CN108699390A - Hard paint and stacked film - Google Patents

Hard paint and stacked film Download PDF

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Publication number
CN108699390A
CN108699390A CN201780014286.0A CN201780014286A CN108699390A CN 108699390 A CN108699390 A CN 108699390A CN 201780014286 A CN201780014286 A CN 201780014286A CN 108699390 A CN108699390 A CN 108699390A
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CN
China
Prior art keywords
ingredient
hard
stacked film
hard paint
paint
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Pending
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CN201780014286.0A
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Chinese (zh)
Inventor
七岛祐
泉达矢
樫尾干广
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Lintec Corp
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Lintec Corp
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Priority to CN202110806095.6A priority Critical patent/CN113528007A/en
Publication of CN108699390A publication Critical patent/CN108699390A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention is:Hard paint contains following (A) ingredients, (B) ingredient and (C) ingredient;And stacked film, there is the hard conating formed using the hard paint.(A) ingredient:Organo-silicon compound (B) ingredient with reactive functional groups and hydrolization group:Multi-thioalcohol compound (C) ingredient:Inorganic filler with reactive functional groups.According to the present invention, providing with good efficiency can form hardness high and the hard paint of marresistance and the excellent hard conating of resistance to bend(ing) and the stacked film with the hard conating for using the hard paint to be formed.

Description

Hard paint and stacked film
Technical field
The present invention relates to high hardness, marresistance and the excellent hard conating of resistance to bend(ing) can be formed with good efficiency Paint and the stacked film with the hard conating for using hard paint formation firmly.
Background technology
In recent years, the display devices such as various displays have touch panel, be used as data input device the case where it is also gradual Become more.
When using such touch panel, in general, making pen, referring to and contacted with the surface of touch panel.Therefore, to touch panel Surface, it is desirable that will not be damaged because pen, the contact referred to are repeated.
Therefore, it had carried out that hard conating is arranged to the resin film for constituting touch panel in the past.
For example, in patent document 1, describe containing organo-silicon compound and polythiol with reactive functional groups The resin composition for formation of transparent coating layer for closing object, the method for forming transparent coating using the resin combination.In addition, should In document, pliability, hardness, marresistance and the resistance to abrasion of the transparent coating formed using the resin combination are also described Property is excellent.
Existing technical literature
Patent document
Patent document 1:No. 2010/103944 pamphlet of International Publication No..
Invention content
The subject that the invention solves
As described above, in patent document 1, pliability, hardness, marresistance and the abrasion resistence of the transparent coating are described Etc. excellent.
However, in order to form such transparent coating, need that resin combination is made fully to cure, according to condition of cure, have Shi Wufa forms the transparent coating with target capabilities.
The present invention carries out in view of the foregoing, it is therefore intended that, hardness height, anti-scratch can be formed with good efficiency by providing The hard paint of wound property and the excellent hard conating of resistance to bend(ing) and with the stacked film for using hard conating that the hard paint formed.
The means used to solve the problem
The inventors of the present invention in order to solve the above problems, have made intensive studies for hard paint.Itself as a result, it has been found that, by using containing There are organo-silicon compound with reactive functional groups and hydrolization group, multi-thioalcohol compound and with reactive functional The hard paint of the inorganic filler of group can form hardness height and the hard conating of excellent scratch resistance, to complete with good efficiency At the present invention.
Therefore, according to the present invention, the stacked film of the hard paint and following (4) of following (1) ~ (3) is provided.
(1) hard paint, containing following (A) ingredients, (B) ingredient and (C) ingredient,
(A) ingredient:Organo-silicon compound with reactive functional groups and hydrolization group
(B) ingredient:Multi-thioalcohol compound
(C) ingredient:Inorganic filler with reactive functional groups.
(2) according to the hard paint described in (1), wherein the content of aforementioned (B) ingredient is 50 ~ 120 matter relative to (A) ingredient Measure %.
(3) according to the hard paint described in (1) or (2), wherein the content of aforementioned (C) ingredient relative to (A) ingredient be 30 ~ 130 mass %.
(4) stacked film, is the stacked film with substrate layer and hard conating, and aforementioned hard conating is to use in (1) ~ (3) to appoint Hard paint described in one and formed.
