CN104080877B - Anti-fingerprint adhesive agent and manufacture method, hard coat compositions, the base material with hard coat and touch screen - Google Patents
Anti-fingerprint adhesive agent and manufacture method, hard coat compositions, the base material with hard coat and touch screen Download PDFInfo
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- CN104080877B CN104080877B CN201380007252.0A CN201380007252A CN104080877B CN 104080877 B CN104080877 B CN 104080877B CN 201380007252 A CN201380007252 A CN 201380007252A CN 104080877 B CN104080877 B CN 104080877B
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- Prior art keywords
- hard coat
- compound
- hydrolysable silanes
- manufacture method
- group
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 230000003666 anti-fingerprint Effects 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 38
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- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
-
- 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
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention provides a kind of by being added in the hard coat resin of photo-curable use, the surface of hard coat of gained can be given with sufficient hardness, soil resistance, particularly anti-fingerprint tack, and can also substantially ensure that outward appearance and the light resistance of anti-fingerprint tack of hard coat, and few partial hydrolysis condensate and the manufacture method thereof of carrying capacity of environment, blended the hard coat compositions of this partial hydrolysis condensate and there is the base material of hard coat, touch screen.A kind of anti-fingerprint adhesive agent, it is made up of partial hydrolysis condensate, and this partial hydrolysis condensate is the partial hydrolysis condensate of hydrolysable silanes compound mixture, and it comprises CnF2n+1(n≤6), fluorine atom containing ratio are 2.5～40 mass % and have ethylene double bond.A kind of hard coat compositions, wherein, contains this partial hydrolysis condensate and the optical polymerism composition of 0.01～20 mass % relative to the total solid composition of compositions.
Description
Technical field
The present invention relates to anti-fingerprint adhesive agent and manufacture method thereof, hard coat compositions, there is the base of hard coat
Material and touch screen.
Background technology
The touch screen used such as smart mobile phone and panel computer is in use owing to contacting the finger of people, so easily adhering to
The lipid dirt of fingerprint, sebum, antiperspirant etc..And, lipid dirt, once adhere to, is not easy to come off, additionally, along with the power of light
Deng can be obvious, there is infringement observability and problem attractive in appearance.Also indicate that in display glass, optical element, sanitary equipment
Also same problem is deposited in Deng.
Then, as solving the means of problem that caused by the attachment of lipid dirt, it is proposed that various at optical component
Even if surface formation has lipid dirt is difficult to the technology of the attachment attachment also stain-proofing layer of the performance of easy wiping.Surface has
In the optical component of stain-proofing layer, it is positioned at outermost stain-proofing layer its surface portion when wiping and easily causes damage.Therefore, needing
In the case of substrate surface to be given is with mechanical strengths such as mar proofs, needs to arrange hard coat at substrate surface, there is system
Make the problem that operation becomes complicated.
In order to solve this problem, such as patent documentation 1 is recorded the compositions comprising following component has been coated on base material
On so that it is solidification, form the technology of the excellent hard coat of the soil resistance such as excellent in wear resistance, anti-fingerprint tack, compositions
Comprise: the active energy beam of the multi-functional polymerizable monomer composition comprising (methyl) acryloyl group with more than 2 is solid
The polymerizable monomer of the property changed, comprises the functional group of active energy ray-curable, shows water and oil repellant in molecular structure
Position and the water and oil repellant imparting agent of specific divalent alkyl, and active energy beam polymerization initiator.
Additionally, patent documentation 2 describes in tunicle formation compositions and used to have perfluoroalkyl and holo-fluorine polyester
The manufacture method of fluoro organopolysiloxane resins.In embodiment, the hydrolysable silanes compound that makes there is perfluoroalkyl or
It hydrolyzes under given conditions with the mixture of the hydrolysable silanes compound with organic group (not having fluorine atom), obtains
Fluoro organopolysiloxane resins.And, use this resin and the adaptation of tunicle, abrasion-resistant fastness properties, fast light that formed
Property, anti fouling performance, water repellency, antireflection, low-refraction and the transparency excellent.
Prior art literature
Patent documentation
Patent documentation 1: International Publication the 2004/044062nd
Patent documentation 2: No. 4711080 publication of Japanese Patent Laid
Summary of the invention
Invent technical problem to be solved
But, in using hard coat obtained by the compositions described in patent documentation 1, for soil resistance, the most fast light
Property can be insufficient.
Fluoro organopolysiloxane resins described in patent documentation 2 is due to have perfluoroalkyl that carbon number is 8
Hydrolysable silanes compound is raw material, so carrying capacity of environment is high.Additionally, the hardness of the tunicle obtained by this resin is not filled
Point.
The present invention is the invention completed in view of the foregoing, it is therefore intended that provide a kind of by being added on photo-curable
Hard coat resin uses, and can give the surface of hard coat of gained with sufficient hardness, soil resistance, particularly anti-fingerprint
Tack, and outward appearance and the light resistance of soil resistance, particularly anti-fingerprint tack of hard coat can also be substantially ensured that, and
Partial hydrolysis condensate that carrying capacity of environment is few and manufacture method thereof.
The present invention also aims to provide a kind of blended above-mentioned partial hydrolysis condensate can be formed hardness fully, anti-
The hard coat compositions of the hard coat of dirt, particularly anti-fingerprint tack and light resistance and excellent appearance with
And there is the base material of hard coat obtained by this hardcoat compositions of use, use obtained by the base material with this hard coat
Touch screen.
Solve the technical scheme that technical problem is used
The present invention provides anti-fingerprint adhesive agent and manufacture method, the hard coat of the composition with following [1]～[14]
The base material that by compositions, there is hard coat and touch screen.
[1] a kind of anti-fingerprint adhesive agent, it is by the partial hydrolysis condensate structure that fluorine atom containing ratio is 2.5～40 mass %
Become, above-mentioned partial hydrolysis condensate be comprise represent with following formula (a-1) hydrolysable silanes compound (a-1), with following formula (a-2)
The mixture of the hydrolysable silanes compound (a-2) represented and the hydrolysable silanes compound (a-3) represented with following formula (a-3)
Partial hydrolysis condensate；
[changing 1]
Rf-Q1-SiX1 3…(a-1)
RH1 p-SiX2 (4-p)…(a-2)
Symbol in formula (a-1), (a-2) and (a-3) is as follows:
Rf: the perfluoroalkyl of carbon number 1～6 or with Rf1ORf21 valency group of the carbon number 2～100 of-expression, its
In, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It it is the perfluor alkylene can between carbon-to-carbon atom with etheric oxygen atom
Base；
Q1: the divalent organic group without fluorine atom of carbon number 1～10；
Y: there is the group of ethylene double bond；
Q2: the divalent organic group without fluorine atom of carbon number 1～6；
RH1、RH2: the alkyl of carbon number 1～6；
X1、X2、X3: hydrolization group；
The integer of p:0～3；
Q:1 or 2；
R:0 or 1；Q+r is the number of 1 or 2；
Wherein, the X in formula (a-1)1, and the X in formula (a-2) or formula (a-3)2、X3、RH1、Y-Q2When existing multiple, that
This can be similar and different.
[2] the anti-fingerprint adhesive agent of [1], wherein, the fluorine atom containing ratio of above-mentioned partial hydrolysis condensate is 20～40 matter
Amount %, the R in above-mentioned formula (a-1)fIt it is the perfluoroalkyl of carbon number 1～6 or with Rf1ORf2The carbon number 2～40 of-expression
1 valency group, wherein, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It is that can to have ethereal oxygen between carbon-to-carbon atom former
The perfluorinated alkylidene of son.
[3] manufacture method of a kind of anti-fingerprint adhesive agent, it is the side of the anti-fingerprint adhesive agent manufacturing above-mentioned [1] or [2]
Method, wherein, in the presence of water, organic solvent and acid, makes the hydrolysis of hydrolysable silanes compound mixture, partial condensates, manufactures
Fluorine atom containing ratio is the partial hydrolysis condensate of 2.5～40 mass %；In said hydrolyzed silane compound mixture, relatively
In the above-mentioned hydrolysable silanes compound (a-1) represented with (a-1) of 100 moles, comprise with the mol ratio of 1～23000 mole
The above-mentioned hydrolysable silanes compound (a-2) represented with (a-2), comprises above-mentioned with (a-3) with the mol ratio of 20～11500 moles
The hydrolysable silanes compound (a-3) represented.
[4] manufacture method of the anti-fingerprint adhesive agent of [3], wherein, above-mentioned partial hydrolysis condensate is to make hydrolysable silanes
Compound mixture hydrolysis, partial condensates and the partial hydrolysis condensate that manufactures；In said hydrolyzed silane compound mixture,
Said hydrolyzed silane compound (a-1) relative to 100 moles, comprises said hydrolyzed silicon with the mol ratio of 1～800 mole
Hydride compounds (a-2), comprises said hydrolyzed silane compound (a-3) with the mol ratio of 20～300 moles.
[5] manufacture method of the anti-fingerprint adhesive agent of [3] or [4], wherein, mixes relative to said hydrolyzed silane compound
Compound 100 mass parts, the addition of above-mentioned water is 5～100 mass parts.
[6] manufacture method of the anti-fingerprint adhesive agent of [4], wherein, relative to said hydrolyzed silane compound mixture
100 mass parts, the addition of above-mentioned water is 5～40 mass parts.
[7] manufacture method of the anti-fingerprint adhesive agent any one of [3]～[6], wherein, above-mentioned organic solvent comprises and has
Hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
[8] manufacture method of the anti-fingerprint adhesive agent any one of [3]～[7], wherein, above-mentioned acid is nitric acid.
