WO2022030399A1

WO2022030399A1 - Laminate and fabric coating composition

Info

Publication number: WO2022030399A1
Application number: PCT/JP2021/028418
Authority: WO
Inventors: 幸広植木
Original assignee: ナガセケムテックス株式会社
Priority date: 2020-08-04
Filing date: 2021-07-30
Publication date: 2022-02-10
Also published as: CN116133843A; TW202214793A

Abstract

Provided are: a laminate that has a functional film having both durability and dust resistance; and a composition for forming the functional film. Moreover, provided are: a fabric coating composition that can exhibit excellent dust resistance against powder dust fouling when applied to a fabric; and a functional fabric that has a functional film composed of a cured product of said fabric coating composition. The present invention pertains to a laminate having an arithmetic average height Sa of 10-50 nm and a minimum autocorrelation length Sal of 300-2,000 nm, and composed of a base material and a functional film having a water contact angle of 70-130º, wherein the functional film contains silicon, oxygen, carbon, and fluorine. Moreover, the present invention pertains to a fabric coating composition containing fluoro group-containing alkoxysilane or a hydrolyzed partial condensate thereof.

Description

Compositions for laminates and fabric coatings

The present invention has a functional film comprising a laminate, a composition for forming a functional film of the laminate, a composition for coating a dough, and a cured product of the composition for coating the dough. Regarding the fabric.

Coating agents are required to have various functions, and are used in various applications such as furniture, interiors, automobiles, housing materials, traffic signs, home appliances, and displays. In recent years, in these applications, there is a demand for sustainable dust resistance that prevents the adhesion of dirt such as dust.

Patent Document 1 describes an invention in which pores are provided inside the film and the surface of the film is provided with an uneven structure to impart antifouling property by a dust adhesion prevention function. However, although it has an uneven structure, it is a hydrophilic film, so it is limited to outdoor applications where a cleaning effect by rainwater can be expected, and its dustproof performance is not sufficient. On the other hand, Patent Document 2 describes an invention in which water- and oil-repellent properties are imparted by the formed surface irregularities to impart antifouling properties regardless of the environment in which they are used, but etching is performed by plasma discharge. Therefore, the surface has a sharp shape, the strength is weak, and the durability is low.

Further, neither of Patent Documents 1 and 2 assumes a fabric (fabric) as a base material, and does not provide a composition capable of exhibiting dust resistance against dust stains when applied to the fabric. rice field.

Japanese Unexamined Patent Publication No. 2017-226764 Japanese Unexamined Patent Publication No. 6-116430

An object of the present invention is to provide a laminate having a functional film having both dust resistance and durability, and a composition for forming the functional film. Further, the present invention provides a functional film comprising a dough coating composition capable of exhibiting excellent dust resistance against dust stains when applied to a dough, and a cured product of the dough coating composition. It is an object of the present invention to provide a functional fabric having.

The present inventor has studied to reduce the adhesive force of dust, and found that a functional film containing silicon, oxygen, carbon, and fluorine has a specific water contact angle and a specific surface surface. We have found that if the unevenness is formed with a specific regularity, the contact area of dust can be reduced and high dust resistance can be maintained for a long period of time, and the present invention has been completed.

That is, the present invention comprises a functional membrane having an arithmetic mean height Sa of 10 to 50 nm, a minimum autocorrelation length Sal of 300 to 2000 nm, and a water contact angle of 70 to 130 °, and a substrate. It relates to a laminate in which the functional film contains silicon, oxygen, carbon, and fluorine.

The functional membrane preferably contains inorganic particles and a cured product of a partially hydrolyzed partial condensate of alkoxysilane.

The base material is preferably a plastic base material, a glass base material, or a metal base material.

It is preferable that the functional membrane has a positive DTA peak at 200 to 600 ° C. in the differential thermal analysis DTA measurement.

The film thickness of the functional film is preferably 1 μm or less.

The present invention also relates to a composition for forming a functional film in the laminated body.

The present invention also relates to a composition containing a partially hydrolyzed condensate of alkoxysilane having a fluoro group and inorganic particles.

Further, it is preferable to contain a hydrolyzed partial condensate of alkoxysilane containing no fluoro group.

The ratio of the number of carbon atoms to the number of silicon atoms in the molecule (C / Si ratio) in the hydrolyzed partial condensate of alkoxysilane containing no fluoro group is preferably 0.1 to 4.

It is preferable that the inorganic particles are inorganic particles having a reactive group.

Further, it is preferable to include an adhesion improver.

It is preferable that the functional film obtained by curing the composition has a positive DTA peak at 200 to 600 ° C. in the differential thermal analysis DTA measurement.

It is preferable that the inorganic particles are inorganic particles having a positive DTA peak at 200 to 600 ° C. in the differential thermal analysis DTA measurement.

Furthermore, the present invention relates to a dustproof coating composition containing the above composition.

Further, the present inventor has found that a composition containing an alkoxysilane having a fluoro group or a partially hydrolyzed partial condensate thereof exhibits excellent dust resistance against dust stains when applied to a dough. Completed the invention.

That is, the present invention relates to a composition for coating a dough, which comprises an alkoxysilane having a fluoro group or a partially hydrolyzed partial condensate thereof.

It is preferable that the dough coating composition further contains an alkoxysilane containing no fluoro group or a partially hydrolyzed condensate thereof.

The ratio of the number of carbon atoms to the number of silicon atoms in the molecule (C / Si ratio) in the alkoxysilane containing no fluoro group or its hydrolyzed partial condensate is preferably 0.1 to 4.

It is preferable that the dough coating composition further contains inorganic particles.

It is preferable that the dough coating composition further contains an adhesion improver.

The dough coating composition is preferably used for dustproofing.

The present invention also relates to a functional fabric having a functional film made of a cured product of the composition on the surface of the fabric.

After sprinkling Kanto Loam (JIS Z 8901, 8 types of test powder 1) on the functional membrane and removing it at an angle of 90 °, the dust adhesion rate, which is the adhesion ratio of residual dust to the entire functional membrane region, is 5. % Or less is preferable.

The water contact angle of the functional membrane is preferably 100 to 140 °.

It is preferable that the material of the fabric is one or more selected from the group consisting of natural fibers, synthetic fibers, regenerated fibers, functional fibers, and metal fibers.

The functional fabric preferably has a primer layer between the functional membrane and the fabric.

The laminate of the present invention has a specific water contact angle in a functional film containing silicon, oxygen, carbon, and fluorine, and has a specific arithmetic mean height Sa and a minimum autocorrelation length Sa1 on the surface. Since it has irregularities, it can maintain high dust resistance for a long period of time. Further, since the composition for coating a dough of the present invention contains an alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof, it can exhibit excellent dust resistance against dust stains when applied to a dough. It can be suitably used as a composition for coating a fabric.

