CN106536651A - Agent for forming adhesive coating for aluminum oxide or aluminum substrate - Google Patents

Agent for forming adhesive coating for aluminum oxide or aluminum substrate Download PDF

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Publication number
CN106536651A
CN106536651A CN201580040161.6A CN201580040161A CN106536651A CN 106536651 A CN106536651 A CN 106536651A CN 201580040161 A CN201580040161 A CN 201580040161A CN 106536651 A CN106536651 A CN 106536651A
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Prior art keywords
overlay film
aluminium
closely sealed
film forming
forming agent
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Granted
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CN201580040161.6A
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CN106536651B (en
Inventor
大田政太郎
饭沼洋介
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • 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
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Human Computer Interaction (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is an agent for forming an adhesive coating for an aluminum oxide or aluminum substrate, the agent capable of forming a film by a wet coating method. An agent for forming an adhesive coating for an aluminum oxide or aluminum substrate, the agent containing an aluminum salt and a hydrolysis/condensation product of an alkoxysilane component including at least one species selected from alkoxysilanes represented by formula (I) and formula (II). (Formula (1)): Si(OR1)4 (I); (Formula (2)): R2 mSi(OR3)4-m (II). In the formulas, R1 and R3 independently represent a C1-5 alkyl group, R2 represents a hydrogen atom, and m represents an integer from 1 to 3.

Description

The closely sealed overlay film forming agent of aluminum oxide substrate or aluminium base
Technical field
The present invention relates to the closely sealed overlay film forming agent of the aluminum oxide substrate such as sapphire glass or aluminium base.
Background technology
Aluminum oxide of the sapphire glass for monocrystalline, with stone, transparent, heat-resisting and insoluble in excellent as chemicals Heterogeneity.As hardness is high, be difficult the speciality for scratching, sapphire glass can be used for clock and watch cover glass (windshield), The touch panel substrate of the cover glass of camera lens, smart mobile phone or panel computer.
The marresistance for scratching is difficult when base material is rubbed by other materials in order to improve, it is also known that had in piece tables such as glass The technology of the anti-fouling agents such as face coating fluorine system compound, silicon systems compound.By coating anti-pollution agent, smoothness of the surface improves, i.e., Impact applying, it is also possible to relax the impact using slickness, excellent marresistance can be obtained.In addition, by antifouling The coating of agent, moreover it is possible to obtain water repellent, refuse oil and be difficult to be stained with the effect of fingerprint.
If the coating anti-pollution agent on sapphire glass, high rigidity by sapphire glass and stain-proofing layer can be expected Shuffle effect and obtain substantially excellent marresistance.But, adaptation of the aluminum oxide such as sapphire glass generally with anti-fouling agent Difference, the marresistance that cannot be expected.It is in order to avoid the problem, previously reported that oxygen is formed by the dry coating method under vacuum Change aluminium (Al2O3) and silica (SiO2) closely sealed auxiliary layer method (patent document 1).
In addition, it was recently reported that by sputtering silica (SiO on sapphire glass2) and silicon nitride (SiNx) film forming, so Afterwards by the technology (patent document 2) of stain-proofing layer film forming.Based on sputtering, PVD (physical vapour deposition (PVD)s；Physical Vapor Deposition), CVD (chemical vapor depositions；Chemical Vapor Deposition) etc. dry coating method film forming true Carry out in empty, need expensive main equipment.In addition, also there is the size of the base material of energy film forming, shape being restricted Problem.
On the other hand, based on wet coating methods such as flexible printing, rotary coating, ink-jet, slot coated, rod painting, sprayings Film forming is cheap and can form film at high speed.But, be still unaware of can bonding wet abundant with aluminum oxide method, in order to Coating anti-pollution agent, it is necessary to carry out the film forming based on dry coating method of high cost.
Prior art literature
Patent document
Patent document 1：United States Patent (USP) discloses 2014/0087197A1
Patent document 2：No. 5435168 publications of Japanese Patent Publication No.
