WO2018003810A1 - Solution de composition antisalissure, et procédé de fabrication de celle-ci - Google Patents

Solution de composition antisalissure, et procédé de fabrication de celle-ci Download PDF

Info

Publication number
WO2018003810A1
WO2018003810A1 PCT/JP2017/023613 JP2017023613W WO2018003810A1 WO 2018003810 A1 WO2018003810 A1 WO 2018003810A1 JP 2017023613 W JP2017023613 W JP 2017023613W WO 2018003810 A1 WO2018003810 A1 WO 2018003810A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
composition solution
alkyl group
antifouling
general formula
Prior art date
Application number
PCT/JP2017/023613
Other languages
English (en)
Japanese (ja)
Inventor
麻貴 廣永
宮田　壮
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2018525185A priority Critical patent/JP6431247B2/ja
Priority to CN201780039174.0A priority patent/CN109312190B/zh
Priority to KR1020187033470A priority patent/KR102479607B1/ko
Publication of WO2018003810A1 publication Critical patent/WO2018003810A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives

Definitions

  • the present invention relates to an antifouling composition solution and a method for producing the same.
  • a molded product such as a mirror, a glass container, or a glass decorative article does not adhere to the surface such as water droplets, scratches, and dirt.
  • the surface of such a molded product is provided with antifouling properties such as water repellency by coating with a film made of an antifouling substance or by applying an antifouling sheet. ing.
  • Patent Document 1 discloses a substrate such as glass by a laminate having a base layer formed of an inorganic compound and a water-repellent film that covers the surface of the base layer and is formed of a fluorine-containing compound.
  • a water-repellent film-coated article coated with a material is disclosed.
  • An object of the present invention is to provide an antifouling composition solution having a long pot life (pot life) and a method for producing the same.
  • the present inventors have disclosed an antifouling composition solution comprising a hydrolyzate of a tetrafunctional silane compound having a specific structure and a hydrolyzate of a trifunctional silane compound having a specific structure and a metal catalyst and water.
  • the inventors have found that the above problems can be solved, and have completed the present invention. That is, the present invention provides the following [1] to [15].
  • An antifouling composition solution obtained by blending a hydrolyzate of the following component (A) and a hydrolyzate of the following component (B) with a metal catalyst (D) and water (E).
  • R 2 represents an alkyl group of 1 to 24 carbon, the alkyl group may have a substituent.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • [2] The antifouling composition solution according to [1], wherein the component (B) contains at least one of the following components (B-1).
  • Component (B-1) Trifunctional silane compound represented by the following general formula (b-1) R 4 Si (OR 5 ) r (X 3 ) 3-r (b-1)
  • R 4 represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 5 represents an alkyl group having 1 to 6 carbon atoms, and X 3 represents a halogen atom. If R 5 and X 3 there are a plurality, the plurality of R 5 and X 3 are either identical to one another or may be different.
  • r represents an integer of 0 to 3.
  • Component (B-2) Trifunctional silane compound represented by the following general formula (b-2) R 6 Si (OR 7 ) s (X 4 ) 3-s (b-2)
  • R 6 represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent.
  • R 7 represents an alkyl group having 1 to 6 carbon atoms, and X 4 represents a halogen atom. If R 7 and X 4 there are a plurality, a plurality of R 7 and X 4, are identical to each other or may be different.
  • the blending amount of the metal catalyst (D) is 0.01 mol% or more and 50.00 mol% or less with respect to 100 mol% of the total blending amount of the component (A) and the component (B).
  • Step (1) Hydrolyzing the following component (A) and the following component (B)
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • X 1 represents a halogen atom.
  • R 1 and X 1 there are a plurality the plurality of R 1 and X 1 are also identical to each other or may be different.
  • p represents an integer of 0 to 4.
  • R 2 represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • Step (2) Step [10] of mixing the metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1).
  • (2) is a step of mixing water (E) after mixing the metal catalyst (D), or a step of mixing the metal catalyst (D) and water (E) at the same time, as described in [9] above.
  • a method for producing an antifouling composition solution [11] The method for producing an antifouling composition solution according to [9] or [10], wherein the acid catalyst (C) is used in the step (1).
  • the acid catalyst (C) is at least one selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, odoric acid, p-toluenesulfonic acid, and trifluoroacetic acid.
  • the amount of the acid catalyst (C) is 0.010 mol% or more and 1.000 mol% or less with respect to 100 mol% of the total amount of the component (A) and the component (B) [ The manufacturing method of the antifouling composition solution as described in [11] or [12].
  • R 2 represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • an antifouling composition solution having a long pot life (pot life) and a method for producing the same can be provided.
  • the antifouling composition solution of the present invention comprises a hydrolyzate of a tetrafunctional silane compound [component (A)] represented by the general formula (a) and a trifunctional silane compound represented by the general formula (b). It is an antifouling composition solution comprising a hydrolyzate of [Component (B)] and a metal catalyst (D) and water (E).
  • the antifouling composition solution of this invention may contain the acid catalyst (C) mentioned later other than these components, and others other than these components The additive may be contained.
  • the alkoxy group (OR 1 in the general formula (a) and the general formula (b) in the component (A) and the component (B) in the antifouling composition oR 3) is hydrolyzed, a hydrolyzate of hydrolyzate and of component (a) having a silanol group of uncondensed (B) is produced.
  • the silanol groups in these hydrolysates are condensed to form a polymer, whereby the coating film formed from the antifouling composition is cured to form an antifouling layer.
  • the antifouling composition solution can achieve excellent curability in a short time using the metal catalyst (D).
  • the antifouling composition solution when the antifouling composition solution is prepared and then stored for a long time and then cured, the curability thereof is lowered, and sufficient curability may not be obtained. Therefore, in view of obtaining an antifouling composition solution having a long pot life (also referred to as “pot life”), the antifouling composition solution has room for further study. Such a decrease in curability is assumed to occur for the following reason. As described above, the curing reaction of the antifouling composition proceeds in two stages: a hydrolysis reaction at the former stage and a condensation reaction at the latter stage.
  • the present inventors have made the final curing reaction after sufficiently proceeding the hydrolysis reaction between the component (A) and the component (B) in order to control the curability of the antifouling composition solution.
  • the present inventors effectively added water (E) to the hydrolyzate of component (A) and hydrolyzate of component (B), thereby effectively condensing silanol groups. It was estimated that it was possible to suppress this and was examined.
  • the present inventors have found that an antifouling composition solution having a longer pot life can be obtained and completed the present invention.
  • water (E) is blended later with respect to a system in which the hydrolyzate of component (A) and the hydrolyzate of component (B) are present.
  • a system in which the hydrolyzate of component (A) and the hydrolyzate of component (B) are present Refers to water.
  • the comparison described later is performed. As shown in the example, it is difficult to obtain the effect of the present application.