Invention effect
According to the present invention, the hard conating that hardness is high, marresistance and resistance to bend(ing) are excellent can be formed with good efficiency by providing Hard paint and with the stacked film for using hard conating that the hard paint formed.
Specific implementation mode
Hereinafter, being divided into 1) hard paint and 2) the present invention will be described in detail for the project of stacked film.
1) hard paint
The hard paint of the present invention contains following (A) ingredients, (B) ingredient and (C) ingredient,
(A) ingredient:Organo-silicon compound with reactive functional groups and hydrolization group
(B) ingredient:Multi-thioalcohol compound
(C) ingredient:Inorganic filler with reactive functional groups.
It is (following to be also referred to as that the hard paint of the present invention contains the organo-silicon compound with reactive functional groups and hydrolization group For " organo-silicon compound (A) ") it is used as (A) ingredient.
Reactive functional groups in organo-silicon compound (A) are to refer to react with the sulfydryl of (B) ingredient and form chemistry The group of key.
As the reactive functional groups, vinyl, allyl, styryl, (methyl) acryloxy etc. can be enumerated Group with carbon-to-carbon unsaturated bond;Epoxy group;Isocyanate group;Sulfydryl etc..Wherein, it is however preferred to have carbon-to-carbon unsaturated bond Group, more preferably vinyl.
Hydrolization group in organo-silicon compound (A) is to refer to form siloxanes key (Si-O- by hydrolysis Si keys) group.
As the hydrolization group, it is 1 ~ 10, preferably that can enumerate the carbon atom numbers such as methoxyl group, ethyoxyl, positive propoxy For 1 ~ 5 alkoxy;The aryloxy group that the carbon atom numbers such as phenoxy group are 6 ~ 15, preferably 6 ~ 10;Formyloxy, acetoxyl group, third The acyloxy that the carbon atom numbers such as acyloxy are 1 ~ 10, preferably 1 ~ 5;Halogen atoms such as chlorine atom, bromine atom etc..Wherein, preferably For carbon atom number be 1 ~ 10 alkoxy or carbon atom number be 1 ~ 10 acyloxy, more preferably carbon atom number be 1 ~ 10 acyl-oxygen Base.
As organo-silicon compound (A), following formula (I) compounds represented can be enumerated.
[Change 1]
In formula (I), R1Indicate the group with reactive functional groups, R2Indicate hydrolization group, R3Indicate do not have reactive official The non-hydrolyzable group that can be rolled into a ball.
X is 1,2 or 3, and y is that 1,2 or 3, z is 0,1 or 2, and x, y, z adds up to 4.
X, when y or z is 2 or more, multiple R1,R2Or R3Can be identical, it can also be different from each other.
As R1, reactive functional groups, the group with reactive functional groups can be enumerated.It, can as these concrete examples There is the group of vinyl to enumerate vinyl, ethyleneoxy methyl etc.;Allyl, allyloxy methyl etc. have allyl Group;Styryl, styrylmethyl etc. have the group of styryl;(methyl) acryloyl group, 3- (methyl) acryloyl Oxygroup propyl etc. has the group of (methyl) acryloyl group;Epoxy group, glycidyl, 3- glycidoxypropyl groups etc. have ring The group of oxygroup;Isocyanate group, 3- isocyanatopropyls etc. have the group of isocyanate group;Sulfydryl, 3- mercaptopropyis Deng the group etc. with sulfydryl.Wherein, it is however preferred to have the group of carbon-to-carbon unsaturated bond, more preferably vinyl.Here, (first Base) acryloyl group refers to acryloyl group or methylacryloyl(It is same as below).
R1Carbon atom number be preferably 2 ~ 20, more preferably 2 ~ 10.
As R2, aforementioned hydrolization group can be enumerated.
R2Carbon atom number be preferably 0 ~ 15, more preferably 0 ~ 10.
As R3, the alkane that the carbon atom numbers such as methyl, ethyl, n-propyl, isopropyl are 1 ~ 20, preferably 1 ~ 15 can be enumerated Base;The aryl etc. that the carbon atom numbers such as phenyl, 1- naphthalenes are 6 ~ 20, preferably 6 ~ 15.
