JP6997897B1 - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of exhibiting excellent dust resistance against fiber stains when applied to a substrate, and a laminate having a functional film made of a cured product of the composition. A composition containing (A) inorganic particles and (B) titanium alkoxide or a partially hydrolyzed condensate thereof. [Selection diagram] None

Description

The present invention relates to a composition and a laminate having a functional film composed of a cured product of the composition.

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. Further, since not only dirt such as dust but also fiber dirt such as cotton dust is generated indoors or in a car, countermeasures against these are required.

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. As described above, there is still room for improvement in dust resistance and durability against dust stains. Further, neither of Patent Documents 1 and 2 has an issue of dust resistance against fiber stains such as cotton dust.

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

The present invention provides a composition capable of exhibiting excellent dust resistance against fiber stains when applied to a substrate, and a laminate having a functional film made of a cured product of the composition. With the goal.

The present inventors have found that a composition containing inorganic particles and a titanium alkoxide or a partially hydrolyzed partial condensate thereof exhibits excellent dust resistance against fiber stains when applied to a substrate. The present invention has been completed.

That is, the present invention relates to a composition containing (A) inorganic particles and (B) titanium alkoxide or a partially hydrolyzed condensate thereof.

The composition of the present invention preferably further contains an alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof.

The present invention also relates to a composition for a fiber dust adhesion prevention coating containing the above composition.

The present invention also relates to a dustproof coating composition containing the above composition.

The present invention also relates to a laminate having a substrate and a functional film made of a cured product of the composition.

After the test dust is sprinkled on the functional membrane and removed at an angle of 90 °, the fiber adhesion ratio, which is the adhesion ratio of the residual fibers to the entire functional membrane region, is preferably 10% or less.

The water contact angle of the functional membrane is preferably 65 to 135 °.

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

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

Since the composition of the present invention contains inorganic particles and titanium alkoxide or a partially hydrolyzed partial condensate thereof, it can exhibit excellent dust resistance against fiber stains when applied to a substrate.

<< Composition >>
The composition of the present invention contains (A) inorganic particles and (B) titanium alkoxide or a partially hydrolyzed condensate thereof. The composition of the present invention has excellent dust resistance and can be applied as a dustproof coating composition. In particular, since it exhibits excellent dust resistance against fiber stains, it is suitably applied as a fiber dust adhesion prevention coating composition. can.

<(A) Inorganic particles>
Since the composition of the present invention contains (A) inorganic particles, irregularities are formed on the surface of the functional film, the installation area of fiber stains is reduced, and the functional film has excellent dust resistance. (A) 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, compounds in which metal oxides are doped with different elements, and the like. Be done. 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 against fiber stains. (A) One type of inorganic particles may be used alone, or two or more types may be used in combination.

The particle size of the inorganic particles (A) is not particularly limited, but is preferably 1 to 1000 nm, more preferably 10 to 100 nm. When it is within the above range, it is excellent in dust resistance against fiber stains.

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, it tends to be excellent in dust resistance and durability against fiber stains.

<(B) Titanium alkoxide or its hydrolyzed partial condensate>
(B) Titanium alkoxide or a partially hydrolyzed partial condensate thereof is a component that exhibits dust resistance against fiber stains when the composition of the present invention is applied to a substrate.

As the titanium alkoxide, one represented by the following general formula (1) can be used.
Ti (OR ¹ ) ₄ (1)
(In the general formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms.)

The alkyl group of R ¹ has 1 to 12 carbon atoms, but is preferably 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a hexyl group and the like. The four groups represented by OR ¹ in the general formula (1) may be different from each other or may be the same.

More specific titanium alkoxides include, for example, titanium tetramethoxyd, titanium tetraisopropoxide, titanium tetranormal propoxide, titanium tetraisobutoxide, titanium tetranormal butoxide, titanium tetraethoxydo, titanium tetra-2-ethylhexoside, and the like. Examples thereof include tetratershary butyl titanate. These may be used alone or in combination of two or more.

The partially hydrolyzed condensate of titanium alkoxide is not particularly limited as long as it is a condensate of titanium alkoxides represented by the general formula (1). Examples thereof include heptamer (7-mer) and tetranormal butoxytitanium decamer (10-mer). The degree of polymerization of the hydrolyzed partial condensate of titanium alkoxide is preferably 2 to 12. The composition of the present invention preferably contains a hydrolyzed partial condensate of titanium alkoxide from the viewpoint of film forming property and dust resistance against fiber stains.

Examples of the hydrolyzed partial condensate of titanium alkoxide include those obtained by hydrolyzing and condensing titanium alkoxide by an existing method such as JP-A-2008-156280. As the titanium alkoxide, the above-mentioned compound can be used. One of these titanium alkoxides may be used alone, or two or more of them may be used in combination for hydrolysis partial condensation. Further, if at least one kind of titanium alkoxide is contained, an alkoxysilane which is not a titanium alkoxide may be used in combination for hydrolysis partial condensation.