[9] a kind of hard coat compositions, it is hard containing following part hydrolytic condensate and optical polymerism composition
Matter coating composition, wherein, the content of the following part hydrolytic condensate in the total solid composition of above-mentioned composition is 0.01
～20 mass %；
Partial hydrolysis condensate: comprise represent with following formula (a-1) hydrolysable silanes compound (a-1), with following formula (a-2)
The mixture of the hydrolysable silanes compound (a-2) represented and the hydrolysable silanes compound (a-3) represented with following formula (a-3)
Partial hydrolysis condensate, and the fluorine atom containing ratio of this partial hydrolysis condensate is 2.5～40 mass %；
[changing 2]
Rf-Q1-SiX1 3…(a-1)
RH1 p-SiX2 (4-p)…(a-2)
Symbol in formula (a-1), (a-2) and (a-3) is as follows:
Rf: the perfluoroalkyl of carbon number 1～6 or with Rf1ORf21 valency group of the carbon number 2～100 of-expression, its
In, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It it is the perfluor alkylene can between carbon-to-carbon atom with etheric oxygen atom
Base；
Q1: the divalent organic group without fluorine atom of carbon number 1～10；
Y: there is the group of ethylene double bond；
Q2: the divalent organic group without fluorine atom of carbon number 1～6；
RH1、RH2: the alkyl of carbon number 1～6；
X1、X2、X3: hydrolization group；
The integer of p:0～3；
Q:1 or 2；
R:0 or 1；Q+r is the number of 1 or 2；
Wherein, the X in formula (a-1)1, and the X in formula (a-2) or formula (a-3)2、X3、RH1、Y-Q2When existing multiple, that
This can be similar and different.
[10] the hard coat compositions of [9], wherein, the fluorine atom containing ratio of above-mentioned partial hydrolysis condensate be 20～
40 mass %, the R in above-mentioned formula (a-1)fIt it is the perfluoroalkyl of carbon number 1～6 or with Rf1ORf2The carbon number 2 of-expression
～the 1 valency group of 40, wherein, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It is can to have ethereal between carbon-to-carbon atom
The perfluorinated alkylidene of oxygen atom.
[11] the hard coat compositions of [9] or [10], wherein, above-mentioned optical polymerism composition contains optical polymerism chemical combination
Thing and Photoepolymerizationinitiater initiater.
[12] the hard coat compositions any one of [9]～[11], wherein, above-mentioned hard coat compositions solidifies
Film be at least transparent relative to luminous ray.
[13] a kind of base material with hard coat, it includes base material；With at least part of surface of above-mentioned base material
The hard coat that the cured film formed by the hard coat compositions any one of [9]～[11] is constituted.
[14] a kind of touch screen, it includes the base material with hard coat described in above-mentioned [13].
Invention effect
The anti-fingerprint adhesive agent of the present invention, by being added in the hard coat resin of photo-curable use, can give institute
The surface of the hard coat obtained is with sufficient hardness, anti-fingerprint tack.Additionally, the excellent in light-resistance in their characteristic and ring
Border load is few.
The manufacture method of the anti-fingerprint adhesive agent of the present invention can manufacture the hard coat tree by being added on photo-curable
Fat uses, the surface of hard coat of gained can be given with sufficient hardness, the anti-fingerprint adhesive agent of anti-fingerprint tack.
The hard coat compositions of the present invention can be formed on base material has good outward appearance, sufficient hardness, antifouling
Property, the hard coat of anti-fingerprint tack.
The base material with hard coat of the present invention and employ the touch screen of the base material with this hard coat, it is hard
The outward appearance of matter coating is good, and hardness is abundant, and soil resistance, anti-fingerprint tack are excellent, and its light resistance is the most excellent.
Detailed description of the invention
Below embodiments of the present invention are illustrated.
When " fingerprint " in this specification refers to the surface with Fingertip touch article, it is attached to antiperspirant and the sebum composition of finger tip
The figure stricture of vagina adhered to Deng the form on the surface the figure stricture of vagina of finger tip to be transferred in these article.
" total solid composition " in this specification refers to the hard coat shape in the composition contained by hard coat compositions
Become composition, by hard coat compositions remnant after 140 DEG C of heating remove solvent in 24 hours.Specifically, represent molten
The total composition beyond volatile ingredient that agent etc. are volatilized by heating in hard coat forming process etc..It addition, total solid
The amount of composition also can be calculated by input amount.
In this specification, film obtained by hard coat compositions will be coated with and be referred to as " film ", its dried shape will be made
State be referred to as " film ", additionally, will make its solidify obtained by film be referred to as " cured film ".Additionally, use hard coat compositions and shape
The hard coat become refers to this " cured film ".
The term of (methyl) acryloxy used in this specification etc. " (methyl) acryloxy ... " represents " third
Alkene acyloxy ... " and " methacryloxy ... " both meanings.Further, described later to " (methyl) acrylic ... "
Term similarly represent " acrylic ... " and " methacrylic acid group ... " both meanings.
The compound represented with formula (a-1) in this specification is denoted as compound (a-1).Other compounds are too.
" partial condensate (A) " it is denoted as by below the partial hydrolysis condensate in the present invention.Additionally, by the present invention
" photopolymerizable compound " is also denoted as " photopolymerizable compound (B) ", and " Photoepolymerizationinitiater initiater " is also denoted as " Photoepolymerizationinitiater initiater
(C)”。
Anti-fingerprint tack in this specification refers to be provided simultaneously with the water and oil repellant of above-mentioned non-cohesive fingerprint and attachment
The character of both removability of fingerprint.Anti-fingerprint tack and soil resistance are by water contact angle and the numerical value of oleic acid contact angle
It is evaluated.
Further, in this specification, unless otherwise specified, % represents quality %.
[anti-fingerprint adhesive agent]
The anti-fingerprint adhesive agent of the present invention is by the portion that partial condensate (A), i.e. fluorine atom containing ratio are 2.5～40 mass %
Dividing hydrolytic condensate to constitute, this partial hydrolysis condensate is to comprise the hydrolysable silanes compound (a-represented with following formula (a-1)
1) the hydrolysable silanes compound (a-2), represented with following formula (a-2) and the hydrolysable silanes compound represented with following formula (a-3)
(a-3) partial hydrolysis condensate of mixture.
[changing 3]
Rf-Q1-SiX1 3…(a-1)
RH1 p-SiX2 (4-p)…(a-2)
Symbol in formula (a-1), (a-2) and (a-3) is as follows:
Rf: the perfluoroalkyl of carbon number 1～6 or with Rf1ORf21 valency group of the carbon number 2～100 of-expression, its
In, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It it is the perfluor alkylene can between carbon-to-carbon atom with etheric oxygen atom
Base；
Q1: the divalent organic group without fluorine atom of carbon number 1～10；
Y: there is the group of ethylene double bond；
Q2: the divalent organic group without fluorine atom of carbon number 1～6；
RH1、RH2: the alkyl of carbon number 1～6；
X1、X2、X3: hydrolization group；
The integer of p:0～3；
Q:1 or 2；
R:0 or 1；Q+r is the number of 1 or 2；
Wherein, the X in formula (a-1)1, and the X in formula (a-2) or formula (a-3)2、X3、RH1、Y-Q2When existing multiple, that
This can be similar and different.
Partial condensate (A) in the present invention is derived from hydrolysable silanes chemical combination by containing with above-mentioned scope in compound
The fluorine atom of thing (a-1), can give and use the hard formed containing the hard coat compositions of this partial condensate (A) to be coated with
The surface of layer is with excellent water and oil repellant.Think by making the surface of hard coat have water and oil repellant, transfer from finger tip
It is in, on the surface of hard coat, the state do not adhered to the moisture on surface and sebum composition etc..It is in the sebum composition of this state
Etc. can easily wipe.I.e. it may be said that adhere to excellent anti-fingerprint by using partial condensate (A) that hard coat can be given
Property.
It addition, the fluorine atom containing ratio in partial condensate (A) is 2.5～40 mass %, more preferably 3～40 mass %,
The most more preferably 20～40 mass %, spy is well 25～40 mass %, preferably 30～40 mass %.
If below the higher limit of above-mentioned scope, then good with the compatibility of photopolymerization compounds described later (B), solidification
Outward appearance and the anti-fingerprint tack of film are good.It addition, fluorine atom containing ratio is the fluorine in the per unit mass of partial condensate (A)
The ratio of atomic mass, can be calculated by method described later.
Partial condensate (A) in the present invention is derived from the unit of hydrolysable silanes compound (a-2), part contracting by containing
The compound (A) dissolubility in varsol and film property are excellent.
Partial condensate (A) in the present invention is by containing having the ethylene being derived from hydrolysable silanes compound (a-3)
The group of double bond, it is possible to carry out radical polymerization.With described later as main constituent in the hard coat compositions containing it
The binding affinity excellence of the group containing ethylene double bond that photopolymerizable compound (B) is had, can suppress partial condensate (A)
Oozing out from hard coat.
Additionally, the partial condensate (A) in the present invention preferably has silanol group.Silanol radix is relative to every 1
Silicon atom is preferably 0.2～3.5, more preferably 0.2～2.0, and spy is well 0.5～1.5.If the lower limit in above-mentioned scope
More than value, then when using hard coat compositions to form hard coat, partial condensate (A) is difficult to steam from substrate surface
Send out.If below the higher limit of above-mentioned scope, then contain in the hardcoat compositions of partial condensate (A), partial condensates
Being difficult to coagulation between thing (A), storage-stable is good.
It addition, silanol radix in partial condensate (A) can by by29The Si with silanol group that Si-NMR measures
Base calculates with the peak area ratio of Si base without silanol group.
The partial condensate (A) of the composition anti-fingerprint adhesive agent of the present invention be comprise hydrolysable silanes compound (a-1)～
(a-3) partial hydrolysis of the mixture (hereinafter also referred to " hydrolysable silanes compound mixture ") of hydrolysable silanes compound
Condensation substance.Hereinafter each hydrolysable silanes compound is illustrated.
(hydrolysable silanes compound (a-1))
Hydrolysable silanes compound (a-1) is the fluorine-containing water-disintegrable silane compound represented with following formula (a-1).
Rf-Q1-SiX1 3…(a-1)
In formula (a-1), RfIt it is the perfluoroalkyl of carbon number 1～6 or with Rf1ORf2The carbon number 2～100 of-expression
1 valency group, wherein, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It is can to have etheric oxygen atom between carbon-to-carbon atom
Perfluorinated alkylidene；Q1It it is the divalent organic group without fluorine atom of carbon number 1～10；X1It it is hydrolization group.Wherein, 3
Individual X1Each other can be similar and different.
Compound (a-1) is because having Rf, so being formed by compositions by hard coat containing partial condensate (A)
Hard coat shows the anti-fingerprint tack of excellence.Compound (a-1) is because having Rf, so will be containing partial condensate
(A) when hard coat compositions is coated on base material, RfBase is easily concentrated and is present in the side contrary with base material of film (i.e.