The content of the invention
Problems to be solved by the invention
It is an object of the present invention to provide arranging the work(such as anti-fouling agent on the aluminum oxide substrates such as sapphire glass or aluminium base During energy property film, it is clipped in and plays the effect for improving their adaptation between the two, and film forming can be carried out using wet coating method Aluminum oxide substrate or aluminium base with closely sealed overlay film forming agent.
For solution to problem
The present inventor has made intensive studies to achieve these goals, as a result completes this with following main ideas It is bright.
1. the closely sealed overlay film forming agent of a kind of aluminum oxide substrate or aluminium base, it is characterised in that containing alkoxy silane Hydrolytic condensate and aluminium salt.
2. the closely sealed overlay film forming agent according to above-mentioned 1, wherein, the hydrolytic condensate of alkoxy silane is comprising being selected from The hydrolytic condensate of the alkoxy silane composition of at least a kind in following formula (I)s and the alkoxy silane shown in (II).
Si(OR1)4 (I)
R2 mSi(OR3)4-m (II)
In above-mentioned formula (I) and (II), R1And R3The alkyl of carbon number 1～5, R is represented independently of one another2Represent optionally quilt Selected from the group of halogen atom, vinyl, methacryloxy, acryloxy, styryl, phenyl and cyclohexyl composition In at least a kind replace and optionally with the alkyl of heteroatomic carbon number 1～20, hydrogen atom, halogen atom, vinyl, Methacryloxy, acryloxy, styryl, phenyl, cyclohexyl, amino, glycidoxy, sulfydryl, isocyanates Base or urea groups.M represents 1～3 integer.
3. the closely sealed overlay film forming agent according to above-mentioned 1 or 2, wherein, above-mentioned aluminium salt is selected from aluminium chloride, nitric acid Aluminium, aluminum sulfate, aluminium acetate, oxalic acid aluminium, sulfamic acid aluminium, sulfonic acid aluminium, acetoacetate aluminium, aluminium acetylacetonate and their basic salt At least a kind in the group of composition.
4. the closely sealed overlay film forming agent according to any one of above-mentioned 1～3, wherein, above-mentioned aluminium salt is nitric acid aluminium salt.
5. the closely sealed overlay film forming agent according to any one of above-mentioned 1～4, wherein, aluminium atom is relative to silicon atom The mol ratio (Al/ (Si+Al)) of the summation of the molal quantity (Al) of total mole number (Si) and aluminium atom is 0.1～0.5.
6. the closely sealed overlay film forming agent according to any one of above-mentioned 1～5, which is also containing selected from N- methyl-pyrrols Alkanone, ethylene glycol, dimethylformamide, dimethyl acetamide, diethylene glycol, propane diols, hexylene glycol and their derivative group Into group at least a kind as anti-precipitation agent.
7. a kind of overlay film, which is obtained using the closely sealed overlay film forming agent any one of above-mentioned 1～6.
8. a kind of aluminum oxide substrate or aluminium base, which has the closely sealed overlay film described in above-mentioned 7.
9. a kind of touch panel, which has the closely sealed overlay film described in above-mentioned 7.
10. the forming method of the closely sealed overlay film of a kind of aluminum oxide substrate or aluminium base, wherein, for by above-mentioned 1～6 Closely sealed overlay film forming agent described in any one coats the film of aluminum oxide substrate or aluminium base, enters at 100～600 DEG C Row roasting.
The effect of invention
With regard to the closely sealed overlay film forming agent of the present invention, the aluminum oxide substrates such as sapphire glass are applied to by coating etc. Or aluminium base and form overlay film, and be formed on the functional membranes such as anti-fouling agent such that it is able to give excellent marresistance etc. Characteristic.For example, according to the present invention, the touch panel cover glass with excellent soil resistance and marresistance can be obtained.Gold The surface of category aluminium can aoxidize in atmosphere and form aluminum oxide overlay film, therefore the closely sealed overlay film forming agent of the present invention can be used for Metal aluminum substrate purposes.