  • the condensation reaction between silanol groups of the hydrolyzate of component (A) and the hydrolyzate of component (B) is an equilibrium reaction, and water is generated by the condensation reaction. That is, the condensation reaction is dehydration condensation. Therefore, with respect to the hydrolyzate of component (A) and the hydrolyzate of component (B), the presence of water (E) to be blended later causes the condensation reaction (dehydration condensation) to proceed as an equilibrium reaction. Presumed to be suppressed.
  • each component contained in the antifouling composition solution of the present invention will be described.
  • the antifouling composition solution of the present invention contains a hydrolyzate of the component (A) described later.
  • the hydrolyzate of component (A) is obtained by hydrolyzing the alkoxy group in component (A) and has a silanol group in its molecular structure.
  • Component (A) tetrafunctional silane compound represented by general formula (a)
  • the component (A) is a tetrafunctional silane compound represented by the following general formula (a).
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • X 1 represents a halogen atom.
  • R 1 and X 1 there are a plurality the plurality of R 1 and X 1 are also identical to each other or may be different.
  • p represents an integer of 0 to 4.
  • the carbon number of the alkyl group that can be selected as R 1 is preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less.
  • Examples of the alkyl group that can be selected as R 1 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, Examples thereof include an n-hexyl group, a neopentyl group, and a methylpentyl group.
  • a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the alkyl group that can be selected as R 1 may be either linear or branched, but is preferably linear.
  • the halogen atom that can be selected as X 1 is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.
  • a component (A) it is preferable to contain the silane type compound whose p in the said general formula (a) is 4.
  • the antifouling composition solution of the present invention contains the hydrolyzate of component (B) together with the hydrolyzate of component (A).
  • the hydrolyzate of component (B) is obtained by hydrolyzing the alkoxy group in component (B) and has a silanol group in its molecular structure.
  • Component (B) Trifunctional silane compound represented by the general formula (b)
  • Component (B) is a trifunctional silane compound represented by the following general formula (b).
  • R 2 represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • the alkyl group that can be selected as R 2 has 1 to 24 carbon atoms.
  • the carbon number of the alkyl group exceeds 24, the curability of the antifouling composition solution is inferior.
  • the carbon number of the alkyl group increases, the antifouling composition solution is likely to gel, and the surface state of the antifouling layer formed from the antifouling composition solution tends to deteriorate.
  • the carbon number of the alkyl group is preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less.
  • the carbon number of the alkyl group that can be selected as R 2 does not include the carbon number of any substituent that the alkyl group may have.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -Nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, isopropyl group, iso
  • the alkyl group that can be selected as R 2 may be either linear or branched, but the antifouling layer formed from the curability of the antifouling composition solution and the antifouling composition solution From the viewpoint of improving the surface state, it is preferably a straight chain.
  • the alkyl group that can be selected as R 2 may have a substituent.
  • substituents include halogen atoms such as chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; amino group; cyano group; mercapto group; epoxy group; glycidoxy group; A cycloalkyl group having 3 to 12 ring carbon atoms (preferably 6 to 10 ring carbon atoms); an aryl group having 6 to 12 ring carbon atoms; a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom And a heteroaryl group having 6 to 12 ring atoms, an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), an aryloxy group having 6 to 12 ring carbon atoms, and the like.
  • the substituent may be further substituted.
  • the alkyl group that can be selected as R 2 is preferably an alkyl group having no substituent.
  • the alkyl group that can be selected as R 3 and the halogen atom that can be selected as X 2 are the same as the alkyl group that can be selected as R 1 and the halogen atom that can be selected as X 1 in the general formula (a). Is mentioned.
  • the component (B) preferably includes a trifunctional silane compound in which q in the general formula (b) is 3.
  • Condition (I) In the relationship between the component (A) and the component (B), an antifouling composition solution that satisfies the following condition (I) is preferable.
  • the [(A) / (B)] (molar ratio) is more preferably 0.10 or more, still more preferably 0.50 or more, still more preferably 0.80 or more, and even more preferably. Is 1.00 or more.
  • the [(A) / (B)] (molar ratio) is preferably 50.00 or less.
  • the [(A) / (B)] (molar ratio) is 50.00 or less, it is formed from the antifouling composition solution due to the presence of the alkyl group represented by R 2 in the component (B).
  • the applied antifouling layer has better water repellency.
  • the [(A) / (B)] (molar ratio) is more preferably 30.00 or less, still more preferably 25.00 or less, still more preferably 20.00 or less, and even more preferably. Is 10.00 or less.
  • the compounding quantity (molar amount) of a component (A) is a viewpoint which improves the sclerosis
  • the said compounding quantity (molar amount) becomes like this.
  • it is 98.00 mol% or less, More preferably, it is 96.00 mol% or less, More preferably, it is 94.00 mol% or less, More preferably, it is 90.00 mol% or less It is.
  • “content (mol) of hydrolyzate of component (A)” in the antifouling composition solution of the present invention is substantially “mixing amount (mol) of component (A) before hydrolysis”. Can be regarded as the same. The same applies to the component (B), the component (B-1), and the component (B-2).
  • Component (B-1) Trifunctional silane compound represented by formula (b-1)
  • the component (B) preferably contains at least one component (B-1) which is a trifunctional silane compound represented by the following general formula (b-1).
  • R 4 represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 5 represents an alkyl group having 1 to 6 carbon atoms, and X 3 represents a halogen atom. If R 5 and X 3 there are a plurality, the plurality of R 5 and X 3 are either identical to one another or may be different.
  • r represents an integer of 0 to 3.
  • the alkyl group that can be selected as R 4 has 6 to 24 carbon atoms. It is preferable that the alkyl group represented by R 4 has 6 or more carbon atoms because an antifouling layer having good water repellency can be obtained. From such a viewpoint, R 4 is preferably 8 or more. Further, the preferable upper limit value of the carbon number of the alkyl group represented by R 4 is the same as the preferable upper limit value of R 2 described above, preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less. . Setting reasons of each of upper preferable values are also as described above for R 2. The carbon number of the alkyl group that can be selected as R 4 does not include the carbon number of any substituent that the alkyl group may have.
  • alkyl group examples include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n- Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n- Tricosyl group, n-tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, neopentyl group,
  • the alkyl group that can be selected as R 4 may be either linear or branched, but the antifouling layer formed from the curability of the antifouling composition solution and the antifouling composition solution From the viewpoint of improving the surface state, it is preferably a straight chain.
  • the alkyl group that can be selected as R 4 is preferably an n-nonyl group, an n-decyl group, or an n-dodecyl group from the same viewpoint.
  • the alkyl group that can be selected as R 4 may have a substituent.
  • the substituent which the alkyl group which can be selected as R ⁇ 4 > has has the same thing as what was mentioned above about the substituent which the alkyl group which can be selected as R ⁇ 2 > has.