Air side).I.e., partial condensate (A) is easily concentrated and is present in the side contrary with base material.
In formula (a-1), from the standpoint of the viewpoint of carrying capacity of environment and the dissolubility general solvent are excellent, RfDo not wrap
The perfluoroalkyl of carbon atom quantity more than 7.
RfStructure can enumerate linear chain structure, branched structure, ring structure or part there is the structure of ring, preferably straight chain knot
Structure.
As RfIt is the concrete example during perfluoroalkyl of carbon number 1～6, following group can be enumerated.
F(CF2)4-、F(CF2)6-。
RfIt is with Rf1ORf21 valency group (R of the carbon number 2～100 of-expressionf1It is the perfluor alkane of carbon number 1～6
Base, Rf2It is the perfluorinated alkylidene can between carbon-to-carbon atom with etheric oxygen atom) time, from the hydrolysable silanes with other
From the standpoint of the compatibility of compound, carbon number more preferably 2～80, spy is well 2～40.
Rf2Preferably (Rf3O)x(in formula, Rf3Being the perfluorinated alkylidene of carbon number 1～10, x is the integer of 1～99).Rf3
Can be straight-chain, it is also possible to be branch-like.Consider from the easness of synthesis, Rf3Carbon number particularly preferably 1～5.As
(Rf3O) concrete example, can enumerate following group.
(CF2O)、(CF2CF2O)、(CF2CF2CF2O)、(CF(CF3)CF2O)、(CF2CF2CF2CF2O) etc..
In the case of X is more than 2, (Rf3O) unit can be one kind or two or more, not limits its binding sequence.Can
Be made up of multiple unit block, random, alternately in any one configuration mode.
As RfIt is with Rf1ORf2-represent 1 valency group of carbon number 2～100 time concrete example, can enumerate following
Group.
CF3OCF3CF2CF2-、CF3OCF(CF3)CF2-、CF3OCF(CF3)CF2OCF(CF3)-。
F(CF2)2OCF2CF2OCF2-、F(CF2)2OCF2CF2OCF2CF2-、F(CF2)2OCF2CF2OCF2CF2OCF2CF2OCF2-、F(CF2)2OCF2CF2OCF2CF2OCF2CF2OCF2CF2-、F(CF2)2OCF(CF3)
CF2OCF(CF3)-。
F(CF2)3OCF2-、F(CF2)3OCF2CF2-、F(CF2)3OCF(CF3)-、F(CF2)3OCF(CF3)CF2-、F(CF2)3OCF(CF3)CF2OCF2CF2-、F(CF2)3OCF(CF3)CF2OCF(CF3)-、F(CF2)3OCF(CF3)CF2OCF(CF3)CF2-、
CF3O(CF2CF2O)x1CF2-the integer of 1～49 (x1 be), F (CF2)3O(CF(CF3)CF2O)x2CF(CF3)-(x2 is 1～31
Integer), F (CF2)2O(CF2CF2OCF2CF2CF2CF2O)x3CF2CF2OCF2CF2CF2-the integer of 1～15 (x3 be), F (CF2)2O
(CF2CF2OCF2CF2CF2CF2O)x4CF2CF2OCF2CF2CF2CF2The integer of 1～15 (x4 be).
Q in compound (a-1)1It is the divalent organic group without fluorine atom of carbon number 1～10, is to connect RfAnd water
Solution property silicyl (-SiX1 3) divalent organic group.Q1Be combined with Si with the key on right side, the key in left side and RfIn conjunction with carrying out table
When showing, specifically, it is preferably with-(CH2)i1-the integer of 1～5 (i1 be) ,-CH2O(CH2)i2-the integer of 1～4 (i2 be) ,-
SO2NR1-(CH2)i3-(R1Hydrogen atom, methyl or ethyl, i3 be more than 1 and with R1The total of carbon number be calculated as 4 with
Under integer) ,-(C=O)-NR1-(CH2)i4-(R1Same as described above, i4 be more than 1 and with R1The total of carbon number
Be calculated as the integer of less than 4) ,-(CH2)i5-OC (=O)-(CH2)i6-S-(CH2)i7-(i5, i6 and i7 are separately 1～5
Integer) ,-(CH2)i5-OC (=O)-(CH2)i6-NH-(CH2)i7-(i5, i6 and i7 are same as described above) ,-(CH2)i5-OC (=O)-
(CH2)i6-N(CH3)-(CH2)i7-(i5, i6 and i7 are same as described above) ,-(CH2)i5-OC (=O)-(CH2)i6-N(C6H5)-
(CH2)i7The group that-(i5, i6 and i7 are same as described above) represents.As Q1, more preferably-(CH2)2-、-(CH2)3-and-(CH2)2-
OC (=O)-(CH2)2-S-(CH2)3-, spy is well-(CH2)2-and-(CH2)2-OC (=O)-(CH2)2-S-(CH2)3-。
It addition, RfWhen being perfluoroalkyl, as above-mentioned Q1, preferably with-(CH2)i1-(i1 is same as described above) ,-(CH2)i5-
OC (=O)-(CH2)i6-S-(CH2)i7The group that-(i5, i6 and i7 are same as described above) represents.I1 is the integer of 2～4, and spy is well
2.I5, i6 and i7 are separately preferably the integer of 2～4, and spy is well 2 or 3.
Additionally, RfWhen being the perfluoroalkyl containing etheric oxygen atom, as above-mentioned Q1, preferably with-(CH2)i1-、-CH2O
(CH2)i2-、-SO2NR1-(CH2)i3-,-(C=O)-NR1-(CH2)i4Group (the i1～4 and R of-expression1Same as described above).i1
Being the integer of 2～4, spy is 2 well.
In formula (a-1), X1Represent the hydrolization group with silicon atom bonding.As X1, alkoxyl, aryloxy group, halogen can be enumerated
The hydrogen of atom, acyloxy, amino and amino is by alkyl substituted group etc..Wherein, as X1, preferably carbon number 1～4
Alkoxyl or halogen atom, spy is well methoxyl group, ethyoxyl, chlorine atom.Methoxyl group and ethyoxyl become hydroxyl by hydrolysis
Base (silanol group), and then make the reaction of formation Si-O-Si key easily be smoothed out at the intermolecular condensation reaction that carries out.
As the preferred concrete example of compound (a-1), following compound can be enumerated.
F(CF2)4CH2CH2Si(OCH3)3、F(CF2)4CH2CH2Si(OCH2CH3)3、F(CF2)4CH2CH2SiCl3、F(CF2)6CH2CH2Si(OCH3)3、F(CF2)6CH2CH2Si(OCH2CH3)3、F(CF2)6CH2CH2SiCl3。
CF3OCF2CF2CF2CH2CH2Si(OCH3)3、F(CF2)2O(CF2)2O(CF2)2O(CF2)2OCF2CH2CH2Si
(OCH2CH3)3、CF3OCF(CF3)CF2CH2CH2CH2Si(OCH3)3。
F(CF2)2O(CF2)2OCF2CH2CH2CH2Si(OCH3)3、F(CF2)2O(CF2)2O(CF2)2CH2CH2Si(OCH3)3。
F(CF2)3O(CF2)2CH2CH2SiCl3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3、CF3O
(CF2CF2O)x1CF2C (=O) NHCH2CH2CH2Si(OCH3)3The integer of 1～49 (x1 be), F (CF2)3O(CF(CF3)CF2O)x2CF(CF3)CH2CH2Si(OCH3)3The integer of 1～31 (x2 be), F (CF2)2O(CF2CF2OCF2CF2CF2CF2O)x3(CF2)2O
(CF2)3C (=O) NHCH2CH2CH2Si(OCH3)3The integer of 1～15 (x3 be), F (CF2)2O(CF2CF2OCF2CF2CF2CF2O)x4
(CF2)2O(CF2)4CH2CH2CH2Si(OCH3)3The integer of 1～15 (x4 be), F (CF2)6CH2CH2OC (=O)
CH2CH2SCH2CH2CH2Si(OCH3)3、F(CF2)6CH2CH2OC (=O) CH (CH3)CH2SCH2CH2CH2Si(OCH3)3、[F(CF2)6CH2CH2OC (=O) CH2CH2]2NCH2CH2CH2Si(OCH3)3、F(CF2)6CH2CH2OC (=O) CH2CH2NHCH2CH2CH2Si
(OCH3)3、[F(CF2)6CH2CH2OC (=O) CH (CH3)CH2]2NCH2CH2CH2Si(OCH3)3、F(CF2)6CH2CH2OC (=O)
CH2CH(CH3)NHCH2CH2CH2Si(OCH3)3、F(CF2)6CH2CH2OC (=O) CH2CH2N(CH3)CH2CH2CH2Si(OCH3)3、F
(CF2)6CH2CH2OC (=O) CH2CH(CH3)N(CH3)CH2CH2CH2Si(OCH3)3、F(CF2)6CH2CH2OC (=O) CH2CH2N
(C6H5)CH2CH2CH2Si(OCH3)3、F(CF2)6CH2CH2OC (=O) CH2CH(CH3)N(C6H5)CH2CH2CH2Si(OCH3)3。
In the present invention, as compound (a-1), the most particularly preferably use F (CF2)6CH2CH2Si(OCH3)3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3、CF3O(CF2CF2O)8CF2C (=O) NHCH2CH2CH2Si(OCH3)3、KY-
108 (trade name, Shin-Etsu Chemial Co., Ltd (chemistry work society of SHIN-ETSU HANTOTAI) make, there is above-mentioned Rf1ORf2-Q1-base and 3 alkane
The silane compound of epoxide).
It addition, the hydrolysable silanes compound of the raw material as the partial condensate (A) in the present invention, compound (a-1)
Can be used alone a kind, it is possible to and use two or more.
Additionally, in the partial condensate of the present invention (A), the compound (a-1) in hydrolysable silanes compound mixture
Content is the amount making to be reached above-mentioned scope by the fluorine atom containing ratio in the partial condensate (A) of this mixture gained.
(hydrolysable silanes compound (a-2))
Hydrolysable silanes compound (a-2) is together as the partial condensate (A) of the present invention with above-claimed cpd (a-1)
Raw material, i.e. hydrolysable silanes compound use the compound represented with following formula (a-2).
