained after the weather resistance test. In contrast, in antifouling components B1 - B4, the antifouling performance is lost after the weather resistance test.

[0760] [Table 4]

[0761]

[0762] As described above, the present invention has been described using embodiments, but the technical scope of the present invention is not limited to the scope described in the above embodiments. It is obvious to those skilled in the art that various changes or improvements can be made to the above embodiments. It can be clearly understood from the description of the scope of claims that such changed or improved modes are also included in the technical scope of the present invention.

[0763] Regarding the implementation order of each process such as the operations, procedures, steps, and stages of the method shown in the claims, the description, and the drawings, it should be noted that as long as there is no specific indication of "earlier", "before", etc., and the substances generated by the previous process are not used in the subsequent process, it can be implemented in any order. Regarding the operation flow in the claims, the description, and the drawings, even if it is described using "first", "then", etc. for the convenience of explanation, it does not mean that it must be implemented in that order.

[0764] Symbol Explanation

[0765] 10: Anti-fouling component; 110: Substrate; 120: Base layer; 130: Anti-fouling layer.

Claims

1. A manufacturing method of an anti-fouling component, characterized in that, Comprising: A substrate forming stage of forming a base layer on the surface of one side of a substrate; And An antifouling layer forming stage of forming an antifouling layer containing a perfluoropolyether group-containing silane compound on the base layer.

2. The method for manufacturing an antifouling component according to claim 1, wherein: The base layer has nano-scale unevenness, In the antifouling layer forming stage, the antifouling layer is formed at least in the concave portions of the unevenness.

3. The method for manufacturing an antifouling component according to claim 2, wherein: The substrate forming stage includes: A stage of coating the substrate with a base resin composition on the substrate and drying it; and A stage of forming unevenness from the dried base resin composition.

4. The method for manufacturing an antifouling component according to claim 3, wherein: The base resin composition contains an organosilicon resin including a T unit structure and a Q unit structure, The stage of forming unevenness from the dried base resin composition includes a pretreatment of the dried base resin composition to modify the T unit structure into silica.

5. The method for manufacturing an antifouling component according to claim 4, wherein: The pretreatment is carried out by exposure to light with a wavelength of 150 - 200 nm.

6. The method for manufacturing an antifouling component according to claim 5, wherein: The pre-treatment is performed by exposing in such a manner that the cumulative illuminance reaches a range of 200 to 6000 mJ / cm 2 .

7. The method for manufacturing an antifouling component according to claim 4, wherein: The pretreatment is carried out by applying an Ar / O2 mixed gas plasma within an output range of 0.2 - 1.0 kW.

8. The method for manufacturing an antifouling component according to claim 4 or 5, wherein: The pretreatment is carried out by applying an Ar / O2 mixed gas plasma with a flow rate in the range of 2000 - 5000 sccm and an oxygen fraction in the range of 0.03 - 0.

4.

9. The method for manufacturing an antifouling component according to any one of claims 3 - 8, wherein: For the substrate, the coating in the stage of coating the substrate with a base resin composition and drying it is carried out such that the coating film thickness becomes 1 - 20 μm.

10. The method for manufacturing an antifouling component according to any one of claims 3 - 9, wherein: For the substrate, the drying in the stage of coating the substrate with a base resin composition and drying it is carried out at a temperature of 100 - 150 °C for 10 - 120 minutes.

11. The method for manufacturing an antifouling component according to any one of claims 3 - 10, wherein: Before the stage of coating the substrate with a base resin composition on the substrate and drying it for the substrate, the substrate forming stage further includes a stage of coating a primer composition on the substrate.

12. The method for manufacturing an antifouling component according to any one of claims 1 - 11, wherein: The substrate is glass or resin.

13. The method for manufacturing an antifouling component according to claim 2, wherein: The average pitch width of the convex portions of the unevenness is 5 - 18 nm.

14. The method for manufacturing an antifouling component according to claim 2 or 13, wherein: The surface roughness Rz of the concavo-convex surface is 3 to 15 nm.

15. The manufacturing method of the antifouling component according to any one of claims 1 to 14, characterized in that: The contact angle when one surface contacts water is 105 to 120°.

16. The manufacturing method of the antifouling component according to any one of claims 1 to 15, characterized in that: The pencil hardness on one surface side is HB or more.

17. The manufacturing method of the antifouling component according to any one of claims 1 to 16, characterized in that: The antifouling component is used to cover at least a part of the display portion of the display.

18. The manufacturing method of the antifouling component according to any one of claims 1 to 16, characterized in that: The antifouling component is used to cover at least a part of the touch portion of the touch panel.

19. The manufacturing method of the antifouling component according to any one of claims 1 to 16, characterized in that: The antifouling component is used to cover at least a part of the surface of the sensor.

20. An anti-fouling component, characterized in that, Comprising: A substrate; A base layer provided on the substrate; and An antifouling layer provided on the base layer, The Δ haze before and after the Taber abrasion test on the antifouling layer side of the antifouling component is 8 or less, The contact angle of water after the Taber abrasion test on the antifouling layer side of the antifouling component is 85° or more.

21. The antifouling component according to claim 20, characterized in that: The base layer contains silicone resin.

22. The antifouling component according to claim 21, characterized in that: The silicone resin contains a Q unit structure and a T unit structure.

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