  • the alkyl group that can be selected as R 4 is preferably an alkyl group having no substituent.
  • the alkyl group that can be selected as R 5 and the halogen atom that can be selected as X 3 are the same as the alkyl group that can be selected as R 1 and the halogen atom that can be selected as X 1 in the general formula (a). Is mentioned.
  • the trifunctional silane compounds represented by the general formula (b-1) may be used alone or in combination of two or more.
  • the component (B-1) preferably includes a trifunctional silane compound in which r in the general formula (b-1) is 3.
  • Component (B-2) Trifunctional silane compound represented by general formula (b-2)
  • the component (B) preferably contains at least one component (B-2) which is a trifunctional silane compound represented by the following general formula (b-2).
  • R 6 represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent.
  • R 7 represents an alkyl group having 1 to 6 carbon atoms, and X 4 represents a halogen atom. If R 7 and X 4 there are a plurality, a plurality of R 7 and X 4, are identical to each other or may be different.
  • s represents an integer of 0 to 3.
  • the alkyl group that can be selected as R 6 has 1 to 3 carbon atoms. When the carbon number of the alkyl group is within this range, the curability of the antifouling composition solution is excellent.
  • the carbon number of the alkyl group that can be selected as R 6 does not include the carbon number of any substituent that the alkyl group may have.
  • Examples of the alkyl group that can be selected as R 6 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of obtaining curability, a methyl group or an ethyl group is preferable, and a methyl group is more preferable. .
  • the alkyl group that can be selected as R 6 may have a substituent.
  • a substituent having alkyl groups may be selected as R 6 may be the same as those described above for the substituent having alkyl groups may be selected as R 2.
  • the alkyl group that can be selected as R 6 is preferably an alkyl group having no substituent.
  • the alkyl group that can be selected as R 7 and the halogen atom that can be selected as X 4 are the same as the alkyl group that can be selected as R 1 and the halogen atom that can be selected as X 1 in the general formula (a). Is mentioned.
  • the trifunctional silane compounds represented by the general formula (b-2) may be used alone or in combination of two or more.
  • the component (B-2) preferably contains a trifunctional silane compound in which s is 3 in the general formula (b-2).
  • the antifouling composition solution used in the present invention more preferably contains both the component (B-1) and the component (B-2) as the component (B) which is a raw material of the hydrolyzate of the component (B). .
  • component (B-1) and component (B-2) as component (B)
  • the curability and antifouling composition of the antifouling composition solution is higher than when either is used alone.
  • the surface state of the antifouling layer formed from the physical solution can be improved.
  • Condition (II) Ratio of the amount (molar amount) of component (B-1) to the total amount (molar amount) of component (B-1) and component (B-2) [(B-1) / ⁇ (B-1) + (B-2) ⁇ ] (molar ratio) is 0.020 or more [(B-1) / ⁇ (B-1) + (B-2) ⁇ ] (molar ratio) is , 0.020 or more, the static friction coefficient and the dynamic friction coefficient of the antifouling layer formed from the antifouling composition solution are low, and the friction characteristics are excellent.
  • the antifouling layer formed from the antifouling composition solution has better water repellency.
  • the [(B-1) / ⁇ (B-1) + (B-2) ⁇ ] (molar ratio) is more preferably 0.035 or more, still more preferably 0.045 or more. Still more preferably, it is 0.050 or more, More preferably, it is 0.100 or more, More preferably, it is 0.150 or more, More preferably, it is 0.250 or more, More preferably, it is 0.500 or more.
  • the upper limit of the [(B-1) / ⁇ (B-1) + (B-2) ⁇ ] (molar ratio) is preferably 0.995 or less, more preferably 0.990 or less, and still more preferably It is 0.980 or less, More preferably, it is 0.950 or less, More preferably, it is 0.850 or less.
  • the antifouling composition solution of the present invention contains the component (B-1) and the component (B-2) as a trifunctional silane compound so as to satisfy the conditions (I) and (II). Therefore, the antifouling layer formed from the antifouling composition solution is preferable because both high surface hardness and low friction coefficient can be achieved. In addition, by including the component (B-2), an improvement in the weather resistance of the antifouling layer formed from the antifouling composition solution can be expected.
  • the blending amount (molar amount) of component (B-1) depends on the curability and antifouling properties of the antifouling composition solution. From the viewpoint of improving the surface state of the antifouling layer formed from the soiling composition solution, the total amount (molar amount) of component (A), component (B-1) and component (B-2) is 100 mol%. On the other hand, it is preferably 0.30 mol% or more, more preferably 0.50 mol% or more, still more preferably 1.00 mol% or more, and still more preferably 5.00 mol% or more. And the said compounding quantity (molar amount) becomes like this.
  • the blending amount (molar amount) of component (B-2) is the curability of the antifouling composition solution. From the viewpoint of improving the surface state of the antifouling layer formed from the antifouling composition solution, the total amount (molar amount) of component (A), component (B-1) and component (B-2) is 100.
  • it is 0.50 mol% or more with respect to mol%, More preferably, it is 0.80 mol% or more, More preferably, it is 1.00 mol% or more, More preferably, it is 1.30 mol% or more. And the said compounding quantity (molar amount) becomes like this. Preferably it is 40.00 mol% or less, More preferably, it is 38.00 mol% or less, More preferably, it is 25.00 mol% or less, More preferably, it is 18.00 mol% It is as follows.
  • the component (B-1) and the component (B-2) are used in combination as the component (B), the combination of the component (B-1) in the relationship between the component (A) and the component (B-1)
  • the ratio [(A) / (B-1)] (molar ratio) of the amount (molar quantity) of component (A) to the quantity (molar amount) is from the viewpoint of improving the curability of the antifouling composition solution.
  • the [(A) / (B-1)] (molar ratio) is preferably 300.0 or less.
  • the [(A) / (B-1)] (molar ratio) is 300.0 or less, the presence of an alkyl group represented by R 4 in the component (B-1) makes it an antifouling composition.
  • the antifouling layer formed from a product has better water repellency.
  • the [(A) / (B-1)] (molar ratio) is more preferably 200.0 or less, still more preferably 150.0 or less, still more preferably 100.0 or less, more More preferably, it is 90.0 or less, More preferably, it is 50.0 or less, More preferably, it is 10.0 or less.
  • the ratio (mole ratio) of the blending amount (molar amount) of component (A) to the amount (molar amount) is not particularly limited and is preferably 1.0 or more.
  • the [(A) / (B-2)] (molar ratio) is preferably 70.0 or less, more preferably 50.0 or less, and further preferably 20.0 or less.
  • component (B-1) and component (B-2) are used in combination as component (B), component (A), component (B-1) and component (B-2)
  • the ratio of the blending amount (molar amount) of component (A) to the total blending amount (molar amount) of B-1) and component (B-2) [(A) / ⁇ (B-1) + (B-2) ⁇ ] (Molar ratio) is preferably 0.01 or more, more preferably 0.10 or more, still more preferably 0.50 or more, still more preferably 0.80 or more, and even more preferably 1.00 or more. .
  • the [(A) / ⁇ (B-1) + (B-2) ⁇ ] (molar ratio) is preferably 50.00 or less, more preferably 25.00 or less, and even more preferably 20.00 or less. More preferably, it is 10.00 or less.
  • the total amount of component (B-1) and component (B-2) in component (B) Is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, relative to 100% by mass of the total amount of the component (B). More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, and Preferably it is 100 mass% or less. Further, the content is more preferably 100% by mass.
