JP7267343B2 - laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate and a composition for forming a functional film of the laminate.

Coating agents are required to have various functions and are used in various applications such as furniture, interiors, automobiles, housing construction materials, traffic signs, home electric appliances, and displays. In recent years, in these applications, there has been a demand for durable dust resistance to prevent adhesion of dirt such as dust.

Patent Literature 1 describes an invention in which pores are provided inside the film and an uneven structure is provided on the film surface to impart antifouling properties due to the function of preventing adhesion of dust. However, although it has an uneven structure, since it is a hydrophilic film, it is limited to outdoor applications where a washing effect with rainwater can be expected, and the dustproof performance is not sufficient. On the other hand, in Patent Document 2, by imparting water and oil repellency to the surface unevenness formed, it is possible to impart antifouling properties regardless of the environment in which it is used. It has a sharp shape and is weak in strength and low in durability.

JP 2017-226764 A JP-A-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.

The present inventors have studied how to reduce the adhesion of dust, and found that a functional film containing silicon, oxygen, carbon, and fluorine has a specific water contact angle and a specific water contact angle on the surface. The inventors 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 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 present invention relates to a laminate in which the functional film contains silicon, oxygen, carbon and fluorine.

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

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

The functional film preferably has a positive DTA peak at 200 to 600° C. in differential thermal analysis DTA measurement.

It is preferable that the film thickness of the functional film is 1 μm or less.

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

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

Furthermore, it preferably contains a hydrolyzed partial condensate of an 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 0.1-4.

The inorganic particles are preferably inorganic particles having a reactive group.

Furthermore, it is preferable that an adhesion improver is included.

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

The inorganic particles are preferably inorganic particles having a positive DTA peak at 200 to 600° C. in differential thermal analysis DTA measurement.

Furthermore, the present invention relates to a dustproof coating composition comprising said composition.

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 minimum autocorrelation length Sa1 on the surface. Since it has unevenness, it can maintain high dust resistance for a long time.

<<Laminate>>
The laminate of the present invention comprises 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 wherein the functional film contains silicon, oxygen, carbon and fluorine. By setting the water contact angle to 70 to 130°, it becomes difficult for dust to adhere, and by providing specific irregularities with specific regularity, the contact area can be reduced. In the present invention, due to the combined effect of both, when the laminate is tilted, dust dirt rolls off due to gravity.

<Base material>
Materials for the substrate include plastic, glass, metal, concrete, brick, sandstone, mortar, and cement. Among these, plastic, glass and metal are preferred from the viewpoint of versatility. Plastics include polyethylene terephthalate (PET), polyethylene naphthalate, polyester resins such as modified polyester, polyethylene (PE) resins, polypropylene (PP) resins, polystyrene resins, polyolefin resins such as cyclic olefin resins, and polyvinyl chloride. , vinyl resins 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, tri Acetyl cellulose (TAC) resin etc. are mentioned. Examples of metals include stainless steel, iron, copper, steel, special steel, aluminum, aluminum alloys, and silver.

<Functional film>
The arithmetic mean height Sa of the functional film is 10-50 nm, preferably 15-40 nm. Within the above range, the dust resistance is excellent. Here, the arithmetic mean height Sa can be measured according to ISO25178, which is a standard for surface properties.

The minimum autocorrelation length Sal of the functional film is 300-2000 nm, preferably 500-1500 nm. Within the above range, the dust resistance is excellent. Here, the minimum autocorrelation length Sal can be measured according to ISO25178, which is a standard for surface texture. When Sal is small, the surface shape becomes regular and dense, and conversely, when it is large, the surface shape becomes irregular and sparse.

The water contact angle of the functional film is 70-130°, preferably 90-120°. Within the above range, the dust resistance is excellent. Here, the water contact angle can be measured by the liquid method.

Although the film thickness of the functional film is not particularly limited, it is preferably 1 μm or less, more preferably 0.01 to 1 μm, even more 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 optimal for the uses described later.

Although the total light transmittance of the laminate is not particularly limited, it is preferably 80% or more, more preferably 85% or more. When it is within the above range, it can be applied to applications where visibility is required.