<< Laminated body >>
The laminate of the present invention is composed of a functional film having an arithmetic mean height Sa of 10 to 50 nm, a minimum autocorrelation length Sal of 300 to 2000 nm, and a water contact angle of 70 to 130 °, and a substrate. The functional film is characterized by containing silicon, oxygen, carbon, and fluorine. By setting the water contact angle to 70 to 130 °, it is difficult for dust to adhere, and by providing specific irregularities with specific regularity, the ground contact area can be reduced. In the present invention, due to the combined effect of both, when the laminate is tilted, dust stains roll off due to gravity.

<Base material>
Examples of the material of the base material include plastic, glass, metal, concrete, brick, sandstone, mortar, cement and the like. Among these, plastic, glass and metal are preferable from the viewpoint of versatility. Examples of plastics include polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, and cyclic olefin resin, and polyvinyl chloride. , Vinyl chloride resin such as polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin, polycarbonate (PC) resin, polyamide resin, polyimide resin, acrylic resin, bird Acetylcellulose (TAC) resin and the like can be mentioned. Examples of the metal include stainless steel, iron, copper, steel, special steel, aluminum, aluminum alloy, silver and the like.

<Functional membrane>
The arithmetic mean height Sa of the functional membrane is 10 to 50 nm, preferably 15 to 40 nm. When it is within the above range, the dustproof property is excellent. Here, the arithmetic mean height Sa can be measured in accordance with ISO 25178, which is a standard for surface texture.

The minimum autocorrelation length Sal of the functional membrane is 300 to 2000 nm, preferably 500 to 1500 nm. When it is within the above range, the dustproof property is excellent. Here, the minimum autocorrelation length Sal can be measured in accordance with ISO 25178, which is a standard for surface texture. When Sal is small, the surface shape becomes regular and dense, and when Sal is large, the surface shape becomes irregular and sparse.

The water contact angle of the functional membrane is 70 to 130 °, preferably 90 to 120 °. When it is within the above range, the dustproof property is excellent. Here, the water contact angle can be measured by the sessile drop method.

The film thickness of the functional film is not particularly limited, but is preferably 1 μm or less, more preferably 0.01 to 1 μm, further preferably 0.05 to 0.8 μm or less, and particularly preferably 0.1 to 0.5 μm. Within the above range, sufficient dust resistance and durability can be obtained, which is most suitable for the applications described later.

The total light transmittance of the laminated body is not particularly limited, but is preferably 80% or more, and more preferably 85% or more. Within the above range, it can also be applied to applications that require visibility.

The haze value of the laminate is not particularly limited, but is preferably 4% or less, more preferably 3.5% or less.

The pencil hardness of the functional film is not particularly limited, but HB or higher is preferable, and F or higher is more preferable. If it is HB or higher, it can be applied to a wide range of applications. The upper limit of the pencil hardness is not particularly limited, and 9H or less is preferable. Here, the pencil hardness can be measured according to JIS-K5600-5-4.

The adhesion of the functional film to the substrate is preferably 70/100 or more, more preferably 100/100 or more. Here, the adhesion can be measured according to the checkerboard peeling test of JIS K5600.

After sprinkling Kanto Loam (JIS Z 8901, 8 types of test powder 1) on the functional membrane and removing it at an angle of 90 °, the dust adhesion rate, which is the adhesion ratio of residual dust to the entire area of the functional membrane, is 5% or less is preferable, and 3% or less is more preferable. The method of sprinkling dust on the functional film and the method of removing the adhering dust are not particularly limited, and various methods can be preferably used. For example, after sprinkling a predetermined amount of dust on the functional membrane, the dust may be sifted off by tilting it at 90 ° and lightly dropping it from a height of 3 cm on the table three times and tapping it. Further, the image capture of the functional film is not particularly limited, and a plurality of images may be captured by a method in which dust can be visually recognized in the entire functional film region. The binarization process of the captured image is not particularly limited, and known image processing software or the like may be used.

The functional membrane preferably has a positive DTA peak at 200 ° C. to 600 ° C., and more preferably has a positive DTA peak at 300 ° C. to 600 ° C. in the differential thermal analysis DTA measurement. Here, the DTA can be measured with a differential thermogravimetric meter. The positive DTA peak is a peak generated during the dehydration condensation reaction of silanol groups on the surface of the inorganic particles.

The functional membrane contains silicon, oxygen, carbon, and fluorine. Here, the inclusion of each element can be confirmed by elemental analysis of the raw material components and the functional film. Further, the content of each element can also be calculated from the blending amount of the raw material component, and can also be obtained by elemental analysis of the functional film. The content of these four elements is preferably 20 to 50% by weight of silicon, 30 to 60% by weight of oxygen, 5 to 25% by weight of carbon, and 0.1 to 20% by weight of fluorine. It is more preferable that silicon is 25 to 35% by weight, oxygen is 40 to 55% by weight, carbon is 10 to 20% by weight, and fluorine is 1 to 15% by weight. Further, the functional membrane preferably contains inorganic particles and a cured product of a partially hydrolyzed condensate of alkoxysilane.

The functional film is obtained by applying a composition for forming a functional film to a base material and then curing the composition to obtain a laminate in which the functional film is laminated on the base material. The composition may be applied directly on at least one surface of the base material, or may be applied on the base material after a primer layer or the like is provided on the base material in advance. The primer layer is not particularly limited as long as it can impart coatability to the base material and adhesion between the base material and the functional film, but it is preferable to include a binder. Further, a cross-linking agent, a catalyst, a surfactant, a leveling agent, a pigment, a dye and the like can be appropriately contained.

The composition for forming the functional film preferably contains an alkoxysilane having a fluoro group or a hydrolyzed partial condensate thereof together with the inorganic particles, and preferably contains a hydrolyzed partial condensate of the alkoxysilane having a fluoro group. Is more preferable, and it is even more preferable to contain an alkoxysilane having no fluoro group or a hydrolyzed partial condensate thereof in addition to the alkoxysilane having a fluoro group or a hydrolyzed partial condensate thereof.

The composition can be applied to the substrate by a general method. The curing conditions are not particularly limited, but in the case of heat curing, conditions at 70 to 1000 ° C. for 1 to 130 minutes can be mentioned. When it is cured by exposure, a light irradiation amount of 5 to 2000 mJ / cm ² can be mentioned.