  • the hydrolyzate of component (A) and the hydrolyzate of component (B) used in the antifouling composition solution of the present invention are acid catalysts (C) from the viewpoint of further improving the curability of the antifouling composition solution. It is preferable that it is a hydrolyzate hydrolyzed using (1).
  • the acid catalyst (C) is not particularly limited as long as it has a function of promoting hydrolysis of the reactive functional groups of the component (A) and the component (B).
  • the antifouling composition solution from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, odoric acid, p-toluenesulfonic acid, and trifluoroacetic acid It is preferable to include one or more selected, and more preferable to include hydrochloric acid.
  • said acid catalyst (C) you may use individually or in combination of 2 or more types.
  • the antifouling composition solution of the present invention further contains a metal catalyst (D) together with the hydrolyzate of component (A) and the hydrolyzate of component (B).
  • a metal catalyst (D) together with the hydrolyzate of component (A) and the hydrolyzate of component (B).
  • the metal catalyst (D) is not included, the condensation reaction of the hydrolyzate of component (A) and the hydrolyzate of component (B) cannot be effectively promoted, and the antifouling composition solution Curability cannot be improved sufficiently. Further, in the case of the antifouling composition solution not containing the metal catalyst (D), the curing reaction cannot sufficiently proceed at a relatively low temperature (130 ° C. or lower).
  • an antifouling layer formed from the antifouling composition solution on a substrate having low heat resistance such as a vinyl chloride resin, under a low temperature that can suppress the thermal shrinkage of the substrate. If an antifouling layer is to be formed, the antifouling layer composition solution may be insufficiently cured. On the other hand, if the curing is attempted at a relatively high temperature (over 130 ° C.) in order to allow the curing reaction to proceed sufficiently, there is a risk that the substrate will shrink.
  • the metal catalyst (D) is preferably a metal catalyst that does not require light irradiation for the expression of catalytic action.
  • the “metal catalyst that does not require light irradiation for the expression of a catalytic action” means a catalytic action for the condensation reaction of the hydrolyzate of component (A) and the hydrolyzate of component (B). This refers to a metal catalyst that does not require light irradiation in order to express
  • light irradiation is required for the expression of a catalytic action such as titanium oxide (TiO 2 ) and zinc oxide (ZnO), which causes oxidation and reduction reactions by generating electrons and holes by light irradiation.
  • the antifouling composition solution contains the above-described “metal catalyst that does not require light irradiation for the expression of catalytic action”, it is possible to avoid problems that may occur when a photocatalyst is used.
  • the problem that may occur when using the photocatalyst is, for example, a decrease in water repellency due to an increase in the surface roughness of the antifouling layer resulting from the photocatalyst itself being a solid substance, There is a problem such as a decrease in water repellency due to the hydrophilicity imparting effect of the photocatalyst.
  • the metal catalyst (D) is preferably at least one selected from the group consisting of a titanium catalyst, a zirconium catalyst, a palladium catalyst, a tin catalyst, an aluminum catalyst, and a zinc catalyst.
  • the titanium-based catalyst is preferably a compound other than a photocatalyst containing a titanium atom, for example, titanium alkoxide, titanium chelate, titanium acylate, etc., including titanium hydroxide, acetate, carbonate, It may be sulfate, nitrate, chloride or the like.
  • titanium alkoxide include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, and the like.
  • titanium chelate examples include titanium acetylacetonate such as titanium diisopropoxybis (acetylacetonate) and titanium tetraacetylacetonate; titanium ethylacetoacetate such as titanium diisopropoxybis (ethylacetoacetate); Titanium triethanolamate such as propoxybis (triethanolaminate); titanium tetraoctylene glycolate, titanium dioctyloxybis (octylene glycolate), titanium di-2-ethylhexoxybis (2-ethyl-3- And titanium octylene glycolate such as hydroxy hexoxide); titanium lactate, titanium lactate ammonium salt and the like.
  • titanium acylate examples include polyhydroxy titanium stearate.
  • the zirconium-based catalyst is preferably a compound other than a photocatalyst containing a zirconium atom, for example, zirconium alkoxide, zirconium chelate, zirconium acylate and the like, zirconium hydroxide, acetate, carbonate, It may be sulfate, nitrate, chloride or the like.
  • zirconium alkoxide include zirconium tetranormal propoxide, zirconium tetranormal butoxide and the like.
  • zirconium chelate examples include zirconium acetylacetonate such as zirconium tributoxy monoacetylacetonate and zirconium tetraacetylacetonate; zirconium ethylacetoacetate such as zirconium dibutoxybis (ethylacetoacetate); zirconyl chloride compound and zirconium lactate ammonium. Examples include salts. Examples of the zirconium acylate include a zirconium octylate compound and zirconium stearate.
  • the palladium-based catalyst is preferably a compound other than a photocatalyst containing a palladium atom, and examples thereof include palladium, palladium chloride, palladium hydroxide, palladium carbon catalyst (Pd / C) and the like.
  • the tin-based catalyst is preferably a compound other than a photocatalyst containing a tin atom.
  • examples thereof include an organic tin compound such as dimaleate, dioctyltin mercaptide, and dioctyltin thiocarboxylate, or an inorganic tin compound.
  • the aluminum-based catalyst is preferably a compound other than a photocatalyst containing an aluminum atom, and examples thereof include an aluminum acetoacetate complex and an aluminum acetylacetonate complex.
  • aluminum acetoacetate complexes include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, Examples thereof include isopropoxyaluminum monostearyl acetoacetate, diisopropoxyaluminum monoisostearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl- ⁇ -alanate monolauryl acetoacetate, and aluminum trisacetylacetonate.
  • aluminum acetylacetonate complexes include monoacetylacetonate aluminum bis (isobutyl acetoacetate) chelate, monoacetylacetonate aluminum bis (2-ethylhexyl acetoacetate) chelate, monoacetylacetonate aluminum bis (dodecylacetoacetate) Chelate, monoacetylacetonate aluminum bis (oleyl acetoacetate) chelate, and the like.
  • the zinc-based catalyst is preferably a compound other than a photocatalyst containing a zinc atom, such as zinc-chromium oxide, zinc-aluminum oxide, zinc-aluminum-chromium oxide, zinc-chromium-manganese oxidation. Products, zinc-iron oxide, zinc-iron-aluminum oxide, and the like.
  • a metal catalyst (D) you may use individually or in combination of 2 or more types. In addition, it effectively promotes the condensation reaction between silane compounds, improves the curability of the antifouling composition solution, and can prevent the antifouling from proceeding at a relatively low temperature (130 ° C. or lower). From the viewpoint of preparing a conductive composition solution, it is preferable to contain at least the titanium-based catalyst.
  • the titanium catalyst is preferably a titanium chelate, more preferably titanium ethyl acetoacetate, titanium acetylacetonate or titanium octylene glycolate, still more preferably titanium ethyl acetoacetate, and titanium diisopropoxybis (ethyl acetoacetate). Even more preferred.
  • the blending amount (molar amount) of the metal catalyst (D) in the antifouling composition solution is a viewpoint of improving the curability of the antifouling composition solution, and the curing reaction even at a relatively low temperature (130 ° C. or less) From the viewpoint of making the antifouling composition solution capable of proceeding, it is preferably 0.010 mol% or more, more preferably, with respect to 100 mol% of the total blending amount (molar amount) of component (A) and component (B) Is at least 0.100 mol%, more preferably at least 0.150 mol%, even more preferably at least 0.300 mol%, even more preferably at least 0.500 mol%, even more preferably at least 1.000 mol%. It is.
  • the said compounding quantity becomes like this.