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

The pencil hardness of the functional film is not particularly limited, but is preferably HB or higher, more preferably F or higher. If it is HB or more, it can be applied to a wide range of uses. 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 cross-cut peeling test of JIS K5600.

The adhesion rate of dust to the functional film is preferably 5% or less, more preferably 3% or less. Here, the adhesion rate of dust can be measured by the method described in Examples.

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

Functional films contain silicon, oxygen, carbon, and fluorine. Here, the inclusion of each element can be confirmed by elemental analysis of raw material components and the functional film. Also, the content of each element can be calculated from the blending amount of the raw material components, and can also be determined 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. More preferably, silicon is 25-35% by weight, oxygen is 40-55% by weight, carbon is 10-20% by weight, and fluorine is 1-15% by weight. Moreover, the functional film preferably contains inorganic particles and a cured product of a hydrolyzed partial condensate of alkoxysilane.

A functional film is obtained by applying a composition for forming a functional film to a substrate and then curing the composition to obtain a laminate in which the functional film is laminated on the substrate. The composition may be applied directly onto at least one surface of the substrate, or may be applied onto the substrate after a primer layer or the like has been provided on the substrate 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 preferably contains a binder. Moreover, a cross-linking agent, a catalyst, a surfactant, a leveling agent, a pigment, a dye, and the like can be included as appropriate.

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 in addition to the alkoxysilane having a fluoro group or its hydrolyzed partial condensate, it is even more preferable to contain an alkoxysilane containing no fluoro group or its hydrolyzed partial condensate.

Application of the composition to the substrate can be performed by a general method. Curing conditions are not particularly limited, but in the case of heat curing, conditions include 70 to 1000° C. for 1 to 130 minutes. In the case of curing 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 unevenness. Although the inorganic particles are not particularly limited, examples thereof include metal oxide fine particles, nitrides, composite oxides composed of two or more metal elements, and compounds in which metal oxides are doped with different elements. Specific examples of metal oxide fine particles include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO , _Fe3O4 ), copper oxides ₍ CuO, _Cu2O ), zinc oxide (ZnO), yttrium oxide ( _Y2O3 ), niobium oxide ( _Nb2O5 ), molybdenum oxide ( _{MoO3 )} , _indium oxide ( _{In2O3 , In2O} ), tin _oxide ( _SnO2 ), _tantalum oxide (Ta2O5), tungsten oxide ( _{WO3 , W2O5} ), lead oxide (PbO, _PbO2 ), 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. Among these, zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), and silicon oxide (silica) are preferable from the viewpoint of dust resistance. One type of inorganic particles may be used alone, or two or more types may be used in combination.

The particle diameter of the inorganic particles is not particularly limited, but is preferably 1 to 1000 nm, more preferably 10 to 100 nm. Within the above range, the dust resistance is excellent.

The inorganic particles preferably have reactive substituents, and the reactive substituents may include organic reactive substituents. Examples of organic reactive substituents include epoxy groups, methacryl groups, isocyanate groups, and the like. For reactive substituents, for example, when the inorganic particles are silica, since there are many hydroxyl groups on the surface, the reactive substituents are introduced by reacting the hydroxyl groups with a silane coupling agent or the like. be able to.

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

The amount of the inorganic particles is preferably 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, even more preferably 20 to 70 parts by weight, based on 100 parts by weight of the solid content. Within the above range, the dust resistance and durability tend to be excellent.

(Fluoro-containing alkoxysilane or hydrolyzed partial condensate thereof)
An alkoxysilane having a fluoro group or a hydrolyzed partial condensate thereof is a component that imparts water repellency.

Alkoxysilanes having a fluoro group include trifluoropropyltrimethoxysilane, perfluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorododecyltrimethoxysilane, and the like. Among them, perfluorooctyltriethoxysilane and heptadecafluorodecyltrimethoxysilane are preferred from the viewpoint of water repellency.
Moreover, one of these alkoxysilanes having a fluoro group may be used alone, or two or more thereof may be used in combination. Moreover, if at least one kind of alkoxysilane having a fluoro group is included, an alkoxysilane not containing a fluoro group may be used in combination.