Description of the drawings
Fig. 1 is typical example, the i.e. touch panel using aluminum oxide substrate obtained from closely sealed overlay film forming agent of the invention With the schematic cross-section of cover glass.
Specific embodiment
The closely sealed overlay film forming agent of the present invention contains the hydrolytic condensate of the alkoxy silane as (A) and as (B) The aluminium salt of composition.
＜ (A) composition ＞
It is comprising selected from the alkane shown in following formula (I)s and (II) as the hydrolytic condensate of the alkoxy silane of (A) composition The hydrolytic condensate of the alkoxy silane composition of at least a kind in TMOS.
Si(OR1)4 (I)
R1Represent the alkyl of carbon number 1～5.From from the viewpoint of reactivity, as OR1Base, preferably methoxyl group, ethoxy Base or propoxyl group.
The concrete example of the alkoxy silane shown in formula (I) is included, but is not limited to these.Such as four methoxies can be included Base silane, tetraethoxysilane, tetraisopropoxysilan, four positive propoxy silane, four n-butoxy silanes, four sec-butoxy silicon Alkane, four tert-butoxy silanes, four amoxy silane etc..
When alkoxy silane shown in formula (I) is 40 moles of below % in whole alkoxy silanes, cannot fill sometimes The hardness divided, therefore preferably 40 moles more than %.More preferably 50 moles more than %.More preferably 80 moles % with On.
R2 mSi(OR3)4-m (II)
R2Expression be optionally selected from by halogen atom, vinyl, methacryloxy, acryloxy, styryl, At least a kind in the group of phenyl and cyclohexyl composition replaces and optionally the alkyl with heteroatomic carbon number 1～20, hydrogen are former Son, halogen atom, vinyl, methacryloxy, acryloxy, styryl, phenyl, cyclohexyl, amino, epoxy third Epoxide, sulfydryl, NCO or urea groups.It should be noted that R1、R2And R3For it is multiple when, R1、R2And R3Earth's surface independent of one another Show above-mentioned definition.
R3The alkyl of carbon number 1～5 is represented, m represents 1～3 integer.It should be noted that R3For it is multiple when, R3That This independently represents above-mentioned definition.From from the viewpoint of reactivity, as OR3Base, preferably methoxy or ethoxy.
The concrete example of the alkoxy silane shown in formula (II) is included, but is not limited to these.Such as 3- first can be included Base acryloxypropyl trimethoxy silane, 3- methacryloxypropyls, methacryloxy MTMS, methacryloxymethyl triethoxysilane, 3- acryloxypropyl trimethoxy silanes, 3- acryloxypropyl triethoxysilanes, acryloyl-oxyethyl trimethoxy silane, three ethoxy of acryloyl-oxyethyl Base silane, styryl ethyl trimethoxy silane, styryl ethyl triethoxysilane, 3- (N- styrylmethyl -2- Aminoethylamino) propyl trimethoxy silicane, 4- (trimethoxysilyl) styrene, vinyltrimethoxy silane, VTES, 3,3,3- trifluoro propyl trimethoxy silanes, 3- chloropropyl triethoxysilanes, 3- bromopropyls three Ethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, diethyldiethoxysilane, diethyl two Methoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane trimethylethoxysilane, trimethyl methoxy Silane, 3- (2- aminoethylaminopropyls) trimethoxy silane, 3- (2- aminoethylaminopropyls) triethoxysilane, 2- Aminoethylaminomethyl trimethoxy silane, 2- (2- aminoethylthio ethyls) triethoxysilane, 2- (3,4- epoxide rings Hexyl) ethyl trimethoxy silane, 3- glycidoxypropyl dimethoxysilanes, 3- glycidoxypropyl group trimethoxies Base silane, 3- glycidoxypropyl diethoxy silanes, 3- glycidoxypropyl group triethoxysilanes, 3- sulfydryls third Ethyl triethoxy silicane alkane, mercapto methyl trimethoxy silane, 3- isocyanates propyl-triethoxysilicanes, 3- mercaptopropyi front threes TMOS, 3-amino propyl methyl diethoxy silane, 3- dimethyl Ethoxysilanes, γ-three second of urea propyl group TMOS, γ-urea propyl trimethoxy silicane, γ-urea propyl group tripropoxy silane etc..
