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

Abstract

In the first aspect of the present invention, a method for manufacturing an antifouling member is provided, comprising: a step of providing nano-order irregularities on one surface of a base material; and a step for forming an antifouling layer containing a perfluoropolyether-containing silane compound in at least a recessed portion of the irregularities.

Description

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

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

[0002] It is known that the use of fluorine-based compounds in the treatment of a substrate can impart water repellency, oil repellency, and stain resistance to the substrate (see, for example, Patent Documents 1 and 2). [Patent Document 1] JP 2014-218639 A [Patent Document 2] JP 2017-082194 A

[0003] In a first aspect of the present invention, there is provided a method for manufacturing an antifouling member. The method includes a base formation step and an antifouling layer formation step. In the base formation step, a base layer may be formed on one surface of a substrate. In the antifouling layer formation step, an antifouling layer containing a perfluoropolyether-containing silane compound may be formed on the base layer.

[0004] In the above, the underlayer may have nano-order unevenness, and the antifouling layer may be formed at least on the concave portions of the unevenness in the antifouling layer forming step.

[0005] In the above, the base forming step may include a drying step and a roughening step. In the drying step, the base resin composition may be applied to a substrate and dried. In the roughening step, roughness may be formed in the dried base resin composition.

[0006] In the above, the base resin composition may include a silicone resin including a T unit structure and a Q unit structure. The step of forming irregularities in the dried base resin composition may include pretreating the dried base resin composition to modify the T unit structure into silica.

[0007] In the above, the pretreatment may be carried out by exposure to light with a wavelength of 150 to 200 nm.

[0008] In the above, the pretreatment is carried out at an integrated illuminance of 200 to 6000 mJ / cm ２ The exposure may be carried out so that the range is

[0009] In the above, the pretreatment is Ar / O２ This may be achieved by applying a mixed gas plasma within the power range of 0.2 to 1.0 kW.

[0010] In the above, the pretreatment is Ar / O ２ The mixed gas plasma may be applied at a flow rate of 2000 to 5000 sccm and an oxygen fraction in the range of 0.03 to 0.4.

[0011] In the above, the coating in the stage of coating the base resin composition on the substrate and drying may be carried out so that the coating film thickness becomes 1 to 20 μm.

[0012] In the above, the drying in the step of applying the base resin composition to the substrate and drying it may be carried out at a temperature of 100 to 150° C. for 10 to 120 minutes.

[0013] In the above, the base forming step may further include a step of applying a primer composition onto the substrate before the step of applying and drying the base resin composition onto the substrate.

[0014] In the above, the substrate may be glass or resin.

[0015] In the above, the average pitch width of the convex portions of the irregularities may be 5 to 18 nm.

[0016] In the above, the surface roughness (Rz) of the irregularities may be 3 to 15 nm.

[0017] In the above, the contact angle when water comes into contact with one surface side may be 105 to 120°.

[0018] In the above, the pencil hardness of the one surface side may be HB or higher.

[0019] In the above, the antifouling member may be used to cover at least a part of the display area of ​​the display.

[0020] In the above, the antifouling member may be used to cover at least a part of the touch area of ​​the touch panel.

[0021] In the above, the antifouling member may be used to cover at least a part of the surface of the sensor.

[0022] In a second aspect of the present invention, there is provided an antifouling member comprising a substrate, an undercoat layer provided on the substrate, and an antifouling layer provided on the undercoat layer. The antifouling layer side may have a ΔHaze of 8 or less before and after a Taber abrasion test. The antifouling layer side may have a water contact angle of 85° or more after a Taber abrasion test.

[0023] In the above, the underlayer may contain a silicone resin.

[0024] In the above, the silicone resin may contain a Q unit structure and a T unit structure.

[0025] The above summary of the invention does not list all of the necessary features of the present invention, and subcombinations of these features may also be inventions.

[0026] 1 shows an example of an antifouling member 10 according to this embodiment; 2 shows another example of an antifouling member 10 according to this embodiment; 3 shows an example of a flow of a method for manufacturing the antifouling member 10 according to this embodiment; 4 shows an example of S100 in the flow of FIG. 3 when a base layer 120 is provided.

[0027] The present invention will be described below through embodiments of the invention, but the following embodiments do not limit the scope of the invention as claimed. Furthermore, not all of the combinations of features described in the embodiments are necessarily essential to the solution of the invention.

[0028] 1 and 2 show an example of an antifouling member 10 according to this embodiment. The antifouling member 10 is a surface protection member that is resistant to adhesion of dirt and other contaminants and facilitates removal of any adhered contaminants. The antifouling member 10 is applied to products or components (e.g., automobiles, mobile devices such as smartphones, optical products such as cameras, measuring instruments such as sensors, other machinery, electrical products, etc.) where adhesion of dirt (e.g., dust, pollen, fingerprints, oil, etc.) is undesirable. For example, the antifouling member 10 is used to cover at least a portion of the display area of ​​a display, to cover at least a portion of the touch area of ​​a touch panel, or to cover at least a portion of the surface of a sensor. The antifouling member 10 has nano-order irregularities on one surface, and an antifouling layer 130 is provided on the concave portions of the irregularities.

[0029] In FIG. 1, the antifouling member 10 includes a substrate 110, an underlayer 120, and an antifouling layer 130, and the underlayer 120 has a surface with nano-order irregularities.

[0030] The substrate 110 serves to support the irregularities and the antifouling layer 130 provided on the antifouling member 10. The substrate 110 can be selected from a variety of materials depending on the purpose for which the antifouling member 10 is used. For example, the substrate 110 may be formed from any material, including glass, resin, metal, ceramics, semiconductors, fiber materials, fur, leather, wood, porcelain, and stone. When the antifouling member 10 is provided in an optical product or a component thereof, such as a display or touch panel, the substrate 110 may be formed from a transparent material, such as glass or resin. The substrate 110 may have any shape as long as there is a location where irregularities can be provided, and may be, for example, a plate-like shape.

[0031] The underlayer 120 is provided on one surface of the substrate 110 and is a layer that supports the antifouling layer 130. The underlayer 120 may also function as a hard coat layer that imparts abrasion resistance to the antifouling member 10. The underlayer 120 may be made of an abrasion-resistant material, such as an inorganic material such as silica or a metal oxide, or a relatively hard organic material such as a silicone resin, an acrylic resin, a melamine resin, or a urethane resin.

[0032] In the example shown in FIG. 1 , the base layer 120 is provided with irregularities. By providing irregularities on the base layer 120, which is the layer below the antifouling layer 130, the antifouling layer 130 is surrounded and protected by the convex portions, and the antifouling layer 130 fits into the concave portions, thereby firmly bonding the antifouling layer 130 to the base layer 120. Conventionally, the antifouling layer on the surface of an antifouling member is worn away by friction caused by wiping off stains or by long-term use, resulting in a shortened duration of antifouling performance. On the other hand, with the antifouling member 10 of this embodiment, the antifouling layer 130 is firmly held in place by the irregularities, making it possible to maintain the antifouling performance for a longer period of time. Furthermore, the nano-order irregularities ensure the transparency of the antifouling member 10.

[0033] As an example, the underlayer 120 may be composed of a silicone resin having an uneven surface. The silicone resin may contain Q unit structures and T unit structures. The concave portions of the uneven surface may contain more T unit structures than the convex portions. In such a case, the underlayer 120 does not become too hard, and when applied to the substrate 110, the occurrence of cracks in deterioration tests such as heat resistance tests can be suppressed. Active silanol groups (Si—OH) may be exposed at least partially on the surfaces of the convex portions and concave portions (especially the surface of the concave portions). This can further strengthen the bond with the antifouling layer 130. A method for forming the concave portions and convex portions of the silicone resin will be described later.

[0034] The cross section of the convex portions of the unevenness can have various shapes, for example, the cross section of the convex portions may have a rectangular tip, a tapered or inversely tapered tip, a pointed tip, a curved tip such as a hemisphere, etc.

[0035] The average pitch width (average peak-to-peak length) of the convex portions of the unevenness may be 5 to 18 nm, and preferably 7 to 15 nm. If the average pitch width is equal to or less than a predetermined size, the transparency of the antifouling member 10 can be ensured. Furthermore, if the average pitch width is equal to or greater than a predetermined size, the antifouling layer 130 can be held more firmly.

[0036] The surface roughness (Rz) of the unevenness may be 3 to 15 nm, and preferably 5 to 15 nm. If the surface roughness (Rz) is a predetermined value or less, the transparency of the antifouling member 10 can be ensured. Furthermore, if the surface roughness (Rz) is a predetermined value or more, the antifouling layer 130 can be held more firmly.

[0037] The antifouling layer 130 is formed on the side of the base layer 120 opposite the substrate 110 (i.e., on the outermost surface of the antifouling member 10) and prevents deposits such as dirt from adhering to the surface of the antifouling member 10. The antifouling layer 130 may be formed at least in the recesses among the unevenness of the base layer 120. For example, as shown in FIG. 1 , the antifouling layer 130 may be formed only in the recesses.

[0038] Alternatively, the antifouling layer 130 may be formed not only on the recessed portions but also on the protruding portions. In this case, the antifouling layer 130 on the protruding portions may be partially or completely peeled off due to transportation, use, wiping off of deposits, etc. of the product. Even in such a case, the antifouling layer 130 is firmly held in place by the recessed portions. Therefore, the antifouling performance of the antifouling member 10 can be maintained.

[0039] The antifouling layer 130 may be provided on at least the bottom surfaces of the recesses and / or the upper surfaces of the protrusions. The antifouling layer 130 may be provided on the entire or part of the side surfaces of the recesses and / or protrusions, or may not be provided at all.

[0040] The height in the normal direction (the vertical direction in FIG. 1 ) of one surface of the antifouling layer 130 formed in the recesses of the base layer 120 may not exceed the convex portions of the unevenness of the base layer 120. For example, it is desirable that the height of the antifouling layer 130 in the recesses does not exceed the convex portions in at least about half of the recesses. In the example of FIG. 1 , the height in the normal direction of one surface of the antifouling layer 130 formed in the recesses is the same as the height of the convex portions of the base layer 120 (i.e., flush with the upper surfaces of the convex portions). Furthermore, the thickness of the antifouling layer 130 on the recesses is preferably 1 to 10 nm.

[0041] The antifouling performance of the antifouling layer 130 is exhibited in the surface portion, but if the antifouling layer 130 in the recessed portions is too thick, it may cause haze (clouding) of the antifouling member. By not making the antifouling layer 130 in the recessed portions too thick, haze (clouding) of the antifouling member can be prevented. Note that the thick portions of the antifouling layer 130 on the convex portions are relatively easily worn away by wiping or the like, so the problem of haze (clouding) is unlikely to occur.

[0042] The antifouling layer 130 may be formed of a material that is oil-repellent and / or water-repellent. For example, the antifouling layer 130 may contain a fluorine-containing silane compound. Examples of the fluorine-containing silane compound include a perfluoropolyether-containing silane compound, a perfluoroalkyl group-containing silane compound, and an isocyanuric skeleton-containing silane compound. Details of the material of the antifouling layer 130 will be described later.

[0043] The antifouling member 10 may have a contact angle of 105 to 120° when water comes into contact with one surface (for example, the antifouling layer 130 side). This allows the antifouling member 10 to exhibit water repellency and exhibit antifouling performance. Furthermore, the antifouling member 10 may have a contact angle of 85° or more, preferably 90° or more, after Abrasion Test 1 and / or Abrasion Test 2 described below. This allows the antifouling member 10 to exhibit antifouling performance for a long period of time.

[0044] The antifouling member 10 may have a pencil hardness of HB or higher on one surface (e.g., the antifouling layer 130 side), which allows the antifouling member 10 to maintain sufficient abrasion resistance to maintain the antifouling layer 130 for a longer period of time.

[0045] The antifouling member 10 may have, on one surface (e.g., the side facing the antifouling layer 130), a ΔHaze (the increase in haze value between before and after the test) in a Taber abrasion test based on the ASTM D1044 standard (or Abrasion Test 2 described below) of 10 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 2 or less. This enables the antifouling member 10 to retain the antifouling layer 130 for a longer period of time and to maintain sufficient abrasion resistance to maintain transparency.

[0046] In the embodiment of Fig. 2, the antifouling member 10 includes a substrate 110 and an antifouling layer 130. In Fig. 2, the underlayer 120 is not present, and the surface of the substrate 110 is provided with irregularities. This results in direct contact between the substrate 110 and the antifouling layer 130. In the embodiment of Fig. 2, the antifouling layer 130 is firmly held in place by the irregularities, thereby achieving the same effect as in the embodiment of Fig. 1. The matters described in Fig. 1, such as the material and shape of the substrate 110 and the antifouling layer 130, as well as the size, contact angle, and hardness of the irregularities, also apply to the embodiment of Fig. 2, and therefore will not be described again.

[0047] 1 and 2, the antifouling member 10 includes the substrate 110 and the antifouling layer 130 (and further includes the base layer 120 in FIG. 1), but other layers may also be provided. For example, the antifouling member 10 may be provided with layers such as a primer layer, an antireflection layer, an antiglare layer, an insulating layer, an adhesive layer, a release layer, a polarizing layer, and / or a retardation layer, as needed.

[0048] 3 shows an example of a flow chart of a method for manufacturing the antifouling member 10 of this embodiment. The antifouling member 10 may be manufactured by performing at least a part of S100 to S200.

[0049] In S100, nano-order irregularities are provided on the surface of the substrate 110. The substrate 110 may be the one described with reference to Figures 1 and 2. For example, the irregularities may be formed on the substrate 110 by providing an underlayer 120 on which nano-order irregularities are provided on the substrate 110.

[0050] 4 shows an example of S100 in the flow of FIG. 3 when providing the underlayer 120. S100 in FIG. 3 may be executed by performing the processes of S110 to S130 in FIG.

[0051] In S110, the base resin composition is applied onto the substrate 110. The base resin composition may be an organosiloxane-based hard coating agent having a T unit structure and a Q unit structure. The base resin composition may further include one or more of a UV absorber, a catalyst, and a solvent.