As organo-silicon compound (A), vinyltrimethoxysilane, vinyltriethoxysilane, second can be enumerated The silane compounds containing vinyl such as alkenyl triacetoxysilane, vinyl trichlorosilane, vinyl tribromosilane;Allyl Trimethoxy silane, allyltriethoxysilane, allyl triacetoxysilane, allyltrichlorosilane, allyl three The silane compound containing allyl such as bromo-silicane;γ-acryloyloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-acryloxypropyl trichlorosilane, γ-acryloxypropyl tribromosilane etc. contains γ-acryloyl The silane compound of oxygroup alkyl;γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl Triethoxysilane, γ-methacryloxypropyl trichlorosilane, γ-methacryloxypropyl tribromosilane etc. contains The silane compound of γ-methacryloxyalkyl;α-glycidoxyethyl trimethoxy silane, α-glycidoxy second Ethyl triethoxy silicane alkane, beta epoxide Among trimethoxy silane, beta epoxide Among triethoxysilane, α-ring Oxygen Among trichlorosilane, α-glycidoxyethyl tribromosilane, beta epoxide Among trichlorosilane, beta epoxide The silane compound etc. containing epoxy group such as Among tribromosilane.
Wherein, as organo-silicon compound (A), the preferably silane compound containing vinyl, more preferably vinyl three Acetoxylsilane.
Organo-silicon compound (A) can be used alone, or two or more is applied in combination.
The hard paint of the present invention contains multi-thioalcohol compound and is used as (B) ingredient.
By using the hard paint containing multi-thioalcohol compound except aforementioned organic silicon compound (A), can be formed The hard conating that bright property is excellent, pencil hardness is high, resistance to bend(ing) is excellent.
Multi-thioalcohol compound refers to the compound in the molecule with 2 or more sulfydryls.
As multi-thioalcohol compound, ethylenebis (mercaptoacetate), ethylenebis (3-thiopropionate) can be enumerated The compound that equal sulfydryls number is 2;Trimethylolethane trimethacrylate (mercaptoacetate), trimethylolethane trimethacrylate (3-thiopropionate), The compound that the sulfydryls numbers such as trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-thiopropionate) are 3;Season Penta tetrol four (mercaptoacetate), pentaerythrite four (3-thiopropionate), dipentaerythritol six (mercaptoacetate), two seasons penta The compound etc. that the sulfydryls numbers such as tetrol six (3-thiopropionate) are 4 or more.
Wherein, as multi-thioalcohol compound, the compound that compound or sulfydryl number that preferably sulfydryl number is 3 are 4 or more, More preferably trimethylolpropane tris (mercaptopropionic acid ester).
Multi-thioalcohol compound can be used alone, or two or more is applied in combination.
The content of multi-thioalcohol compound is not particularly limited.The content of multi-thioalcohol compound is usually relative to (A) ingredient 50 ~ 120 mass %, preferably 60 ~ 100 mass %, more preferably 60 ~ 90 mass %.
If forming hard conating using the very few hard paint of the content of multi-thioalcohol compound, it is likely that in stacked film It crimps.On the other hand, if using the excessive hard paint of multi-thioalcohol compound, it is likely that be difficult to be formed with high hardness hard Coating.
The hard paint of the present invention contains the inorganic filler with reactive functional groups, and (it refers to by moditied processing in table The inorganic filler of reactive functional groups has been imported on face;Hereinafter, sometimes should (C) ingredient be known as " inorganic filler (C) ") conduct (C) ingredient.
By using the hard painting for containing inorganic filler (C) except aforementioned organic silicon compound (A) and multi-thioalcohol compound Agent can form the hard conating that the transparency is excellent, pencil hardness is high, resistance to bend(ing), resistance to bend(ing), crimpiness are excellent.
The reactive functional groups for including in inorganic filler (C) are to refer to react with the sulfydryl of (B) ingredient and form chemistry The group of key.As the reactive functional groups, it can enumerate as the reactive functional groups of organo-silicon compound (A) and show Same functional group.Wherein, it is however preferred to have the group of carbon-to-carbon unsaturated bond, more preferably (methyl) acryloxy.
As the inorganic constituents (constituent of the inorganic filler before moditied processing) for constituting inorganic filler (C), Ke Yiju Go out metal oxide, metal hydroxides, metal salt etc..