RH1 p-SiX2 (4-p)…(a-2)
In formula (a-2), RH1It is the alkyl of carbon number 1～6, the preferably alkyl or phenyl of carbon number 1～4, more preferably
Being methyl or ethyl, spy is methyl well.X2It is hydrolization group, can use and the X in above formula (a-1)1And preferred configuration is identical
Group.P is the integer of 0～3.Wherein, when p is 2 or 3,2 or 3 RH1, and (4-p) individual X2Each other can different or phase
With.
Compound (a-2) is preferably 4 functionality compounds that p is 0 or 3 functionality compounds that p is 1, and spy is well 4 officials
Can property compound.Compound (a-2) can be used alone a kind can also two or more and use.Two or more and used time, it is possible to by 2
Functionality compounds and/or 1 functionality compounds and 4 functionality compounds and/or 3 functionality compounds also use.
In partial condensate (A), owing to being derived from the R in the unit of compound (a-1)fAnd show water and oil repellant.This
Outward, it is derived from the unit of compound (a-2), when p is 0, there is the advantage that the film property in partial condensate (A) is excellent.It is derived from
In the unit of compound (a-2), when p is 1,2 or 3 (, there is RH1Time), owing to there is a certain degree of RH1, partial condensate
(A) easily it is dissolved in varsol, may select relatively when there is the film forming hard coat compositions on the surface of base material
Advantage for solvent at a low price.
As the concrete example of compound (a-2), following compound can be enumerated.Additionally, as compound (a-2), it is possible to
The most in advance the partial hydrolysis of compound (a-2) obtained by multiple compounds (a-2) partial hydrolysis condensation is contracted to use
Compound.It addition, for other hydrolysable silanes compound too, it is possible to use its partial hydrolysis condensate.
Si(OCH3)4、Si(OCH2CH3)4、CH3Si(OCH3)3、CH3Si(OCH2CH3)3、CH3CH2Si(OCH3)3、
CH3CH2Si(OCH2CH3)3、(CH3)2Si(OCH3)2、(CH3)2Si(OCH2CH3)2、Si(OCH3)4Partial hydrolysis condensate (example
The methyl silicate 51 (trade name: メ チ Le シ リ ケ ト 51) made such as COLCOAT Co., Ltd. (コルコ ト society), Si
(OCH2CH3)4The partial hydrolysis condensate (ethyl silicate 40 (trade name: エ チ Le シ リ of such as COLCOAT Co., Ltd.
ケ ト 40), silester 48 (trade name: エ チ Le シ リ ケ ト 48), Tama Chemicals Co., Ltd. (rub more chemistry work
Society) esters of silicon acis 45 (trade name: シ リ ケ ト 45) made).
Additionally, compound (a-2) can be used alone a kind can also two or more and use.
It addition, the content of the hydrolysable silanes compound (a-2) in hydrolysable silanes compound mixture rubs relative to 100
Your hydrolysable silanes compound (a-1), the hydrolysable silanes compound (a-2) of preferably 1～23000 mole, more preferably 1～
15000 moles, the most more preferably 1～3000 mole, spy is well 1～800 mole, preferably 1～400 mole.
(hydrolysable silanes compound (a-3))
Hydrolysable silanes compound (a-3) is the water comprising the group with ethylene double bond represented with following formula (a-3)
Solution property silane compound, can be with above-claimed cpd (a-1), compound (a-2) together as the partial condensate (A) of the present invention
Raw material uses.
[changing 4]
In formula (a-3), represent the X of hydrolization group3Can use and the X in above formula (a-1)1And preferred configuration is identical
Group.Additionally, RH2Can use and the R in above formula (a-2)H1And the group that preferred configuration is identical.
Y in formula (a-3) is the group with ethylene double bond；Q2It it is the divalent without fluorine atom of carbon number 1～6
Organic group.Q is 1 or 2；R is 0 or 1；Q+r is the number of 1 or 2.Wherein, there is multiple Y-in said hydrolyzed silane compound
Q2And X3Time, they each other can be similar and different.
Compound (a-3) is because having Y, so combining at the hard coat that will contain rewarding partial condensate (A)
When the film of thing carries out photocuring, on the surface of this film, can make between partial condensate (A) or part contracting between this group
Compound (A) and the radical polymerisation with ethylene double bond of the photopolymerizable compound (B) contained by hard coat compositions.Cause
This, after photocuring, have and make partial condensate (A) easily concentrate the effect being present in hard coat, particularly its surface, i.e.
After making life-time service, it is possible to make the surface of hard coat keep water and oil repellant, give the effect making anti-fingerprint tack lasting.
As the Y in formula (a-3), preferably (methyl) acryloxy, ethenylphenyl etc., spy is well (methyl) propylene
Acyloxy.
Q in formula (a-3)2It is to connect hydrolyzable silyl group (-SiX3 (4-q-r)(RH2)r) and the link group of Y, specifically may be used
Enumerate the alkylidene of carbon number 2～6, phenylene etc..Wherein, preferably-(CH2)3-。
In formula (a-3), when q is 2,2 Y-Q2Can be same to each other or different to each other；When q+r is 1,3 X3Can be mutually the same
Or it is different；When q+r is 2,2 X3Can be same to each other or different to each other.
In formula (a-3), preferably q is 1, r is 0 or 1.
As the concrete example of compound (a-3), following compound can be enumerated.
CH2=C (CH3)COO(CH2)3Si(OCH3)3、
CH2=C (CH3)COO(CH2)3Si(OC2H5)3、
CH2=CHCOO (CH2)3Si(OCH3)3、
CH2=CHCOO (CH2)3Si(OC2H5)3、
[CH2=C (CH3)COO(CH2)3]CH3Si(OCH3)2、
[CH2=C (CH3)COO(CH2)3]CH3Si(OC2H5)2。
It addition, the hydrolysable silanes compound of the raw material as the partial condensate (A) in the present invention, compound (a-3)
Can be used alone a kind, it is possible to and use two or more.
It addition, the content of the hydrolysable silanes compound (a-3) in hydrolysable silanes compound mixture rubs relative to 100
Your hydrolysable silanes compound (a-1), preferably 20～11500, more preferably 20～8000 moles, the most more preferably 20～
2000, spy is well 20～300 moles, preferably 50～200 moles.
As the hydrolysable silanes compound mixture of the raw material of the partial condensate (A) in the present invention, except above-mentioned chemical combination
Thing (a-1), compound (a-2) and compound (a-3) outward, as required, such as, exist to improve the partial condensate (A) of gained
The compatibility in hard coat compositions or control the purposes such as reactive, it is also possible to comprise beyond these compounds is water-disintegrable
Silane compound.Fluorine atom containing ratio in the partial condensate (A) of gained is in the range of 2.5～40 mass %, hydrolysis
Property silane compound mixture in compound (a-1) relative to 100 moles of the content of other hydrolysable silanes compounds, change
Compound (a-2) and the total amount of compound (a-3), preferably 1～100 mole.
Partial condensate (A) in the present invention is made up of the partial hydrolysis condensate of hydrolysable silanes compound mixture,
Described hydrolysable silanes compound mixture is by hydrolysable silanes compound (a-1), hydrolysable silanes compound (a-2), hydrolysis
Property silane compound (a-3) and other hydrolysable silanes compounds of suitably blending as required constitute.Wherein, as this
Partial condensate (A) in invention, preferably will by hydrolysable silanes compound (a-1), hydrolysable silanes compound (a-2) and
The mixture that hydrolysable silanes compound (a-3) is constituted carries out partial condensate (A) obtained by partial hydrolysis condensation.As these feelings
Hydrolysable silanes compound (a-1) in hydrolysable silanes compound mixture under condition, hydrolysable silanes compound (a-2) and
The content of hydrolysable silanes compound (a-3), as long as the fluorine atom containing ratio in the partial condensate of gained (A) reaches 2.5
～40 the content of mass % be just not particularly limited, such as, the preferably hydrolysable silanes compound (a-1) relative to 100 moles,
Containing the hydrolysable silanes compound (a-2) of 1～23000 mole, the hydrolysable silanes compound (a-3) of 20～11500 moles,
Spy is well the hydrolization compound (a-1) relative to 100 moles, containing the hydrolysable silanes compound (a-2) of 1～800 mole,
The hydrolysable silanes compound (a-3) of 20～300 moles.
Partial condensate (A) in the present invention is the partial hydrolysis contracting of the hydrolysable silanes compound mixture of above-mentioned raw materials
Compound, it is common that the mixture being made up of the multiple condensation substance that the degree of polymerization is different.I.e., such as the water-disintegrable silanization of raw material
Compound, uses by hydrolysable silanes compound (a-1), hydrolysable silanes compound (a-2) and hydrolysable silanes compound (a-3)
In the case of the mixture constituted manufactures partial condensate (A), form the knot with the average composition formula represented with following formula (1)
The condensation substance of structure.
Here, partial condensate (A) is product (the partial hydrolysis condensation that remaining has hydrolization group or silanol group
Thing), therefore, it is difficult to be represented by the chemical formula this product, assume that part manufactured as above with the average composition formula that formula (1) represents
Chemical formula when hydrolization group or silanol group all become siloxane bond in hydrolytic condensate.
[changing 5]
In formula (1), Rf、Q1、RH1、Y、Q2、RH2Same as described above with the preferred scope of p, q, r.S, t, u are that the degree of polymerization is different
Multiple fluorine containing silane compound mixture in each unit averagely there is number.
Partial condensate (A) in the present invention is as represented by with formula (1), and main chain is by the big polysiloxanes key of bond energy
Constitute, so light resistance is good.
Can speculate in the partial condensate (A) of the structure with the average composition formula represented with formula (1), being respectively derived from
The unit of compound (a-1), compound (a-2) and compound (a-3) is random arrangement.It addition, the s in average composition formula (1):
T is as the content ratio of the compound (a-2) in hydrolysable silanes compound mixture Yu compound (a-1), the most above-mentioned
In the range of.It addition, s:u is as the content ratio of the compound (a-3) in this mixture Yu compound (a-1), more fortunately go up
In the range of stating.If it is represented with s:t:u, the relation of the most preferably 100:1～23000:20～11500 (mol ratio), special
It is well 100:1～800:20～300 (mol ratio).