  • it is 50.000 mol% or less, More preferably, it is 30.000 mol% or less, More preferably, it is 20.000 mol% or less, More preferably, it is 10.000 mol% or less More preferably, it is 6.000 mol% or less, and still more preferably 3.000 mol% or less.
  • the content of the metal catalyst (D) in the antifouling composition solution allows the curing reaction to proceed even at a relatively low temperature (130 ° C. or lower) from the viewpoint of improving the curability of the antifouling composition solution.
  • it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more.
  • the said content becomes like this.
  • it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 2 mass% or less.
  • the said content can also be computed from the compounding quantity at the time of mix
  • the water (E) used in the present invention is preferably pure water such as distilled water, deionized water, purified water, RO (Reverse Osmosis) water, or ultrapure water.
  • water (E) refers to water to be blended later with respect to the system in which the hydrolyzate of component (A) and the hydrolyzate of component (B) are present. Say. Therefore, for example, water previously mixed to hydrolyze the component (A) and the component (B) and water used to dilute the acid catalyst (C) are excluded.
  • the blending amount (molar amount) of water (E) in the antifouling composition solution is the blending amount (moles) of the component (A) and the component (B) from the viewpoint of improving the curability of the antifouling composition solution.
  • it is 100,000 mol% or less, More preferably, it is 50,000 mol% or less, More preferably, it is 10,000 mol% or less, More preferably, it is 5,000 mol% or less. More preferably, it is 2,000 mol% or less, still more preferably 1,000 mol% or less, and still more preferably 500 mol% or less.
  • the total content of water including water (E) in the antifouling composition solution is preferably 0.01% by mass or more, more preferably from the viewpoint of improving the curability of the antifouling composition solution. It is 0.05 mass% or more, More preferably, it is 1.00 mass% or more, More preferably, it is 2.50 mass% or more, More preferably, it is 5.00 mass% or more. And the said content becomes like this. Preferably it is 99.00 mass% or less, More preferably, it is 95.00 mass% or less, More preferably, it is 90.00 mass% or less, More preferably, it is 70.00 mass% or less, More preferably Is 50.00 mass% or less, more preferably 25.00 mass% or less.
  • the total content of the water includes, for example, water used for diluting the acid catalyst (C) and water contained in other components.
  • the content of all the water contained in a dirty composition solution is said.
  • the content is calculated from, for example, the amount of water (E), the amount of water in the acid catalyst (C), and the amount of water generated by dehydration condensation of the components (A) and (B).
  • magnesium sulfate can be added to the antifouling composition solution to adsorb water, and the water content can be measured by the Karl Fischer method.
  • the antifouling composition solution may contain other additives in addition to the above-described components as long as the effects of the present invention are not impaired.
  • other additives include a resin component, a curing agent, an anti-aging agent, a light stabilizer, a flame retardant, a conductive agent, an antistatic agent, and a plasticizer.
  • the content of these additives is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, based on the total amount of the antifouling composition solution. More preferably, it is 0 to 2% by mass.
  • the said content can also be computed from the compounding quantity at the time of mix
  • the total compounding amount of the component (A), the component (B), and the metal catalyst (D) in the antifouling composition solution is 100% by mass of all active ingredients in the antifouling composition solution.
  • the said compounding quantity becomes like this. More preferably, it is 100 mass%.
  • the active ingredient in the antifouling composition solution is a liquid component excluding a solvent (water or an organic solvent) that is not directly involved in the reaction, among the components contained in the antifouling composition solution. And a component that is solid at room temperature.
  • the antifouling composition solution of the present invention has a long pot life and can maintain good curability even when it is used after a certain period of time has elapsed after preparation.
  • the pot life is, for example, preferably 24 hours or more, more preferably 168 hours or more, further preferably 336 hours or more, and preferably 4,500 hours or less.
  • the antifouling composition solution of the present invention can exhibit good curability even after a long time has elapsed since its preparation. is there.
  • the antifouling composition solution of the present invention includes the antifouling composition solution after 24 hours from the preparation of the antifouling composition solution.
  • Step (1) Hydrolyzing the following component (A) and the following component (B)
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • X 1 represents a halogen atom.
  • R 1 and X 1 there are a plurality the plurality of R 1 and X 1 are also identical to each other or may be different.
  • p represents an integer of 0 to 4.
  • Component (B) Trifunctional silane compound represented by the following general formula (b) R 2 Si (OR 3 ) q (X 2 ) 3-q (b)
  • R 2 represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • Step (2) Step of mixing the metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1).
  • Step (1) is a step of hydrolyzing component (A) and component (B).
  • the said component (A) and component (B) are the same as the component (A) and component (B) mentioned above, respectively,
  • the suitable aspect is also the same.
  • the compounding quantity of a component (A) and a component (B) is also the same as the compounding quantity of the component (A) and component (B) mentioned above, and the suitable range is also the same.
  • the method for hydrolyzing the component (A) and the component (B) is not particularly limited, but is preferably hydrolyzed using the acid catalyst (C).
  • an acid catalyst (C) it is the same as the acid catalyst (C) mentioned above,
  • the suitable aspect is also the same.
  • the blending amount (molar amount) of the acid catalyst (C) is 100 mol% of the total blending amount (molar amount) of the component (A) and the component (B).
  • it is preferably 0.010 mol% or more, more preferably 0.030 mol% or more, still more preferably 0.050 mol% or more, still more preferably 0.060 mol% or more.
  • the blending amount (molar amount) is preferably 1.000 mol% or less, more preferably 0.500 mol% or less, still more preferably 0.100 mol% or less, still more preferably 0.075 mol% or less. It is.
  • the temperature when performing the step (1) is the reactive functional group of the component (A) and the component (B).
  • the temperature is not particularly limited as long as it can be hydrolyzed, but is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 15 ° C. or higher, from the viewpoint of suppressing the progress of unintended condensation reaction due to heating. . And the said temperature becomes like this.
  • it is 100 degrees C or less, More preferably, it is 75 degrees C or less, More preferably, it is 50 degrees C or less, More preferably, it is 40 degrees C or less.
  • the reaction time when performing the hydrolysis reaction in the step (1) is the same as that of the component (A) and the component (B).
  • the reaction time can be appropriately adjusted according to each of the above conditions.
  • the reaction time is preferably 0.10 hours or more, more preferably 0.15 hours or more, still more preferably 0.20 hours or more, and even more.
  • it is 0.25 hours or more.
  • the said reaction time becomes like this.
  • it is 24.00 hours or less, More preferably, it is 12.00 hours or less, More preferably, it is 3.00 hours or less, More preferably, it is 1.00 hour or less.
  • the component (A) and the component (B) may be dissolved in an organic solvent to form a silane-based compound solution and hydrolyzed.
  • organic solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, mineral spirit, and the like.
  • the total concentration of component (A) and component (B) in the silane compound solution obtained in step (1) should be a concentration that allows hydrolysis of the reactive functional groups of component (A) and component (B).