It should be noted that from storage stability and low-temperature bake when hardness from the viewpoint of, the present invention's closely sealed covers The hydrolytic condensate of the alkoxy silane contained in film forming agent is preferably below 5 aggressiveness, more preferably 2～4 aggressiveness.
The hydrolytic condensate of the alkoxy silane can be condensed in the presence of alkali and water.The amount of alkali is relative to alkoxyl Silane is preferably 0.01 times mole～2 times moles, more preferably 0.05 times mole～1 times mole.The amount of water is relative to alkane TMOS is preferably 0.5 times mole～10 times moles, more preferably 1 times mole～5 times moles.
＜ (B) composition ＞
As the aluminium salt that contains in the closely sealed overlay film forming agent of the present invention, can include aluminium chloride, aluminum nitrate, aluminum sulfate, Aluminium acetate, oxalic acid aluminium, sulfamic acid aluminium, sulfonic acid aluminium, acetoacetate aluminium, aluminium acetylacetonate, their hydrate, aqueous salt or alkali Formula salt.
Wherein, from from the viewpoint of the storage-stable of the easiness and overlay film forming agent that obtain, particularly preferred aluminum nitrate Salt.
The anti-precipitation agent ＞ of ＜
From from the viewpoint of storage stability, in the closely sealed overlay film forming agent of the present invention, anti-precipitation agent is preferably comprised.Anti- analysis Go out agent for preventing aluminium salt from separating out in overlay film when overlay film being formed by the closely sealed overlay film forming agent of the present invention.
As anti-precipitation agent, N- methyl-pyrrolidons, ethylene glycol, dimethylformamide, dimethylacetamide can be included Amine, diethylene glycol, propane diols, hexylene glycol, their derivative etc., it is possible to use a kind in them or be used in mixed way 2 kinds with On.
＜ organic solvent ＞
The closely sealed overlay film forming agent of the present invention is usually contained for making above-mentioned (A) composition and (B) composition dissolve or scattered Organic solvent.The organic solvent is preferably in the film for forming closely sealed overlay film forming agent and heats the film and obtains closely sealed Dissipate during overlay film, do not residue in the closely sealed overlay film to be formed.Accordingly, as the organic solvent, make above-mentioned (A) composition and (B) composition dissolve well or disperse, and boiling point to be preferably 60～250 DEG C, more preferably 75～200 DEG C of solvent be suitable 's.
As the example of organic solvent, can include the esters such as the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanol, ethyl acetate, The ketones such as the ethers such as the glycols such as ethylene glycol and its ether derivant, ester derivant, diethyl ether, acetone, MEK, cyclohexanone, benzene, Toluene etc. is aromatic hydrocarbon etc..Wherein, from from the viewpoint of the residual and coating of solvent, preferred alcohol, propyl alcohol or the third two Alcohol monomethyl ether.
＜ other compositions ＞
The present invention closely sealed overlay film forming agent can not damage in the range of effect of the present invention comprising it is other than the above into Point, such as inorganic particles, metal oxygen alkane (metalloxane) monomer, metal oxygen alkane oligomer, metal oxygen alkane polymer, crosslinking The compositions such as agent, organic polymer, levelling agent, surfactant.