As metal oxide, silica, titanium oxide, aluminium oxide, boehmite, chromium oxide, nickel oxide, oxygen can be enumerated Change copper, titanium oxide, zirconium oxide, indium oxide, zinc oxide etc..
As metal hydroxides, aluminium hydroxide etc. can be enumerated.
As metal salt, the metal carbonates such as calcium carbonate, magnesium carbonate can be enumerated;The metal sulfates such as calcium sulfate, barium sulfate Salt;Metal silicates such as alumina silicate, calcium silicates, magnesium silicate etc..
Wherein, as the inorganic constituents for constituting inorganic filler (C), preferably metal oxide, more preferably silica.
The shape of inorganic filler (C) can be spherical, chain, needle-shaped, plate, sheet, it is rodlike, fibrous etc. any one, It is preferably spherical.Here, spherical refers to also referring to including ellipsoid of revolution, oval, golden flat sugared shape, cocoon-like other than proper sphere shape Etc. can be approximately sphere it is polyhedron-shaped including approximate sphericity.
The size of inorganic filler (C) is not particularly limited.The average grain diameter of inorganic filler (C) is usually 5 ~ 1000nm, excellent It is selected as 7 ~ 500nm, more preferably 10 ~ 100nm, particularly preferred 10 ~ 30nm.
Average grain diameter by making inorganic filler (C) can form the transparency with good efficiency within the above range Excellent and excellent scratch resistance hard conating.
The average grain diameter of inorganic filler (C) specific surface area can calculate obtained from as BET method.
In the hard paint of the present invention, inorganic filler (C) can be used alone, or two or more is applied in combination.
The content of inorganic filler (C) is not particularly limited.The content of inorganic filler (C) relative to (A) ingredient be usually 30 ~ 130 mass %, preferably 60 ~ 125 mass %.
Particularly, if using inorganic filler (C) content relative to(A)Ingredient is the hard paint of 90 ~ 125 mass %, then It is easy to form hard conating with high hardness.
In addition, if using inorganic filler (C) content relative to(A)Ingredient is the hard paint of 90 ~ 125 mass %, then holds Easily form the hard conating of excellent scratch resistance.
The present invention hard paint in a range that does not hinder the effect of the present invention, can contain in addition to (A) ingredient, (B) at Divide, the other compositions except (C) ingredient.As other compositions, solvent, Photoepolymerizationinitiater initiater can be enumerated.
The coating of hard paint containing solvent is excellent, therefore by using the hard paint containing solvent, can be with good Efficiency form thin hard conating.
As solvent, the aromatic hydrocarbons such as the aliphatic hydrocarbons such as hexane, heptane, hexamethylene series solvent, toluene, dimethylbenzene can be enumerated Series solvent;The halogenations hydrocarbon system solvents such as dichloromethane, 1,2- dichloroethanes;Methanol, ethyl alcohol, propyl alcohol, butanol, 1- methoxyl groups -2- third The alcohol series solvents such as alcohol;The ketone series solvents such as acetone, methyl ethyl ketone, 2 pentanone, methyl iso-butyl ketone (MIBK), isophorone;Ethyl acetate, The ester series solvents such as butyl acetate;Cellosolves series solvent such as ethyl cellosolve etc..
Solvent can be used alone, or two or more is applied in combination.
When the hard paint of the present invention contains solvent, the content of solvent is preferably such that the solid constituent of the hard paint of the present invention Concentration reaches the amount of 30 ~ 95 mass % or more, more preferably so that reaching the amount of 35 ~ 90 mass %, further preferably so that reaching To the amount of 40 ~ 85 mass %.
By using the hard paint containing Photoepolymerizationinitiater initiater, after being coated with hard paint, gained can be made with good efficiency Curing of coating.
As Photoepolymerizationinitiater initiater, it can be cited for example that benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2,2- dimethoxys- 2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketone, 1- hydroxy cyclohexylphenyls Base phenyl ketone, 2- methyl-1s-[4- (methyl mercapto) Ben Jis ]- 2- morpholinoes -propyl- 1- ketone, 4- (2- hydroxyl-oxethyls) (hydroxyl of phenyl -2 Base -2- propyl) ketone, benzophenone, to phenyl benzophenone, 4,4'Diethylamino benzophenone, dichloro benzophenone, 2- Tectoquinone, 2- ethyl hydrazine, 2- tertiary butyls anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyls thioxanthones, 2- diurils Ton ketone, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, benzil dimethyl acetal, acetophenone dimethylacetal, to two Methylaminobenzoic acid ester etc..