The number-average molecular weight (Mn) of the partial condensate (A) in the present invention is more fortunately 500 less than 10000, more preferably
500 less than 5000, spy is fortunately 500 less than 3000.Number-average molecular weight (Mn) if above-mentioned lower limit with
On, then when using hard coat compositions to form hard coat, the surface migration of partial condensate (A) is high, with a small amount of
Add and also can show good anti-fingerprint tack, so the hardness of cured film is good.Number-average molecular weight (Mn) is if be less than
Above-mentioned higher limit, then partial condensate (A) in hard coat compositions with solvent and the excellent compatibility of other compositions.Also
Have, it is not easy to being separated, the storage-stable of hard coat compositions is good.
The number-average molecular weight (Mn) of partial condensate (A) can be regulated by selective response condition etc..
[manufacture method of anti-fingerprint adhesive agent]
Constitute the partial condensate (A) that fluorine atom containing ratio is 2.5～40 mass % of the anti-fingerprint adhesive agent of the present invention
Can by make hydrolysable silanes compound mixture hydrolyze and partial condensates manufactures, described hydrolysable silanes compound mixture
Above-mentioned water-disintegrable silicon is comprised with the content that the fluorine atom containing ratio in the partial condensate (A) of gained is 2.5～40 mass %
Hydride compounds (a-1), hydrolysable silanes compound (a-2), hydrolysable silanes compound (a-3).
Specifically, can be by including the partial condensate of following reaction process (hereinafter referred to as " reaction process (I) ")
(A) manufacture method manufactures.
Reaction process (I): in the presence of water, organic solvent and acid, makes the hydrolysis of hydrolysable silanes compound mixture, portion
Divide the operation of condensation, the hydrolysable silanes compound (a-in described hydrolysable silanes compound mixture, relative to 100 moles
1), hydrolysable silanes compound (a-2) is comprised with the mol ratio of 1～23000 mole, with the mol ratio bag of 20～11500 moles
Containing water-disintegrable silane compound (a-3).
The reaction of this hydrolysis and partial condensates is to generate silanol by the hydrolysis of hydrolization group as above
Base and generate the reaction of siloxane bond by the dehydration condensation between silanol group.
It addition, in partial condensate (A), its fluorine atom containing ratio is 20～40 mass %, above-mentioned hydrolysable silanes
R in compound (a-1)fIt it is the perfluoroalkyl of carbon number 1～6 or with Rf1ORf21 valency group of the carbon number 2～40 of-expression
(Rf1It it is the perfluoroalkyl of carbon number 1～6；Rf2It it is the perfluor alkylene can between carbon-to-carbon atom with etheric oxygen atom
Base) in the case of, can reaction process (I) be set in the presence of water, organic solvent and acid, make hydrolysable silanes compound mix
Hydrate hydrolysis, the operation (hereinafter also referred to reaction process (Ia)) of partial condensates, in described hydrolysable silanes compound mixture,
Hydrolysable silanes compound (a-1) relative to 100 moles, comprises hydrolysable silanes compound with the mol ratio of 1～800 mole
(a-2), hydrolysable silanes compound (a-3) is comprised with the mol ratio of 20～300 moles.In the following description, reaction process (I)
In various conditions etc. comprise the condition etc. of reaction process (Ia).Wherein, particularly in reaction process (Ia), there is preferred stripe
In the case of part, reaction process (Ia) is further described.
As the amount of water used in reaction process (I), mix relative to the hydrolysable silanes compound of 100 mass parts
Thing, preferably 5～100 mass parts, more preferably 5～80 mass parts.Additionally, in the case of reaction process (Ia), as used
The amount of water, relative to the hydrolysable silanes compound mixture of 100 mass parts, preferably 5～40 mass parts, spy is well 5～25
Mass parts.By making the water yield within the above range, hydrolysis and partial condensates can be easily controlled.
The effect of the catalyst making hydrolysable silanes compound hydrolysis, partial condensates is played in acid.As acid, salt can be enumerated
The mineral acid of acid, sulphuric acid, nitric acid, phosphoric acid etc., the organic acid of acetic acid, oxalic acid, maleic acid etc..Wherein preferred nitric acid.As acid
Amount, relative to the hydrolysable silanes compound mixture of 100 mass, preferably 0.01～10 mass parts, spy is well 0.01～1 matter
Amount part.
As organic solvent used in reaction process (I), can enumerate and make hydrolysable silanes compound hydrolysis, contracting
Normally used organic solvent when closing reaction.Specifically can enumerate methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butanol, different
The alcohols such as butanol, ethylene glycol, glycerol, propylene glycol, the ketone such as acetone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, 2-methyl cellosolve, 2-
The cellosolve class such as ethoxy ethanol, butoxy ethanol, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) second
The carbitol classes such as alcohol, 2-(2-Butoxyethoxy) ethanol, methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, breast
Acid N-butyl, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, diglycol monotertiary first
Ether acetic acid ester, diethylene glycol monoethyl ether acetas, diethylene glycol monobutyl ether acetas, propylene glycol methyl ether acetate, ethylene glycol diethyl
Acid esters, propylene-glycol diacetate, 3-ethoxyl ethyl propionate, adnoral acetate, butyl lactate, gamma-butyrolacton, 3-methyl-
The esters such as 3-methoxybutyl acetas, glycerol triacetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol two fourth
Ether, triethylene glycol dimethyl ether., tetraethylene glycol dimethyl ether, Propylene Glycol Dimethyl Ether, butyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether etc..In reaction process (I), as organic solvent, can make
With two (trifluoromethyl) benzene etc. containing fluorous solvent.These organic solvents may be used alone, two or more kinds can also be used.
In the present invention, the partial condensate (A) of gained is as it has been described above, preferably have silanol group.Additionally, the part of gained
Condensation substance (A) is blended in hard coat compositions mostly together with the organic solvent used in reaction process (I).Therefore,
As the organic solvent used in reaction process (I), preferably use the organic solvent of above-mentioned silanol group stabilisation.As inciting somebody to action
The organic solvent of silanol group stabilisation, can enumerate have hydroxyl, 25 DEG C time ratio dielectric constant (ε) 5～20 scope
Compound.
Specifically can enumerate carbon number 2～the monoalkyl ether acetate solvent of glycols of 8, single alkane of glycols
Base ether solvents, glyme kind solvent, carbon number 2～the hydro carbons alcohol etc. of 4.More specifically, as glycols
Monoalkyl ether acetate solvent can enumerate propylene glycol methyl ether acetate (ε: 8.3), as the monoalky lether solvent of glycols
Propylene glycol monomethyl ether (ε: 12.3) can be enumerated, 2-propanol (ε: 19.92) etc. can be enumerated as hydro carbons alcohol.As forming hydrogen bond
The propylene glycol monomethyl ether of protic polar solvent, the stabilization effect of its silanol group is high, thus particularly preferably.
From the viewpoint of can be by silanol group sufficient stabilization, organic solvent the most only by have hydroxyl, 25 DEG C time
Constitute than the dielectric constant (ε) compound in the range of 5～20.But, organic solvent can contain as required except this change
Compound beyond compound, now, in terms of the stabilization effect of silanol group from the point of view of, relative to the total amount of organic solvent,
More fortunately comprise in the range of 10～100 mass % have hydroxyl, 25 DEG C time ratio dielectric constant (ε) in the range of 5～20
Compound, spy is well to comprise in the range of 20～100 mass %.
Reaction process (I) is preferably to be implemented under the reaction temperature of room temperature to solvent boiling point, under suitable stirring condition.
As the response time, specifically also depend on the amount of used material composition, reaction temperature, stirring condition etc., but preferably
Being 0.5～24 hour, spy is well 1～18 hour.After reaction terminates, for the partial condensate (A) of gained, it is also possible to do not remove
Organic solvent so that it is be included in the hard coat compositions of the present invention.Organic solvent can also be removed by conventional method
After by partial condensate (A) separate, then make it be included in hard coat compositions.
[hard coat compositions]
The hard coat compositions of the present invention contains above-mentioned partial condensate (A) and optical polymerism composition, partial condensates
The content of thing (A) is 0.01～20 mass % relative to the total solid composition of said composition.
Optical polymerism composition contains photopolymerizable compound (B), preferably possibly together with Photoepolymerizationinitiater initiater (C).
The hard coat compositions of the present invention can also contain organic solvent (D), silicon dioxide microparticle (E) as required
Additive with other.
The hard coat compositions of the present invention preferably make its solidify obtained by film, i.e. cured film at least relative to visible
Light is transparent.Cured film is preferably water white film but it also may be the film of tinted clear.Obtain water white film
Or in the case of the film of tinted clear, hard coat compositions does not preferably contain the additive of the transparency hindering cured film.
Such as, the coloring powder such as pigment hinders the transparency, so preferably not blending in hard coat compositions.On the other hand,
The powder being made up of the such transparency material with the refractive index roughly equal with cured film of silicon dioxide microparticle (E) will not drop
The low transparency, can be blended in hard coat compositions as the additive of the mar proof that can improve cured film.
(partial condensate (A))
The hard coat compositions of the present invention contains above-mentioned partial condensate (A).
Total in hard coat compositions of the content of the partial condensate (A) in the hard coat compositions of the present invention
Being 0.01～20 mass % in solid constituent, preferably 0.1～10 mass %, spy is well 0.1～5 mass %.By making part
Within the above range, the storage-stable of hard coat compositions is good for the content of condensation substance (A).By this hard coat group
The soil resistance on the surface of the hard coat that compound obtains and anti-fingerprint tack are good, and can obtain having the table that outward appearance is good
The hard coat in face.
(photopolymerizable compound (B))
Photopolymerizable compound (B) in the hard coat compositions of the present invention is by causing in photopolymerization described later
Irradiate light in the presence of agent (C) and start polyreaction, the general designation of the compound solidified because of polymerization.It is different with kind with condition,
Only photopolymerizable compound (B) the most also can occur photopolymerization, but is generally used together with Photoepolymerizationinitiater initiater (C).