The manufacture ＞ of the closely sealed overlay film forming agents of ＜
The present invention closely sealed overlay film forming agent by will be as above-mentioned (A) composition selected from the alkane shown in formula (I) and (II) At least a kind in TMOS is mixed in the organic solvent containing water with the aluminium salt as (B) composition and is manufactured.Formula (I) and (II) there is hydrolyzing/condensing in the alkoxy silane shown in, be converted into hydrolytic condensate by contacting with water.Thus, the present invention Closely sealed overlay film forming agent can be dissolving in organic solvent or the dispersedly hydrolytic condensate containing alkoxy silane and aluminium The form of the composition of salt and obtain.
With regard to organic solvent used herein, also including including preferred characteristics, it is possible to use the closely sealed overlay film with the present invention The above-mentioned organic solvent identical material contained in forming agent.
For the content of each composition in the closely sealed overlay film forming agent of the present invention, will be used as the alkoxy silane of (A) composition Hydrolytic condensate and when being converted with the solid constituent of metal oxide as the aluminium salt of (B) composition, preferably 0.1～ 20 mass %, more preferably 0.5～6 mass %.When content is more than 20 mass %, the storage-stable of composition is deteriorated, and The film thickness monitoring of the diaphragm for being formed becomes difficult.On the other hand, when being below 0.1 mass %, resulting diaphragm Lower thickness, needs repeatedly to form film to obtain the thickness for specifying, the manufacture of closely sealed overlay film is complicated.
The water yield used in hydrolysis as the alkoxy silane of (A) composition is with mol ratio (amount (mole) of water)/used The total moles of alkoxy silane) meter preferably more than 0.5, more preferably 1～5.When the mol ratio is more than 0.5, above-mentioned alcoxyl The hydrolysis of base silane fully improves film forming, and the closely sealed film strength of covering obtained by making increases.
It should be noted that in above-mentioned hydrolysis, when the aqueous salt as the aluminium salt of (B) composition coexists, the water content is joined With reaction, therefore for the water yield used in hydrolysis, need to count the water content of slaine in.
The temperature during hydrolysis of alkoxy silane is preferably carried out in the range of 20～100 DEG C.Wherein, it is appropriate from obtaining From the viewpoint of the condensation product of molecular weight, more preferably 25～80 DEG C of scope.As the time of hydrolysis, fit from molecular weight is obtained When condensation product from the viewpoint of, preferably 30 minutes～48 hours, more preferably 30 minutes～24 hours.
Anti- precipitation agent can be hydrolyzed in the presence of aluminium salt in alkoxy silane/condensation reaction when add, it is also possible to Add after their hydrolyzing/condensing reaction terminates.
With regard to anti-precipitation agent, the aluminium of aluminium salt is converted into into aluminum oxide, the weight rate of (anti-precipitation agent/aluminum oxide) is preferably More than 1, more preferably 2～20.When the ratio is less than 1, film prevents the effect that metal is salted out from diminishing when being formed.
The hydrolytic condensate of the alkoxy silane as (A) composition contained in the closely sealed overlay film forming agent with regard to the present invention With the containing ratio of the aluminium salt as (B) composition, aluminium atom relative to silicon atom total mole number (Si) and aluminium atom mole The mol ratio (Al/ (Si+Al)) of the summation of number (Al) is preferably 0.1～0.5, more preferably 0.2～0.4.The mol ratio is 0.1 During the above, for less than 0.5 when, it is possible to increase as the closely sealed characteristic of target.
The closely sealed overlay film ＞ of ＜
The closely sealed overlay film forming agent of the present invention is coated into the surface as aluminum oxide substrate or aluminium base and is oxidized aluminium The substrate of covering, and carry out roasting such that it is able to closely sealed overlay film is obtained in substrate surface.
As the closely sealed overlay film forming agent for using the present invention, in the method that substrate surface forms its film, it is possible to use each Plant rubbing method to carry out.It is, for example possible to use dip coating, method of spin coating, spraying coating method, brushing method, roller transfer method, silk screen Print process, ink-jet method, flexible printing method etc..