(Inorganic particles)
Inorganic particles are components that form specific irregularities. The inorganic particles are not particularly limited, and examples thereof include metal oxide fine particles, nitrides, composite oxides composed of two or more kinds of metal elements, and compounds in which a metal oxide is doped with a different element. Specific examples of the metal oxide fine particles include zinc oxide (ZrO ₂ ), titanium oxide (TIO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO). , Fe ₃ O ₄ ), Copper Oxide (CuO, Cu ₂ O), Zinc Oxide (ZnO), Yttrium Oxide (Y ₂ O ₃ ), Niobide Oxide (Nb ₂ O ₅ ), Molybdenum Oxide (MoO ₃ ), Indium Oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₅ , Sb ₂ O ₅ ), germanium oxide (GeO ₂ , GeO) and the like can be mentioned. Among these, zirconium oxide (ZrO ₂ ), titanium oxide (TIO ₂ ), and silicon oxide (silica) are preferable from the viewpoint of dust resistance. Further, elemental metals, halides and the like can also be used. Specific examples of the halide include copper fluoride (CuF, CuF ₂ ), copper chloride (CuCl, CuCl ₂ ), copper bromide (CuBr, CuBr ₂ ), copper iodide (CuI), and silver fluoride (Ag). _2F , AgF, AgF _2, AgF ₃ ), silver chloride (AgCl), silver bromide (AgBr), silver iodide (AgI) and the like can be mentioned. Examples of elemental metals include copper, silver, and gold. One kind of inorganic particles may be used alone, or two or more kinds may be used in combination.

The particle size of the inorganic particles is not particularly limited, but is preferably 1 to 1000 nm, more preferably 10 to 100 nm. When it is within the above range, the dustproof property is excellent.

The inorganic particles preferably have a reactive substituent (reactive group), and the reactive substituent may contain an organic reactive substituent. Examples of the organic reactive substituent include an epoxy group, a methacrylic group, an isocyanate group and the like. For example, when the inorganic particles are silica, a large number of hydroxyl groups are present on the surface, so that a reactive substituent can be introduced by reacting the hydroxyl groups with a silane coupling agent or the like.

The inorganic particles preferably have a positive DTA peak at 200 ° C. to 600 ° C., and more preferably have a positive DTA peak at 300 ° C. to 600 ° C. in the differential thermal analysis DTA. Within the above range, the functional film has excellent durability.

The blending amount of the inorganic particles is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, still more preferably 20 to 70% by weight, based on the solid content. Within the above range, dust resistance and durability tend to be excellent.

(Alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof)
Alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof is a component exhibiting water repellency.

The alkoxysilane having a fluoro group is not particularly limited as long as it is a silane compound having a fluoro group and an alkoxy group. As the fluoro group, a fluoroalkyl group, a fluoroaryl group, a perfluoroalkyl group, a perfluoropolyether group and the like are preferable, and a perfluoroalkyl group is more preferable. Further, the number of alkoxy groups is preferably 3 or less. Specific examples thereof include trifluoropropyltrimethoxysilane, perfluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorododecyltrimethoxysilane. Of these, perfluorooctyltriethoxysilane and heptadecafluorodecyltrimethoxysilane are preferable in terms of dust resistance and water repellency.
In addition, one type of alkoxysilane having these fluoro groups may be used alone, or two or more types may be used in combination. Further, as long as it contains at least one type of alkoxysilane having a fluoro group, an alkoxysilane not containing a fluoro group may be used in combination.

Examples of the hydrolyzed partial condensate of the alkoxysilane having a fluoro group include those obtained by hydrolyzing and condensing the alkoxysilane having a fluoro group by an existing method. As the alkoxysilane having a fluoro group, the above-mentioned compound can be used. One of these alkoxysilanes having a fluoro group may be used alone, or two or more of them may be used in combination for hydrolysis partial condensation. Further, as long as it contains at least one type of alkoxysilane having a fluoro group, hydrolysis partial condensation may be carried out in combination with an alkoxysilane not containing a fluoro group. Alkoxysilanes having a fluoro group tend to form micelles in the composition because the alkoxy group is hydrophilic and the fluoro group is hydrophobic. However, when used as a hydrolyzed partial condensate, micelles can be formed. It is suppressed, it is easy to orient the fluoroalkyl group on the film surface, and the durability of the functional film tends to be improved.

The blending amount of the alkoxysilane having a fluoro group or the hydrolyzed partial condensate thereof is not particularly limited, but is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, and 3 to 50% by weight in the solid content. % Is more preferable. Within the above range, a functional film having both dust resistance and durability tends to be formed.

(Alkoxysilane containing no fluoro group or its hydrolyzed partial condensate)
Alkoxysilane containing no fluoro group or a partially hydrolyzed partial condensate thereof is a component that imparts durability (wear resistance, hardness) and suppresses deterioration of dust resistance over time. Further, the alkoxysilane containing no fluoro group or a partially hydrolyzed partial condensate thereof binds firmly to the inorganic particles, suppresses dropping off due to an external stimulus to the functional film, and can maintain a high level of dust resistance. The hydrolyzed partial condensate of an alkoxysilane containing no fluoro group is not limited as long as it is a hydrolyzed partial condensate obtained by subjecting an alkoxysilane containing no fluoro group to a condensation reaction with hydrolysis. Examples thereof include those obtained by subjecting an alkoxysilane represented by (1), which does not contain a fluoro group, to hydrolysis and condensation reaction.
SiR ¹ ₄ (1)
In the general formula (1), R ¹ is a hydrogen, a hydroxyl group, an alkoxy group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, respectively, and one or more R ¹ is an alkoxy group. The alkoxy group, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may each have a substituent.

Of the four R ^1s in the general formula (1), monoalkoxysilane when one R ¹ is an alkoxy group, dialkoxysilane when two R ^1s are alkoxy groups, and three R ^1s are alkoxy groups. When is, it is a trialkoxysilane, and when the four ^R1s are alkoxy groups, it is a tetraalkoxysilane, and any of these may be used. In addition, one of these alkoxysilanes may be used alone, or two or more thereof may be used in combination. When trialkoxysilane or tetraalkoxysilane is contained, a hydrolyzed partial condensate having a branched structure can be obtained, and the hydrolyzed partial condensate having a branched structure has a high film density when cured to form a coating film, and has high strength and moisture resistance. Has excellent heat resistance and heat resistance. By using dialkoxysilane, the molecular weight of the partially hydrolyzed condensate can be adjusted and flexibility can be imparted. By using monoalkoxysilane, the molecular weight of the partially hydrolyzed condensate can be adjusted.