Examples of hydrolytic partial condensates of alkoxysilanes having a fluoro group include those obtained by subjecting alkoxysilanes having a fluoro group to hydrolytic condensation by existing techniques. As the alkoxysilane having a fluoro group, the compounds described above can be used. One of these fluoro group-containing alkoxysilanes may be used alone, or two or more of them may be used in combination for hydrolytic partial condensation. Moreover, if at least one kind of alkoxysilane having a fluoro group is included, an alkoxysilane not containing a fluoro group may be used in combination for hydrolytic partial condensation. Alkoxysilanes having a fluoro group tend to form micelles in the composition because the alkoxy group is hydrophilic and the fluoro group is hydrophobic. It is suppressed, the fluoroalkyl groups are easily oriented on the film surface, and the durability of the functional film tends to be improved.

The amount of the alkoxysilane having a fluoro group or its hydrolyzed partial condensate is not particularly limited, but is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, based on 100% by weight of the solid content. ~50% by weight is more preferred. Within the above range, there is a tendency that a functional film having both dust resistance and durability can be formed.

(Alkoxysilane containing no fluoro group or hydrolyzed partial condensate thereof)
The hydrolyzed partial condensate of alkoxysilane containing no fluoro group is a component that imparts durability (abrasion resistance, hardness) and suppresses deterioration of dust resistance over time. The hydrolyzed partial condensate of alkoxysilane containing no fluoro group is not limited as long as it can form a hydrolyzed partial condensate by hydrolysis and condensation reaction. For example, it is represented by the following general formula (1). Examples thereof include those obtained by hydrolysis and condensation reaction of alkoxysilanes containing no fluoro group.
SiR ¹ ₄ (1)
In general formula (1), each R ¹ is hydrogen, a hydroxyl group, an alkoxy group, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and one or more R ¹ is an alkoxy group. Alkoxy groups, aliphatic hydrocarbon groups and aromatic hydrocarbon groups may each have a substituent.

Of the four R ¹ in general formula (1), when one R ¹ is an alkoxy group, monoalkoxysilane, when two R ¹ are alkoxy groups, dialkoxysilane, and three R ¹ are alkoxy groups. is a trialkoxysilane, and when four R ¹ are alkoxy groups, it is a tetraalkoxysilane, and any of these may be used. Moreover, these alkoxysilanes may be used individually by 1 type, and may use 2 or more types together. When trialkoxysilane or tetraalkoxysilane is contained, a hydrolyzed partial condensate with a branched structure can be obtained, and when the hydrolyzed partial condensate with a branched structure is cured to form a coating film, the film density is high, and the strength and moisture resistance are high. Excellent heat resistance and heat resistance. By using the dialkoxysilane, the molecular weight of the hydrolyzed partial condensate can be adjusted and flexibility can be imparted. By using monoalkoxysilane, the molecular weight of the hydrolyzed partial condensate can be adjusted.

The alkoxy group includes, for example, C _1-4 alkoxy groups such as methoxy group and ethoxy group.

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

Substituents possessed by aliphatic hydrocarbon groups and aromatic hydrocarbon groups include crosslinkable functional groups such as (meth)acryl groups, (meth)acryloxy groups, vinyl groups and epoxy groups, primary amino groups and secondary amino groups. groups, thiol groups, and styryl groups.

Examples of alkoxysilanes containing no fluoro group include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methoxytrimethylsilane, bis( triethoxysilyl)methane, bis(trimethoxysilyl)methane, bis(trimethoxysilyl)propane, bis(triethoxysilyl)propane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)hexane, bis(trimethoxy) silyl)octane, bis(triethoxysilyl)octane, bis(triethoxysilyl)ethylene, bis(trimethoxysilylmethyl)ethylene, 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, etc. Silane compounds having a hydrocarbon group; Silane compounds 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-aminopropylmethyldimethoxysilane Silane compounds having a primary amino group such as silane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Silane compounds having (meth)acrylic groups such as propylmethyldimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, Silane compounds having a vinyl group such as vinylmethyldimethoxysilane; β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltri Ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Silane compounds having an epoxy group such as triethoxysilane; Silane compounds having an isocyanate group such as 3-isocyanatopropyltriethoxysilane; 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(glycidylmethyl)-5-(3-trimethoxysilylpropyl)isocyanurate, 1-glycidylmethyl-3-(2-propen-1-yl)-5-(3-triethoxy Silylpropyl)isocyanurate, 1,3-dimethyl-5-(3-triethoxysilylpropyl)isocyanurate and other isocyanurate group-containing silane compounds. Among these, tetraalkoxysilanes, silane compounds having an aliphatic hydrocarbon group, and silane compounds having an aromatic hydrocarbon group are preferable from the viewpoint of durability and substrate applicability, and tetramethoxysilane, tetraethoxysilane, methyl More preferred are trimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methoxytrimethylsilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