Then, the film for being formed at substrate surface is heated at a temperature of such as 50～100 DEG C, preferably 60～80 DEG C and is made After dried coating film, more than 100 DEG C, at a temperature of preferably 100～600 DEG C, more preferably 300～600 DEG C roasting more than 10 minutes, It is preferred that 0.5～2 hour such that it is able to obtain the closely sealed overlay film of dense membrane structure.These heating can use baking oven, heat The devices such as plate are carrying out.It should be noted that the above-mentioned heating for making dried coating film can also be omitted.
Operate as discussed above, overlay film is formed on aluminum oxide substrate by the closely sealed overlay film forming agent of the present invention.This is closely sealed Overlay film can be used as forming the closely sealed auxiliary layer function of smears on its surface, and the smears is used for forming various Characteristic overlay film.For example, when anti-fouling agent is used as smears, can obtain the oxidation that surface has excellent anti-scratch Flaw characterization overlay film Aluminium base.
＜ aluminum oxide substrate ＞
The closely sealed overlay film forming agent of the present invention is for forming closely sealed overlay film on the surface of aluminum oxide substrate or aluminium base.That is, Closely sealed overlay film is formed on the surface of aluminum oxide substrate, then, forms what is obtained by specific smears on the surface of closely sealed overlay film Functional membrane.Closely sealed overlay film is formed directly into the surface of aluminum oxide substrate by the closely sealed overlay film forming agent of the invention described above.
As one of functional membrane, stain-proofing layer can be included.Stain-proofing layer can pass through coating anti-pollution agent and carry out roasting And formed.Sapphire glass is used as substrate, the overlay film obtained by the closely sealed overlay film forming agent of the present invention is formed on, is connect And form the overlay film 2 obtained by anti-fouling agent, so as to obtain excellent marresistance.
Closely sealed overlay film, the thickness of functional membrane are both preferably 5～1000nm, more preferably 10～400nm.
The closely sealed overlay film forming agent of the present invention is effective for the aluminum oxide of various crystal structures.Except aoxidizing as monocrystalline Outside the sapphire glass of aluminium, the aluminum oxide of polycrystalline or amorphous is can be also used for.
In addition, the surface of metallic aluminium can aoxidize in atmosphere and form aluminum oxide overlay film, therefore the closely sealed overlay film of the present invention Forming agent can be used for the structure formed by metal aluminum substrate.
In the present invention, the functional membrane being arranged on closely sealed overlay film is not particularly limited.As concrete example, can include by Anti-fouling agent, coating, bonding agent, antireflection agent, water repellent, hydrophilizing agent, oil-repellent agent, oleophylic agent, hard paint, anti-slip material etc. are obtained Overlay film.
＜ touch panels cover glass ＞
As the typical example of the aluminum oxide substrate obtained using the closely sealed overlay film forming agent of the present invention, Fig. 1 institutes can be included The touch panel cover glass for showing.Schematic cross-sections of the Fig. 1 for touch panel cover glass.Touch panel cover glass 1 clips closely sealed overlay film 3 on the surface of sapphire glass 4 with functional membrane 2.Closely sealed overlay film 3 is using the closely sealed of the present invention Overlay film forming agent is formed directly into the overlay film on the surface of sapphire glass.As one of functional membrane 2, can include antifouling Layer.Stain-proofing layer by coating anti-pollution agent and can carry out roasting and be formed.
The closely sealed overlay film obtained by the overlay film forming agent of the present invention is formed on sapphire glass, is subsequently formed anti-fouling agent Film, so as to be rubbed using finger, object, it is also possible to which anti-fouling agent is maintained on sapphire glass.Thereby, it is possible to prevent Using marresistance during touch panel, water repellency, the deterioration of oil repellent and it is stained with the problem of fingerprint etc..
Embodiment
Embodiment described below, illustrates the present invention, but the present invention not the being limited to property solution because of following embodiments etc. Release.