Photopolymerizable compound (B) is preferably containing the multi-functional list in 1 intramolecular with more than 2 ethylene double bonds
Body (hereinafter also referred to " monomer (b-1) ").Additionally, as required preferably containing the list in 1 intramolecular with 1 ethylene double bond
The monomer (hereinafter also referred to " monomer (b-2) ") of functionality.Photopolymerizable compound (B), by containing monomer (b-1), utilizes
The irradiation of light, specifically ultraviolet, electron ray, X-ray, lonizing radiation and high-frequency ray etc. solidifies.It addition, it is above-mentioned
Partial condensate (A) is the compound with ethylene double bond, and photopolymerizable compound (B) does not comprise and is equivalent to partial condensate
(A) compound.
As monomer (b-1), there is the group of more than 2 ethylene double bonds (hereinafter also referred to as long as have in 1 intramolecular
" polymerizable functional group ") compound be just not particularly limited.As polymerizable functional group, preferably (methyl) acryloyl group,
The α of vinyl, pi-allyl etc., β-unsaturated group, spy is well (methyl) acryloyl group.Wherein it is easier to preferably by ultraviolet
The acryloyl group of polymerization.It addition, monomer (b-1) can be two or more polymerism official's energy of a total of more than 2 in 1 molecule
The compound of group, it is also possible to be the compound of the identical polymerizable functional group of a total of more than 2.
The quantity of the polymerizable functional group in 1 molecule of monomer (b-1) is more than 2, and spy is well more than 3.1 molecule list
The upper limit of the number of the polymerizable functional group that body (b-1) is had is not particularly limited, but typically about 50, preferably 30
Individual.Additionally, as monomer (b-1), from the viewpoint of the mar proof showing height, preferably 1 molecule has more than 3
Polymerizable functional group, the compound that molecular weight is less than 120 of every 1 functional group.As the monomer (b-meeting such condition
1), following compound can be enumerated.
The polyester as tetramethylolmethane or polypentaerythritol with (methyl) acrylic acid reaction product, this polyester can be enumerated
It is the multi-functional compounds having more than 3, more preferably 4～20 (methyl) acryloyl groups, specifically can enumerate trihydroxy methyl third
Alkane three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two seasons penta 4
Alcohol six (methyl) acrylate etc..
Additionally, intramolecular has the compound (hereinafter also referred to " propylene containing (methyl) acryloyl group of amino-formate bond
Acid carbamate ") amino-formate bond played the effect of doubtful crosslinking points by the effect of its hydrogen bond, even if not making every 1
The molecular weight of functional group is little to above-mentioned degree, it is also possible to show sufficiently high mar proof, thus preferable.As meeting this
The monomer (b-1) of the condition of sample, preferably following compound.
Reaction as tetramethylolmethane or polypentaerythritol and polyisocyanates and hydroxyalkyl (methyl) acrylate generates
The propenoic methyl carbamate of thing, this propenoic methyl carbamate is to have more than 3, more preferably 4～20 (methyl) acryloyls
The multi-functional compounds of base；
The reaction of poly-(methyl) acrylate and polyisocyanates as the hydroxyl of tetramethylolmethane or polypentaerythritol
The propenoic methyl carbamate of product, this propenoic methyl carbamate is to have more than 3, more preferably 4～20 (methyl) third
The multi-functional compounds of enoyl-.
Monomer (b-1) can be used alone a kind, it is also possible to two or more is also used.
As monomer (b-2), as long as the compound that 1 intramolecular has 1 polymerizable functional group is just not particularly limited.
The polymerizable functional group being had as monomer (b-2), preferably (methyl) acryloyl group.
As monomer (b-2), specifically can enumerate with CH2=C (R4)COOCzH2z+1(R4Being hydrogen atom or methyl, z is 1～13
Integer；CzH2z+1Can be linear chain structure or branched structure) (methyl) alkyl acrylate of representing.As monomer (b-2),
One (methyl) allyl acrylate, (methyl) benzyl acrylate, butoxyethyl group (methyl) acrylate, one (methyl) can be enumerated
Acrylic acid butanediol ester, butoxytriglycol (methyl) acrylate, t-butylamino ethyl (methyl) acrylate, 3-
Chloro-2-hydroxypropyl (methyl) acrylate, (methyl) 2 cyanoethyl acrylate, (methyl) cyclohexyl acrylate, 2,3-dibromo
Propyl group (methyl) acrylate, (methyl) acrylic acid dicyclopentenyl ester, N, N-diethylamino ethyl (methyl) acrylate, N,
N-dimethyl aminoethyl (methyl) acrylate, 2-ethoxyethyl group (methyl) acrylate, 2-(2-ethoxy ethoxy)
Ethyl (methyl) acrylate, (methyl) 2-EHA, list (methyl) glycerol acrylate, (methyl) acrylic acid contract
Water glyceride, (methyl) acrylic acid 17 fluorine ester in the last of the ten Heavenly stems, (methyl) acrylic acid 2-hydroxy methacrylate, 2-hydroxyl-3-(methyl) acryloyl
Epoxide hydroxypropyltrimonium chloride, 2-hydroxypropyl (methyl) acrylate, 3-(methyl) acryloxypropyl trimethoxy
Silane, 2-methoxy ethyl (methyl) acrylate, methoxyl group diethylene glycol (methyl) acrylate, methoxy triethylene
(methyl) acrylate, methoxyl group TEG (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, methoxy
Base cyclododecane triolefin (methyl) acrylate, morpholine (methyl) acrylate, Nonylphenoxy Polyethylene Glycol (methyl) third
Olefin(e) acid ester, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) acrylic acid octafluoro pentyl ester, phenoxy group hydroxypropyl
(methyl) acrylate, Phenoxyethyl (methyl) acrylate, phenoxy group diethylene glycol (methyl) acrylate, phenoxy group four
Ethylene glycol (methyl) acrylate, phenoxy group six ethylene glycol (methyl) acrylate, phenoxy group (methyl) acrylate, poly-the third two
Alcohol (methyl) acrylate, 2-sodium sulfonate ethyoxyl (methyl) acrylate, four fluoropropyls (methyl) acrylate, (methyl) third
Olefin(e) acid tetrahydrochysene bran ester, (methyl) acrylic acid trifluoro ethyl ester, vinyl acrylate, N-caprolactam, N-vinyl pyrrole
Alkanone, bicyclopentadiene (methyl) acrylate, acrylic acid different norborneol ester etc..
Monomer (b-2) can be used alone a kind, it is also possible to two or more is also used.
The content of the monomer (b-1) in photopolymerizable compound (B) is preferably total relative to photopolymerizable compound (B)
Amount is 20～100 mass %.In photopolymerizable compound (B), monomer (b-1) if ratio within the above range, then by firmly
The excellent in wear resistance of the hard coat that the cured film of matter coating composition is constituted.The ratio more preferably 50 of monomer (b-1)～
100 mass %, spy is well 70～100 mass %.
The content of the monomer (b-2) in photopolymerizable compound (B) is 0 relative to the total amount of photopolymerizable compound (B)
～80 mass %.In photopolymerizable compound (B), monomer (b-2) if ratio within the above range, then the hardness of cured film
Well and film shrinkage factor is suitable, thus without the warpage of the base material with hard coat.The ratio of monomer (b-2) is more preferable
Being 0～50 mass %, spy is well 0～30 mass %.
Here, monomer (b-1) and monomer (b-2) can be as required with by multiple monomers (b-1) or multiple monomers (b-1)
With monomer (b-2) (co) polymerization in advance obtained by the form of (being total to) oligomer or pre-(co) polymer use.As in the case of this
Photopolymerizable compound (B) in should (being total to) oligomer or content of pre-(co) polymer, derive from the repetition of monomer (b-1)
The content of unit, relative to the scope of total amount 20～100 mass % more fortunately of photopolymerizable compound (B), derives from monomer
(b-2) content of repetitive is relative to the scope of total amount 0～80 mass % more fortunately of photopolymerizable compound (B).Also
Having, derive from ratio more preferably 50～100 mass % of the repetitive of monomer (b-1), spy is well 70～100 mass %.Come
Coming from ratio more preferably 0～50 mass % of the repetitive of monomer (b-2), spy is well 0～30 mass %.
The content of the photopolymerizable compound (B) in the total solid composition in hard coat compositions be preferably 40～
98.99 mass %, more preferably 50～95 mass %, spy is well 55～90 mass %.
(Photoepolymerizationinitiater initiater (C))
The Photoepolymerizationinitiater initiater (C) that the hard coat compositions of the present invention is used is as long as have and draw as photopolymerization
The compound of the function sending out agent is just not particularly limited, but preferably utilizes light to produce the compound of free radical.
As Photoepolymerizationinitiater initiater (C), aryl ketones Photoepolymerizationinitiater initiater (such as acetophenones, hexichol specifically can be enumerated
Ketone, alkyl amino Benzophenones, benzil class, benzoin class, benzoin ethers, benzil dimethyl ketal class, adjacent benzene first
Acyl essence of Niobe class, α-acyl group oxime esters etc.), sulfur-bearing class Photoepolymerizationinitiater initiater (such as thioether class, thioxanthene ketone etc.), acyl group
Phosphinoxides (such as acyl group diaryl phosphine oxide etc.), other Photoepolymerizationinitiater initiaters.
Photoepolymerizationinitiater initiater (C) can be used alone a kind, it is also possible to two or more is also used.Additionally, Photoepolymerizationinitiater initiater (C)
Can be applied in combination with photosensitizer such as amines.
As Photoepolymerizationinitiater initiater, following compound can be enumerated.
4-phenoxydichloroacetophenone, the 4-tert-butyl group-dichloroacetophenone, the 4-tert-butyl group-trichloroacetophenone, diethoxybenzene
Ethyl ketone, 2-hydroxy-2-methyl-1-phenyl acrylate-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl acrylate-1-ketone, 1-(4-
Dodecylphenyl)-2-methyl-prop-1-ketone, 1-{4-(2-hydroxyl-oxethyl) phenyl-2-hydroxy-2-methyl-propyl-1-ketone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-{ 4-(methyl mercapto) phenyl }-2-morpholinyl acrylate-1-ketone.
Benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl base
Ether, benzil dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl benzophenone, hydroxyl
Benzophenone, acrylated benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 3,3 ', 4,4 '-four (tert-butyl group mistakes
Oxidation carbonyl) benzophenone, 9,10-phenanthrenequione, camphorquinone, dibenzosuberenone, 2-ethyl-anthraquinone, 4 ', 4 "-diethyl hexichol
Phthalein lactone, (1-phenyl-1,2-propanedione-2 (o-ethoxy carbonyl) oxime), α-acyl group oxime ester, methyl benzoylformate.