In the 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) is preferably 0.1 to 4, more preferably 0.15 to 3.0. More preferably, 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 respectively the number of silicon atoms and the number of carbon atoms contained in one molecule of the hydrolyzate of the starting alkoxysilane. When two or more 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 hydrolyzed partial condensate of alkoxysilane containing no fluoro group is not particularly limited, but is preferably 1 to 90 parts by weight, more preferably 5 to 80 parts by weight, and 10 to 70 parts by weight based on 100 parts by weight of the solid content. More preferred. Within the above range, there is a tendency that a functional film having both dust resistance and durability can be formed.

Hydrolytic partial condensates of alkoxysilanes having fluoro groups and hydrolytic partial condensates of alkoxysilanes containing no fluoro groups can be produced, for example, by subjecting alkoxysilanes to hydrolytic partial condensation under acidic conditions. Partial hydrolysis condensation is carried out by hydrolysis of the alkoxy groups of the alkoxysilane to form hydroxyl groups and condensation reaction between the formed hydroxyl groups. These reactions can be carried out in one step. In the hydrolyzed partial condensate, some hydroxyl groups resulting from hydrolysis of alkoxy groups may remain.

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

In the hydrolytic partial condensation reaction of alkoxysilane, it is preferable to add water in an amount equal to or more than the number of equivalents of the alkoxy groups of the alkoxysilane. The amount of water added is preferably 100 to 500,000 mol, more preferably 500 to 100,000 mol, even more preferably 1,000 to 50,000 mol, per 100 mol of the alkoxy group of the alkoxysilane.

In the hydrolytic 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 include organic catalysts such as formic acid, acetic acid, glacial acetic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and polystyrenesulfonic acid. Examples include acids, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, aluminum halides such as aluminum chloride and aluminum bromide, inorganic acids such as aluminum nitrate, acidic silica gel, and acidic silica sol. Among these, volatile acids that do not leave a catalyst in the film after film formation are preferred, organic acids with a boiling point of 200° C. or less are more preferred, and formic acid and acetic acid are even more preferred. By using an acidic catalyst, effects such as acceleration of the hydrolytic partial condensation reaction and stabilization of the hydrolytic partial condensate can be obtained.

The pH during the hydrolytic partial condensation reaction is preferably 1-7, more preferably 2-7, and even more preferably 3-4. A desired hydrolyzed partial condensate can be obtained by setting the content within this range.

The amount of catalyst added is preferably 0.0001 to 20% by weight, more preferably 0.0001 to 10% by weight, based on the amount of alkoxysilane. By setting it as this range, a hydrolysis partial condensation reaction progresses rapidly, and it is easy to remove by heating.

The hydrolytic partial condensation reaction may be carried out without using a solvent, but a solvent may be used if necessary. Examples of such solvents 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; ,4-butanetriol, triols such as 1,2,3-butanetriol; ethers such as tetrahydrofuran (THF); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl Ether, glycol ethers such as 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- 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, since they can efficiently form a hydrolyzed partial condensate. These solvents may be used singly or in combination of two or more. The solvent may be a mixed liquid with water as described above. When used as a mixed liquid, a mixed liquid of water and a water-soluble organic solvent is preferable, and a mixed liquid of water and alcohol is more preferable.

The blending amount of the solvent is preferably 1 to 50,000 parts by weight, more preferably 10 to 5,000 parts by weight, and still more preferably 20 to 1,000 parts by weight with respect to 100 parts by weight of the alkoxysilane.