[compound and its abbreviation]
TEOS：Tetraethoxysilane AN：Aluminum nitrate nonahydrate
EtOH：Ethanol PGME：Propylene glycol monomethyl ether
HG：Hexylene glycol PB：Propylene glycol monobutyl ether
BCS：Ethylene glycol monobutyl ether
Anti-fouling agent：The manufacture of FT-Net companies, P-5425-0.2
1 ＞ of ＜ embodiments
EtOH (22.49g), water (7.42g) and AN (12.88g) is put in four mouthfuls of reaction flasks, is stirred.Then, Input EtOH (28.60g) and TEOS (28.60g), stir 1 hour at 20 DEG C, so as to prepare solution.
The solution (30g) is mixed with HG (14g), PB (10.5g), BCS (10.5g) and PGME (35g), it is close so as to obtain Close overlay film forming agent.
2 ＞ of ＜ embodiments
EtOH (22.93g), water (6.6g) and AN (19.62g) is put in four mouthfuls of reaction flasks, is stirred.Then, Input EtOH (25.43g) and TEOS (25.43g), are stirred 1 hour, in a water bath so as to prepare solution.
The solution (30g) is mixed with HG (14g), PB (10.5g), BCS (10.5g) and PGME (35g), it is close so as to obtain Close overlay film forming agent.
1 ＞ of ＜ comparative examples
In four mouthfuls of reaction flasks for possessing return duct put into EtOH (33.87g), as the TEOS of alkoxy silane (34.72g), it is stirred.Then, it was added dropwise with 30 minutes and puts into EtOH (16.94g), water (13.6g) and contain 60 weight of nitric acid The aqueous solution (0.88g) of amount %, is stirred.Then, flow back 3 hours, naturally cool to room temperature, so as to prepare solution.
The solution (30g) is mixed with HG (14g), PB (10.5g), BCS (10.5g) and PGME (35g), it is close so as to obtain Close overlay film forming agent.
[making of the sapphire glass with anti-fouling agent film]
Using spin coater, the closely sealed overlay film forming agent of above-described embodiment 1,2 and comparative example 1 is respectively coated in thickness Sapphire glass (monocrystalline sapphire glass, the surface roughness of 0.7mm：Below), 3 minutes are carried out with 80 DEG C on hot plate It is dried.Then, heat 30 minutes at 150 DEG C or 300 DEG C in dustless baking oven, so as to obtain the enforcement of 50～100nm of thickness The closely sealed overlay film of example and comparative example.
Then, using spin coater, the anti-fouling agent as the smears for forming functional membrane is coated subsidiary The substrate of the closely sealed overlay film obtained by embodiment and comparative example.Then, with 80 DEG C of dryings 3 minutes on hot plate, then, dustless Heated 20 minutes with 170 DEG C in baking oven, there is so as to manufacture surface the sapphire glass of anti-fouling agent film.
In comparative example 2, the closely sealed overlay film forming agent that embodiment and comparative example is not used carries out film, has made in sapphire The substrate of anti-fouling agent film is formed directly with glass substrate.
[abrasion performance evaluation：Steel wool marresistance is tested]
It is being held on the platform of reciprocating marresistance testing machine (Daiei science essence device makes the manufacture of Co., Ltd. of institute) On the surface of the sapphire glass substrate made by above-described embodiment and comparative example, with area as 2cm2Square pad contact Mode loads steel wool (Japanese steel wool Co., Ltd. manufacture, the registration mark of #0000 grades：BON STAR), by above-mentioned pad With imposed load 1000g, it is per minute carry out 25 reciprocal speed from 0 time back and forth rubbed to 1000 times it is reciprocal. Often rub 200 times back and forth, using contact angle meter (manufacture of consonance interface science Co., Ltd., DM-701), carry out the water of 3 μ L of liquid measure Contact angle determination.Measurement result is shown in table 1 in the lump.
[table 1]
As shown in table 1, even if the sapphire glass substrate with anti-fouling agent of embodiment 1,2 carries out 800 reciprocal steel wires Cotton rubs, and water contact angle is also more than 90 °, and from 20 ° initial of deficient change, confirmation can obtain good marresistance.