  • the hydrolysis of the component (A) and the hydrolysis of the component (B) may be performed independently.
  • the component (A) and the component (B) are mixed and then the component ( A) and component (B) are hydrolyzed.
  • Step (2) is a step of mixing the metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1).
  • the metal catalyst (D) and water (E) are the same as the metal catalyst (D) and water (E) described above, respectively, and the preferred embodiments thereof are also the same.
  • the compounding quantity of a metal catalyst (D) and water (E) is also the same as the compounding quantity of the metal catalyst (D) and water (E) mentioned above, The suitable range is also the same.
  • the order of mixing the metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1) is not particularly limited, but the metal catalyst It is preferable to mix water (E) after mixing (D), or to mix metal catalyst (D) and water (E) simultaneously.
  • water (E) in step (2) By mixing water (E) in step (2), an antifouling composition solution having a long pot life can be obtained.
  • the hydrolyzate of component (B), and the concentration of the solution containing the metal catalyst (D) may be appropriately adjusted.
  • the organic solvent include the various organic solvents described above.
  • the total concentration of the hydrolyzate of component (A), hydrolyzate of component (B), and metal catalyst (D) in the solution is preferably 0.20 mol / L or more, more preferably 0.40 mol / L or more, more preferably 0.50 mol / L or more.
  • concentration becomes like this.
  • it is 3.00 mol / L or less, More preferably, it is 2.00 mol / L or less, More preferably, it is 1.00 mol / L or less.
  • the metal catalyst (D) and water (E) are used for each hydrolyzate. May be mixed with each other after mixing, or the metal catalyst (D) and water (E) are mixed after mixing the hydrolyzate of component (A) and the hydrolyzate of component (B). May be.
  • the metal catalyst (D) and water (E) are preferably mixed with the mixture of the hydrolyzate of component (A) and the hydrolyzate of component (B).
  • a solution obtained by blending water (E) with a hydrolyzate of the following component (A) and a hydrolyzate of the following component (B) can be used.
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • X 1 represents a halogen atom.
  • p represents an integer of 0 to 4.
  • R 2 represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, and X 2 represents a halogen atom. If R 3 and X 2 there are a plurality, the plurality of R 3 and X 2 are either identical to one another or may be different.
  • q represents an integer of 0 to 3.
  • the hydrolyzate of component (A), the hydrolyzate of component (B), and water (E) are the hydrolyzate of component (A), hydrolyzate of component (B), and water (described above), respectively. It is the same as E), and its preferred embodiment is also the same.
  • the manufacturing method of the said solution is the manufacturing method of the said antifouling composition solution except not using a metal catalyst (D) at the process (2) of the manufacturing method of the antifouling composition solution mentioned above. It can be manufactured using a similar method.
  • the said solution may contain the organic solvent used when melt
  • the antifouling composition solution can be obtained by mixing the metal catalyst (D) with the solution.
  • the metal catalyst (D) is the same as the metal catalyst (D) described above, and the preferred embodiment thereof is also the same.
  • the antifouling composition solution can be prepared and used by mixing the metal catalyst (D) with the solution.
  • the amount of component (A), the amount of component (B), the amount of water (E), and the total content of water in the solution are as follows when the metal catalyst (D) is blended with the solution.
  • the amount is preferably the same as the preferred blending amount and content of each component in the antifouling composition solution described above.
  • the object to which the antifouling composition of the present invention is applied is not particularly limited as long as antifouling property is required, but glass, metal, alloy, semiconductor, rubber, cloth, plastic, ceramics, It can be suitably used for wood, paper, fiber and the like, and can be more suitably used for glass and metal. Moreover, it can be used suitably also for a metal oxide film or a resin coating surface.
  • coating the said antifouling composition to a to-be-coated body it melt
  • Examples of a method for applying the antifouling composition solution to an object to be coated include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, and blade coating. Dip coating method, curtain coating method, die coating method, gravure coating method and the like.
  • FIG. 1 is a cross-sectional view of an antifouling sheet having a substrate, which is an example of an antifouling sheet obtained using the antifouling composition solution.
  • seat which has a base material the antifouling sheet
  • FIG. 2 is also a cross-sectional view of an antifouling sheet having no substrate, which is an example of the antifouling sheet obtained using the antifouling composition solution.
  • the antifouling sheet having no base material for example, as shown in FIG. 2A, the antifouling sheet 2a has a configuration in which the antifouling layer 11 is sandwiched between two release materials 14 and 14 ′. Is mentioned.
  • the antifouling sheet 2b is further provided with an adhesive layer 13 between the antifouling layer 11 and the release material 14 ′. Also good.
  • the antifouling layer of the antifouling sheet can be formed from the above-described antifouling composition solution of the present invention.
  • the thickness of the antifouling layer is preferably 0.001 ⁇ m or more, more preferably 0.005 ⁇ m or more, still more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, and still more preferably 0.10 ⁇ m or more. It is.
  • the thickness is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, still more preferably 15 ⁇ m or less, still more preferably 5.0 ⁇ m or less, still more preferably 1.0 ⁇ m or less, and even more preferably 0.80 ⁇ m or less. It is.
  • Examples of the substrate that can be used for the antifouling sheet include a paper substrate, a resin film, a resin sheet, a substrate obtained by laminating a paper substrate with a resin, a porous substrate such as a fiber sheet, a glass sheet, and a metal.
  • a foil, a metal sheet, etc. are mentioned, It can select suitably according to the use of an antifouling sheet.
  • Examples of the paper constituting the paper substrate include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper and the like.
  • Examples of the resin constituting the resin film or resin sheet include polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. , Ethylene-methacrylic acid copolymer vinyl resin; polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane; Examples thereof include urethane resins such as polyurethane.
  • Examples of the base material obtained by laminating a paper base material with a resin include laminated paper obtained by laminating the paper base material with a thermoplastic resin such as polyethylene.
  • the fiber sheet examples include various fiber sheets such as woven fabric, non-woven fabric, and knit.
  • the fiber sheet is preferably a fiber sheet containing at least one selected from the group consisting of organic fibers and inorganic fibers, more preferably at least one selected from the group consisting of cellulose nanofibers, synthetic fibers and glass fibers.
  • the fiber sheet to contain, More preferably, the glass fiber sheet containing at least glass fiber is mentioned.
  • organic fiber examples include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid; aliphatic polyamides such as nylon 6 and nylon 66; Examples of wholly aromatic polyamides such as meta-aramids; polyvinyl alcohol (PVA); synthetic fibers spun from the aforementioned resins, various natural pulps such as NBKP, LBKP, and abaca pulp, and cellulose nanofibers derived from the natural pulp. .
  • polyolefin resins such as polyethylene and polypropylene
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid
  • aliphatic polyamides such as nylon 6 and nylon 66
  • wholly aromatic polyamides such as meta-aramids