Examples of the alkoxy group include C _1-4 alkoxy groups such as a methoxy group and an ethoxy group.

Examples of the aliphatic hydrocarbon group include C ₁ such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. _-20 Alkyl groups can be mentioned. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group and a xylyl group, and an aralkyl group such as a benzyl group.

Substituents of the aliphatic and aromatic hydrocarbon groups include crosslinkable functional groups such as (meth) acrylic group, (meth) acryloxy group, vinyl group and epoxy group, primary amino group and secondary amino. Examples include a group, a thiol group, a styryl group and the like.

Examples of the alkoxysilane not containing a fluoro group include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methoxytrimethylsilane, and bis ( Triethoxysilyl) methane, bis (trimethoxysilyl) methane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) hexane, bis (trimethoxy) Fat group such as silyl) octane, bis (triethoxysilyl) octane, bis (triethoxysilyl) ethylene, bis (trimethoxysilylmethyl) ethylene, 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane Silane compound having a hydrocarbon group; Silane compound having an aromatic hydrocarbon group such as phenyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane; bis- [3-( Triethoxysilyl) propyl] amine, bis- [3- (trimethoxysilyl) propyl] amine, bis [3- (trimethoxysilyl) propyl] ethylenediamine, N-2- (aminoethyl) -3-aminopropyltrimethoxy Silane compounds having a secondary amino group such as silane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminophenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-aminopropylmethyldimethoxy Silane compounds having a primary amino group such as silane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Silane compound having a (meth) acrylic group such as propylmethyldimethoxysilane; silane compound having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane; β-glycidoxyethyl Trimethoxysilane, β-glycidoxyethyl triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypro Epoxy groups such as pillmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Silane compound having; Silane compound having an isocyanate group such as 3-isocyanatepropyltriethoxysilane; 1,3,5-tris (methyldimethoxysilylpropyl) isocyanurate, 1,3,5-tris (methyldiethoxysilylpropyl) Isocyanurate, 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (triethoxysilylpropyl) isocyanurate, 1,3,5-tris (trimethoxysilylethyl) isocyanurate , 1,3- (di-2-propen-1-yl) -5- (3-triethoxysilylpropyl) isocyanurate, 1- (2-propen-1-yl) -3,5-bis (3-) Triethoxysilylpropyl) isocyanurate, 1,3-bis (3-trimethoxysilylpropyl) isocyanurate, 1-glycidylmethyl-3,5-bis (3-trimethoxysilylpropyl) isocyanurate, 1,3-bis (Glysidylmethyl) -5- (3-trimethoxysilylpropyl) isocyanurate, 1-glycidylmethyl-3- (2-propen-1-yl) -5- (3-triethoxysilylpropyl) isocyanurate, 1, Examples thereof include silane compounds having an isocyanurate group such as 3-dimethyl-5- (3-triethoxysilylpropyl) isocyanurate. Among these, tetraalkoxysilane, a silane compound having an aliphatic hydrocarbon group, and a silane compound having an aromatic hydrocarbon group are preferable from the viewpoint of durability and substrate applicability, and tetramethoxysilane, tetraethoxysilane, and methyl. More preferred are trimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methoxytrimethylsilane, phenyltrimethoxysilane and phenyltriethoxysilane.

In an alkoxysilane containing no fluoro group or a partially hydrolyzed condensate thereof, the ratio of the number of carbon atoms to the number of silicon atoms in the molecule (C / Si ratio) is preferably 0.1 to 4, preferably 0.15 to 3.0. Is more preferable, and 0.2 to 2.0 is even more preferable. Within the above range, the functional film tends to be excellent in dust resistance, durability and substrate applicability. Here, the number of silicon atoms and the number of carbon atoms are the numbers of silicon atoms and carbon atoms contained in one molecule of the hydrolyzate of alkoxysilane as a raw material, respectively. When two or more types of alkoxysilanes containing no fluoro group are used in combination, the ratio can be derived by calculating the total number of carbon atoms and the total number of silicon atoms based on the number of molecules of each compound.

The blending amount of the alkoxysilane containing no fluoro group or the hydrolyzed partial condensate thereof is not particularly limited, but is preferably 1 to 90% by weight, more preferably 5 to 80% by weight, and 10 to 70% by weight in the solid content. Is even more preferable. Within the above range, a functional film having both dust resistance and durability tends to be formed.

The hydrolyzed partial condensate of alkoxysilane having a fluoro group and the hydrolyzed partial condensate of alkoxysilane not containing a fluoro group can be produced, for example, by hydrolyzing partial condensation of alkoxysilane under acidic conditions. Hydrolysis partial condensation is carried out by the formation of hydroxyl groups by hydrolysis of the alkoxy group of alkoxysilane, and the condensation reaction between the formed hydroxyl groups. These reactions can be done in one step. A part of the hydroxyl group obtained by hydrolyzing the alkoxy group may remain in the hydrolyzed partial condensate.

The temperature conditions during the reaction are not particularly limited, but are preferably 25 to 200 ° C, more preferably 30 to 150 ° C, and even more preferably 40 to 120 ° C. The time condition is not particularly limited, but is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours, and even more preferably 0.1 to 36 hours.

In the hydrolysis partial condensation reaction of alkoxysilane, it is preferable to add water having an equivalent number or more of the alkoxy groups of alkoxysilane. The amount of water added is preferably 100 to 500,000 mol, more preferably 500 to 100,000 mol, still more preferably 1,000 to 50,000 mol, based on 100 mol of the alkoxy group of alkoxysilane.

In the hydrolysis partial condensation reaction, a catalyst may be used depending on the reactivity of the alkoxysilane used. Examples of the catalyst include acidic catalysts, and specific examples thereof include organics such as formic acid, acetic acid, glacial acetic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and polystyrenesulfonic acid. Examples thereof include acid, hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, boric acid, aluminum chloride, aluminum halide such as aluminum bromide, inorganic acids such as aluminum nitrate, acidic silica gel and acidic silica sol. Among these, a volatile acid in which the catalyst does not remain in the film after film formation is preferable, an organic acid having a boiling point of 200 ° C. or lower is more preferable, and formic acid and acetic acid are further preferable. By using an acidic catalyst, the effects of promoting the hydrolyzed partial condensation reaction and stabilizing the hydrolyzed partial condensate can be obtained.

The pH at the time of the hydrolysis partial condensation reaction is preferably 1 to 7, more preferably 2 to 7, and even more preferably 3 to 4. Within this range, a hydrolyzed partial condensate having high stability over time can be obtained, and when blended in the composition, the dispersibility of the hydrolyzed condensate in the composition and the liquid stability of the composition are ensured. To.