The blending amount of titanium alkoxide or a partially hydrolyzed partial condensate thereof is not particularly limited, but is preferably 1 to 90% by weight, more preferably 5 to 80% by weight, still more preferably 10 to 70% by weight, and 20% by weight of the solid content. ~ 60% by weight is particularly preferable. Within the above range, a functional film having excellent dust resistance against fiber stains tends to be formed.

The composition of the present invention may optionally contain other components. Examples of other components include an alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof, an alkoxysilane containing no fluoro group or a partially hydrolyzed condensate thereof, an adhesion improver, an epoxy resin, an acrylate, a melamine, and the like. Curable resin, acrylic resin, polyester resin, urethane resin, polyolefin resin and other thermoplastic resins, antistatic agents such as conductive polymers, carbon materials, polymerization initiators, leveling agents, surfactants, photosensitizers, Examples thereof include defoaming agents, neutralizing agents, antioxidants, mold release agents, ultraviolet absorbers, thickeners, solvents and the like.

(Alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof)
When an alkoxysilane having a fluoro group or a partially hydrolyzed condensate thereof is contained, it is preferable because water repellency can be imparted to the functional membrane.

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 fluorine atom, a fluoroalkyl 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 against fiber stains.
In addition, one type of alkoxysilane having these fluorogroups may be used alone, or two or more types may be used in combination. Further, it may be used in combination with an alkoxysilane that does not contain a fluoro group, which will be described later.

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 composition of the present invention preferably contains a hydrolyzed partial condensate of alkoxysilane having a fluoro group.

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 2 to 50% by weight in the solid content. % Is even more preferable, and 2 to 30% by weight is particularly preferable. Within the above range, a functional film having both dust resistance and durability against fiber stains tends to be formed.

The hydrolyzed partial condensate of alkoxysilane having 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 desired hydrolyzed partial condensate can be obtained.

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.

(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 against fiber stains over time. 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 (2), which does not contain a fluoro group, to hydrolysis and condensation reaction.
SiR ² ₄ (2)
In the general formula (2), R ² is a hydrogen, a hydroxyl group, an alkoxy group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, respectively, and one or more R ² 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 ^2s in the general formula (2), monoalkoxysilane when one ^R2 is an alkoxy group, dialkoxysilane when ^two R2s are alkoxy groups, and three ^R2s are alkoxy groups. When is, it is a trialkoxysilane, and when the four ^R2s 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 groups 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 compounds having a (meth) acrylic group such as propylmethyldimethoxysilane; silane compounds 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 pyrumethyldimethoxysilane, 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 against fiber stains, durability and applicability to a base material. 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 hydrolyzed partial condensate of alkoxysilane containing no fluoro group can be produced by the same method as the above-mentioned hydrolyzed partial condensate of alkoxysilane having a fluoro group.

(Adhesion improver)
The composition of the present invention may contain an adhesion improver from the viewpoint of improving the adhesion between the base material and the functional film. 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.

(Antistatic agent)
By blending an antistatic agent with the composition of the present invention, the conductivity of the functional film made of the cured product of the composition is improved, and the adhesion of fiber stains due to static electricity is suppressed, so that the dust resistance against fiber stains is suppressed. Can be improved. The antistatic agent is not particularly limited, and examples thereof include a surfactant, an ionic compound, carbon black, a conductive filler, and a conductive polymer, but the conductive polymer is preferable in terms of dust resistance. Conventionally known conductive polymers can be used as the conductive polymer, and specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, derivatives thereof, and dopants thereof. Complex and the like. These conductive polymers may be used alone or in combination of two or more.

As the conductive polymer, a conductive polymer containing at least one thiophene ring in the molecule is preferable. The reason is that the inclusion of the thiophene ring in the molecule makes it easy to form a highly conductive molecule.

As the conductive polymer, poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a polyanion is more preferable. This is because it is extremely excellent in conductivity and chemical stability. Further, when poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a polyanion is contained, a functional film can be formed at a low temperature in a short time. It can be done and has excellent productivity.

The blending amount of the conductive polymer is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, further preferably 2 to 50% by weight, and particularly preferably 3 to 10% by weight in the solid content. .. Within the above range, the dustproof property against fiber stains tends to be excellent.

(Leveling agent)
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.

(solvent)
The solvent is not particularly limited as long as it is not water, but for example, 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 dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether (ethyl cellosolve) and other ethylene glycol ethers; methyl cellosolve acetate, ethyl cellosolve acetate and other ethylene glycol alkyl ether acetates; diethylene glycol diethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as dimethyl ether, diethylene glycol 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; Alkylenes such as propylene glycol monomethyl 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, etc. Glycol monoalkyl 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-Hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, dimethyl succinate, die succinate Examples thereof include esters such as chill, diethyl adipic acid, 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. Diethylene glycol monoethyl ether acetate and methyl amylketone are more preferred. 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 0.5 to 8% by weight, still more preferably 1 to 5% by weight. Within the above range, the liquid stability tends to improve.