  • polyvinyl alcohol (PVA) synthetic fibers spun from the a
  • the inorganic fibers include glass fibers; ceramic fibers made of ceramic raw materials such as alumina, alumina-silica, zirconia; metal fibers made of iron, copper, brass, titanium, aluminum, stainless steel, and the like.
  • a synthetic fiber is a PVA fiber.
  • metal foil or a metal sheet which consists of various metals, such as aluminum, nickel, stainless steel, copper, brass, titanium, or tungsten, is mentioned.
  • a base material with a primer layer provided with a primer layer on the surface of the base material described above is used. May be.
  • a component which comprises a primer layer a polyester-type resin, a urethane type resin, a polyester urethane type resin, an acrylic resin etc. are mentioned, for example, These resin may be used individually or in combination of 2 or more types. .
  • a base material used for an antifouling sheet a base material with a weathering layer in which a weathering layer made of a polymer ultraviolet absorber is further provided on the surface of the base material or the surface of the base material with a primer layer ( A primer layer may be provided between the weather-resistant layer and the base material).
  • the polymer ultraviolet absorber has a structure in which an ultraviolet absorption skeleton is covalently bonded in a polymer structure, and preferably has a weight average molecular weight of 5,000 or more, more preferably 10,000 or more. is there.
  • the base material used for the antifouling sheet is a resin film or a resin sheet
  • a surface treatment such as an oxidation method or a roughening method may be performed.
  • the oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • corrugated method For example, a sandblasting method, a solvent processing method, etc. are mentioned.
  • These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the antifouling layer and the operability.
  • a metal vapor deposition film or a metal vapor deposition sheet in which a metal is vapor-deposited on the surfaces of various substrates described above may be used.
  • a metal vapor deposition film or a metal vapor deposition sheet in which a metal is vapor-deposited on the surfaces of various substrates described above may be used.
  • limit especially as said metal For example, various metals, such as aluminum, nickel, iron, copper, gold
  • the thickness of the substrate is appropriately set according to the use of the antifouling sheet, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoints of handleability and economy. It is.
  • the base material further contains an ultraviolet absorber other than the above-described polymer ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant, and the like. Also good.
  • a release material that can be used for an antifouling sheet As an example of a release material that can be used for an antifouling sheet, a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, and the like are used. The thing etc. which apply
  • coated are mentioned.
  • a base material for the release material for example, a paper base material, a resin film, a resin sheet, and a base material obtained by laminating a paper base material with a resin, which can be used as a base material of one aspect of the antifouling sheet of the present invention Etc.
  • the release agent examples include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release material is not particularly limited, and is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • the two release materials may be the same as or different from each other.
  • an antifouling sheet When an antifouling sheet has an adhesive layer, it can select suitably as an adhesive which constitutes the adhesive layer according to a use of an antifouling sheet.
  • the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and curable pressure-sensitive adhesives that are cured by energy rays such as ultraviolet rays. These pressure-sensitive adhesives may be used alone or in combination of two or more.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1 to 100 ⁇ m, more preferably 5 to 80 ⁇ m.
  • the antifouling sheet obtained by using the antifouling layer composition solution of the present invention includes, for example, architectural window glass, automotive window glass, windshield glass for vehicles, aircraft, ships, etc., water tanks, ship bottom windows, and ship bottoms. Films that prevent the adhesion of marine organisms, road panels such as soundproof walls, mirrors installed in bathrooms, glass containers, glass ornaments, etc. It is suitable as an antifouling sheet for preventing the above.
  • Comparative Example 3 For 0.01M hydrochloric acid used in step 1, purified water is blended in advance as shown in Table 1 as the acid catalyst (C), and no water (E) is blended in step 2. Except for this, an antifouling composition solution was prepared in the same manner as in Example 1.
  • an antifouling sheet was prepared using the following method. A slide glass was used as the substrate. The antifouling composition solutions prepared in each Example and each Comparative Example were prepared and then dip-coated on the substrate to form a coating film using the coating solution that was allowed to stand for 24 hours as a coating solution. Next, the coating film was dried at 80 ° C. for 2 minutes to prepare an antifouling sheet for evaluation.
  • ⁇ Curability of antifouling composition solution> Visually observe the antifouling layer after rubbing the antifouling layer surface of each evaluation antifouling sheet prepared using the antifouling composition solution prepared in each Example and each Comparative Example 20 times with a finger. Then, the curability of the antifouling layer was evaluated according to the following criteria. -A: A change was not seen compared with before rubbing with a finger. B: Discolored slightly white, but acceptable. C: Discolored white. -D: The antifouling layer could not be formed because the coating film made of the antifouling composition was not cured.
  • the water contact angle of the antifouling layer was determined using the fully automatic contact angle measuring device (product name “DM-701”) manufactured by Kyowa Interface Science Co., Ltd., and the antifouling composition prepared in each Example and each Comparative Example. About the antifouling layer surface of each antifouling sheet for evaluation produced using a solution, it measured as a contact angle with respect to 2 microliters of water.
  • the antifouling composition solution of Example 1 or 2 has good curability even when the antifouling composition solution is used after storage for 24 hours after preparation.
  • the antifouling layer produced from the antifouling composition solution had good surface condition and water repellency.
  • the antifouling composition solutions of Comparative Examples 1 to 3 were inferior in curability when used after storage for 24 hours after preparation.
  • the antifouling composition solution of the present invention has good curability even after long-term storage, and the surface state and water repellency of the antifouling layer formed from the antifouling composition are also good. Therefore, the antifouling composition solution of the present invention is preferably used even when the pot life is long and it takes time from the preparation of the antifouling composition solution to the formation of the antifouling layer. Can do.
  • the antifouling composition solution can also be suitably used when storage, transportation, etc. are necessary after preparation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Catalysts (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne une solution de composition antisalissure qui est constituée par mélange d'un catalyseur métallique (D) et d'une eau (E), dans un hydrolysat d'un composé silane tétra-fonctionnel〔composant（Ａ）〕possédant une structure spécifique, et un hydrolysat d'un un composé silane tri-fonctionnel〔composant（B）〕possédant une structure spécifique.
PCT/JP2017/023613 2016-06-29 2017-06-27 Solution de composition antisalissure, et procédé de fabrication de celle-ci WO2018003810A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018525185A JP6431247B2 (ja) 2016-06-29 2017-06-27 防汚性組成物溶液、及びその製造方法
CN201780039174.0A CN109312190B (zh) 2016-06-29 2017-06-27 防污性组合物溶液及其制造方法
KR1020187033470A KR102479607B1 (ko) 2016-06-29 2017-06-27 방오성 조성물 용액, 및 그 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016129421 2016-06-29
JP2016-129421 2016-06-29