The amount of the catalyst added is preferably 0.0001 to 20 parts by weight, more preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of alkoxysilane. Within this range, the hydrolysis partial condensation reaction proceeds rapidly and can be easily removed by heating.

The hydrolysis partial condensation reaction may be carried out without using a solvent, but a solvent may be used if necessary. Examples of such a solvent include alcohols such as methanol, ethanol, propanol and butanol; glycols such as ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol and propylene glycol; glycerin, 1, 2 , 4-Butantriol, 1,2,3-Butantriol and other triols; Ethers such as tetrahydrofuran (THF); Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, Ethylene glycol dimethyl ether, Diethylene glycol monomethyl Glycol ethers such as ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate (PGMEA), 3-methoxybutyl-1- Examples thereof include alkylene glycol monoalkyl ether acetates such as acetate; aromatic hydrocarbons such as toluene and xylene; and ketones such as methyl ethyl ketone, methyl isobutyl ketone (MIBK), methyl amyl ketone and cyclohexanone. Among these, water-soluble organic solvents such as alcohols, glycols, and triols are preferable, and alcohols and glycols are particularly preferable, because a partially hydrolyzed condensate can be efficiently formed. One of these solvents may be used alone, or two or more of them may be mixed and used. Further, as the solvent, the above-mentioned mixed solution with water may be used, and when used as a mixed solution, a mixed solution of water and a water-soluble organic solvent is preferable, and a mixed solution of water and alcohol is more preferable.

The amount of the solvent to be blended is preferably 1 to 50,000 parts by weight, more preferably 10 to 5,000 parts by weight, still more preferably 20 to 1,000 parts by weight, based on 100 parts by weight of alkoxysilane.

When the hydrolyzed partial condensate does not precipitate in water or a water-soluble organic solvent, it can be determined that the hydrolyzed partial condensate has been obtained. If the condensation reaction proceeds excessively, the water solubility decreases, and gelation or suspension occurs in water or a water-soluble organic solvent.

(Adhesion improver)
The composition for forming the functional film preferably contains an adhesion improving agent from the viewpoint of improving the adhesion between the functional film and the substrate.

The adhesiveness improving agent is not particularly limited, but for example, silane coupling agents such as epoxysilanes, aminosilanes, acrylicsilanes, vinylsilanes, and styrylsilanes, titanate coupling agents, aluminum coupling agents, and acryloyl. Examples thereof include isocyanates such as isocyanates and blocked isocyanates. These may be used alone or in combination of two or more. The blending amount of the adhesion improver is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight, based on the solid content. Within the above range, the adhesion between the functional film and the substrate tends to be excellent.

The composition for forming the functional film may optionally contain other components. Other components include, for example, curable resins such as epoxy resins, acrylates and melamines, thermoplastic resins such as acrylic resins and polyester resins, urethane resins and polyolefin resins, conductive polymers, carbon materials, polymerization initiators and leveling. Examples thereof include agents, surfactants, photosensitizers, defoaming agents, neutralizers, antioxidants, mold release agents, ultraviolet absorbers, thickeners, solvents and the like.

The leveling agent is not particularly limited, and for example, polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyether ester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, and polyester-modified acrylic group-containing polydimethyl. Siloxane-based compounds such as siloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-based compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethylene ethanol; poly Polyether-based compounds such as oxyethylene alkylphenyl ether, propylene oxide polymer, ethylene oxide polymer; carboxylic acids such as palm oil fatty acid amine salt and gum rosin; castor oil sulfate esters, phosphoric acid esters, alkyl ether sulfates, sorbitan fatty acids Ester-based compounds such as esters, sulfonic acid esters, and succinic acid esters; Sulfate compounds such as alkylaryl sulfonic acid amine salts and dioctyl sulfosuccinate; Phosphate compounds such as sodium lauryl phosphate; Palm oil fatty acid ethanol amide and the like. Amid compounds; acrylic compounds and the like can be mentioned.

The blending amount of the leveling agent is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight, still more preferably 0.05 to 0.5% by weight, based on the solid content of the composition.

The solvent is not particularly limited, but for example, water; alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether (methyl cellosolve), and the like. Ethylene glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether (ethyl cellosolve); ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as dibutyl ether and diethylene glycol ethylmethyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether; propylene glycol monomethyl ether Alkylene glycol monoalkyls such as ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxybutyl-1-acetate Ether acetates; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, 2- Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, dimethyl succinate, diethyl succinate, hydrangea Examples thereof include esters such as diethyl pinate, diethyl malonate, and dibutyl oxalate. Among these, ethylene glycol ethers, alkylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferable, and ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), and the like. More preferred are diethylene glycol monoethyl ether acetate and methyl amylketone. These solvents may be used alone or in combination of two or more.

The solid content of the composition is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 3 to 5% by weight. Within the above range, the liquid stability tends to improve.

Since the laminate of the present invention has a functional film having high durability and dust resistance on a base material, automobiles, housing materials, furniture, interiors, home appliances, traffic signs, medical appliances, signboards, shutters, etc. It can be suitably applied to applications where durability and dust resistance are required.

<< Composition >>
The composition of the present invention is characterized by containing a hydrolyzed partial condensate of alkoxysilane having a fluoro group and inorganic particles. Further, it is preferable to contain an alkoxysilane containing no fluoro group or a partially hydrolyzed condensate thereof. Alkoxysilane having a fluoro group or a hydrolyzed partial condensate thereof, inorganic particles, an alkoxysilane containing no fluoro group or a hydrolyzed partial condensate thereof are as described above. The composition of the present invention is preferably acidic. Since the composition of the present invention can maintain high dust resistance for a long period of time, it can be suitably applied for dustproof coating.

<< Composition for fabric coating >>
The dough coating composition of the present invention contains an alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof. The dough coating composition of the present invention exhibits excellent dust resistance against dust stains when applied to a dough.

(Alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof)
Alkoxysilane having a fluoro group or a partially hydrolyzed partial condensate thereof is a component that exhibits dust resistance and water repellency against dust stains when the composition for coating the dough is applied to the dough. The dough coating composition preferably contains a hydrolyzed partial condensate of alkoxysilane having a fluoro group.

Specific examples of the alkoxysilane having a fluoro group and a method for producing a hydrolyzed partial condensate of the alkoxysilane having a fluoro group (hydrolyzed partial condensation reaction) are the same as those of the laminate of the present invention.