On the other hand, reciprocal steel wool rubs the sapphire glass substrate with anti-fouling agent of comparative example 1,2 due to 800 times Wipe, water contact angle becomes less than 90 °, reduces more than 20 °.
Industrial applicability
With soil resistance film as clipping the feature that formed by the overlay film that obtains of closely sealed overlay film forming agent of the present invention The excellent scratch resistance of the aluminum oxide substrate of film, can act as cover glass (windshield), the shield of camera lens of clock and watch Touch panel substrate of glass, smart mobile phone, panel computer etc. etc..
It should be noted that quote saying for Japanese patent application 2014-111610 filed in 29 days Mays in 2014 herein Bright book, claims, the full content of drawing and description summary, used as the disclosure of the specification of the present invention.
Description of reference numerals
1 touch panel, 2 functional membrane of cover glass
3 closely sealed coating layer, 4 sapphire glass substrate

Claims (10)

1. a kind of closely sealed overlay film forming agent of aluminum oxide substrate or aluminium base, it is characterised in that the water containing alkoxy silane Solution condensation product and aluminium salt.
2. closely sealed overlay film forming agent according to claim 1, wherein, the hydrolytic condensate of alkoxy silane is comprising being selected from The hydrolytic condensate of the alkoxy silane of at least a kind in the group that the alkoxy silane shown in following formula (I)s and (II) is constituted,
Si(OR1)4 (I)
R2 mSi(OR3)4-m (II)
In above-mentioned formula (I) and (II), R1And R3The alkyl of carbon number 1～5, R is represented independently of one another2Expression is optionally selected from In the group be made up of halogen atom, vinyl, methacryloxy, acryloxy, styryl, phenyl and cyclohexyl At least a kind alkyl for replacing and optionally there is heteroatomic carbon number 1～20, hydrogen atom, halogen atom, vinyl, methyl Acryloxy, acryloxy, styryl, phenyl, cyclohexyl, amino, glycidoxy, sulfydryl, NCO or Urea groups, m represent 1～3 integer.
3. closely sealed overlay film forming agent according to claim 1 and 2, wherein, the aluminium salt is selected from aluminium chloride, nitric acid Aluminium, aluminum sulfate, aluminium acetate, oxalic acid aluminium, sulfamic acid aluminium, sulfonic acid aluminium, acetoacetate aluminium, aluminium acetylacetonate and their basic salt At least a kind in the group of composition.
4. the closely sealed overlay film forming agent according to any one of claims 1 to 3, wherein, the aluminium salt is nitric acid aluminium salt.
5. the closely sealed overlay film forming agent according to any one of Claims 1 to 4, wherein, aluminium atom is relative to silicon atom The mol ratio (Al/ (Si+Al)) of the summation of the molal quantity (Al) of total mole number (Si) and aluminium atom is 0.1～0.5.
6. the closely sealed overlay film forming agent according to any one of Claims 1 to 5, which is also containing selected from N- methyl-pyrrols Alkanone, ethylene glycol, dimethylformamide, dimethyl acetamide, diethylene glycol, propane diols, hexylene glycol and their derivative group Into group at least a kind as anti-precipitation agent.
7. a kind of overlay film, its usage right require the closely sealed overlay film forming agent any one of 1～6 and obtain.
8. a kind of aluminum oxide substrate or aluminium base, which has the overlay film described in claim 7.
9. a kind of touch panel, which has the overlay film described in claim 7.
10. the forming method of the closely sealed overlay film of a kind of aluminum oxide substrate or aluminium base, wherein, for by claim 1～6 Closely sealed overlay film forming agent described in any one coats the film of aluminum oxide substrate or aluminium base, enters at 100～600 DEG C Row roasting.
CN201580040161.6A 2014-05-29 2015-05-27 Adhesive coating forming agent for alumina substrate or aluminum substrate Active CN106536651B (en)

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