Photoepolymerizationinitiater initiater can be used alone, or two or more is applied in combination.
The hard paint of the present invention is when containing Photoepolymerizationinitiater initiater, the solid of the content of Photoepolymerizationinitiater initiater relative to hard paint Ingredient total amount is usually 0.01 ~ 10 mass %, preferably 0.5 ~ 10 mass %.
The hard paint of the present invention contains aforementioned (A) ingredient, (B) ingredient and (C) ingredient.Also, (A) ingredient, (C) ingredient In include reactive functional groups can be reacted with the sulfydryl for including in (B) ingredient, and these reactive functional groups also can It reacts with each other.
Like this, hard paint of the invention can utilize both reactions that the reaction of sulfydryl participation and sulfydryl are not involved in, because This can form hardness height and the hard conating of excellent scratch resistance by using the hard paint of the present invention.
In addition, when previous reaction functional group being made to react with each other, it usually needs irradiation ultraviolet light, electron ray isoreactivity energy Ray or heating are measured, therefore reactive functional groups are faster carried out with the reaction more mutual than reactive functional groups of reacting of sulfydryl. Also, the reactive functional groups are addition reaction with reacting for sulfydryl, which occurs the contraction that will not cause hard conating.
On the other hand, it if the mutual reaction of reactive functional groups is carried out with degree more than necessity, generates local Cure shrinkage, it is possible to reduce optical characteristics, crimpiness.
Therefore, the amount for suitably adjusting (B) ingredient uses the unreacted reaction after the reacting of reactive functional groups and sulfydryl Property functional group will not be remaining excessive hard paint, the excellent hard conating of optical characteristics, crimpiness, resistance to bend(ing) can be formed.
2) stacked film
The stacked film of the present invention is the stacked film for having substrate layer and hard conating, which is characterized in that aforementioned hard conating uses this hair Bright hard paint and formed.
The substrate layer of the stacked film of the present invention is constituted for keeping hard conating.
The type of substrate layer is not particularly limited.For example, can synthetic resin film be used as substrate layer.
As synthetic resin film, it can be cited for example that polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene- Vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate (PBT), Polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, three The films such as cellulose acetate, cellophane, makrolon.
In the present invention, can priming coat be set at least one face of aforementioned substrates layer.As aforementioned priming coat, as long as The good layer of adaptation relative to the adaptation for the hard conating being arranged on it and relative to aforementioned substrates layer, then its type It is not particularly limited.As priming coat, acrylic acid series priming coat, Polyester priming coat, polyurethane series priming coat, silicon can be used The known priming coats such as ketone system priming coat, rubber series priming coat.The thickness of priming coat is usually 0.01 ~ 20 μm, is preferably 0.1~15μm。
The thickness of substrate layer (synthetic resin film) is not particularly limited, and can suitably be determined according to purposes of stacked film etc. It is fixed.
The thickness of substrate layer is usually 10 ~ 500 μm, preferably 20 ~ 200 μm.
The hard conating for constituting the stacked film of the present invention is formed using the hard paint of the present invention.
The thickness of hard conating is usually 0.1 ~ 50 μm, preferably 0.5 ~ 20 μm.
Hard conating can pass through the synthetic resin film in substrate layer(Or priming coat)The hard paint, simultaneously of the upper coating present invention Make gained curing of coating and is formed.
As in synthetic resin film(Or priming coat)The method of the upper hard paint of coating, is not particularly limited, public affairs may be used The method known.For example, rolling method, curtain flow coat method, silk rod coating method, reversed rubbing method, gravure coating process, intaglio plate can be enumerated Reversed rubbing method, air knife rubbing method, kiss mold coating method, scraper for coating method, smooth rubbing method, roller knife rubbing method etc..
The method of curing of coating is set to be not particularly limited.For example, can be by irradiating ultraviolet light, electron ray etc. to film Active energy beam and make curing of coating.
Ultraviolet light irradiation can be carried out by high-pressure sodium lamp, Fusion H lamps, xenon lamp etc..Ultraviolet irradiation amount is preferred Illumination is 50 ~ 1000mW/cm2, light quantity be 50 ~ 1000mJ/cm2Left and right.