[0052] The Q unit structure may be contained in the base resin composition as silica gel particles (colloidal silica). The silica gel particles will later give the shape of the convex portions of the unevenness, and may preferably have a diameter of 1 to 100 nm, preferably 10 to 50 nm, and more preferably 10 to 20 nm. Here, the diameter may be the median diameter D50, which is the particle size at which the cumulative volume becomes 50% by volume when the volume-based particle size distribution is measured by a laser diffraction / scattering particle size distribution measurement method.

[0053] The T unit structure may be contained in the undercoat resin composition as an organosilsesquioxane polymer. The Q unit structure may be uniformly dispersed in a matrix of the T unit structure. The Q unit structure may be contained in an amount of 5 to 50 wt %, preferably 15 to 35 wt %, based on the sum of the T unit structure and the Q unit structure.

[0054] For example, a base resin composition containing a T unit structure and a Q unit structure can be obtained by hydrolyzing colloidal silica and an alkyltrialkoxysilane (e.g., methyltrimethoxysilane) and then condensing them.

[0055] The T unit structure and / or the Q unit structure may at least partially incorporate a skeleton having an ultraviolet absorbing function. Examples of skeletons having an ultraviolet absorbing function include 4,6-dibenzoyl-2-(3-trialkoxysilylalkyl)resorcinol (specifically, 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol, etc., as described in JP-A-7-278525, and hydroxybenzophenone-based compounds as described in JP-A-57-21476 and JP-A-57-21432. Examples of the base resin composition that can be used include Hardcoat AS4700, AS4700F, PHC587C, and PHC587C2 manufactured by Momentive Corporation.

[0056] As the organosilsesquioxane polymer that becomes the T unit structure, Component A described in JP-A-2021-531387 may be used. For example, as the organosilsesquioxane polymer, Component A represented by an organic alkoxysilane of the formula (R1)dSi(OR2)4-d may be used. １ is C １ -C ３ Monovalent hydrocarbons, preferably C １ -C ３ It may be an alkyl radical, more preferably a methyl or ethyl group. ２ is C １ -C ３ A monovalent hydrocarbon or hydrogen radical, where d can be 0, 1, or 2. As an example, component A can be methyltrimethoxysilane.

[0057] Component A includes methyltrimethoxysilane, methyltriethoxysilane, or mixtures thereof, which can form partial condensates. Additional organoalkoxysilanes include, but are not limited to, tetraethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, tetramethoxysilane, dimethyldimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, and the like.

[0058] Component A may be present in an amount of from about 5 weight percent to about 99.9 weight percent, from about 10 weight percent to about 90 weight percent, or even from about 20 weight percent to about 80 weight percent, based on the total weight of the underlying resin composition.

[0059] The catalyst may be at least one selected from the group consisting of 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)).

[0060] Catalysts can be added to the primer resin composition as needed for a particular purpose or intended use. Generally, the catalyst may be added in an amount sufficient to effectively catalyze the curing reaction, but not to affect or impair the physical properties of the coating. In one embodiment, the catalyst is provided in an amount ranging from 1 ppm to about 75 ppm, from about 10 ppm to about 70 ppm, or even from about 20 ppm to about 60 ppm, where ppm represents parts per million by weight based on the total weight of the primer resin composition.

[0061] The catalyst can be added directly to the underlying resin composition or dissolved in a solvent or other suitable carrier. The solvent can be a polar solvent such as methanol, ethanol, n-butanol, t-butanol, n-octanol, n-decanol, 1-methoxy-2-propanol, isopropyl alcohol, ethylene glycol, tetrahydrofuran, dioxane, bis(2-methoxyethyl)ether, 1,2-dimethoxyethane, acetonitrile, benzonitrile, methyl ethyl ketone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidinone (NMP), and propylene carbonate.

[0062] The UV absorber can also be selected from a combination of inorganic and organic UV absorbers. Examples of suitable organic UV absorbers include, but are not limited to, those capable of co-condensing with silanes. Such UV absorbers are disclosed in U.S. Patent Nos. 4,863,520, 4,374,674, 4,680,232, and 5,391,795, the entire contents of which are incorporated herein by reference. Specific examples include 4-[gamma-(trimethoxysilyl)propoxyl]-2-hydroxybenzophenone, 4-[gamma-(triethoxysilyl)propoxyl]-2-hydroxybenzophenone, and 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol. When using a UV absorber capable of co-condensing with silanes, the UV absorber should be co-condensed with the other reactive species by thoroughly mixing the coating composition prior to application to the substrate. Co-condensing the UV absorbers prevents degradation of coating performance caused by leaching of free UV absorbers into the environment during weathering.

[0063] The solvent can be selected from aliphatic alcohols, glycol ethers, alicyclic alcohols, aliphatic esters, alicyclic esters, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic compounds, halogenated alicyclic compounds, halogenated aromatic compounds, aliphatic ethers, alicyclic ethers, amide solvents, sulfoxide solvents, or combinations of two or more thereof. Examples of suitable solvents include, but are not limited to, alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, methoxypropanol, ethylene glycol, diethylene glycol butyl ether, or combinations thereof. Other polar organic solvents such as acetone, methyl ethyl ketone, ethylene glycol monopropyl ether, and 2-butoxyethanol can also be utilized. 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 mixtures of two or more thereof. The amount of solvent in the primer resin composition is preferably about 25% to about 85% by weight, more preferably about 40% to about 80% by weight, and most preferably about 50% to about 75% by weight, all based on the total weight of the composition. The composition may also contain a catalyst. The catalyst is not particularly limited, and any suitable catalyst for curing the primer resin composition can be used.

[0064] The primer resin composition may contain other materials or additives to provide the coating with desired properties for a specific purpose or intended use. The primer resin composition of the present invention may also contain a surfactant as a leveling agent. Examples of suitable surfactants include, but are not limited to, surfactants such as Silwet® and CoatOSil® available from Momentive Performance Materials, Inc. of Albany, NY, silicone polyethers under the FLUORAD™ brand manufactured by 3M Company of St. Paul, Minn., and polyether-polysiloxane copolymers such as BYK®-331 manufactured by BYK®-Chemie. Suitable antioxidants include, but are not limited to, hindered phenols (e.g., IRGANOX® 1010 manufactured by Ciba Specialty Chemicals).

[0065] The coating method may be various coating methods such as dip coating, spin coating, flow coating, spray coating, roll coating, and gravure coating, or printing methods such as letterpress printing, gravure printing, lithographic printing, reverse printing, and inkjet printing.

[0066] The thickness of the applied undercoat resin composition may be 1 to 20 μm, preferably 3 to 10 μm.

[0067] In S110, before applying the base resin composition, a primer composition for improving adhesion between the base 110 and the base resin composition may be applied to the base 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 urethane acrylate resin composition.

[0068] Next, in S120, the base resin composition applied in S110 is dried. For example, heat curing may be performed at a temperature of 100 to 150°C, preferably 120 to 130°C, for 10 to 120 minutes, preferably 30 to 60 minutes. Drying may be performed using a hot air drying oven, a hot plate, an infrared heater, or the like.

[0069] Next, in S130, unevenness is formed on the dried base resin composition. For example, the unevenness is formed by pretreating the base resin composition. This is because the T unit structure of the base resin composition is changed to silica (SiO ２ ), causing volume shrinkage. For example, the pretreatment may be exposure to light or plasma treatment. Specifically, ozone and active oxygen radicals are generated from oxygen in the atmosphere by irradiation with UV light during exposure, and these react with the Si-alkyl group contained in the T unit structure. As a result, the Si-alkyl group contained in the T unit structure is decomposed into a silanol group and an aldehyde, and two silanol groups are further condensed to form silica (SiO ２ The aldehyde further reacts with water to form CO ２ In this way, the T unit structure is decomposed into silica (SiO ２ When the surface is modified to the desired shape, volume shrinkage occurs, and the areas where volume shrinkage occurs become depressed, forming recesses.

[0070] Depending on the exposure conditions, silica (SiO ２ It is believed that there are components that remain as T structural units without being modified to the Q structural unit. As a result, the convex portions of the unevenness are composed of Q structural units, and the concave portions of the unevenness contain Q structural units and T structural units.

[0071] On the other hand, the Q unit structure (colloidal silica) does not undergo chemical changes or volume shrinkage upon exposure to light. As a result, recesses are formed only in areas of the undercoat resin composition layer that contain a large amount of T unit structures, and protrusions are formed in areas that contain a large amount of Q unit structures. In this way, an undercoat layer 120 having projections and recesses is formed.

[0072] Silanol groups remain on the surface of the underlayer 120 formed in this manner. In particular, in the recesses, some of the silanol groups decomposed from the T unit structures remain without condensation. In addition, some Si-alkyl groups derived from the T unit structures remain in the recesses. As a result, the composition ratio of carbon atoms contained in the recesses is higher than that of the protrusions. As a result of the large number of carbon atoms and silanol groups remaining in the recesses, they bond more strongly to the antifouling layer 130 containing a perfluoropolyether-containing silane compound, etc., thereby improving the durability of the antifouling layer 130. The molar concentration of carbon atoms can be measured using an X-ray photoelectron spectroscopy analyzer.

[0073] The light source used for exposure may be any light source capable of modifying the T unit structure to silica, and may have a wavelength of, for example, about 150 to 190 nm. Specifically, an excimer lamp, an excimer laser, F ２ The exposure may be carried out using a laser or the like.

[0074] The exposure was performed at an integrated illuminance of 300 mJ / cm ２ The irradiation may be performed so that the cumulative illuminance is 1000 mJ / cm or more. ２ If it is less than this, the decomposition and condensation of the T unit structure may be insufficient, and the unevenness may not be formed sufficiently.

[0075] The exposure was performed at an integrated illuminance of 6000 mJ / cm ２ The dose may be set to 6000 mJ / cm or less. ２ If the integrated illuminance exceeds 6000 mJ / cm, there may not be enough silanol groups remaining on the surface of the recesses, resulting in insufficient adhesion to the antifouling layer 130. ２ Even if the integrated illuminance exceeds 6000 mJ / cm 2 , the base layer 120 itself is formed, which sufficiently contributes to improving the durability of the antifouling layer. Therefore, it is not necessary to increase the integrated illuminance to 6000 mJ / cm 2 . ２ There is no need to do the following:

[0076] Instead of / in addition to exposure, Ar / O ２ A plasma treatment using a mixed gas plasma or the like may be applied. In this case, Ar / O ２The flow rate of the mixed gas plasma may be set to 2000 sccm or more. If the flow rate is less than 2000 sccm, the decomposition and condensation of the T unit structure may be insufficient, resulting in insufficient formation of the irregularities.

[0077] Ar / O ２ The flow rate of the mixed gas plasma may be set to 5000 sccm or less. If the flow rate exceeds 5000 sccm, there is a risk that not enough silanol groups will remain on the surface of the recesses, resulting in insufficient adhesion to the antifouling layer 130.

[0078] Ar / O ２ The output of the mixed gas plasma may be 0.2 kW or more. If the output is less than 0.2 kW, the decomposition and condensation of the T unit structure may be insufficient, resulting in insufficient formation of the irregularities.

[0079] Ar / O ２ The mixed gas plasma may be applied so that the output is 1.0 kW or less. If the output exceeds 1.0 kW, there is a risk that not enough silanol groups will remain on the surface of the recesses, resulting in insufficient adhesion to the antifouling layer 130. ２ The mixed gas plasma may be applied so that the oxygen fraction is 0.03 to 0.4.

[0080] 4, the underlayer 120 is obtained by exposing the organosiloxane-based hard coating agent to light, but the method is not limited to this. The underlayer 120 may be obtained by forming nano-order irregularities by performing nanoimprinting, photolithography, plasma treatment, laser treatment, or the like on a thin film formed from a resin material or the like.

[0081] 4, S100 may be performed by forming irregularities on the substrate 110. For example, the desired irregularities may be formed on the substrate 110 by etching, nanoimprinting, photolithography, plasma treatment, laser treatment, or the like. In this case, the antifouling member 10 shown in FIG. 2 is formed. After S100, the process of S200 is performed.

[0082] In S200, the antifouling layer 130 is formed on the unevenness formed in S100. For example, the antifouling layer 130 may be formed by forming a layer of a fluorine-containing silane compound having oil and / or water repellency on the unevenness. The antifouling layer 130 may be formed by applying a composition containing a fluorine-containing silane compound onto the unevenness and drying it.

[0083] Examples of the fluorine-containing silane compound include perfluoroalkyl group-containing silane compounds (particularly perfluoropolyether-containing silane compounds), isocyanuric skeleton-containing silane compounds, and the like.

[0084] An example of the perfluoroalkyl group-containing silane compound is a compound represented by the following formula (I): [A] ｂ１ Q ２ [B] ｂ２ (I) [wherein: Q ２ is a linking group having a valence of (b1+b2), and A is R ｆ３ -O-R ｆ２ -, and R ｆ２ is a poly(oxyfluoroalkylene) chain, R ｆ３ is a perfluoroalkyl group, and B is one -R １２ -(SiR ２ ｒ X ２ ３－ｒ ) and is a monovalent group containing no fluorine atom, R １２ is a hydrocarbon group having 2 to 10 carbon atoms which may have an etheric oxygen atom between carbon atoms or at the end opposite to the end to which Si is bonded, or which may have —NH— between carbon atoms, ２ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, ２ are each independently a hydroxyl group or a hydrolyzable group, r is an integer from 0 to 2, and Q ２and B does not contain a cyclic siloxane structure, b1 is an integer of 1 to 3, and b2 is an integer of 2 to 9, and when b1 is 2 or more, b1 As may be the same or different, and b2 Bs may be the same or different.

[0085] In formula (I), A is R ｆ３ -O-R ｆ２ - is a group represented by the formula:

[0086] R ｆ３ is a perfluoroalkyl group, preferably having 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. ｆ３ may be linear or branched. Among them, the linear group: CF ３ (CF ２ ) ｍ３－１ (wherein m3 is 1 to 20, preferably 1 to 6), and more preferably CF ３ - or CF ３ (CF ２ ) ２ - and especially CF ３ (CF ２ ) ２ - is preferred.