If 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 improver from the viewpoint of improving the adhesion between the functional film and the substrate.

The adhesion improver is not particularly limited, but examples include epoxysilanes, aminosilanes, acrylicsilanes, vinylsilanes, silane coupling agents such as styrylsilanes, titanate coupling agents, aluminum coupling agents, and acryloyl isocyanate. and isocyanates such as blocked isocyanate. These may be used alone or in combination of two or more. The amount of the adhesion improver compounded is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, and even more preferably 1 to 20 parts by weight based on 100 parts by weight of the solid content. Within the above range, the adhesiveness between the functional film and the substrate tends to be excellent.

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

The leveling agent is not particularly limited. Siloxane-based compounds such as siloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane; fluorine-based compounds such as perfluoroalkylcarboxylic acids and perfluoroalkylpolyoxyethylene ethanol; Polyether compounds such as oxyethylene alkylphenyl ether, propylene oxide polymer, ethylene oxide polymer; carboxylic acid such as coconut oil fatty acid amine salt, gum rosin; castor oil sulfate, phosphate, alkyl ether sulfate, sorbitan fatty acid Ester compounds such as esters, sulfonic acid esters, and succinic acid esters; sulfonate compounds such as alkylarylsulfonic acid amine salts and dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; coconut oil fatty acid ethanolamides, etc. amide compounds; acrylic compounds and the like.

The content 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.

Examples of solvents include, but are not limited to, 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); 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 ethyl methyl 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 Alkylene glycol monoalkyl 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 Esters such as ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, dimethyl succinate, diethyl succinate, diethyl adipate, diethyl malonate, dibutyl oxalate, etc. and the like. Among these, ethylene glycol ethers, alkylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), More preferred are diethylene glycol monoethyl ether acetate and methyl amyl ketone. 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, and even more preferably 3 to 5% by weight. Within the above range, liquid stability tends to be improved.

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

<<Composition>>
The composition of the present invention is characterized by containing a hydrolyzed partial condensate of alkoxysilane having a fluoro group and inorganic particles. Furthermore, it preferably contains an alkoxysilane or a hydrolyzed partial condensate thereof that does not contain a fluoro group. The alkoxysilane having a fluoro group or its hydrolyzed partial condensate, the inorganic particles, the alkoxysilane containing no fluoro group or its hydrolyzed partial condensate are as described above. Since the composition can maintain high dust resistance for a long period of time, it can be suitably applied as a dust-proof coating.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. Hereinafter, "parts" or "%" mean "parts by weight" or "% by weight", respectively, unless otherwise specified.

Various chemicals used in Examples and Comparative Examples are collectively described below.
(1) Alkoxysilane and its hydrolyzed partial condensate tetraethoxysilane (TEOS) (manufactured by Tama Chemical Industry Co., Ltd.)
Methyltriethoxysilane (MTES) (manufactured by Dow Toray 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)
Inorganic particles 3 (manufactured in Synthesis Example 8)
(3) Adhesion improver blocked isocyanate (manufactured by Asahi Kasei Chemicals Corporation, WM44-L70G)
(4) Solvent ethanol (AP-7) (manufactured by Japan Alcohol Sales Co., Ltd.)
Pure water (PW)
(5) Base plastic film (manufactured by Toray Industries, Inc., Lumirror)
White glass plate (manufactured by Taiyu Kizai Co., Ltd.)
Metal aluminum plate (A-1050P, manufactured by Taiyu Kizai Co., Ltd.)

The laminates produced in Examples were evaluated by the following methods.
<Film thickness>
The film thickness was measured with a stylus surface profiler (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)>
It was measured using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd.

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

<Water contact angle>
It was measured using DM-501Hi manufactured by Kyowa Interface Science Co., Ltd. according to the droplet method.

<Adhesion rate>
Kanto loam (JIS Z 8901, 8 types of test powder 1) was sprinkled on the functional film, and after removing it by leaning it at 90°, a photograph was taken. The photographed photograph was processed with image software, and the ratio of residual dust to the entire area was calculated as the adhesion rate.