Publications (1)

Publication Number Publication Date
WO2018003810A1 true WO2018003810A1 (fr) 2018-01-04

Family

ID=60786048

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/023613 WO2018003810A1 (fr) 2016-06-29 2017-06-27 Solution de composition antisalissure, et procédé de fabrication de celle-ci

Country Status (5)

Country Link
JP (1) JP6431247B2 (fr)
KR (1) KR102479607B1 (fr)
CN (1) CN109312190B (fr)
TW (1) TW201816013A (fr)
WO (1) WO2018003810A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180982A1 (fr) * 2017-03-31 2018-10-04 住友化学株式会社 Composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006192717A (ja) * 2005-01-13 2006-07-27 Nippon Steel Corp 表面処理金属，その製造方法および表面処理液
JP2010163584A (ja) * 2009-01-16 2010-07-29 Kyushu Hi-Tech:Kk 化学床保護用可撓性付与常温硬化型無機質コーティング剤
WO2016175208A1 (fr) * 2015-04-30 2016-11-03 リンテック株式会社 Composition antisalissure, feuille antisalissure et procédé permettant de produire une feuille antisalissure

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4862992B2 (ja) * 2006-04-14 2012-01-25 信越化学工業株式会社 防汚性付与剤、防汚性コーティング剤組成物、防汚性被膜及びその被覆物品
JP4775600B2 (ja) * 2008-11-26 2011-09-21 信越化学工業株式会社 室温硬化性オルガノポリシロキサン組成物
WO2010143645A1 (fr) * 2009-06-12 2010-12-16 石原産業株式会社 Agent de revêtement de blindage anti-infrarouge proche durcissable à températures ordinaires, film de blindage anti-infrarouge proche, et procédé de fabrication associé
JP2010285574A (ja) 2009-06-15 2010-12-24 Konica Minolta Holdings Inc 撥水膜被覆物品、建築用窓ガラス及び車両用窓ガラス
CN104736649B (zh) * 2012-10-31 2017-06-30 荷兰联合利华有限公司 疏水涂层

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006192717A (ja) * 2005-01-13 2006-07-27 Nippon Steel Corp 表面処理金属，その製造方法および表面処理液
JP2010163584A (ja) * 2009-01-16 2010-07-29 Kyushu Hi-Tech:Kk 化学床保護用可撓性付与常温硬化型無機質コーティング剤
WO2016175208A1 (fr) * 2015-04-30 2016-11-03 リンテック株式会社 Composition antisalissure, feuille antisalissure et procédé permettant de produire une feuille antisalissure

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180982A1 (fr) * 2017-03-31 2018-10-04 住友化学株式会社 Composition

Also Published As

Publication number Publication date
TW201816013A (zh) 2018-05-01
KR20190022483A (ko) 2019-03-06
CN109312190A (zh) 2019-02-05
JP6431247B2 (ja) 2018-11-28
JPWO2018003810A1 (ja) 2018-10-11
KR102479607B1 (ko) 2022-12-20
CN109312190B (zh) 2021-02-26

Similar Documents

Publication Publication Date Title
JP6007355B1 (ja) 防汚性組成物、及び防汚性シート
KR102602313B1 (ko) 방오성 조성물, 방오성 시트, 및 방오성 시트의 제조 방법
JP6111004B1 (ja) 防汚性組成物、防汚性シート、及び防汚性シートの製造方法
JP6389582B1 (ja) 撥液性組成物、撥液性シート及びそれらの製造方法
JP6431247B2 (ja) 防汚性組成物溶液、及びその製造方法
JP6263309B2 (ja) 防汚性シートの製造方法
JP6263310B2 (ja) 防汚性シートの製造方法
JP6635582B2 (ja) 防汚性シートの製造方法
JP6645094B2 (ja) 防汚性シートの製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018525185

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187033470

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17820164

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17820164

Country of ref document: EP

Kind code of ref document: A1