[0087] R ｆ２ is a poly(oxyfluoroalkylene) chain. ｆ２ For example, -(C ｘ F ２ｘ O) ｙ -(x is an integer from 1 to 6, y is an integer of 2 or more, and each -C ｘ F ２ｘ The O- units may be the same or different. ｘ F ２ｘ The O-unit may be linear or branched, for example, -CF ２ CF ２ CF ２ CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ CF ２ O-, -CF ２ CF２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ O-, -CF(CF ３ )CF ２ O-, -CF ２ CF ２ O-, -CF ２ O-. y can be appropriately adjusted depending on the desired number average molecular weight. The preferred upper limit of y is 200.

[0088] R ｆ２ may be a combination of a plurality of units, and in this case, each unit may be present in any of a block, alternating, or random configuration. For example, from the viewpoint of excellent light resistance, -CF ２ CF ２ CF ２ CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ It is preferable that the compound contains —O—, and the proportion of these structures present is preferably large. From the viewpoint of ease of synthesis, —CF ２ CF ２ CF ２ CF ２ O- and -CF ２ CF ２ -CF, a unit combining O- and ２ CF ２ O-CF ２ CF ２ CF ２ CF ２ It is O-.

[0089] R ｆ２ Specifically, -(CF ２ CF ２ CF ２ CF ２ CF ２ CF ２ O)ｎ３ -(CF ２ CF ２ CF ２ CF ２ CF ２ O) ｎ４ -(CF ２ CF ２ CF ２ CF ２ O) ｎ５ -(CF ２ CF ２ CF ２ O) ｎ６ -(CF(CF ３ )CF ２ O) ｎ７ -(CF ２ CF ２ O) ｎ８ -(CF ２ O) ｎ９ - (wherein n3, n4, n5, n6, n7, n8 and n9 each independently represent 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 may be present in any of block, alternating or random configuration).

[0090] R ｆ２ As for {(CF ２ O) ｎ１１ (CF ２ CF ２ O) ｎ１２}, (CF ２ CF ２ O) ｎ１３ , (CF ２ CF ２ CF ２ O) ｎ１４ , (CF ２ CF ２ O-CF ２ CF ２ CF ２ CF ２ O) ｎ１５ is preferred, and {(CF ２ O) ｎ１１ (CF ２ CF ２ O) ｎ１２}, (CF ２ CF ２ CF ２ O) ｎ１４where 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 n11 CFs ２ O and n12 CFs ２ CF ２ The bonding order of O is not limited. n13 and n14 are integers of 2 to 200, and n15 is an integer of 1 to 100.

[0091] In formula (I), R ｆ３ -O-R ｆ２ The number (b1) of groups A represented by - is an integer of 1 to 3. In formula (I), when a plurality of groups A are present, 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 resulting surface treatment layer. When the perfluoroalkyl group-containing silane compound has a plurality of groups A, R ｆ３ -O-R ｆ２ This is preferable in that the density of the - groups becomes high and the abrasion resistance of the surface treatment layer becomes excellent.

[0092] In formula (I), the group B is one -R １２ -(SiR ２ ｒ X ２ ３－ｒ ) (hereinafter referred to as “Group (B ａ ) at its terminal and does not contain a cyclic siloxane structure or a fluorine atom.

[0093] The group B is specifically —Y ａ -R １２ -(SiR ２ ｒ X ２ ３－ｒ ) is a group represented by the formula: ａ - to form the group (B ａ ) and Q ２ are concatenated. ａ Y is a single bond or a divalent organic group that does not contain a cyclic siloxane structure or a fluorine atom. ａis, for example, an alkylene group (e.g., an alkylene or arylene group having 8 to 16 carbon atoms) containing an arylene group such as a phenylene group having 6 to 8 carbon atoms at its terminal, a divalent group in which an alkylene group (e.g., 1 to 20 carbon atoms) is bonded to a silalkylene structure (e.g., 1 to 10 carbon atoms, 2 to 10 Si atoms) or a silarylene structure (e.g., 1 to 10 carbon atoms, 2 to 10 Si atoms), and the group (B ａ The terminal on the Y ) side is other than an alkylene group. ａ Q to which ２ The atoms Y are atoms that constitute the main chain, and specific examples thereof include Si, C, and N. ａ is preferably a single bond.

[0094] R １２ is a hydrocarbon group having 2 to 10 carbon atoms which may have an etheric oxygen atom between carbon atoms or at the end opposite to the bond to Si, or which may have -NH- between carbon atoms. ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ OCH ２ CH ２ CH ２ -, -OCH ２ CH ２ CH ２ - (where the right side is bonded to Si) is preferred, and in terms of excellent light resistance of the water-repellent film, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ In formula (I), R of the group B is preferably 0 or 1. １２ may or may not all be the same group.

[0095] X ２ is a hydroxyl group or a hydrolyzable group, and the hydrolyzable group is １The examples and preferred embodiments of the hydrolyzable group in the above are applicable. r is an integer of 0 to 2, and from the viewpoint of excellent adhesion and durability, 0 or 1 is preferred, and 0 is more preferred. X ２ If there are multiple X ２ may be the same or different, but are preferably the same in terms of availability.

[0096] R ２ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may contain a substituent. Examples of the hydrocarbon group include linear or branched alkyl groups. Among these, from the viewpoint of availability, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, and methyl or ethyl groups are more preferred. Examples of the substituent include halogen atoms (e.g., chlorine atoms). The R to which Si is bonded ２ The number r is an integer from 0 to 2. ２ If there are multiple R ２ may be the same or different, but are preferably the same in terms of availability.

[0097] In formula (I), the number of groups B represented by b2 is an integer of 2 to 9. Therefore, the number of groups (B ａ The number of groups (B) is 2 to 9. ａ ) is a group that contributes to the light resistance and abrasion resistance of the resulting water-repellent film. ａ The number of ) is preferably 2 to 4 in view of excellent light resistance and abrasion resistance of the resulting water-repellent film.

[0098] The multiple groups B contained in the perfluoroalkyl group-containing silane compound may be the same or different. ａ ) may be the same or different.

[0099] In formula (I), Q ２ is a (b1+b2)-valent linking group. ２is, for example, a hydrocarbon group, which may have an ester bond, an ether bond, an amide bond, a urethane bond, a phenylene group, -S-, a divalent amino group, a silalkylene structure, a silarylene structure, or a siloxane structure (excluding cyclic siloxane structures) at the terminal or between carbon atoms, and a hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom. A hydrogen atom of the hydrocarbon group may be substituted with a hydroxyl group, and the number of substituted hydroxyl groups is preferably 1 to 5. The hydrocarbon group may be linear or branched. Q ２ The number of carbon atoms in the group is preferably 1 to 20, and more preferably 1 to 10.

[0100] Furthermore, Q ２ In the formula (I), the group A and the group B may be bonded to the same atom, but it is preferable that they are bonded to different atoms, and it is more preferable that the bonded atoms are as far apart as possible within the molecule.

[0101] Also, Q ２ is directly bonded to an atom other than the end of the molecular chain, -SiR ０ ｒ１ X ４ ３－ｒ１ (R ０ , X ４ , and r1 are each a group (B ａ ) R ２ , X ２ ) as the perfluoroalkyl group-containing silane compound, ａ It is preferable that the perfluoroalkyl group-containing silane compound does not have a hydrolyzable silyl group other than —SiR ０ ｒ１ X ４ ３－ｒ１ When the -SiR ０ ｒ１ X ４ ３－ｒ１ is SiR of compound (1) １ ｐ X １ ３－ｐ and a perfluoroalkyl group-containing silane compound, SiR ２ ｒ X ２ ３－ｒWhen calculating the molar ratio of SiR ２ ｒ X ２ ３－ｒ shall not be included in the

[0102] In one embodiment, the perfluoroalkyl group-containing silane compound is represented by the following formulae (A1), (A2), (B1), (B2), (C1), and (C2):

[0103] wherein PFPE, at each occurrence, independently represents a group of the formula: -(OC ４ F ８ ) ａ - (OC ３ F ６ ) ｂ - (OC ２ F ４ ) ｃ -(OCF ２ ) ｄ - (wherein a, b, c, and d each independently represent an integer of 0 to 200, the sum of a, b, c, and d is at least 1, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript a, b, c, or d is arbitrary in the formula); Rf each independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; R ２１ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R ２２ each occurrence independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; n1 is (—SiR ２１ ｎ１ R ２２ ３－ｎ１ ) units are independently an integer of 0 to 3; provided that in formulas (A1) and (A2), at least one n1 is an integer of 1 to 3; X ５ each independently represents a single bond or a divalent to decavalent organic group; each β independently represents an integer of 1 to 9; each β' independently represents an integer of 1 to 9; X ７each independently represents a single bond or a divalent to decavalent organic group; each γ independently represents an integer of 1 to 9; each γ' independently represents an integer of 1 to 9; R ａ is independently at each occurrence -Z １ -SiR ７１ ｐ１ R ７２ ｑ１ R ７３ ｒ１ represents; Z １ represents, independently in each occurrence, an oxygen atom or a divalent organic group; R ７１ represents, independently at each occurrence, R ａ' represents; R ａ' is R ａ and R ａ Medium, Z １ The number of Si atoms linearly linked via R groups is at most 5; ７２ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R ７３ each occurrence independently represents a hydrogen atom or a lower alkyl group; each occurrence independently represents an integer of 0 to 3; each occurrence independently represents an integer of 0 to 3; each occurrence independently represents an integer of 0 to 3; and each occurrence independently represents an integer of 0 to 3; provided that in formulas (B1) and (B2), at least one q1 is an integer of 1 to 3; R ｂ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R ｃ each occurrence independently represents a hydrogen atom or a lower alkyl group; k1 each occurrence independently represents an integer from 1 to 3; l1 each occurrence independently represents an integer from 0 to 2; m1 each occurrence independently represents an integer from 0 to 2; provided that in the unit enclosed in parentheses with γ, the sum of k1, l1 and m1 is 3; X ９each independently represents a single bond or a divalent to decavalent organic group; each δ independently represents an integer of 1 to 9; each δ' independently represents an integer of 1 to 9; R ｄ is independently at each occurrence -Z ２ -CR ８１ ｐ２ R ８２ ｑ２ R ８３ ｒ２ represents; Z ２ represents, independently in each occurrence, an oxygen atom or a divalent organic group; R ８１ represents, independently at each occurrence, R ｄ' represents; R ｄ' is R ｄ and R ｄ Medium, Z ２ The number of Cs linked in a linear chain via R groups is at most 5; ８２ is independently at each occurrence -Y-SiR ８５ ｎ２ R ８６ ３－ｎ２ Y independently in each occurrence represents a divalent organic group; R ８５ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R ８６ represents, independently in each occurrence, a hydrogen atom or a lower alkyl group; n2 represents (—Y—SiR ８５ ｎ２ R ８６ ３－ｎ２ ) units independently represent an integer of 0 to 3; provided that in formulas (C1) and (C2), at least one n2 is an integer of 1 to 3; R ８３ each occurrence independently represents a hydrogen atom, a hydroxyl group, or a lower alkyl group; p2 each occurrence independently represents an integer of 0 to 3; q2 each occurrence independently represents an integer of 0 to 3; r2 each occurrence independently represents an integer of 0 to 3; R ｅ is independently at each occurrence -Y-SiR ８５ ｎ２ R８６ ３－ｎ２ represents; R ｆ are each independently in each occurrence a hydrogen atom, a hydroxyl group, or a lower alkyl group; k2 is each independently in each occurrence an integer of 0 to 3; l2 is each independently in each occurrence an integer of 0 to 3; m2 is each independently in each occurrence an integer of 0 to 3; with the proviso that in formulas (C1) and (C2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3.

[0104] Formulas (A1) and (A2):

[0105]

[0106] In the above formulas (A1) and (A2), PFPE is independently at each occurrence -(OC ６ F １２ ) ａ - (OC ５ F １０ ) ｂ - (OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - is a group represented by the formula. In the formula, a, b, c, d, e, and f are each independently an integer 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. Furthermore, the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.

[0107] The above a and b are each preferably 0 or more and 30 or less, and may be 0.

[0108] In one aspect, the above 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, even more preferably an integer of 5 or less, and may be 0.

[0109] In one embodiment, the sum of a, b, c and d is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less.

[0110] In one embodiment, the sum of e and f is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more.

[0111] These repeating units may be linear or branched, but are preferably linear. For example, -(OC ６ F １２ )- is -(OCF ２ CF ２ CF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ CF ２ CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF ２ CF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF ２ CF ２ CF (CF ３))-, etc., but preferably -(OCF ２ CF ２ CF ２ CF ２ CF ２ CF ２ )-. -(OC ５ F １０ )- is -(OCF ２ CF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF ２ CF (CF ３ ))-, etc., but preferably -(OCF ２ CF ２ CF ２ CF ２ CF ２ )-. -(OC ４ F ８ )- is -(OCF ２ CF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ CF ２ ) -, -(OCF ２ CF (CF ３ )CF ２ ) -, -(OCF ２ CF ２ CF (CF ３ )) -, -(OC(CF ３ ) ２ CF ２ ) -, -(OCF ２ C (CF ３ ) ２ )-,-(OCF(CF ３)CF(CF ３ ))-,-(OCF(C ２ F ５ )CF ２ )- and -(OCF ２ CF (C ２ F ５ ))-, but preferably -(OCF ２ CF ２ CF ２ CF ２ )-. -(OC ３ F ６ )- is -(OCF ２ CF ２ CF ２ )-,-(OCF(CF ３ )CF ２ )- and -(OCF ２ CF (CF ３ ))-, but preferably -(OCF ２ CF ２ CF ２ )-. Also, -(OC ２ F ４ )- is -(OCF ２ CF ２ )- and -(OCF(CF ３ ))-, but preferably -(OCF ２ CF ２ )-.

[0112] In one embodiment, the PFPE is —(OC ３ F ６ ) 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). Preferably, the PFPE is -(OCF ２ CF ２ CF ２ ) 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(CF ３ )CF ２ ) 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 -(OCF ２ CF ２ CF ２ ) 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).