4-benzoyl-4 '-dimethyl diphenyl sulfide, thiaxanthone, CTX, 2-methyl thiaxanthone, 2,4-diformazan
Base thiaxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone, 2,4,
6-trimethyl benzoyl diphenyl base phosphine oxide, benzoyl diphenyl phosphine oxide, 2,6-dimethylbenzoyl dipheny oxide
Change phosphine, double (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.
The content of the Photoepolymerizationinitiater initiater (C) in the total solid composition in hard coat compositions is preferably 1～15 matter
Amount %, more preferably 3～15 mass %, spy is well 3～10 mass %.If within the above range, then combined with hard coat
The compatibility of the photopolymerizable compound (B) in thing and curable are good, and the hardness of the cured film formed is good.
(organic solvent (D))
The hard coat compositions of the present invention can contain organic solvent (D).By containing organic solvent (D), improving
Said composition coating on base material.Additionally, in hard coat compositions, partial condensate (A) can be made stably to deposit
?.As organic solvent (D), as long as can uniform dissolution or dispersion hard coat compositions in as must composition and contain
Partial condensate (A), photopolymerizable compound (B) and Photoepolymerizationinitiater initiater (C), and two contained as any composition
Silicon oxide particle (E) or other additives, and not there is the reaction that each composition contained with hard coat compositions reacts
The solvent of property, is not particularly limited.
Organic solvent (D) can be used alone a kind, it is also possible to two or more is also used.The usage amount of organic solvent (D) relative to
The photopolymerizable compound (B) of 100 mass parts is preferably below 10000 mass parts, and spy is well below 5000 mass parts.
As the lower alcohols such as organic solvent (D), preferably ethanol, butanol, isopropanol, methyl iso-butyl ketone (MIBK), methyl second
The ketones such as base ketone, acetone, twoThe ethers such as alkane, diethylene glycol dimethyl ether, oxolane, methyl t-butyl ether, the molten fibre of methyl
The organic solvent of the glycol ethers etc. such as agent, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether.Additionally, acetic acid can be used just
The esters such as butyl ester, isoamyl acetate, diethylene glycol monoacetate, propylene glycol methyl ether acetate, more fluoride hexane, many methyl fluorides ring
How fluoro-the polyfluoro aliphatic hydrocarbon of the carbon numbers such as hexane, 1,3-dimethyl cyclohexane 5～12, double (trifluoromethyl) benzene etc. is polyfluorinated organic
The halogenated hydrocarbon of aromatic hydrocarbons, polyfluorinated aliphatic hydrocarbon etc., the hydro carbons etc. such as toluene, dimethylbenzene, hexane.Painting from hard coat compositions
From the viewpoint of cloth is good, the dissolubility of particularly preferred photopolymerizable compound (B) and the suitable positive fourth of acetic acid of evaporation rate
Ester.
It addition, as it has been described above, come from the viewpoint making partial condensate (A) stable existence hard coat compositions
See, preferably have hydroxyl, 25 DEG C time ratio dielectric constant (ε) 5～20 the compound of scope.As the matter that can form hydrogen bond
The stabilization effect of the silanol group of the propylene glycol monomethyl ether of sub-property polar solvent is high, thus particularly preferably.
From the viewpoint of the stabilization effect of silanol group, relative to the total amount of organic solvent, have hydroxyl, 25 DEG C time
The content of ratio dielectric constant (ε) compound in the range of 5～20 be preferably in the range of 10～100 mass %, special
It is well in the range of 20～100 mass %.
Containing in the case of organic solvent (D) in hard coat compositions, preferably according to the base forming hard coat
The kind of material, selects suitable organic solvent (D).Such as, base material is the feelings of the aromatic polycarbonate resin that solvent resistance is low
Under condition, the organic solvent (D) that preferably use is low to the dissolubility of aromatic polycarbonate resin, applicable use lower alcohols,
Glycol ethers, esters, ethers, their mixture etc..
(silicon dioxide microparticle (E))
The hard coat compositions of the present invention can comprise silicon dioxide microparticle (E) as required.By containing titanium dioxide
Silicon particle (E), can improve the mar proof of hard coat.
As silicon dioxide microparticle (E), preferably silica sol.Silica sol is with glue in disperse medium
The ultra micron of the scattered silicic acid anhydride of body shape, disperse medium is not particularly limited, but preferably water, lower alcohols, cellosolve class etc..
As concrete disperse medium, water, methanol, ethanol, isopropanol, n-butyl alcohol, ethylene glycol, methyl cellosolve, ethyl can be enumerated molten
Fine agent, butyl cellosolve, propylene glycol monomethyl ether, dimethyl acetylamide, toluene, dimethylbenzene, methyl acetate, acetic acid second
Ester, pentyl acetate, acetone etc..
The mean diameter of silicon dioxide microparticle (E) is not particularly limited, but in order to make the cured film after solidification, i.e. hard
Coating shows high transparent, preferably 1～1000nm, more preferably 1～200nm, and spy is well 1～50nm.
In order to improve the dispersion stabilization of silicon dioxide microparticle (E), it is also possible to microparticle surfaces to be used hydrolysable silanes chemical combination
The hydrolysate of thing uses after modifying.Here, " surface is hydrolyzed what thing had been modified " represents the hydrolysate of hydrolysable silanes compound
The state being physically or chemically combined with the some or all of silanol group on the surface of silicon dioxide microparticle (E), thereby by table
The meaning that face characteristic is modified.It addition, also include the silicon dioxide microparticle that the partial condensate of hydrolysate is combined into.Surface is modified
Can be sent out by part or all such as making the hydrolization group of hydrolysable silanes compound in the presence of silicon dioxide microparticle
Unboiled water solution or hydrolysis and condensation reaction are carried out.
As being combined with on hydrolysable silanes compound, preferably silicon atom, there is (methyl) acryloyl group, amino, epoxy
Hydrolization group or the silane compounds of hydroxyl such as the organic group of the functional groups such as base, sulfydryl and alkoxyl.
In the case of silicon dioxide microparticle (E), its content is relative to the photopolymerizable compound (B) of 100 mass parts
Preferably 0.1～500 mass parts, more preferably 1～300 mass parts, spy is well 10～200 mass parts.If above-mentioned scope, then
The mar proof of cured film after solidification, i.e. hard coat is abundant, easily maintains high transparent and being not likely to produce to be caused by external force
Crackle etc..
(other additives)
In the hard coat compositions of the present invention, as additive other than the above, can not damaged this as required
Blend selected from UV absorbent, light stabilizer, antioxidant, solar heat protection polymerizer, levelling agent in the range of the effect of invention, disappear
Infusion, thickening agent, sagging inhibitor, pigment (organic coloring pigments, inorganic pigment), illuminating colour, infrared absorbent, fluorescence increase
White agent, dispersant, electrically conductive microparticle, antistatic agent, antifoggant, the additive of more than a kind of coupling agent.
It addition, as the hard coat compositions of the present invention, it is also possible to it is that the commercially available light that hard coat is formed is solid
The resin combination (hereinafter also referred to " resin combination (Y) ") of the property changed becomes with the total solid relative to resin combination (Y)
Divide and the ratio that gross mass is 0.01～20 mass % of partial condensate (A) contains compositions obtained by partial condensate (A).
The resin combination (Y) that commercially available hard coat is formed usually contains the photopolymerizable compound (B) one-tenth as optical polymerism
Point, and in most cases possibly together with Photoepolymerizationinitiater initiater (C), and contain various composition the most as described above.
The resin combination (Y) formed as such commercially available hard coat, specifically can enumerate hard coat agent
HC162 (trade name: Ha De U ト HC162, Heng Bang rubber Co., Ltd. (Heng Bangゴ system society) system), hard coat agent combination
Suit 575 (CB) (trade name: Ha De U ト PVC system セ ッ ト 575 (CB), Arakawa Chemical Industries, Ltd.'s (waste river chemistry
Work society) system) etc..
[there is the base material of hard coat]
The base material with hard coat of the present invention includes: base material, and at least part of surface of above-mentioned base material by
The hard coat that the cured film that the hard coat compositions of the invention described above is formed is constituted.
As the base material of formation hard coat, as long as generally require to form soil resistance, particularly anti-fingerprint tack
The base material that the material of hard coat is constituted just is not particularly limited, and preferably uses metal, glass, resin, pottery or a combination thereof (multiple
Condensation material, laminated material etc.) matrix that constitutes.Spy is well the base material that glass or resin etc. are transparent.
As glass, common soda-lime glass, borosilicate glass, alkali-free glass, quartz glass etc. can be enumerated.
In the present invention, as the base material of formation hard coat, using transparent and requiring that soil resistance, particularly anti-fingerprint are attached
In the case of the resin base material of the property and mar proof, especially significant effect can be played, thus preferably.
As such resin, aromatic polycarbonate resin, plexiglass, poly-first specifically can be enumerated
Base acrylimide resin, polystyrene resin, Corvic, unsaturated polyester resin, vistanex, ABS resin,
MS (Methyl Methacrylate-Styrene) resin etc..
The shape of base material and the surface of formation hard coat are not particularly limited, suitably can select according to purposes.Base
In the case of material is tabular, can be flat board, it is also possible to be whole or part there is curvature.The thickness of base material can be hard according to having
The purposes of the base material of matter coating suitably selects, but generally preferable 0.5～10mm.
As the base material used in the present invention, can use its surface is carried out acid treatment (after using dilution according to purpose
Fluohydric acid., sulphuric acid, the process of hydrochloric acid etc.), alkali process (process using sodium hydrate aqueous solution etc.) or discharge process (wait from
Daughter irradiation, corona irradiation, electronbeam irradiation etc.) etc. after base material.
As the method forming hard coat on the surface of base material, generally can use and use with photopolymerizable compound
(B) it is the hard coat compositions of the main body method that forms that on base material the method for hard coat is identical.Specifically, can lead to
Cross and there is the method for following operation manufacture: hard coat compositions is coated on the regulation surface of base material by (1), is formed and is coated with
(wherein, hard coat is by compositions without in the case of solvent, and the film of gained is the most solvent-laden for the film formation process of film
" film ")；(2) the solvent removal step of film is formed by solvent film from base material removes as required；(3) on base material
Film carry out light irradiation, form the photocuring operation of the hard coat as cured film.