On the other hand, electronbeam irradiation can be carried out by electron ray accelerator etc..The exposure of electron ray Preferably 10 ~ 1000krad or so.
When forming hard conating, as needed, it can be dried before the solidification of film or after the solidification of film.
Drying process condition is not particularly limited.Drying temperature is, for example, 40 ~ 150 DEG C, preferably 60 ~ 140 DEG C, when dry Between be, for example, 30 seconds to 1 hour, preferably 1 ~ 30 minute.
Hard conating is formed using the hard paint of the present invention, and hardness is high, and excellent scratch resistance.
If the hard conating for constituting the stacked film of the present invention carries out pencil according to the method described in embodiment and brushes away hardness When experiment, then the hardness of F or more, preferably H or more are usually shown.
The hard conating of the stacked film of the present invention is constituted when evaluating marresistance according to the method described in embodiment, usually Scar is not observed.
The stacked film preferably clear of the present invention is excellent.The stacked film of the present invention is when measuring full light transmittance, preferably It is 89% or more, more preferably 90% or more.There is no special upper limit value, usually 95% or less.
The preferred resistance to bend(ing) of stacked film of the present invention is excellent.The stacked film of the present invention is carried out according to JIS K5600-5-1 When mandrel bend test, preferably 4mm Φ or less, more preferably 2mm Φ or less.
The preferred warpage of stacked film of the present invention is few.If the stacked film of the present invention is evaluated according to the method described in embodiment Crimpiness, then usually 110mm or less, preferably 50mm or less.There is no special lower limiting value, usually 3.5mm or more.
The excellent stacked film of these optical characteristics, resistance to bend(ing), crimpiness is as described above, can by adjusting (A) at Point, (B) ingredient and the amount of (C) ingredient, (A) ingredient for not causing the above degree of necessity, reactive official possessed by (C) ingredient Mutual reaction can be rolled into a ball and manufactured.
The stacked film of the present invention has hardness high and marresistance and the excellent hard conating of resistance to bend(ing), is suitable as touching Control the manufacture material of panel.
Embodiment
Hereinafter, enumerating embodiment, present invention be described in more detail.But the present invention not due to embodiment below by To any restriction.
Part and % in each example in case of no particular description, on the basis of quality.
The compound used in embodiment and comparative example is shown in as follows.
Solution (A1) (Sakai chemical company system, the trade name of organo-silicon compound (vinyltriacetoxy silane): SHC-001B, it is a concentration of 90%)
Solution (B1) (Sakai chemical company system, the commodity of multi-thioalcohol compound (trimethylolpropane tris (3-thiopropionate)) Name:SHC-001A, it is a concentration of 60%)
Inorganic filler (the silica nanometer filler with acryloxy) dispersion liquid (C1) (Nissan Chemical Industries company System, trade name:AC-4130Y, a concentration of 30%, average grain diameter are 40 ~ 50nm)
Inorganic filler(Silica nanometer filler with acryloxy)Dispersion(C2)(Nissan Chemical Industries company System, trade name:AC-2140Z, concentration:40%, average grain diameter:10~15nm).
[Embodiment 1]
By 110 parts of the solution (A1) of organo-silicon compound, 100 parts of solution (B1), the inorganic filler dispersion liquid of multi-thioalcohol compound (C1) it is mixed for 119 parts, gained mixed liquor is diluted with methyl ethyl ketone, prepare the hard paint (1) that solid component concentration is 45%.
In polyethylene terephthalate film (Japan's textile company system, trade name with single side priming coat: PET50A4100, thickness are 50 μm) on, hard paint (1) is coated on the surface of priming coat using silk stick #10, so that solid Film thickness after change reaches 5 μm, irradiates ultraviolet light (light quantity:500mJ/cm2), to make curing of coating.Then, cured coating film is existed 120oIt is 20 minutes dry under C, hard conating is formed, stacked film (1) is obtained.
[Embodiment 2 ~ 9, comparative example 1]
In embodiment 1, hard paint (1) is substituted, prepares hard paint (2) ~ (10) of composition recorded in table 1, layer is manufactured using it In addition to this folded film in the same manner as example 1, respectively obtains stacked film (2) ~ (10).