[0113] In another embodiment, the PFPE is -(OC ４ F ８ ) ｃ - (OC ３ F ６ ) ｄ - (OC ２ F ４ ) ｅ -(OCF ２ ) ｆ -(wherein c and d each independently represent an integer of 0 or more and 30 or less, e and f each independently represent 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 sum of c, d, e and f is at least 5 or more, preferably 10 or more, and the order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula). Preferably, PFPE is -(OCF ２ CF ２ CF ２ CF ２ ) ｃ -(OCF ２ CF ２ CF ２ ) ｄ -(OCF ２ CF ２ ) ｅ -(OCF ２ ) ｆ - is.

[0114] In one embodiment, the PFPE is -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ-(wherein e and f each independently represent 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 occurrence of each repeating unit enclosed in parentheses with the subscript e or f is arbitrary in the formula).

[0115] In yet another embodiment, the PFPE is —(R ６ -R ７ ) ｊ In the formula, R ６ may each independently in each occurrence represent OCF ２ or O.C. ２ F ４ and preferably OC ２ F ４ In the formula, R ７ may each independently in each occurrence represent OC ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups. ７ is O.C. ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８ or a group selected from OC ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups. ２ F ４ , O.C. ３ F ６ and O.C. ４ F ８The combination of two or three groups independently selected from the group consisting of, but not limited to, —OC ２ F ４ O.C. ３ F ６ -, -OC ２ F ４ O.C. ４ F ８ -, -OC ３ F ６ O.C. ２ F ４ -, -OC ３ F ６ O.C. ３ F ６ -, -OC ３ F ６ O.C. ４ F ８ -, -OC ４ F ８ O.C. ４ F ８ -, -OC ４ F ８ O.C. ３ F ６ -, -OC ４ F ８ O.C. ２ F ４ -, -OC ２ F ４ O.C. ２ F ４ O.C. ３ F ６ -, -OC ２ F ４ O.C. ２ F ４ O.C. ４ F ８ -, -OC ２ F ４ O.C. ３ F ６ O.C. ２ F ４ -, -OC ２ F ４ O.C. ３ F ６ O.C. ３ F ６ -, -OC ２ F ４ O.C. ４ F ８ O.C. ２ F ４ -, -OC ３ F６ O.C. ２ F ４ O.C. ２ F ４ -, -OC ３ F ６ O.C. ２ F ４ O.C. ３ F ６ -, -OC ３ F ６ O.C. ３ F ６ O.C. ２ F ４ -, and -OC ４ F ８ O.C. ２ F ４ O.C. ２ F ４ The above j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and is an integer of 100 or less, preferably 50 or less. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ may be either linear or branched, preferably linear. In this embodiment, the PFPE is preferably -(OC ２ F ４ -OC ３ F ６ ) ｊ -or- (OC ２ F ４ -OC ４ F ８ ) ｊ - is.

[0116] In PFPE, the ratio of e to f (hereinafter referred to as the "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 even more preferably 0.2 or more and 1.5 or less. By setting the e / f ratio within the above range, the water repellency, oil repellency, and chemical resistance (e.g., durability against salt water, acid or basic aqueous solutions, acetone, oleic acid, or hexane) of the surface treatment layer obtained from the surface treatment agent of the present disclosure can be further improved. The smaller the e / f ratio, the more improved the water repellency, oil repellency, and chemical resistance of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the more improved the stability of the compound.

[0117] In the above formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

[0118] The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

[0119] The Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably CF ２ H-C １－１５ It is a fluoroalkylene group, and more preferably a perfluoroalkyl group having 1 to 16 carbon atoms.

[0120] The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and is 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 -CF ３ , -CF ２ CF ３ , or -CF ２ CF ２ CF ３is.

[0121] In the above formula, R ２１ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group.

[0122] In the above formula, R ２２ In each occurrence, each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.

[0123] In the above formula, n1 is (—SiR ２１ ｎ１ R ２２ ３－ｎ１ ) units are independently an integer of 0 to 3, preferably 1 to 3, and more preferably 3. However, in the formula, all n1s cannot be 0 at the same time. In other words, in the formula, at least one R ２１ exists.

[0124] In the above formula, X ５ Each of X independently represents a single bond or a divalent to decavalent organic group. ５ In the compounds represented by formulas (A1) and (A2), the compound has a perfluoropolyether moiety (Rf-PFPE moiety or -PFPE- moiety) that mainly provides water repellency and surface slipperiness, and a silane moiety (specifically, -SiR ２１ ｎ１ R ２２ ３－ｎ１ ) and the linker. ５ may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.

[0125] In the above formula, β is an integer of 1 to 9, and β' is an integer of 1 to 9. These β and β' are determined by X ３ In formula (A1), the sum of β and β' is determined according to the valence of X ５ For example, X ５ When X is a decavalent organic group, the sum of β and β' is 10, and 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. ５is a divalent organic group, β and β' are 1. In formula (A2), β is X ５ is the value obtained by subtracting 1 from the valence value of

[0126] Above X ５ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and even more preferably a divalent organic group.

[0127] In one embodiment, X ５ is a divalent to tetravalent organic group, β is 1 to 3, and β' is 1.

[0128] In another embodiment, X ５ is a divalent 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').

[0129]

[0130] Above X ５ Examples of the group include, but are not limited to, a single bond or the following formula: -(R ３１ ) ｐ' -(X ａ ) ｑ' - [In the formula: R ３１ is independently in each occurrence a single bond, —(CH ２ ) ｓ' - or an o-, m- or p-phenylene group, preferably -(CH ２ ) ｓ' -, s' is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2; X ａ is independently at each occurrence -(X ｂ ) ｌ' represents -, and X ｂ each occurrence independently represents an —O—, —S—, o-, m-, or p-phenylene group, —C(O)O—, —Si(R ３３ ) ２ -, -(Si(R ３３ ) ２ O) ｍ' -Si(R ３３ ) ２ --, --CONR３４ --, --O-CONR ３４ -, -NR ３４ - and -(CH ２ ) ｎ' represents a group selected from the group consisting of -, ３３ is independently in each occurrence a phenyl group, C １－６ Alkyl group or C １－６ represents an alkoxy group, preferably a phenyl group or C １－６ R is an alkyl group, more preferably a methyl group; ３４ is independently in each occurrence a hydrogen atom, a phenyl group or C １－６ represents an alkyl group (preferably a methyl group), m' in each occurrence is independently an integer of 1 to 100, preferably an integer of 1 to 20, n' in each occurrence is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, l' in each occurrence is independently an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p' is 0, 1 or 2, q' is 0 or 1, wherein at least one of p' and q' is 1, and the order of occurrence of the repeating units enclosed in parentheses with p' or q' is arbitrary. ３１ and X ａ (Typically R ３１ and X ａ hydrogen atom) is a fluorine atom, C １－３ Alkyl group and C １－３ It may be substituted with one or more substituents selected from fluoroalkyl groups.

[0131] In one embodiment, l' is 1.

[0132] Preferably, the X ５ is -(R ３１ ) ｐ' -(X ａ ) ｑ' -R ３２ - is. R ３２ is a single bond, -(CH ２ ) ｔ'- or an o-, m- or p-phenylene group, preferably -(CH ２ ) ｔ' t' is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ３２ (Typically R ３２ hydrogen atom) is a fluorine atom, C １－３ Alkyl group and C １－３ It may be substituted with one or more substituents selected from fluoroalkyl groups.

[0133] Preferably, the X ５ represents a single bond or -Rf'-X １２ - [wherein, X １２ is C １－２０ alkylene group, -R ３１ -X ｃ -R ３２ - or -X ｄ -R ３２ - [wherein, R ３１ and R ３２ has the same meaning as above.] group, and Rf′ is a single bond or —(C ｌ' F ２ｌ' )-, and l′ is an integer of 1 to 4. The alkylene group may be a group represented by the formula: ｎ H ２ｎ )-structure, which may be substituted or unsubstituted, and may be linear or branched.

[0134] More preferably, the above X ５ is -X ｆ -, -X ｆ -C １－２０ an alkylene group, -X ｆ - (CH ２ ) ｓ' -X ｃ -, -X ｆ - (CH ２ ) ｓ' -X ｃ - (CH ２ ) ｔ' - -X ｆ -X ｄ - or -X ｆ -X ｄ- (CH ２ ) ｔ' In the formula, s' and t' are as defined above. ｆ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group. ｆ The hydrogen atoms in １－３ Alkyl group and C １－３ It may be substituted, and preferably is substituted, with one or more substituents selected from fluoroalkyl groups. ｆ may be linear or branched, preferably linear.

[0135] More preferably, the above X ５ is a single bond or -Rf'-X １３ - [wherein, X １３ is C １－２０ an alkylene group, —(CH ２ ) ｓ' -X ｃ -, -(CH ２ ) ｓ' -X ｃ - (CH ２ ) ｔ' -, -X ｄ - or -X ｄ - (CH ２ ) ｔ' - (wherein s' and t' are as defined above) group, Rf' is a single bond or -(C ｌ' F ２ｌ' )-, and l′ is an integer of 1 to 4.

[0136] In the above formula, X ｃ -O-, -S-, -C(O)O-, -CONR ３４ -, -O-CONR ３４ -, -Si(R ３３ ) ２ -, -(Si(R ３３ ) ２ O) ｍ' -Si(R ３３ ) ２ -, -O-(CH２ ) u' -(Si(R ３３ ) ２ O) ｍ' -Si(R ３３ ) ２ -, -O-(CH ２ ) u' -Si(R ３３ ) ２ —O—Si(R ３３ ) ２ -CH ２ CH ２ -Si(R ３３ ) ２ —O—Si(R ３３ ) ２ -, -O-(CH ２ ) u' -Si(OCH ３ ) ２ OSi(OCH ３ ) ２ -, -CONR ３４ - (CH ２ ) u' -(Si(R ３３ ) ２ O) ｍ' -Si(R ３３ ) ２ -, -CONR ３４ - (CH ２ ) u' -N(R ３４ ) -, or -CONR ３４ -(o-, m- or p-phenylene)-Si(R ３３ ) ２ - [wherein, R ３３ , R ３４ and m' are as defined above, and u' is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ｃ is preferably —O—.

[0137] In the above formula, X ｄ is -S-, -C(O)O-, -CONR ３４ -, -CONR ３４ - (CH ２ ) u' -(Si(R ３３ ) ２ O)ｍ' -Si(R ３３ ) ２ -, -CONR ３４ - (CH ２ ) u' -N(R ３４ ) -, or -CONR ３４ -(o-, m- or p-phenylene)-Si(R ３３ ) ２ wherein each symbol has the same meaning as defined above.

[0138] Particularly preferably, the above X ５ is -X ｆ -, -X ｆ -C １－２０ an alkylene group, -X ｆ - (CH ２ ) ｓ' -X ｃ -, -X ｆ - (CH ２ ) ｓ' -X ｃ - (CH ２ ) ｔ' -, -X ｆ -X ｄ - or -X ｆ -X ｄ - (CH ２ ) ｔ' - [wherein, X ｆ , s' and t' are as defined above.], and X ｃ is —O— or —CONR ３４ -, X ｄ But, -CONR ３４ -, R ３４ is independently in each occurrence a hydrogen atom, a phenyl group or C １－６ It represents an alkyl group (preferably a methyl group).

[0139] In one embodiment, the X ５ is -X ｆ - (CH ２ ) ｓ' -X ｃ -, -X ｆ - (CH ２ ) ｓ' -X ｃ- (CH ２ ) ｔ' -, -X ｆ -X ｄ - or -X ｆ -X ｄ - (CH ２ ) ｔ' - [wherein, X ｆ , s' and t' are as defined above.], and X ｃ But, -CONR ３４ -, X ｄ But, -CONR ３４ -, R ３４ is independently in each occurrence a hydrogen atom, a phenyl group or C １－６ It represents an alkyl group (preferably a methyl group).

[0140] In one embodiment, the X ５ is a single bond, C １－２０ an alkylene group, —(CH ２ ) ｓ' -X ｃ - (CH ２ ) ｔ' - or -X ｄ - (CH ２ ) ｔ' wherein each symbol has the same meaning as defined above.

[0141] Preferably, the X ５ is a single bond or -Rf'-X １４ - [wherein, X １４ is C １－２０ an alkylene group, —(CH ２ ) ｓ' -O-(CH ２ ) ｔ' -, -(CH ２ ) ｓ' -(Si(R ３３ ) ２ O) ｍ' -Si(R ３３ ) ２ - (CH ２ ) ｔ' -, -(CH ２ ) ｓ' -O-(CH ２ )u' -(Si(R ３３ ) ２ O) ｍ' -Si(R ３３ ) ２ - (CH ２ ) ｔ' - or -(CH ２ ) ｓ' -O-(CH ２ ) ｔ' -Si(R ３３ ) ２ - (CH ２ ) u' -Si(R ３３ ) ２ -(C v H ２v ) - [wherein, R ３３ , m', s', t' and u' are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.] group, Rf' is a single bond or -(C ｌ' F ２ｌ' )-, and l′ is an integer of 1 to 4.

[0142] In the above formula, -(C v H ２v )- may be a straight chain or a branched chain, for example, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH(CH ３ ) -, -CH(CH ３ ) CH ２ -It can be.

[0143] Above X ５ The group is a fluorine atom, C １－３ Alkyl group and C １－３ Fluoroalkyl groups (preferably C １－３ and perfluoroalkyl groups).

[0144] In another embodiment, X ５ Examples of groups include the following:

[0145]

[0146] [In the formula, R ４１ are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or C １－６ an alkoxy group, preferably a methyl group; D is -Rf'-X １５ - [wherein, X １５ is -CH ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CF ２ O (CH ２ ) ３ -, -(CH ２ ) ２ -, -(CH ２ ) ３ -, -(CH ２ )4-, -CONH-(CH ２ )-, -CONH-(CH ２ ) ２ -, -CONH-(CH ２ ) ３ -, -CON(CH ３ )-(CH ２ ) ３ -, -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), and

[0147] (In the formula, R ４２ are each independently a hydrogen atom, C １－６ or an alkyl group of C １－６ Rf′ is a single bond or —(C ｌ' F ２ｌ' )-, and l' is an integer of 1 to 4.], E is a group represented by the formula: ２ ) ｎ -(n is an integer of 2 to 6), D is bonded to PFPE in the molecular main chain, and E is bonded to a group opposite to PFPE.]