The blending amount of the alkoxysilane having a fluoro group or the hydrolyzed partial condensate thereof is not particularly limited, but is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, and 3 to 50% by weight in the solid content. % Is more preferable, and 7 to 15% by weight is particularly preferable. The blending amount in the dough coating composition containing the solvent is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, still more preferably 0.25 to 3% by weight. Within the above range, a functional film having both dust resistance and durability against dust stains tends to be formed.

(Alkoxysilane containing no fluoro group or its hydrolyzed partial condensate)
The dough coating composition of the present invention preferably further contains an alkoxysilane containing no fluoro group or a partially hydrolyzed condensate thereof. Alkoxysilane containing no fluoro group or a partially hydrolyzed partial condensate thereof is a component that imparts durability (wear resistance, hardness), and suppresses deterioration of dust resistance against dust stains over time.
Specific examples of an alkoxysilane containing no fluoro group or a partially hydrolyzed partial condensate thereof, C / Si ratio, blending amount, preparation method (including reaction conditions for the partially hydrolyzed condensation reaction, catalyst used for the reaction, solvent, etc.), etc. Is the same as the laminated body of the present invention.

(Inorganic particles)
The dough coating composition of the present invention preferably further contains inorganic particles. By containing the inorganic particles, unevenness can be formed on the surface of the functional film, the contact area of dust stains can be reduced, and the functional film having more excellent dust resistance can be obtained. Specific examples of the inorganic particles, particle size, reactive substituent, DTA peak, blending amount, etc. are the same as those of the laminate of the present invention.

The dough coating composition of the present invention may optionally contain other components. Other components include, for example, an adhesion improver, a curable resin such as epoxy resin, acrylate, and melamine, a thermoplastic resin such as acrylic resin, polyester resin, urethane resin, and polyolefin resin, a conductive polymer, and a carbon material. Examples thereof include polymerization initiators, leveling agents, surfactants, photosensitizers, defoaming agents, neutralizers, antioxidants, mold release agents, ultraviolet absorbers, thickeners, solvents and the like. The dough coating composition of the present invention preferably contains an adhesion improver from the viewpoint of improving the adhesion between the dough and the functional film. Specific examples of the adhesion improver, leveling agent, solvent, blending amount, etc. are the same as those of the laminate of the present invention.

The solid content of the dough coating composition of the present invention is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 3 to 5% by weight. Within the above range, the liquid stability tends to improve.

<< Functional fabric >>
Since the functional fabric of the present invention has a fabric and a functional film made of a cured product of the composition for coating the fabric of the present invention, it exhibits excellent dust resistance against dust stains.

<Dough>
The form of the fabric is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, meshes, and knitted fabrics. The material of the fabric is not particularly limited, and examples thereof include natural fiber, synthetic fiber, regenerated fiber, functional fiber, metal fiber, carbon fiber, and glass fiber. Among these, from the viewpoint of practicality, one or more selected from the group consisting of natural fibers, synthetic fibers, regenerated fibers, functional fibers, and metal fibers is preferable. Examples of natural fibers include cotton, linen, silk and wool. Examples of synthetic fibers include polyester, nylon, acrylic, polyurethane, and polyamide. Examples of the recycled fiber include rayon and cupra. Examples of the functional fiber include fibers having functions such as ultraviolet ray shielding, heat storage and heat retention, moisture absorption, water absorption / sweat absorption, water repellency, waterproofing, flameproofing, conductivity, and antibacterial deodorization. Examples of the metal fiber include those obtained by depositing a metal such as aluminum on a synthetic fiber or the like, in addition to steel, stainless steel, copper, aluminum, gold or silver. The material of the dough may be a single material or a combination of two or more kinds.

<Functional membrane>
The functional film comprises a cured product of the dough coating composition of the present invention.

The functional film is obtained by applying the dough coating composition to the dough, or impregnating the dough coating composition with the dough, and then curing the dough coating composition. When the composition for coating the dough is applied, it may be applied directly on at least one surface of the dough, or it may be transferred, or after a primer layer or the like is previously provided on the base material, the composition may be applied. It may be applied on top. The primer layer is not particularly limited as long as it can impart coatability to the fabric and adhesion between the fabric and the functional film. The primer layer preferably contains a binder, and examples thereof include thermoplastic resins such as polyurethane resin, polypropylene resin, acrylic resin, polyester resin, and polyvinyl chloride resin. Further, a cross-linking agent, a catalyst, a surfactant, a leveling agent, a pigment, a dye and the like can be appropriately contained. The functional fabric of the present invention has a primer layer between the functional membrane and the fabric from the viewpoint of waterproofness, applicability of the composition for coating the fabric to the fabric, and adhesion between the functional film and the fabric. Is preferable.

The application of the dough coating composition to the dough and the impregnation of the dough into the dough coating composition can be performed by a general method. The curing conditions are not particularly limited, but in the case of heat curing, conditions at 70 to 1000 ° C. for 0.5 to 130 minutes can be mentioned. When it is cured by exposure, a light irradiation amount of 5 to 2000 mJ / cm ² can be mentioned.

The water contact angle of the functional membrane is preferably 100 to 140 °, more preferably 100 to 135 °. When it is within the above range, it is excellent in dust resistance against dust stains. Here, the water contact angle can be measured by the sessile drop method.

After sprinkling Kanto Loam (JIS Z 8901, 8 types of test powder 1) on the functional membrane and removing it at an angle of 90 °, the dust adhesion rate, which is the adhesion ratio of residual dust to the entire functional membrane region, is 5% or less is preferable, and 3% or less is more preferable.

The method of sprinkling dust on the functional film and the method of removing the adhering dust are not particularly limited, and various methods can be preferably used. For example, after sprinkling a predetermined amount of dust on the functional membrane, the dust may be sifted off by tilting it at 90 ° and lightly dropping it from a height of 3 cm on the table three times and tapping it. Further, the image capture of the functional film is not particularly limited, and a plurality of images may be captured by a method in which dust can be visually recognized in the entire functional film region. The binarization process of the captured image is not particularly limited, and known image processing software or the like may be used.

Since the functional fabric of the present invention has a fabric and a functional film made of a cured product of the fabric coating composition of the present invention, it has excellent dust resistance against dust stains, and tents such as awning tents, footwear, and bags. , Leather products, work clothes, protective clothing, outdoor wear, body covers, sleeping bags, leisure seats, blinds, curtains, carpets, automobiles and trains, ships, aircraft, strollers and other transportation equipment seats, ceiling materials, wall materials, etc. It can be suitably used for interior materials of buildings of the above, or cloth products such as outer materials such as beds and sofas.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. Hereinafter, "part" or "%" means "part by weight" or "% by weight", respectively, unless otherwise specified.