For the stacked film obtained in embodiment 1 ~ 9 and comparative example 1, conduct the following evaluation.As a result shown in table 1.Table 1 In, " concentration " is the meaning of " solid component concentration ".
[Film thickness evaluates ]
Use thickness gauge (ニ U Application corporations, trade name:MH-15), according to JIS K 7130 (1999), the film of hard conating is measured It is thick.
[Full Guang Xiantousheshuai ]
Use haze meter (Japan's electricity color corporation, trade name:N-DH-2000), according to JIS K 7361-1 (1997), layer is measured The full light transmittance of folded film.
[Qian Biyingdu ]
Brushing away hardness tester using pencil, (peace field essence mechanism makees institute's corporation, trade name:No.553-M), according to JIS K5600-5-4 (1999) carries out pencil scrawl hardness test under conditions of load-carrying is 750g, scrawl speed is 0.5mm/ seconds.
[Marresistance evaluates ]
To the hard conating of stacked film, using steel wool #0000, in 250g/cm2Load-carrying under with the length range of 50mm carry out 10 A round-trip wiping, whether there is or not scars for visual confirmation thereafter, according to benchmark evaluation marresistance below.
◎:Without scar.
○:There is 1 ~ 2 scar.
×:There are countless scars.
[Resistance to bend(ing) evaluates ]
According to JIS K5600-5-1 (1999), mandrel bend test is carried out, the resistance to bend(ing) of stacked film is evaluated.
[Crimpiness evaluates ]
Stacked film is cut into the square of 1 side 10cm, as test film.The test film is statically placed on horizontal platform, The quadrangle measured at this time floats (mm), calculates its aggregate values.
[Table 1]
。
Following the description as shown in Table 1.
The transparency of the hard conating of stacked film (1) ~ (9) obtained in embodiment 1 ~ 9 is excellent, and hardness is high, and anti-scratch Wound property, resistance to bend(ing) are excellent.
In addition, the laminated film obtained in embodiment 5,6 and 9(5),(6),(9)Warpage it is small.
On the other hand, the hardness of the stacked film (10) obtained in comparative example 1 is low, marresistance is poor.

Claims (4)

1. hard paint, containing following (A) ingredients, (B) ingredient and (C) ingredient,
(A) ingredient:Organo-silicon compound with reactive functional groups and hydrolization group
(B) ingredient:Multi-thioalcohol compound
(C) ingredient:Inorganic filler with reactive functional groups.
2. hard paint according to claim 1, wherein the content of (B) ingredient is 50 ~ 120 matter relative to (A) ingredient Measure %.
3. hard paint according to claim 1 or 2, wherein the content of (C) ingredient relative to (A) ingredient be 30 ~ 130 mass %.
4. stacked film is the stacked film with substrate layer and hard conating,
The hard conating is formed using the hard paint described in any one of claim 1 ~ 3.
CN201780014286.0A 2016-03-02 2017-02-27 Hard paint and stacked film Pending CN108699390A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101010400A (en) * 2004-09-01 2007-08-01 触媒化成工业株式会社 Coating liquid for forming transparent coating film and base with transparent coating film
CN102307953A (en) * 2009-03-13 2012-01-04 堺化学工业株式会社 Resin composition for formation of transparent coating layer, and laminate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2406609C2 (en) * 2005-10-27 2010-12-20 Эксонмобил Кемикал Пэйтентс Инк. Structure that comprises jointing layer
JP2008201864A (en) * 2007-02-19 2008-09-04 Nippon Shokubai Co Ltd Coating composition and optical film
CN101790695B (en) * 2007-08-10 2011-12-21 大日本印刷株式会社 Hard coat film
JP6073595B2 (en) * 2011-08-09 2017-02-01 三菱樹脂株式会社 Laminated film for transparent substrates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101010400A (en) * 2004-09-01 2007-08-01 触媒化成工业株式会社 Coating liquid for forming transparent coating film and base with transparent coating film
CN102307953A (en) * 2009-03-13 2012-01-04 堺化学工业株式会社 Resin composition for formation of transparent coating layer, and laminate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郭浩等: "《高校会展管理系列教材 会展展示设计与实务》", 31 August 2005, 上海交通大学出版社 *

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