[0148] Above X ５ Specific examples of the group include: a single bond, or -Rf'-X １０ - [wherein, X １０ is -CH ２ OCH ２ -, -CH ２ O (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ -, -CH ２ O (CH ２ ) ６ -, -CF ２ -CH ２ -O-CH ２ -, -CF ２ -CH ２ -O-(CH ２ ) ２ -, -CF ２ -CH ２ -O-(CH ２ ) ３ -, -CF ２ -CH ２ -O-(CH ２ ) ６ -, -CH ２ O (CH ２ ) ３ Si(CH ３ ) ２ OSi(CH ３ ) ２ (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ Si(CH ３ ) ２ OSi(CH ３ ) ２ OSi(CH ３ ) ２ (CH ２ ) ２ -, -CH ２ O (CH ２ ) ３ Si(CH ３ ) ２ O(Si(CH ３ ) ２ O) ２H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ３ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) １０ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ O(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２０ H ３ ) ２ (CH ２ ) ２ -、 -CH ２ H ２ CHFOCF ２ -、 -CH ２ H ２ CHFOCF ２ CF ２ -、 -CH ２ H ２ CHFOCF ２ CF ２ CF ２ -、 -CH ２ SO ２ CF ２ CF ２ H ２ -、 -CH ２ SO ２ CF ２ CF ２OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF２ CF ２ -、 -CH ２ OCH ２ CHFCF ２ OCF(CF ３ )CF ２ OCF ２ CF ２ CF ２ -、 -CH ２ OCF ２ CHFOCF ２ CF ２ CF ２ -C(O)NH-CH ２ -、 -CH ２ OCH ２ (CH) ２ ) ７ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ２ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ３ ) ２ OSi (OCH) ３ ) ２ (CH) ２ ) ３ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ２ CH ３ ) ２ OSi (OCH) ２ CH ３ ) ２ (CH) ２ ) ３ -、 -CH ２ OCH ２ CH ２ CH ２ Si(OCH ３ ) ２HUNTER ３ ) ２ (CH ２ ) ２ -、 -CH ２ SO ２ CH ２ CH ２ H. ２ CH ３ ) ２ HUNTER ２ CH ３ ) ２ (CH ２ ) ２ -、 -(CH ２ ) ２ -Si(CH ３ ) ２ -(CH ２ ) ２ -、 -CH ２ -、 -(CH ２ ) ２ -、 -(CH ２ ) ３ -、 -(CH ２ ) ４ -、 -(CH ２ ) ５ -、 -(CH ２ ) ６ -、 -CF ２ -、 -(CF ２ ) ２ -、 -CF ２ -CH ２ -、 -CF ２ -(CH ２ ) ２ -、 -CF ２ -(CH ２ ) ３ -、 -CF ２ -(CH ２ ) ４ -、 -CF ２ -(CH ２ ) ５ -、 -CF ２ -(CH ２ ) ６ -、 -CO- -CONH- -CONH-CH ２ -、 -CONH-(CH ２ ) ２ -、 -CONH-(CH ２) ３ -, -CONH-(CH ２ ) ６ -, -CF ２ CONH-, -CF ２ CONHCH ２ -, -CF ２ CONH (CH ２ ) ２ -, -CF ２ CONH (CH ２ ) ３ -, -CF ２ CONH (CH ２ ) ６ -, -CON(CH ３ )-(CH ２ ) ３ -, -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), -CON(CH ３ )-(CH ２ ) ６ -, -CON(Ph)-(CH ２ ) ６ - (wherein Ph means phenyl), -CF ２ -CON (CH ３ )-(CH ２ ) ３ -, -CF ２ -CON(Ph)-(CH ２ ) ３ - (wherein Ph means phenyl), -CF ２ -CON (CH ３ )-(CH ２ ) ６ -, -CF ２ -CON(Ph)-(CH ２ ) ６ - (wherein Ph means phenyl), -CONH-(CH ２ ) ２ NH (CH ２ ) ３ -, -CONH-(CH ２ ) ６ NH (CH ２ ) ３ -, -CH ２ O-CONH-(CH ２ )３ -、 -CH ２ P.S. ２ ) ６ -、 -S-(CH ２ ) ３ -、 -(CH ２ ) ２ H ２ ) ３ -、 -CONH-(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ HUNTER ３ ) ２ HUNTER ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ３ H ３ ) ２ (CH ２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) １０ H ３ ) ２ (CH２ ) ２ -、 -CONH-(CH ２ ) ３ H ３ ) ２ O(Si(CH ３ ) ２ O) ２０ H ３ ) ２ (CH ２ ) ２ -、 -C(O)O-(CH ２ ) ３ -、 -C(O)O-(CH ２ ) ６ -、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -(CH ２ ) ２ -、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -CH(CH ３ )-、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -(CH ２ ) ３ -、 -CH ２ -O-(CH ２ ) ３ -Si(CH ３ ) ２ -(CH ２ ) ２ -Si(CH ３ ) ２ -CH(CH ３ )-CH２ -, -OCH ２ -, -O(CH ２ ) ３ -, -OCFHCF ２ -,

[0149] Rf′ is a single bond or —(C ｌ' F ２ｌ' )-, and l′ is an integer of 1 to 4.

[0150] In a more preferred embodiment, X ５ is X ｅ' represents. ｅ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, -R ５１ -C ６ H ４ -R ５２ -, -R ５１ -CONR ４ -R ５２ -, -R ５１ -CONR ４ -C ６ H ４ -R ５２ -, -R ５１ -CO-R ５２ -, -R ５１ -CO-C ６ H ４ -R ５２ -, -R ５１ -SO ２ NR ４ -R ５２ -, -R ５１ -SO ２ NR ４ -C ６ H ４ -R ５２ -, -R ５１ -SO ２ -R ５２ - or -R ５１ -SO ２ -C ６ H ４ -R ５２ - is. R ５１ and R ５２R each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, and is preferably a single bond or an alkylene group having 1 to 3 carbon atoms. ４ has the same meaning as above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. Examples of the substituent on the alkylene group include halogen atoms, preferably fluorine atoms. The alkylene group is linear or branched, preferably linear.

[0151] In a further preferred embodiment, X ｅ' is a single bond, -X ｆ -, an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X ｆ -C １－６ Alkylene group, preferably -X ｆ -C １－３ An alkylene group, more preferably -X ｆ -C １－２ an alkylene group, ６ H ４ -R ５２' -, -CONR ４' -R ５２' -, -CONR ４' -C ６ H ４ -R ５２' -, -X ｆ -CONR ４' -R ５２' -, -X ｆ -CONR ４' -C ６ H ４ -R ５２' -, -CO-R ５２' -, -CO-C ６ H ４ -R ５２' -, -SO ２ NR ４' -R ５２' -, -SO ２ NR ４' -C ６ H ４ -R ５２' -, -SO ２ -R ５２' -, -SO ２ -C６ H ４ -R ５２' -, -R ５１' -C ６ H ４ -, -R ５１' -CONR ４' -, -R ５１' -CONR ４' -C ６ H ４ -, -R ５１' -CO-, -R ５１' -CO-C ６ H ４ -, -R ５１' -SO ２ NR ４' -, -R ５１' -SO ２ NR ４' -C ６ H ４ -, -R ５１' -SO ２ -, -R ５１' -SO ２ -C ６ H ４ -, -C ６ H ４ --CONR ４' -, -CONR ４' -C ６ H ４ -, -X ｆ -CONR ４' -, -X ｆ -CONR ４' -C ６ H ４ -, -CO-, -CO-C ６ H ４ -, -SO ２ NR ４' -, -SO ２ NR ４' -C ６ H ４ - -SO ２ - or -SO ２ -C ６ H ４ - (wherein, R ５１' and R ５２'are each independently a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and as described above, the alkylene group may be substituted or unsubstituted. Examples of the substituent of the alkylene group include a halogen atom, preferably a fluorine atom. ４' is a hydrogen atom or a methyl group.

[0152] Among the above, X ｅ' is preferably -X ｆ -, an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X ｆ -C １－６ Alkylene group, preferably -X ｆ -C １－３ An alkylene group, more preferably -X ｆ -C １－２ an alkylene group, -CONR ４' -R ５２' -, -CONR ４' -C ６ H ４ -R ５２' -, -X ｆ -CONR ４' -R ５２' -, -X ｆ -CONR ４' -C ６ H ４ -R ５２' -, -R ５１' -CONR ４' -, -R ５１' -CONR ４' -C ６ H ４ -, -CONR ４' -, -CONR ４' -C ６ H ４ -, -X ｆ -CONR ４' -, -X ｆ -CONR ４' -C ６ H ４ -, -R ５１' -CONR ４' - or -R ５１' -CONR ４' -C６ H ４ -, where X ｆ , R ４' , R ５１' and R ５２' have the same meanings as above.

[0153] Among the above, X ｅ' is more preferably -CONR ４' -R ５２' -, -CONR ４' -C ６ H ４ -R ５２' -, -X ｆ -CONR ４' -R ５２' -, -X ｆ -CONR ４' -C ６ H ４ -R ５２' -, -R ５１' -CONR ４' -, -R ５１' -CONR ４' -C ６ H ４ -, -CONR ４' -, -CONR ４' -C ６ H ４ -, -X ｆ -CONR ４' - or -X ｆ -CONR ４' -C ６ H ４ -, it can be.

[0154] In this embodiment, X ｅ' Specific examples of the alkyl group include a single bond, a perfluoroalkylene group having 1 to 6 carbon atoms (for example, -CF ２ -, - (CF ２ ) ２ - etc.), an alkylene group having 1 to 6 carbon atoms, -CF ２ -C １－６ an alkylene group, —CONH—, —CONH-CH ２ -, -CONH-(CH ２ ) ２ - -CONH-(CH２ ) ３ -、 -CF ２ -CONH-、 -CF ２ P.S. ２ -、 -CF ２ P.S. ２ ) ２ -、 -CF ２ P.S. ２ ) ３ -、 -CON(CH ３ )-、 -CON(CH ３ )-CH ２ -、 -CON(CH ３ )-(CH ２ ) ２ -、 -CON(CH ３ )-(CH ２ ) ３ -、 -CF ２ -CON(CH ３ )-、 -CF ２ -CON(CH ３ )CH ２ -、 -CF ２ -CON(CH ３ )-(CH ２ ) ２ -、 -CF ２ -CON(CH ３ )-(CH ２ ) ３ -、 -CH ２ -CONH-, -CH ２ -CONH-CH ２ -、 -CH ２ -CONH-(CH ２ ) ２ -、 -CH ２ -CONH-(CH ２ ) ３ -、 -CF ２ -CH ２ -CONH-、 -CF ２ -CH ２ -CONH-CH ２ -、 -CF ２ -CH ２ -CONH-(CH ２ ) ２ -、 -CF ２ -CH ２-CONH-(CH ２ ) ３ -、 -CONH-C ６ H ４ -、 -CON(CH ３ )-C ６ H ４ -、 -CH ２ -CON(CH ３ )-CH ２ -、 -CH ２ -CON(CH ３ )-(CH ２ ) ２ -、 -CH ２ -CON(CH ３ )-(CH ２ ) ３ -、 -CON(CH ３ )-C ６ H ４ -、 -CF ２ -CONH-C ６ H ４ -、 -CF ２ -CON(CH ３ )-C ６ H ４ -、 -CF ２ -CH ２ -CON(CH ３ )-CH ２ -、 -CF ２ -CH ２ -CON(CH ３ )-(CH ２ ) ２ -、 -CF ２ -CH ２ -CON(CH ３ )-(CH ２ ) ３ -、 -CF ２ -CON(CH ３ )-C ６ H ４ -、 -CO-、 -CO-C ６ H ４ -、 -C ６ H ４ -、 -SO ２ NH-, -SO ２ H ２ -、 -SO ２ H. ２) ２ -, -SO ２ NH-(CH ２ ) ３ -, -SO ２ NH-C ６ H ４ -, -SO ２ N (CH ３ ) -, -SO ２ N (CH ３ )-CH ２ -, -SO ２ N (CH ３ )-(CH ２ ) ２ -, -SO ２ N (CH ３ )-(CH ２ ) ３ -, -SO ２ N (CH ３ )-C ６ H ４ -, -SO ２ -, -SO ２ -CH ２ -, -SO ２ - (CH ２ ) ２ -, -SO ２ - (CH ２ ) ３ - or -SO ２ -C ６ H ４ - etc.

[0155] Among the above list, preferred X ｅ' Examples of the alkylene group include an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 6 carbon atoms (for example, -CF ２ -, - (CF ２ ) ２ - etc.), -CF ２ -C １－６ an alkylene group, —CONH—, —CONH-CH ２ -, -CONH-(CH ２ ) ２ -, -CONH-(CH ２ ) ３ -, -CF ２ CONH-, -CF ２ CONHCH２ -、 -CF ２ P.S. ２ ) ２ -、 -CF ２ P.S. ２ ) ３ -、 -CON(CH ３ )-、 -CON(CH ３ )-CH ２ -、 -CON(CH ３ )-(CH ２ ) ２ -、 -CON(CH ３ )-(CH ２ ) ３ -、 -CF ２ -CON(CH ３ )-、 -CF ２ -CON(CH ３ )CH ２ -、 -CF ２ -CON(CH ３ )-(CH ２ ) ２ -、 -CF ２ -CON(CH ３ )-(CH ２ ) ３ -、 -CH ２ -CONH-, -CH ２ -CONH-CH ２ -、 -CH ２ -CONH-(CH ２ ) ２ -、 -CH ２ -CONH-(CH ２ ) ３ -、 -CF ２ -CH ２ -CONH-、 -CF ２ -CH ２ -CONH-CH ２ -、 -CF ２ -CH ２ -CONH-(CH ２ ) ２ -、 -CF ２ -CH ２ -CONH-(CH ２ ) ３ -、 -CONH-C ６ H ４-, -CON(CH ３ )-C ６ H ４ -, -CH ２ -CON (CH ３ )-CH ２ -, -CH ２ -CON (CH ３ )-(CH ２ ) ２ -, -CH ２ -CON (CH ３ )-(CH ２ ) ３ -, -CON(CH ３ )-C ６ H ４ -CF ２ -CONH-C ６ H ４ -, -CF ２ -CON (CH ３ )-C ６ H ４ -, -CF ２ -CH ２ -CON (CH ３ )-CH ２ -, -CF ２ -CH ２ -CON (CH ３ )-(CH ２ ) ２ -, -CF ２ -CH ２ -CON (CH ３ )-(CH ２ ) ３ -, -CF ２ -CON (CH ３ )-C ６ H ４ -, etc.