<< Laminated body >>
Since the laminate of the present invention has a base material and a functional film made of a cured product of the composition of the present invention, it exhibits excellent dust resistance against fiber stains.

<Base material>
Examples of the material of the base material include plastic, glass, metal, concrete, brick, sandstone, mortar, cement, cotton, linen, silk, wool 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 Examples thereof include acetyl cellulose (TAC) resin, acrylonitrile, butadiene, styrene (ABS) resin and the like. Examples of the metal include stainless steel, iron, copper, steel, special steel, aluminum, aluminum alloy, silver and the like.

Examples of the form of the base material include a molded body, a sheet, a film, and a cloth. Examples of the form of the cloth include woven fabrics, non-woven fabrics, and knitted fabrics.

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

The functional film cures the composition after the composition of the present invention is applied to the substrate, or after the composition of the present invention is impregnated with the substrate when the form of the substrate is a cloth. It is obtained by. When applying, it may be applied directly on at least one surface of the substrate, transferred, or it may be applied on the primer layer or the like after being provided on the substrate in advance. good. 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 coating of the composition on the base material and the impregnation of the base material on the 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 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.

The water contact angle of the functional membrane is not particularly limited, but is preferably 65 to 135 °, more preferably 90 to 130 °. When it is within the above range, it is excellent in dust resistance against fiber stains. 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 fiber adhesion rate to the functional film is preferably 10% or less, more preferably 5% or less. Here, the fiber adhesion rate is the rate of adhesion of residual fibers to the entire area of the functional film after the test dust is sprinkled on the functional membrane and removed at an angle of 90 °, and more specifically, it is described in Examples. It can be measured by the method.

The method of sprinkling the test dust on the functional membrane and the method of removing the adhering test dust are not particularly limited, and various methods can be preferably used. For example, the test dust may be removed by sprinkling a predetermined amount on the functional membrane, 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 membrane is not particularly limited, and a plurality of images may be captured by a method in which the test dust can be visually recognized in the entire functional membrane region. The binarization process of the captured image is not particularly limited, and known image processing software or the like may be used.

The surface resistivity of the functional film is not particularly limited, but is preferably 1 to 10 × 10 ¹⁵ Ω / □, more preferably 10 × 10 ² to 10 × 10 ¹³ Ω / □, and more preferably 10 × 10 ⁵ to 10 × 10 ¹¹ . Ω / □ is more preferable. Here, the surface resistivity can be measured by the method described in the examples.

Since the laminate of the present invention has a base material and a functional film made of a cured product of the composition of the present invention, it is excellent in dustproof property, particularly dustproof property against fiber stains, and is excellent in dustproof property, such as a fan, a propeller, a ventilation port, and an automobile interior. , Furniture, interior, home appliances, medical equipment, factory equipment, textile products such as clothes, and articles used indoors (indoors or in cars) such as film sheets that can be attached to the above-mentioned products.

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) Hydrolyzed partial condensate of titanium alkoxide Produced in Synthesis Example 1 and Synthesis Example 2 (2) Hydrolyzed partial condensate of alkoxysilane containing no fluoro group Manufactured in Synthesis Example 4 (3) Alkoxysilane having a fluoro group Heptadecafluorodecyltrimethoxysilane (HDFDTMOS) (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
(4) Manufactured in Example 3 of Synthesis of Hydrolyzed Partial Condensate of Alkoxysilane Having a Fluoro Group (5) Inorganic Particle OrganoSilica Sol (manufactured by Nissan Chemical Industries, Ltd., IPA-ST-L, Particle Diameter: 45 nm)
(6) Conductive polymer solvent-based PEDOT (manufactured by Tosoh Corporation, SELFTRON_DN-400)
(7) Adhesion improver blocked isocyanate (manufactured by Asahi Kasei Chemicals Co., Ltd., WM44-L70G)
(8) Solvent Isopropanol (IPA) (manufactured by Sagane Bussan Co., Ltd.)
(9) Base metal aluminum plate (manufactured by Taiyu Equipment Co., Ltd., A-1050P)
Polycarbonate sheet (manufactured by TP Giken Co., Ltd., PC-B)
Polypropylene plate (TP-B manufactured by TP Giken Co., Ltd.)
ABS resin plate (manufactured by TP Giken Co., Ltd., ABS-B)
Glass white board (manufactured by Taiyu Equipment Co., Ltd.)

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.).