<Pencil hardness>
It was measured 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 adhesiveness between the substrate and the coating film was measured by a JIS K5600 cross-cut peeling test.

<Scratch resistance>
The functional film was subjected to a scratch resistance test using a Gakushin-type dye 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 (Bemcot, manufactured by Asahi Kasei Co., Ltd.) was attached to the friction element of the Gakushin type dyeing friction fastness tester, and the test was performed by rubbing 10 times while applying a load of 500 g. The water contact angle and adhesion rate were measured by the methods described above.

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

(Synthesis Examples 1-5)
At room temperature, a 500 mL separable flask was charged with water, acetic acid, ethanol, and TEOS, MTES, and PTES in the weight ratios shown in Table 1, heated to 60° C., aged for 36 hours, and hydrolyzed to alkoxysilane. A partial condensate was obtained. The amount of acetic acid was adjusted so that the pH was 3 to 4, and the amount of water and ethanol was adjusted so that the weight ratio of water to ethanol was 50:50, and the solid content concentration of the reaction solution was 15%.

(Synthesis Example 6)
An oligosiloxane containing a fluoro group was synthesized by the method described above, except that heptadecafluorodecyltrimethoxysilane (HDFDTMOS) was used instead of TEOS, MTES, and PTES.

(Synthesis Example 7)
A 500 mL separable flask was charged with 35 mL of water, 10 mL of 28% by weight aqueous ammonia, and 120 mL of ethanol. Next, the silica sol liquid was obtained by depressurizingly distilling and removing ammonia. Inorganic particles 2 were obtained by adding 1 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Toray Co., Ltd., OFS-6040) to this silica sol liquid and stirring for 24 hours. The particle size was measured by a dynamic light scattering method using Microtrac Nanotrac Wave UT151 manufactured by Microtrac Bell Co., Ltd. The DTA peak was measured by the method described above (particle diameter: 100 nm, reactive group: silanol group, DTA peak at 340°C).

(Synthesis Example 8)
A 500 mL separable flask was charged with 35 mL of water, 10 mL of 28% by weight aqueous ammonia, and 120 mL of ethanol. Next, the silica sol liquid was obtained by depressurizingly distilling and removing ammonia. Inorganic particles 3 were obtained by adding 1 g of 3-glycidoxypropyltrimethoxysilane (OFS-6040 manufactured by Dow Toray Co., Ltd.) to this silica sol liquid and stirring for 24 hours. The particle size was measured by a dynamic light scattering method using Microtrac Nanotrac Wave UT151 manufactured by Microtrac Bell Co., Ltd. The DTA peak was measured by the method described above (particle diameter: 130 nm, reactive group: silanol group, DTA peak at 330°C).

(Examples 1 to 21 and Comparative Examples 1 to 4)
Together with the hydrolyzed partial condensate of alkoxysilane prepared in Synthesis Example, each component such as inorganic particles was blended at the solid content ratio shown in Table 1, and a solution of water: ethanol = 30: 70 (weight ratio) was prepared. , to prepare a resin composition by diluting to the solid content shown in Tables 2-4. These compositions had a pH of 3-4. This composition was applied onto the substrates shown in Table 2 using a bar coater. A laminate was obtained by curing at the temperature and time shown in Tables 2 to 4. Each physical property of the functional film was evaluated. The results are shown in Tables 2-4.

Claims (3)

A dustproof coating composition comprising a hydrolyzed partial condensate of an alkoxysilane having a fluoro group, inorganic particles having a particle size of 1 to 1000 nm, and a hydrolyzed partial condensate of an alkoxysilane containing no fluoro group,
The dustproof coating composition, wherein the inorganic particles have a reactive group selected from an epoxy group, a methacrylic group and an isocyanate group , and the amount of the inorganic particles is 10 to 80 parts by weight per 100 parts by weight of the solid content. 2. The dust-proof coating according to claim 1, wherein 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 0.1 to 4. composition. 3. The dustproof coating composition according to claim 1, further comprising an adhesion improver selected from the group consisting of silane coupling agents, titanate coupling agents, aluminum coupling agents and isocyanate compounds.