[0156] Among the above-listed, more preferred X ｅ' Examples include -CONH-, -CONH-CH ２ -, -CONH-(CH ２ ) ２ -, -CONH-(CH ２ ) ３ -, -CF ２ CONH-, -CF ２ CONHCH ２-、 -CF ２ P.S. ２ ) ２ -、 -CF ２ P.S. ２ ) ３ -、 -CON(CH ３ )-、 -CON(CH ３ )-CH ２ -、 -CON(CH ３ )-(CH ２ ) ２ -、 -CON(CH ３ )-(CH ２ ) ３ -、 -CF ２ -CON(CH ３ )-、 -CF ２ -CON(CH ３ )CH ２ -、 -CF ２ -CON(CH ３ )-(CH ２ ) ２ -、 -CF ２ -CON(CH ３ )-(CH ２ ) ３ -、 -CH ２ -CONH-, -CH ２ -CONH-CH ２ -、 -CH ２ -CONH-(CH ２ ) ２ -、 -CH ２ -CONH-(CH ２ ) ３ -、 -CF ２ -CH ２ -CONH-、 -CF ２ -CH ２ -CONH-CH ２ -、 -CF ２ -CH ２ -CONH-(CH ２ ) ２ -、 -CF ２ -CH ２ -CONH-(CH ２ ) ３ -、 -CONH-C ６ H ４ -、 -CON(CH３ )-C ６ H ４ -, -CH ２ -CON (CH ３ )-CH ２ -, -CH ２ -CON (CH ３ )-(CH ２ ) ２ -, -CH ２ -CON (CH ３ )-(CH ２ ) ３ -, -CON(CH ３ )-C ６ H ４ -CF ２ -CONH-C ６ H ４ -, -CF ２ -CON (CH ３ )-C ６ H ４ -, -CF ２ -CH ２ -CON (CH ３ )-CH ２ -, -CF ２ -CH ２ -CON (CH ３ )-(CH ２ ) ２ -, -CF ２ -CH ２ -CON (CH ３ )-(CH ２ ) ３ - or -CF ２ -CON (CH ３ )-C ６ H ４ -, etc.

[0157] The compounds represented by the above formulae (A1) and (A2) can be produced by known methods, for example, the method described in Patent Document 1 or an improved method thereof.

[0158] Formulas (B1) and (B2):

[0159]

[0160] In the above formulae (B1) and (B2), Rf and PFPE have the same meanings as those in the above formulae (A1) and (A2).

[0161] In the above formula, X ７ Each of X independently represents a single bond or a divalent to decavalent organic group. ７ In the compounds represented by formulas (B1) and (B2), the compound has a perfluoropolyether moiety (Rf-PFPE moiety or -PFPE- moiety) that mainly provides water repellency and surface slipperiness, and a silane moiety (specifically, -SiR ａ ｋ１ R ｂ ｌ１ R ｃ ｍ１ Therefore, the X ７ may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.

[0162] In the above formula, γ is an integer of 1 to 9, and γ' is an integer of 1 to 9. These γ and γ' are X ７ In formula (B1), the sum of γ and γ′ is determined according to the valence of X ７ For example, X ７ When X is a decavalent organic group, the sum of γ and γ' is 10, and 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. ７ When X is a divalent organic group, γ and γ' are 1. In formula (B2), γ is X ７ is the value obtained by subtracting 1 from the valence value of

[0163] Above X ７ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and even more preferably a divalent organic group.

[0164] In one embodiment, X ７ is a divalent to tetravalent organic group, γ is 1 to 3, and γ' is 1.

[0165] In another embodiment, X ７is a divalent 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').

[0166]

[0167] Above X ７ Examples of the group include, but are not limited to, X ５ Examples of the above-mentioned examples are the same as those described above.

[0168] In the above formula, R ａ is independently at each occurrence -Z １ -SiR ７１ ｐ１ R ７２ ｑ１ R ７３ ｒ１ Represents.

[0169] During the ceremony, Z １ represents, independently in each occurrence, an oxygen atom or a divalent organic group.

[0170] Above Z １ is preferably a divalent organic group, and is a Si atom (R ａ This does not include those that form a siloxane bond with the Si atom to which the siloxane bond is bonded.

[0171] Above Z １ is preferably C １－６ Alkylene group, -(CH ２ ) ｇ -O-(CH ２ ) ｈ - (wherein g is an integer of 1 to 6, and h is an integer of 1 to 6) or -phenylene-(CH ２ ) ｉ - (wherein i is an integer from 0 to 6), more preferably C １－３ These groups are, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ alkenyl groups, and C ２－６ It may be substituted with one or more substituents selected from alkynyl groups.

[0172] In the formula, R ７１ represents, independently at each occurrence, R ａ' Represents R ａ' is R ａ It has the same meaning as:

[0173] R ａ Medium, Z １ The number of Si atoms connected in a linear chain via the group is 5 at most. ａ In this case, R ７１ If there is at least one ａ Z inside １ There are two or more Si atoms linearly linked via Z groups. １ The maximum number of Si atoms connected in a linear chain via the "R ａ Z in the middle １ The number of Si atoms linearly linked via R ａ -Z linked in a linear chain １ This is equal to the number of repeats of -Si-.

[0174] For example, ａ In the middle Z １ An example in which the Si atom is linked via a group (hereinafter simply referred to as "Z") is shown.

[0175]

[0176] In the above formula, * means the site of bonding to Si in the main chain, and ... means that a specific group other than ZSi is bonded, that is, when all three bonds of the Si atom are ..., it means the end point of the repetition of ZSi. Also, the number on the right side of Si means the number of occurrences of Si linked in a linear chain via Z groups, counted from *. That is, Si ２ The chain where the ZSi repeat ends is "R ａ Z in the middle １ The number of Si atoms linearly linked via Si groups is two. ３ , Si ４ and Si ５ The chains in which the ZSi repeat ends are called "R ａ Z in the middle １The number of Si atoms linearly linked via R groups is 3, 4, and 5. ａ There are multiple ZSi chains in the molecule, but they do not all need to be the same length, and each may be any length.

[0177] In a preferred embodiment, as shown below, ａ Z in the middle １ The number of Si atoms linearly linked via groups is 1 (left formula) or 2 (right formula) in all chains.

[0178]

[0179] In one embodiment, R ａ The number of Si atoms linearly linked via Z groups in the hydroxyl group is one or two, preferably one.

[0180] In the formula, R ７２ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group.

[0181] The term "hydrolyzable group" as used herein means a group that can undergo a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, and -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), and preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, and isobutyl group; and substituted alkyl groups such as chloromethyl group. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. The hydroxyl group is not particularly limited, but may be one generated by hydrolysis of a hydrolyzable group.

[0182] Preferably, R ７２ is -OR (wherein R is a substituted or unsubstituted C １－３ It is more preferable that the alkyl group is a methyl group.

[0183] In the formula, R ７３are each 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.

[0184] wherein p1, at each occurrence, is independently an integer from 0 to 3; q1, at each occurrence, is independently an integer from 0 to 3; and r1, at each occurrence, is independently an integer from 0 to 3, with the proviso that the sum of p1, q1, and r1 is 3.

[0185] In a preferred embodiment, R ａ R at the end of the middle ａ '(R ａ If ' does not exist, R ａ In the above formula (I), q1 is preferably 2 or more, for example, 2 or 3, and more preferably 3.

[0186] In a preferred embodiment, R ａ At least one of the terminals is -Si(-Z １ -SiR ７２ ｑ R ７３ ｒ ) ２ or -Si(-Z １ -SiR ７２ ｑ R ７３ ｒ ) ３ , preferably —Si(—Z １ -SiR ７２ ｑ R ７３ ｒ ) ３ In the formula, (-Z １ -SiR ７２ ｑ R ７３ ｒ ) units are preferably (-Z １ -SiR ７２ ３ In a further preferred embodiment, R ａ The ends of all of the １ -SiR ７２ ｑ R ７３ｒ ) ３ , preferably —Si(—Z １ -SiR ７２ ３ ) ３ It could be.

[0187] In the above formulas (B1) and (B2), at least one R ７２ exists.

[0188] In the above formula, R ｂ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group.

[0189] 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), and preferably -OR. R includes unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and substituted alkyl groups such as chloromethyl group. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. The hydroxyl group is not particularly limited, but may be one generated by hydrolysis of a hydrolyzable group. More preferably, R ｂ is -OR (wherein R is a substituted or unsubstituted C １－３ It is more preferable that the alkyl group is a methyl group.

[0190] In the above formula, R ｃ are each 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.

[0191] wherein k1, at each occurrence, is independently an integer from 0 to 3; l1, at each occurrence, is independently an integer from 0 to 3; and m1, at each occurrence, is independently an integer from 0 to 3, with the proviso that the sum of k1, l1, and m1 is 3.

[0192] In a preferred embodiment, k1, at each occurrence, is independently an integer from 1 to 3; l1, at each occurrence, is independently an integer from 0 to 2; and m1, at each occurrence, is independently an integer from 0 to 2.

[0193] The compounds represented by the above formulas (B1) and (B2) can be obtained, for example, by using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, introducing a hydroxyl group at the terminal, then introducing a group having an unsaturated bond at the terminal, reacting this group having an unsaturated bond with a silyl derivative having a halogen atom, and further introducing a hydroxyl group at the terminal of this silyl group, and reacting the introduced group having an unsaturated bond with the silyl derivative.

[0194] Formulas (C1) and (C2):

[0195]

[0196] In the above formulae (C1) and (C2), Rf and PFPE have the same meanings as those in the above formulae (A1) and (A2).

[0197] In the above formula, X ９ are each independently a single bond or a divalent to decavalent organic group. In the compounds represented by formulas (C1) and (C2), X is understood to be a linker that connects the perfluoropolyether portion (i.e., the Rf-PFPE portion or -PFPE- portion) that primarily provides water repellency and surface slipperiness, etc., to the portion that provides the ability to bond to the substrate (i.e., the group enclosed in parentheses with δ). Therefore, X may be any organic group as long as it allows the compounds represented by formulas (C1) and (C2) to exist stably.

[0198] In the above formula, δ is an integer of 1 to 9, and δ' is an integer of 1 to 9. These δ and δ' can change depending on 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 decavalent organic group, the sum of δ and δ' is 10, and it can be, for example, δ is 9 and δ' is 1, δ is 5 and δ' is 5, or δ is 1 and δ' is 9. In addition, X ９When X is a divalent organic group, δ and δ' are 1. In formula (C2), δ is X ９ is the value obtained by subtracting 1 from the valence of

[0199] Above X ９ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and even more preferably a divalent organic group.

[0200] In one embodiment, X ９ is a divalent to tetravalent organic group, δ is 1 to 3, and δ' is 1.

[0201] In another embodiment, X ９ is a divalent organic group, δ is 1, and δ' is 1. In this case, formulas (C1) and (C2) are represented by the following formulas (C1') and (C2').

[0202]

[0203] Above X ９ Examples of the group include, but are not limited to, X ５ Examples of the above-mentioned examples are the same as those described above.

[0204] In the above formula, R ｄ is independently at each occurrence -Z ２ -CR ８１ ｐ２ R ８２ ｑ２ R ８３ ｒ２ Represents.

[0205] During the ceremony, Z ２ represents, independently in each occurrence, an oxygen atom or a divalent organic group.

[0206] Above Z ２ is preferably C １－６ Alkylene group, -(CH ２ ) ｇ -O-(CH ２ ) ｈ - (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6, and h is an integer of 0 to 6, for example, an integer of 1 to 6), or -phenylene-(CH ２ ) ｉ- (wherein i is an integer from 0 to 6), more preferably C １－３ These groups are, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ alkenyl groups, and C ２－６ It may be substituted with one or more substituents selected from alkynyl groups.

[0207] In the formula, R ８１ represents, independently at each occurrence, R ｄ' Represents R ｄ' is R ｄ It has the same meaning as:

[0208] R ｄ Medium, Z ２ The number of Cs connected in a linear chain via the group is at most 5. ｄ In this case, R ８１ If there is at least one ｄ Z inside ２ There are two or more C atoms linearly linked via Z groups. ２ The maximum number of C atoms connected in a linear chain via the "R ｄ Z in the middle ２ The number of C atoms linearly linked via R ｄ -Z linked in a linear chain ２ This is equal to the number of repetitions of -C-. ａ The same applies to the description of

[0209] In a preferred embodiment, "R ｄ Z in the middle ２ The number of C atoms linearly linked via groups is 1 (left formula) or 2 (right formula) in all chains.

[0210] In one embodiment, R ｄ Z in the middle ２ The number of carbon atoms linked in a linear chain via groups is one or two, preferably one.

[0211] In the formula, R ８２ is -Y-SiR ８５ ｎ２ R８６ ３－２ｎ Represents.

[0212] Y independently in each occurrence represents a divalent organic group.

[0213] In a preferred embodiment, Y is C １－６ Alkylene group, -(CH ２ ) ｇ' -O-(CH ２ ) ｈ' - (wherein g' is an integer of 0 to 6, for example, an integer of 1 to 6, and h' is an integer of 0 to 6, for example, an integer of 1 to 6), or -phenylene-(CH ２ ) ｉ' - (wherein i' is an integer from 0 to 6). These groups include, for example, fluorine atoms, C １－６ Alkyl group, C ２－６ alkenyl groups, and C ２－６ It may be substituted with one or more substituents selected from alkynyl groups.

[0214] In one embodiment, Y is C １－６ Alkylene group, —O—(CH ２ ) ｈ' - or -phenylene-(CH ２ ) ｉ' When Y is the above group, the light resistance, particularly the ultraviolet resistance, can be improved.