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

<Fiber adhesion rate>
The laminates prepared in Examples 1 to 13 and Comparative Examples 1 to 7 were installed with the functional membrane facing up so as to completely fit within an area of 10 cm × 10 cm, and test (cotton) dust was applied to the entire area. (Manufactured by Rijin Co., Ltd.) 0.2 g was sprinkled evenly (the amount of test dust used per 1 cm ² of the area of the functional membrane is 2 mg). The laminate was tilted at 90 ° and lightly dropped from a height of 3 cm on the table three times and tapped (tapped) to remove test dust, and then a photograph was taken. The photograph taken was binarized with image software, and the adhesion ratio of the residual fiber to the entire functional membrane region was calculated and used as the adhesion ratio.

<Surface resistivity>
According to JIS K7194, the surface resistivity was measured with a probe UA and an applied voltage of 10 V to 500 V using a high resta UP (MCP-HT-450, trade name) manufactured by Mitsubishi Chemical Corporation.

(Synthesis Example 1)
In a 1 L separable flask, 340 g (1 mol) of tetra (tert-butoxy) titanium was charged. A solution prepared by dissolving 16.2 g (0.9 mol) of water in 370 g (5 mol) of tert-butanol was added dropwise with stirring, and the mixture was refluxed for 30 minutes. Then, tert-butanol was distilled off from the system by normal pressure and reduced pressure (40 mmHg) to obtain 220 g of a partially hydrolyzed condensate of titanium alkoxide. (Yield 99%)

(Synthesis Example 2)
284 g (1 mol) of tetraisopropoxytitanium was placed in a 1 L separable flask. A solution prepared by dissolving 9 g (0.5 mol) of water in 264.3 g (3 mol) of tert-pentyl alcohol was added dropwise with stirring, and the mixture was refluxed for 30 minutes. Then, isopropyl alcohol was distilled off from the system by normal pressure and reduced pressure (40 mmHg) to obtain 288 g of a partially hydrolyzed condensate of titanium alkoxide. (Yield 91%)

(Synthesis Example 3) Hydrolyzed partial condensate of fluorogroup-containing alkoxysilane At room temperature, water, acetic acid, IPA, and HDFDTMOS are charged in a 500 mL separable flask, heated to 60 ° C., and aged for 36 hours to form a fluorogroup. A hydrolyzed partial condensate of alkoxysilane having the above was obtained. The amount of acetic acid to be blended was such that the pH was 3 to 4, and the amount of water to be blended with IPA was such that the weight ratio of water to IPA was 1:80 and the solid content concentration of the reaction solution was 15%.

(Synthesis Example 4) Hydrolyzed partial condensate of alkoxysilane containing no fluoro group At room temperature, water, acetic acid, ethanol, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.) and methyltriethoxysilane are placed in a 500 mL separable flask. (OFS-6383, manufactured by Toray Dow Co., Ltd.) was charged at a weight ratio of 40:60, heated to 60 ° C., and aged for 36 hours to obtain a hydrolyzed partial condensate of alkoxysilane containing no fluoro group. .. 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. The ratio of the number of carbon atoms to the number of silicon atoms in the molecule (C / Si ratio) in the obtained hydrolyzed partial condensate of alkoxysilane containing no fluoro group was 0.64.

(Examples 1 to 13 and Comparative Examples 1 to 7)
A composition was prepared by blending each component at the solid content ratio shown in Table 1 and diluting to the solid content shown in Table 1 using IPA as a solvent.

In Examples 1 to 13 and Comparative Examples 6 and 7, the obtained compositions were applied onto the substrate shown in Table 1 by a bar coater, cured at the drying temperature and drying time shown in Table 1, and laminated. I got a body. Each physical property of the functional film in the obtained laminate was evaluated by the above-mentioned method. In Comparative Examples 1 to 5, each physical property of the base material itself having no functional film was evaluated. The results are shown in Table 1.

Claims (7)

(A) Inorganic particles and
(B) A composition for a fiber dust adhesion prevention coating containing a composition containing titanium alkoxide or a partially hydrolyzed condensate thereof . The composition for a fiber dust adhesion prevention coating according to claim 1, further comprising an alkoxysilane having a fluoro group or a partially hydrolyzed partial condensate thereof. A laminate having a base material and a functional film made of a cured product of the composition according to claim 1 or 2 . Sprinkle cotton dust on the functional membrane so that the area of the functional membrane is ² mg per 1 cm2, tilt it at 90 °, and lightly drop it from a height of 3 cm on the table three times to remove it, and then tap the functional membrane. The laminate according to claim 3 , wherein the fiber adhesion rate, which is the adhesion ratio of residual fibers to the entire area, is 10% or less. The laminate according to claim 3 or 4 , wherein the functional film has a water contact angle of 65 to 135 ° as measured by the sessile drop method . The laminate according to any one of claims 3 to 5 , 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 3 to 6 , wherein the functional film has a film thickness of 1 μm or less.