Hereinafter, various chemicals used in Examples and Comparative Examples will be collectively described.
(1) Alkoxysilane Tetraethoxysilane (TEOS) (manufactured by Tama Chemical Industry Co., Ltd.)
Methyltriethoxysilane (MTES) (manufactured by Toray Dow Co., Ltd., OFS-6383)
Phenyltriethoxysilane (PTES) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Heptadecafluorodecyltrimethoxysilane (HDFDTMOS) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) Inorganic particles Inorganic particles 1 (manufactured by Nissan Chemical Industries, Ltd., ST-O, particle size: 12 nm, reactive group: silanol group, DTA peak 600 ° C or higher)
Inorganic particles 2 (manufactured in Synthesis Example 7, silica dispersion, particle size: 100 nm, reactive group: silanol group, DTA peak: 340 ° C.)
Inorganic particles 3 (manufactured in Synthesis Example 8)
Inorganic particles 4 (manufactured by Nissan Chemical Industries, Ltd., Snowtex (registered trademark) ST-OL, particle diameter: 45 nm)
(3) Adhesion improver blocked isocyanate (manufactured by Asahi Kasei Chemicals Co., Ltd., WM44-L70G)
(4) Solvent ethanol (AP-7) (manufactured by Japan Alcohol Trading Co., Ltd.)
Pure water (PW)
(5) Base plastic film (manufactured by Toray Industries, Inc., Lumirror)
Glass white board (manufactured by Taiyu Equipment Co., Ltd.)
Metal aluminum plate (manufactured by Taiyu Equipment Co., Ltd., A-1050P)
(6) Fabric Fabric 1 (Made by Color Dyeing Co., Ltd., Polyester Taffeta (Polyester))
Fabric 2 (Made by Teijin Frontier Co., Ltd., Chagall (polyester))

(Synthesis Examples 1 to 5)
At room temperature, water, acetic acid, ethanol, TEOS, MTES, and PTES are charged in a 500 mL separable flask at the weight ratios shown in Table 1, heated to 60 ° C., aged for 36 hours, and fluorogroup-free alkoxy. A partially hydrolyzed condensate of silane was obtained. The amount of acetic acid blended was such that the pH was 3 to 4, the blending amount of water and ethanol was such that the weight ratio of water and ethanol was 50:50, and the solid content concentration of the reaction solution was 15% by weight. Table 1 shows the ratio (C / Si ratio) of the number of carbon atoms to the number of silicon atoms in the molecule in the obtained hydrolyzed partial condensate of alkoxysilane containing no fluoro group.

(Synthesis Example 6)
In addition to using heptadecafluorodecyltrimethoxysilane (HDFDTMOS) instead of TEOS, MTES, and PTES, a hydrolyzed partial condensate of alkoxysilane having a fluoro group was synthesized by the above-mentioned method.

(Synthesis Example 7)
35 mL of water, 10 mL of 28 wt% ammonia water and 120 mL of ethanol were charged in a 500 mL separable flask, the temperature was raised to 45 ° C., a mixture of 15 g of TEOS and 20 mL of ethanol was added dropwise over 30 minutes, and the mixture was stirred for 20 minutes. Next, it was distilled off under reduced pressure to remove ammonia to obtain a silica sol solution. Inorganic particles 2 were obtained by adding 1 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Co., Ltd., OFS-6040) to this silica sol solution and stirring for 24 hours. The particle size was measured by a dynamic light scattering method using a Microtrac Nanotrac Wave UT151 manufactured by Microtrac Bell Co., Ltd. The DTA peak was measured by the method described above (particle size: 100 nm, reactive group: silanol group, DTA peak: 340 ° C.).

(Synthesis Example 8)
35 mL of water, 10 mL of 28 wt% ammonia water and 120 mL of ethanol were charged in a 500 mL separable flask, the temperature was raised to 40 ° C., a mixture of 15 g of TEOS and 20 mL of ethanol was added dropwise over 30 minutes, and the mixture was stirred for 20 minutes. Next, it was distilled off under reduced pressure to remove ammonia to obtain a silica sol solution. Inorganic particles 3 were obtained by adding 1 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Co., Ltd., OFS-6040) to this silica sol solution and stirring for 24 hours. The particle size was measured by a dynamic light scattering method using a Microtrac Nanotrac Wave UT151 manufactured by Microtrac Bell Co., Ltd. The DTA peak was measured by the method described above (particle size: 130 nm, reactive group: silanol group, DTA peak: 330 ° C.).

<< Laminated body >>
(Examples 1 to 21 and Comparative Examples 1 to 4)
Along with the partially hydrolyzed partial condensate of alkoxysilane prepared in the synthesis example, each component such as inorganic particles is blended at the solid content ratio shown in Table 1 and prepared in a solution of water: ethanol = 30:70 (weight ratio). , A resin composition was prepared by diluting to the solid content shown in Tables 2 to 4. In addition, these compositions had a pH of 3-4. This composition was applied on the substrate shown in Table 2 by a bar coater. It was cured at the temperature and time shown in Tables 2 to 4 to obtain a laminated body. Each physical characteristic of the functional membrane was evaluated. The results are shown in Tables 2-4.

The laminate prepared in the examples was evaluated by the following method.
<Film thickness>
The film thickness was measured with a stylus type surface shape measuring instrument (DEKTAK, manufactured by ULVAC, Inc.).

<Arithmetic mean height (Sa) and minimum autocorrelation length (Sal)>
It was measured with a shape analysis laser microscope (manufactured by KEYENCE CORPORATION, VK-X1000) in accordance with ISO25178.

<Transmittance (Tt)>
The measurement was performed using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd.

<Haze>
The measurement was performed using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd.

<Water contact angle>
The measurement was performed using DM-501Hi manufactured by Kyowa Surface Chemistry Co., Ltd. in accordance with the sessile drop method.

<Adhesion rate>
The laminated body is installed with the functional membrane facing up so that it fits completely within an area of 10 cm x 10 cm, and 1 g of Kanto loam (JIS Z 8901, 8 types of test powder 1) functions for the entire area. Sprinkled on the sex membrane (the amount of test dust used per cm ² of the functional membrane area is 10 mg). The functional fabric was tilted at 90 ° and lightly dropped from a height of 3 cm on the table three times and tapped (tapped) to remove dust, and then a photograph was taken. The photograph taken was binarized with image software, and the adhesion ratio of residual dust to the entire functional membrane area was calculated and used as the adhesion ratio.

<Pencil hardness>
The measurement was performed using a pencil scratch hardness tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. according to the test method of JIS-K5600-5-4.