[0215] The above R ８５ represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group.

[0216] The term "hydrolyzable group" as used herein means a group that can undergo a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, and -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), and preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, and isobutyl group; and substituted alkyl groups such as chloromethyl group. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl group or ethyl group is more preferred. The hydroxyl group is not particularly limited, but may be one generated by hydrolysis of a hydrolyzable group.

[0217] Preferably, R ８５ is -OR (wherein R is a substituted or unsubstituted C １－３ alkyl group, more preferably an ethyl group or a methyl group, especially a methyl group).

[0218] The above R ８６ are each 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.

[0219] n2 is (-Y-SiR ８５ ｎ２ R ８６ ３－ｎ２ Each ) unit independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0220] The above R ８３ In each occurrence, each 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 even more preferably a methyl group. In one embodiment, R ８３ represents, independently at each occurrence, a hydrogen atom or a lower alkyl group.

[0221] wherein p2, at each occurrence, is independently an integer from 0 to 3; q2, at each occurrence, is independently an integer from 0 to 3; and r2, at each occurrence, is independently an integer from 0 to 3, with the proviso that the sum of p2, q2, and r2 is 3.

[0222] In a preferred embodiment, R ｄ R at the end of the middle ｄ '(R ｄ If ' does not exist, R ｄ In the above formula (I), q2 is preferably 2 or more, for example, 2 or 3, and more preferably 3.

[0223] In a preferred embodiment, R ｄ At least one of the terminals is —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 ８６ ｒ２ ) units are preferably (—Y—SiR ８５ ３ In a further preferred embodiment, R ｄ The terminals of all of the groups are -C(-Y-SiR ８５ ｑ２ R ８６ ｒ２ ) ３ , preferably —C(—Y—SiR ８５ ３ ) ３ It could be.

[0224] In the above formula, R ｅ is independently at each occurrence -Y-SiR ８５ ｎ２ R ８６ ３－ｎ２where Y and R ８５ , R ８６ and n2 is the above R ８２ This has the same meaning as the description in

[0225] In the above formula, R ｆ In each occurrence, each 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 even more preferably a methyl group. In one embodiment, R ｆ represents, independently at each occurrence, a hydrogen atom or a lower alkyl group.

[0226] wherein k2, in each occurrence, is independently an integer from 0 to 3; l2, in each occurrence, is independently an integer from 0 to 3; and m2, in each occurrence, is independently an integer from 0 to 3, with the proviso that the sum of k2, l2, and m2 is 3.

[0227] In one embodiment, at least one k2 is 2 or 3, preferably 3.

[0228] In one embodiment, k2 is 2 or 3, preferably 3.

[0229] In one embodiment, l2 is 2 or 3, preferably 3.

[0230] 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 formulas, at least two -Y-SiR ８５ ｎ２ R ８６ ３－ｎ２ There is a group.

[0231] 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 can be produced as follows, but is not limited thereto.

[0232] In one embodiment, Rf′ in each of the above embodiments is a single bond in formulas (A1), (B1) and (C1), and X located to the left of PFPE in formulas (A2), (B2) and (C2). ５ In (C ｌ' F ２ｌ' ) and X located to the right of PFPE ５ In (C ｌ' F ２ｌ' )

[0233] In one embodiment, Rf' in each of the above embodiments can be a single bond.

[0234] The perfluoro(poly)ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1) and (C2) are not particularly limited, but may be 5×10 ２ ~1 x 10 ５ The number average molecular weight is preferably 2,000 to 30,000, more preferably 3,000 to 10,000, and even more preferably 3,000 to 8,000. The "number average molecular weight" is measured by GPC (gel permeation chromatography) analysis.

[0235] In the surface treatment agent of the present disclosure, the content of the both-terminal compound is preferably 0.1 mol % or more and 35 mol % or less relative to the total of the compound represented by formula (A1), (B1), and (C1) (hereinafter also referred to as "single-terminal compound") and the compound represented by formula (A2), (B2), or (C2) (hereinafter also referred to as "double-terminal compound"). The lower limit of the content of the double-terminal compound relative to the total of the one-terminal compound and the double-terminal compound is preferably 0.1 mol %, more preferably 0.2 mol %, even more preferably 0.5 mol %, even more preferably 1 mol %, particularly preferably 2 mol %, and especially 5 mol %. The upper limit of the content of the double-terminal compound relative to the total of the one-terminal compound and the double-terminal compound is preferably 35 mol %, more preferably 30 mol %, even more preferably 20 mol %, even more preferably 15 mol % or 10 mol %. The proportion of the both-end compound relative to the total of the one-end compound and the both-end compound is preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, even more preferably 0.2 mol% to 10 mol%, still more preferably 0.5 mol% to 10 mol%, particularly preferably 1 mol% to 10 mol%, for example, 2 mol% to 10 mol% or 5 mol% to 10 mol%. By setting the both-end compound in this range, the friction durability can be further improved.

[0236] Other examples of the perfluoroalkyl group-containing silane compound include the following (1) and (2) described in WO2020 / 019653. R Ｆ１ is independently at each occurrence Rf １ -R Ｆ -O ｑ - and R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ -; Rf １ each occurrence independently represents a C optionally substituted by one or more fluorine atoms; １－１６ Rf is an alkyl group; ２ is a C optionally substituted by one or more fluorine atoms;１－６ is an alkylene group; R Ｆ is, independently in each occurrence, a divalent fluoropolyether group; p is 0 or 1; q is, independently in each occurrence, 0 or 1; R Ｓｉ is independently in each occurrence a monovalent group containing a Si atom to which is bonded a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group; Ｓｉ is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded; X Ａ are each independently a single bond or a divalent to decavalent organic group; α is an integer of 1 to 9; β is an integer of 1 to 9; and γ is each independently an integer of 1 to 9.

[0237] As the isocyanuric skeleton-containing silane compound, for example, the following compound having an isocyanuric skeleton described in WO2018 / 056413 can be used. (In the formula, R １ represents a monovalent organic group containing a polyether chain, X １ and X ２ each independently represents a monovalent group, and the polyether chain has the formula: -(OC ６ F １２ ) ｍ１１ - (OC ５ F １０ ) ｍ１２ - (OC ４ F ８ ) ｍ１３ - (OC ３ X １０ ６ ) ｍ１４ - (OC ２ F ４ ) ｍ１５ -(OCF ２ ) ｍ１６ - (wherein m11, m12, m13, m14, m15 and m16 are independently an integer of 0 or 1 or more; X １０ are independently H, F or Cl, and the order of occurrence of each repeating unit is arbitrary).

[0238] The antifouling layer 130 may be formed by depositing a fluorine-containing silane compound into an uneven film by a deposition process such as PVD (such as vacuum deposition, sputtering, or resistance heating deposition) or CVD.

[0239] Alternatively, the antifouling layer 130 may be formed by dissolving a fluorine-containing silane compound in an organic solvent, applying the solution to the irregularities, and drying the solution. Examples of organic solvents 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-butylene glycol diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve, etc. Examples include rube 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, and the like, and one or more of these may be selected and used.

[0240] The coating method may be various coating methods such as dip coating, spin coating, flow coating, spray coating, roll coating, or gravure coating, or printing methods such as letterpress printing or inkjet printing.

[0241] Drying may be performed under conditions that allow the organic solvent to evaporate and form a solid film of the antifouling layer 130. For example, drying may be performed by heating at 100 to 200°C for 1 to 60 minutes. Note that, because the condensation reaction itself proceeds even at low temperatures, drying may be performed under milder conditions than these (a temperature below 100°C for more than 60 minutes). For example, drying may be performed by leaving the film at room temperature for a long period of time.

[0242] In addition to the fluorine-containing silane compound, the antifouling layer 130 may be formed using a monomer, an oligomer, a polymer, a filler such as silica, or other additives (catalyst, surfactant, polymerization inhibitor, sensitizer, etc.).

[0243] For example, when an isocyanuric skeleton-containing silane compound is used as the fluorine-containing silane compound, in addition to this, (A) a polymerizable coating agent monomer such as a monofunctional and / or polyfunctional acrylate and methacrylate (hereinafter, acrylate and methacrylate will also be collectively referred to as "(meth)acrylate"), a monofunctional and / or polyfunctional urethane (meth)acrylate, a monofunctional and / or polyfunctional epoxy (meth)acrylate, or the like; (B) (b-1) Thermosetting resins such as acrylic polymers, polycarbonate polymers, polyester polymers, polyamide polymers, polyimide polymers, polyethersulfone polymers, cyclic polyolefin polymers, fluorine-containing polyolefin polymers (PTFE, etc.), fluorine-containing cyclic amorphous polymers (CYTOP (registered trademark), TEFLON (registered trademark) AF, etc.), and (b-2) curable monomers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, silicone (meth)acrylate, and (meth)acrylate monomers may be used.

[0244] When a perfluoroalkyl group-containing silane compound is used as the fluorine-containing silane compound, the antifouling layer 130 may be formed by further using a fluoroalkyl silane oligomer mixture in addition to the perfluoroalkyl group-containing silane compound.

[0245] The fluoroalkylsilane oligomer mixture may contain a partial hydrolysis condensate of a fluoroalkylsilane compound represented by the following formula (II): Rf1-Q1-SiR1pX13-p (II) [wherein: Rf1 is ClF2l+1, l is an integer of 1 to 10, Q1 is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, each R1 is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, each X1 is independently a hydroxyl group or a hydrolyzable group, and p is an integer of 0 to 2.] In formula (II), R ｆ１ is C ｌ F ２ｌ＋１ and 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.

[0246] In formula (II), Q １ is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and examples of the hydrocarbon group include a linear or branched alkylene group, and a group having an amide group or an etheric oxygen atom between carbon atoms in a linear or branched alkylene group having 2 to 6 carbon atoms. Among these, a linear alkylene group having 1 to 6 carbon atoms: -(CH ２ ) ｔ - (where t is an integer of 1 to 6) is preferred, and -(CH ２ ) ２ -, -(CH ２ ) ３ - or -(CH ２ ) ４ -, in particular -(CH ２ ) ２ - is preferred.

[0247] In formula (II), R １ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include a linear or branched alkyl group. Among these, from the viewpoint of availability, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred. When a plurality of R １may be the same or different, but are preferably the same in terms of availability.

[0248] In formula (II), X １ is a hydroxyl group or a hydrolyzable group. Here, the term "hydrolyzable group" as used herein means a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, and -O-N=CR. ２ , -NR ２ , -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and preferably -OR (i.e., an alkoxy group). Examples of R include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl groups or ethyl groups are more preferred. The hydroxyl group is not particularly limited, and may be one generated by hydrolysis of a hydrolyzable group.

[0249] X １ When X is a chlorine atom, the reactivity is high and the hydrolysis reaction proceeds sufficiently without the addition of an acid catalyst. １ Compounds in which the atom is a chlorine atom are preferably used.

[0250] In formula (II), p is an integer of 0 to 2, and is preferably 0 or 1, more preferably 0, in terms of excellent adhesion and durability.

[0251] Examples of the compound represented by formula (II) include the following: １ , R １ Exemplary and preferred embodiments are as described above.

[0252] Formula (I-1): CF ３ (CF ２ ) ｌ－１ - (CH ２ ) ｔ -SiX １ ３ Formula (I-2): CF ３ (CF ２ )ｌ－１ - (CH ２ ) ｔ -SiR １ X １ ２

[0253] The fluoroalkylsilane compound represented by formula (II) may be used alone or in combination of two or more. The fluoroalkylsilane compound represented by formula (II) can be produced by a general production method and is commercially available.

[0254] The fluoroalkylsilane oligomer is a compound (SiX) of two or more fluoroalkylsilane compounds represented by the formula (II). １ ) moieties are hydrolyzed and condensed with each other. The fluoroalkylsilane oligomer is usually a mixture containing mainly 2- to 14-mer polymers.

[0255] The degree of oligomerization / condensation is ２９ It can be measured by Si-NMR, and the TO species ( ２９ The values ​​are shown by the integral values ​​of the Si-NMR spectra of T1 (40-48 ppm), T2 (48-54 ppm), T3 (54-63 ppm), and T4 (63-75 ppm). ２９ Si-NMR shows 0-10%, more preferably 0-5%, and even more preferably 0-3% of TO species (40-48 ppm), 0-40%, more preferably 1-30%, and even more preferably 10-25% of T1 species (48-54 ppm), and 20-80%, more preferably 25-75%, and even more preferably 30-70% of T2 species (54-63 ppm). ２９ Explanations of T0, T1, T2, and T3 are given in "Structural Analysis of Silicon-Containing Materials by Si NMR Method," [online], Asahi Glass Research Report 66 (2016), pp. 32-36, Internet <URL: https: / / www.agc.com / innovation / library / pdf / 66-07.pdf>."

[0256] The oligomers are formed by hydrolysis of the compound represented by formula (II). The oligomers can be formed by hydrolysis of the same or different compounds represented by formula (II). The hydrolysis reaction of the compound represented by formula (II) with water can be carried out in the presence or absence of a catalyst. Suitable catalysts include, but are not limited to, acid catalysts, alkali catalysts, organic amine catalysts, or metal catalysts. In one embodiment, the catalyst is 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 will be understood that water can be provided as part of the aqueous catalyst composition.

[0257] The degree of oligomerization ( ２９ The molecular weight (based on Si-NMR analysis) and / or size of the oligomer (based on number average molecular weight) can be adjusted by adjusting the amount of water in the reaction system, by selecting an appropriate catalyst, and / or by selecting appropriate reaction conditions. In particular, the molar ratio of water to silicon is controlled in providing the oligomers of the present disclosure. In one embodiment, the molar ratio of water to silicon (water:silicon) can be about 2.5:1 or less, about 2:1 or less, about 1.5:1 or less, about 1.25:1 or less, about 1:1 or less, about 0.75:1 or less, or about 0.5:1 or less. In one embodiment, 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. Note that ranges other than those listed above can also be defined by combining the upper and lower limits listed above.