<Adhesion>
The adhesion between the base material and the coating film was measured by a grid peeling test of JIS K5600.

<Scratch resistance>
The scratch resistance test of the functional film was performed with a Gakushin dyeing friction fastness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., flat type), and the water contact angle and adhesion rate after the test were measured. A non-woven fabric (Bencot, manufactured by Asahi Kasei Corporation) was attached to the friction element of the Gakushin-dyeing friction fastness tester, and the test was conducted by rubbing 10 times while applying a load of 500 g. The water contact angle and the adhesion rate were measured by the above-mentioned method.

<DTA measurement>
Differential thermal analysis DTA measurement was performed using a differential thermal thermogravimetric meter (TG / DTA6200, manufactured by Seiko Instruments). The measurement conditions were an air atmosphere, a heating rate of 10 ° C./min, and a temperature range of 40 ° C. to 600 ° C. For the DTA measurement of the functional membranes of Examples and Comparative Examples, the functional membranes were scraped off with a spatula or the like, and the obtained powder was used for the measurement. Regarding the DTA measurement of the inorganic particles, the particles were dried in a vacuum drier and then subjected to the measurement.

<< Composition for fabric coating >>
(Examples 22 to 36 and Comparative Examples 5 to 8)
Along with the partially hydrolyzed partial condensate of alkoxysilane prepared in Synthesis Examples 1 to 6, each component such as inorganic particles was blended at the solid content ratio shown in Table 5, and water: ethanol = 30:70 (weight ratio). A composition for dough coating was prepared by diluting with a solution to the solid content shown in Table 5. These dough coating compositions had a pH of 3-4.

In Examples 22 to 36 and Comparative Example 7, the obtained dough coating composition was applied onto the dough shown in Table 5 by a bar coater or a dip, and heated at 150 ° C. for 3 minutes to be cured, and functionalized. I got the dough. In Examples 24 and Comparative Examples 6 and 8, an acrylic resin (Nikazol FX-3750, Tg: −45 ° C., manufactured by Nippon Carbide Industry Co., Ltd., manufactured by Nippon Carbide Industry Co., Ltd.) was applied onto the fabrics shown in Table 5 by a bar coater. After that, the primer layer was formed by heating and drying at 150 ° C. for 3 minutes. In Comparative Example 8, a fluororesin (AG-E082, manufactured by Asahi Glass Co., Ltd.) was further applied onto the primer layer by a bar coater, and dried by heating at 150 ° C. for 3 minutes.

The functional dough produced in the examples was evaluated by the following method. In Comparative Examples 5, 6 and 8, since the functional film was not formed, Comparative Example 5 had the physical characteristics of the dough itself, Comparative Example 6 had the physical properties of the primer layer, and Comparative Example 8 was the fluororesin. Each physical property of the layer was evaluated. The results are shown in Table 5.

<Water contact angle, DTA measurement>
The measurement was carried out in the same manner as in Examples 1 to 21 (laminated body) described above.

<Dust adhesion rate>
It was measured by the same method as the <adhesion rate> in Examples 1 to 21 (laminated body) described above.

Claims

A laminate consisting of a functional membrane having an arithmetic mean height Sa of 10 to 50 nm, a minimum autocorrelation length Sal of 300 to 2000 nm, and a water contact angle of 70 to 130 °, and a substrate.
A laminate in which the functional film contains silicon, oxygen, carbon, and fluorine.
The laminate according to claim 1, wherein the functional film contains inorganic particles and a cured product of a partially hydrolyzed partial condensate of alkoxysilane.
The laminate according to claim 1 or 2, wherein the base material is a plastic base material, a glass base material, or a metal base material.
The laminate according to any one of claims 1 to 3, wherein the functional film has a positive DTA peak at 200 to 600 ° C. in differential thermal analysis DTA measurement.
The laminate according to any one of claims 1 to 4, wherein the functional film has a film thickness of 1 μm or less.
A composition for forming a functional film in the laminate according to any one of claims 1 to 5.
A composition containing a partially hydrolyzed condensate of alkoxysilane having a fluoro group and inorganic particles.
The composition according to claim 7, further comprising a hydrolyzed partial condensate of alkoxysilane containing no fluoro group.
The composition according to claim 8, wherein the ratio (C / Si ratio) of the number of carbon atoms to the number of silicon atoms in the molecule in the hydrolyzed partial condensate of alkoxysilane containing no fluoro group is 0.1 to 4. ..
The composition according to any one of claims 7 to 9, wherein the inorganic particles are inorganic particles having a reactive group.
The composition according to any one of claims 7 to 10, further comprising an adhesion improver.
The composition according to any one of claims 6 to 11, wherein the functional film obtained by curing the composition has a positive DTA peak at 200 to 600 ° C. in differential thermal analysis DTA measurement. thing.
The composition according to any one of claims 6 to 12, wherein the inorganic particles are inorganic particles having a positive DTA peak at 200 to 600 ° C. in differential thermal analysis DTA measurement.
A composition for dustproof coating containing the composition according to any one of claims 6 to 13.
A composition for dough coating, which comprises an alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof.
The dough coating composition according to claim 15, further comprising an alkoxysilane containing no fluoro group or a partially hydrolyzed partial condensate thereof.
The dough according to claim 16, wherein the ratio of the number of carbon atoms to the number of silicon atoms in the molecule (C / Si ratio) in the alkoxysilane containing no fluoro group or its hydrolyzed partial condensate is 0.1 to 4. Composition for coating.
The dough coating composition according to any one of claims 15 to 17, further comprising inorganic particles.
The dough coating composition according to claim 18, wherein the inorganic particles are inorganic particles having a reactive group.
The dough coating composition according to any one of claims 15 to 19, further comprising an adhesion improver.
The dough coating composition according to any one of claims 15 to 20, which is used for dustproofing.
A functional dough having a functional film made of a cured product of the dough coating composition according to any one of claims 15 to 21 on the surface of the dough.
After sprinkling Kanto Loam (JIS Z 8901, 8 types of test powder 1) on a functional membrane and removing it at an angle of 90 °, the dust adhesion rate, which is the ratio of residual dust to the entire area, is 5% or less. The functional fabric according to claim 22.
The functional fabric according to claim 22 or 23, wherein the functional membrane has a water contact angle of 100 to 140 °.
The functional fabric according to any one of claims 22 to 24, wherein the material of the fabric is one or more selected from the group consisting of natural fibers, synthetic fibers, regenerated fibers, functional fibers, and metal fibers. ..
The functional fabric according to any one of claims 22 to 25, which has a primer layer between the functional membrane and the fabric.