[0258] The fluoroalkylsilane oligomer is １ H-NMR, ２９ Structural analysis and composition analysis are possible by Si-NMR, GC (gas chromatography), and LC (liquid chromatography) analysis, and the composition and ratio of a mixture containing multimers of 2 to 14 monomers, the ratio and residual rate of hydrolyzable groups, the degree of condensation, etc. can be measured.

[0259] The number average molecular weight of the fluoroalkylsilane oligomer mixture may be preferably 300 or more, preferably 400 or more, more preferably 500 or more, and even more preferably 800 or more.

[0260] The number average molecular weight of the fluoroalkylsilane oligomer mixture may be preferably 4,500 or less, more preferably 4,000 or less, even more preferably 3,500 or less, and even more preferably 3,000 or less.

[0261] In the present invention, the "number average molecular weight" is measured by GPC (gel permeation chromatography) analysis.

[0262] In the fluoroalkylsilane oligomer mixture, a methoxy group (OCH ３ ) content ratio (OCH ３ / Si, molar ratio) may be preferably 1.5 or more, more preferably 2.0 or more, and even more preferably 2.2 or more. By making this ratio 1.5 or more, friction durability is further improved. Furthermore, the content ratio of methoxy groups to silicon may be preferably 2.8 or less, more preferably 2.7 or less, and even more preferably 2.5 or less. By making this ratio 2.8 or less, wear durability is further improved.

[0263] The ratio of methoxy groups to silicon is: ２９ It can be measured using Si-NMR.

[0264] The amount of the fluoroalkylsilane oligomer mixture may be preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the fluoroalkylsilane oligomer mixture and the perfluoroalkyl group-containing silane compound.

[0265] The amount of the fluoroalkylsilane oligomer mixture may be preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the fluoroalkylsilane oligomer mixture and the perfluoroalkyl group-containing silane compound.

[0266] As described above, according to this embodiment, steps S100 to S200 are performed to form the antifouling layer 130 on the irregularities (the irregularities of the substrate 110 or the underlayer 120). This allows the antifouling layer 130 to be firmly bonded to the irregularities, thereby improving the abrasion resistance and durability of the antifouling layer 130.

[0267] [Examples] Hereinafter, examples of this embodiment will be described with reference to examples.

[0268] [Example 1]

[0269] Preparation of Primer Resin Composition: Acetic acid (2.71 g) and methyltrimethoxysilane (MTMS, 35.21 g) were placed in a small glass bottle, and the mixture was then cooled in an ice bath. Next, a mixture of silica (LUDOX® AS-40, 14.16 g) and water was added to the cooled mixture of silane and acetic acid over approximately 20 minutes. The mixture was slightly heated due to the exothermic reaction of silane hydrolysis and stirred for several hours while cooling to room temperature. Next, a mixture of IPA (isopropyl alcohol) and n-BuOH (n-butanol) was added and mixed for approximately 30 minutes. Next, 4,6-dibenzoyl-2-(3-triethoxysilylpropyl)resorcinol (SDBR) was added to the hydrolysis mixture (2.82 g, 32% SDBR in 1-methoxy-2-propyl alcohol solution) and stirring was continued until the SDBR was dispersed. The reaction mixture was stirred for another day to allow mixing. A 40% solution of tetrabutylammonium acetate (TBAA) in water (0.1 g) and BYK® 302 (0.05 g) were added. The formulation was then fully aged to produce the primer resin composition.

[0270] Preparation of Primer Composition: A primer formulation was prepared by mixing polymethyl methacrylate (PMMA), solvent, and flow control agent. The 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 for over 17 hours in a glass bottle. BYK® 331 (0.03%) flow additive was added to the above mixture to produce the primer composition.

[0271] A polycarbonate substrate was used as the substrate, and the primer composition was applied to the substrate and dried at 120°C for 30 minutes. Then, the primer composition-applied surface of the substrate was coated with the undercoat resin composition by dip coating to a thickness of 8 µm. Then, the coated surface was dried at 120°C for 60 minutes in a hot air drying oven.

[0272] In the exposure step, the dried base resin composition was exposed to light using a Xe excimer lamp (wavelength 172 nm, illuminance 100 mW / cm ２ ) with an integrated illuminance of 300 mJ / cm ２ This formed the underlayer 120. The member obtained in this manner is designated as Example Member 1.

[0273] [Formation of antifouling layer 130] For example member 1 and comparative example member 1, Optool UD120 (manufactured by Daikin Industries, Ltd.), which contains a fluorine-containing silane compound (a perfluoroalkyl group-containing silane compound), was diluted to 0.5 wt % with fluorine-based solvent HFE7200, and then flow-coated to form an antifouling layer 130. The antifouling member obtained from example member 1 is designated as antifouling member A1.

[0274] [Example 2] The integrated illuminance in the exposure process was 2100 mJ / cm ２ The same treatment as in Example 1 was carried out except for the above, to obtain Example member 2 and antifouling member A2.

[0275] [Example 3] The integrated illuminance in the exposure process was 2100 mJ / cm ２ The same treatment as in Example 1 was carried out except that the drying conditions for UD120 were changed to 25° C. for 164 hours, to obtain Example member 3 and antifouling member A3.

[0276] Example 4 After applying the undercoat resin composition, Ar / O ２ The same treatment as in Example 1 was carried out except that the mixed gas plasma irradiation was carried out at a flow rate of 3000 sccm, an oxygen fraction of 0.1, and an output of 0.5 kW. The members obtained in this manner were designated Example Member 4 and Antifouling Member A4.

[0277] [Comparative Example 1] After applying the base resin composition, the same treatment as in Example 1 was carried out, except that no exposure was performed and no antifouling layer was provided. The member obtained in this manner was designated Comparative Example Member 1.

[0278] Comparative Example 2 The same treatment as in Example 2 was carried out except that no antifouling layer was provided. The member thus obtained was designated as Comparative Example Member 2.

[0279] Comparative Example 3 Except for omitting the exposure step, the same treatment as in Example 1 was carried out, and the members thus obtained were designated Comparative Example Member 3 and Antifouling Member B3.

[0280] Comparative Example 4 The same treatment as in Example 1 was carried out, except that after the base resin composition was applied and dried, silica vapor deposition was carried out without exposure, and UD120 was applied by vapor deposition rather than flow coating. The members obtained in this manner were designated Comparative Example Member 4 and Antifouling Member B4.

[0281] [Evaluation of unevenness] [Surface roughness Rz] Atomic force microscope measurement was used to measure the surface roughness (Rz) of Example Member 1 and Comparative Example Member 1. As a result, the Rz of Example Member 1 was 6.62 nm, and the Rz of Comparative Example Member 1 was 2.07 nm.

[0282] [Evaluation of Antifouling Members] [Pencil Hardness] The pencil hardness of the antifouling members A1 and B1 was measured, and both were found to be HB.

[0283] Here, the antifouling members A1 to A4 and the antifouling members B1 to B4 were evaluated for TT, haze, water contact angle, and wipeability with a marker in the initial state after production, after abrasion test 1, after abrasion test 2, and after a weather resistance test. Details of abrasion test 1 and the various evaluation methods are as follows.

[0284] Abrasion Test 1 was carried out as follows: A 2 x 2 cm piece of steel wool was fixed to a cylindrical weight (cylindrical, d = 4 cm, height = 7 cm) with double-sided adhesive tape. The weight was 500 g / cm ２The steel wool piece used was steel wool type #0000 (fine fiber from Rakso, Lahr, Germany). The weight was moved back and forth across a 10 cm long coated surface of the antifouling member 500 times.

[0285] [Abrasion Test 2] Abrasion Test 2 was a Taber abrasion test, and was performed as follows. Using an abrasion tester (Toyo Seiki, TS type), the abrasion test of the antifouling member was performed under the conditions of abrasion wheel: CS-10F type, load: 500 g, and rotation speed: 1000 cycles. Note that Abrasion Test 2 may be performed in accordance with JIS K 7204.

[0286] [Weather resistance test] Using a Super Xenon Weather Meter Model SX75 (Suga Test Instruments Co., Ltd.), a 7.5 kW water-cooled xenon lamp was irradiated for 5000 hours. The irradiation conditions were a wavelength of 300 nm to 400 nm with an irradiance of 62 W / m ２ The temperature of the black panel of the antifouling member was 55° C., and the distance between the lamp and the surface of the antifouling member was 29 cm.

[0287] [Haze Measurement] The degree of light scattering (haze) on the sample surface was measured using a haze meter (Nippon Denshoku, NDH-4000).

[0288] [Total Light Transmittance (TT)] This was measured together with the haze using a haze meter (Nippon Denshoku, NDH-4000).

[0289] [Contact Angle] A 2 μL droplet of pure water was placed on the surface of the antifouling member, and the contact angle with water was measured at five locations using a contact angle meter (DropMaster 701, automatic contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.), and the average was calculated.

[0290] [Magic marker wipeability] Oil-based ink was applied to the surface of the stain-resistant member using an oil-based ink pen (Zebra Corporation's Maki Extra Fine Black), and after drying, the ink was wiped off with a non-soaked Kimwipe, and the appearance was observed. Those in which the oil-based ink was completely wiped off were rated as OK, and those in which the ink remained were rated as NG.

[0291] The results for the initial state are shown below: As shown in the table, the antifouling members B1 and B2 were unable to exhibit sufficient antifouling performance, and the antifouling members B3 and B4 had worse haze than the antifouling members A1 to A4.

[0292] The results after abrasion test 1 were performed on the initial state are shown below. As shown in the table, the antifouling members A1 to A4 maintained their antifouling properties even after abrasion, whereas the antifouling members B1 to B4 lost their antifouling properties after abrasion and the haze also deteriorated significantly.

[0293] The results of abrasion test 2 performed on the initial state are shown below. As shown in the table, the antifouling members A1 to A4 maintained their antifouling properties even after abrasion, whereas the antifouling members B1 to B4 lost their antifouling properties after abrasion.

[0294] The results after the weather resistance test were performed on the initial state are shown below. As shown in the table, the antifouling properties of the antifouling members A1 to A4 were maintained even after the weather resistance test, whereas the antifouling properties of the antifouling members B1 to B4 were lost after the weather resistance test.

[0295] Although the present invention has been described above using the embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various modifications and improvements can be made to the above embodiments. It is clear from the claims that such modifications and improvements can also be included within the technical scope of the present invention.

[0296] It should be noted that the order of execution of each process, such as operations, procedures, steps, and stages, in the methods shown in the claims, the specification, and the drawings, is not specifically stated as "before," "prior to," etc., and can be realized in any order unless the result of a previous process is used in a later process. Even if the operational flow in the claims, the specification, and the drawings is described using "first," "next," etc. for convenience, it does not mean that it is essential to perform the process in this order.

[0297] 10 Antifouling member 110 Substrate 120 Undercoat layer 130 Antifouling layer

Claims

1. a base forming step of forming a base layer on one surface of the substrate; forming an antifouling layer on the underlayer, the antifouling layer including a perfluoropolyether-containing silane compound; A method for manufacturing an antifouling member comprising:

2. the underlayer has nano-order unevenness, In the antifouling layer forming step, the antifouling layer is formed at least on the concave portions of the concave-convex portions. A method for producing the antifouling member according to claim 1.

3. The base forming step includes: applying a base resin composition to the substrate and drying it; forming irregularities on the dried base resin composition; Including, A method for producing the antifouling member according to claim 2.

4. the undercoat resin composition contains a silicone resin containing a T unit structure and a Q unit structure, The step of forming irregularities on the dried base resin composition includes: pretreating the dried base resin composition to modify the T unit structure into silica; A method for producing the antifouling member according to claim 3.

5. The method for producing an antifouling member according to claim 4, wherein the pretreatment is carried out by exposure to light having a wavelength of 150 to 200 nm.

6. The pretreatment is carried out at an integrated illuminance of 200 to 6000 mJ / cm ２ The method for producing an antifouling member according to claim 5, wherein the exposure is carried out so that the range of

7. The pretreatment is performed using Ar / O ２ The method for producing an antifouling member according to claim 4, wherein the method is carried out by applying mixed gas plasma at an output power range of 0.2 to 1.0 kW.

8. The pretreatment is performed using Ar / O ２ The method for producing an antifouling member according to claim 4, wherein the mixed gas plasma is applied at a flow rate of 2000 to 5000 sccm and an oxygen fraction in the range of 0.03 to 0.

4.

9. The coating in the step of coating the base resin composition on the substrate and drying is carried out so that the coating film thickness becomes 1 to 20 μm. A method for producing the antifouling member according to claim 3.

10. The step of applying the base resin composition to the substrate and drying it is carried out at a temperature of 100 to 150°C for 10 to 120 minutes. A method for producing the antifouling member according to claim 3.

11. The base forming step includes: The method further includes applying a primer composition to the substrate before applying and drying the resin composition for forming a base on the substrate. A method for producing the antifouling member according to claim 3.

12. The substrate is glass or resin. A method for producing the antifouling member according to claim 1.

13. The average pitch width of the convex portions of the unevenness is 5 to 18 nm. A method for producing the antifouling member according to claim 2.

14. The surface roughness (Rz) of the irregularities is 3 to 15 nm. A method for producing the antifouling member according to claim 2.

15. The contact angle when water comes into contact with the one surface side is 105 to 120°. A method for producing the antifouling member according to claim 1.

16. The pencil hardness of the one surface side is HB or higher. A method for producing the antifouling member according to claim 1.

17. The antifouling member is used to cover at least a part of the display area of ​​the display. A method for producing the antifouling member according to any one of claims 1 to 16.

18. The antifouling member is used to cover at least a part of the touch area of ​​the touch panel. A method for producing the antifouling member according to any one of claims 1 to 16.

19. The antifouling member is used to cover at least a part of the surface of the sensor. A method for producing the antifouling member according to any one of claims 1 to 16.

20. A substrate; an underlayer provided on the substrate; an antifouling layer provided on the underlayer; Preparation, ΔHaze on the antifouling layer side before and after the Taber abrasion test is 8 or less, the contact angle of water after a Taber abrasion test on the antifouling layer side is 85° or more; Antifouling material.

21. The underlayer contains a silicone resin. The antifouling member according to claim 20.

22. The silicone resin comprises a Q unit structure and a T unit structure. The antifouling member according to claim 21.