(film (film) formation process)
As the method that hard coat compositions is coated on the surface of base material, it is not particularly limited, can use existing
There is known method.Specifically can enumerate dip coating, spin-coating method, flow coat method, spraying process, stick coating method, gravure coating process, rolling method,
The method of scraper for coating method, air knife coating method etc..Here, the thickness of film or film is so that cured film after photocuring, i.e. hard
The thickness of coating reaches the condition of thickness described later and is adjusted.
(solvent removal step)
In the case of base material is formed solvent-laden film, generally carry out for removing being dried of solvent.Drying condition
Different with the hard coat compositions used, but be typically to process about 0.5～5 minute at 40～120 DEG C.
(photocuring operation)
Then, the film on base material is irradiated light, make the photocuring composition in film react and be solidified to form cured film, thus shape
Become hard coat.The light used, preferably ultraviolet, electron ray, X-ray, lonizing radiation and high-frequency ray is irradiated as light
Deng, the ultraviolet of the wavelength with 180～500nm is particularly preferred from cost consideration.As light source, xenon lamp, low-pressure mercury can be used
The ultraviolet lamp of lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp etc., electron ray shine
Injection device, X-ray irradiator, high frequency waves generator etc..
The condition that light irradiates can be with the kind of photopolymerizable compound (B), the kind of Photoepolymerizationinitiater initiater (C), the thickness of film
Degree, the kind etc. of light source suitably change.Usually as the condition of the light exposure to film, preferably 100～5000mJ/cm2, special
It is well 100～1000mJ/cm2.As time of exposure, preferably 0.1～60 second, spy was well 0.5～30 second.Additionally, in order to make
Curing reaction terminates, it is possible to irradiate laggard row heat treated at light.
The thickness of cured film, i.e. hard coat can use various thickness as required.The thickness of hard coat is preferably 0.1
～50 μm, more preferably 0.2～20 μm, spy is well 0.3～10 μm.If the thickness of hard coat is within the above range, the most wear-resisting
Damage is abundant, and the solidification in hard coat deep is also abundant, thus preferably.
The transparency of the hard coat thus formed on the surface of base material is good, and its surface has sufficient hardness,
Water and oil repellant is excellent, long-term performance can go out excellent anti-fingerprint tack.The base material with hard coat of the present invention hard
The character that the above-mentioned water and oil repellant of matter coating surface is relevant is by the partial condensate (A) contained by hard coat compositions
Function produces.
Partial condensate (A) when blending in hard coat compositions, forming hard coat by said method, with
Photopolymerizable compound (B) as the main constituent of hard coat combines.Hard coat, particularly surface exhibits go out by
The excellent water and oil repellant that the fluorine-containing organic group that partial condensate (A) is had produces.Further, partial condensate (A) because of
For with photopolymerizable compound (B) combine, so oozing out from hard coat hardly, can long-term performance go out excellence water repellent refuse
Oiliness.Therefore, the hard coat surface of the base material with hard coat of the present invention is for the lipid of sebum, antiperspirant, cosmetics etc.
The soil resistance of dirt, particularly anti-fingerprint tack are excellent, are difficult to adhere to lipid dirt, even if attachment also is able to easily wiping
Fall.
The base material with hard coat of the present invention has above-mentioned characteristic, so can be used as lipid dirt, particularly fingerprint
Attachment become smart mobile phone and the panel computer etc. of apparent problem use touch screen, display glass, optics unit
The component of part, sanitary equipment etc..In especially significant effect available in the case of touch screen.
<touch screen>
The touch screen of the present invention has the base material with hard coat of the invention described above.This touch screen is with at touch surface table
The mode exposing hard coat arranges the base material with hard coat, is designed to the structure phase with common touch screen in addition
With.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiments.
It addition, example 1～3,9～11,18,19,21～24,26 be embodiment, example 4～8,12～16,20,25 is comparative example, and example 17 is
Reference example.
Each mensuration is carried out by following method.
[number-average molecular weight (Mn)]
Use commercially available GPC determinator (TOSOH Co., Ltd (ソ society) makes, device name: HLC-8320GPC), survey
Multiple monodisperse polystyrene polymer that be set for the standard specimen for molecular weight determination, that the commercially available degree of polymerization is different solidifying
Glue penetration chromatograph (GPC), the relation of molecular weight based on polystyrene and retention time (retention time) draws correction
Curve.
Sample oxolane is diluted to 1.0 mass % so that it is after the filter by 0.5 μm, this sample is used
Above-mentioned GPC determinator measures GPC.
By using above-mentioned calibration trace, the gpc chromatogram of sample being carried out computer analysis, the number calculating this sample is divided equally
Son amount (Mn).
[fluorine atom containing ratio]
, pass through using Isosorbide-5-Nitrae-two (trifluoromethyl) benzene as standard substance19F NMR measures and calculates fluorine atom containing ratio.
[water contact angle]
By sessile drop method, according to the standard of JIS R 3257 " the wellability test method on base plate glass surface ", at base material
On measure surface 3 at placing water droplet, each water droplet is determined.Drop is about 2 μ L/ and drips, and measures and carries out at 20 DEG C.Connect
Feeler is indicated with the meansigma methods (n=3) of 3 measured values.It addition, from the viewpoint of anti-fingerprint tack, water contact angle
As long as can use more than about 90 degree, preferably from about more than 95 degree.
[oleic acid contact angle]
By sessile drop method, according to the standard of JIS R 3257 " the wellability test method on base plate glass surface ", at base material
On measure surface 3 at placing oleic acid, each oleic acid is dripped and is determined.Drop is about 2 μ L/ and drips, and measures and carries out at 20 DEG C.
Contact angle is indicated with the meansigma methods (n=3) of 3 measured values.It addition, from the viewpoint of anti-fingerprint tack, oleic acid connects
As long as feeler can use more than about 55 degree, preferably from about more than 60 degree.
[cured film outward appearance]
According to following standard by gross evaluations cured film outward appearance.
Zero (well): foreign body unconfirmed, uniform film thickness.
△ (can): foreign body unconfirmed, but membrane thickness unevenness.
× (bad): can confirm that foreign body.
[refusing ink]
Ink of refusing after initial stage and following light fastness test is evaluated.Refuse ink by consolidating at gained
Changing surface felt pen (ZEBRA Co., Ltd. (ゼ Block ラ society) system, goods name: the マ ッ キ color) setting-out of film, naked eyes are seen
The attachment state examining ink is evaluated.Evaluation criterion is as described below.
◎ (excellent): refuse ink good, ink is rejected as spherical.
Zero (well): ink do not rejects glomeration, the rejecting of wire occurs, and (live width is less than the nib width of felt pen
50%).
△ (can): there is the rejecting of wire of ink, live width felt pen nib width 50% less than
100%.
× (bad): reject ink hardly, can the clearly setting-out on surface.
[light fastness test]
For the cured film of gained, with daylight weathering tester at Black panel temperature 63 DEG C, with rainfall 12 minutes,
The circulation being dried 48 minutes exposes 500 hours to the open air.
[pencil hardness]
It is determined according to the standard of JIS K 5600.
The abbreviation of the compound used in the embodiment of hard coat compositions and the base material with hard coat is such as
Lower described.
(partial condensate (A))
Employ by the partial condensate liquid (A1-1) obtained in following example 1～6, example 8 and example 18～21～(A6-1),
～(A11-1), (X1-1) and the partial condensate (A7) that obtained by example 7 (A8-1).
(photopolymerizable compound (B))
B-1: dipentaerythritol acrylate.
B-2: three (acryloyl-oxyethyl) isocyanuric acid ester.
(Photoepolymerizationinitiater initiater (C))
C-1:2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-propyl-1-ketone
(organic solvent (D))
D-1: n-butyl acetate.
D-2: propylene glycol monomethyl ether (hereinafter also referred to " PGME ").
(silicon dioxide microparticle (E))
E-1: at the isopropanol decentralized silica sol (dioxide-containing silica: 30 mass %, average of 100 mass parts
Particle diameter: 11nm) the middle 3-methacryloxypropyl trimethoxy silane adding 2.5 mass parts, stirs 3 hours in 50 DEG C
After, in obtained by room temperature curing 12 hours, surface there is the glue of hydrolytic condensate of silane compound containing methylacryloyl
Body silicon dioxide.
[example 1: partial condensate (A1) and the manufacture of partial condensate liquid (A1-1)]
In the 2 liters of flasks possessing blender, put into the 46.75g CF as above-claimed cpd (a-1)3(CF2)5CH2CH2Si(OCH3)3(Asahi Glass Co., Ltd (Asahi Glass society) system), 12.45g are as the Si of above-claimed cpd (a-2)
(OC2H5)4(COLCOAT Co., Ltd. system), 40.8g are as the CH of above-claimed cpd (a-3)2=CHCOO (CH2)3Si(OCH3)3
(Tokyo HuaCheng Industry Co., Ltd (capital chemical conversion work society) system).Then, put into the water of PGME, 12.02g of 607g, obtain
Mixture.
While being stirred at room temperature this mixture, 60% aqueous solution of nitric acid of dropping 0.20g.After completion of dropwise addition, then
Stir 5 hours.Using the PGME solution containing 10 mass % partial condensates (A1) that obtains as partial condensate liquid (A1-1).
The fluorine atom containing ratio of partial condensate (A1) is 34.3 mass %, and number-average molecular weight (Mn) is 740.
With quality (g), table 1 represents that the raw material of partial condensate (A1) forms and the amount of each composition used in manufacture.This
Outward, raw material is formed, molal quantity when compound (a-1) is denoted as 100 moles is shown simultaneously.For used each in manufacturing
The amount of composition, illustrates the mass parts when total amount of compound (a-1)～(a-3) is denoted as 100 mass parts simultaneously.Additionally, simultaneously
Fluorine atom containing ratio, number-average molecular weight (Mn) are shown.
[example 2～6: partial condensate (A2)～(A6) and partial condensate liquid (A2-1)～the manufacture of (A6-1)]
In addition to the proportioning of raw material being changed into as shown in table 1, obtain partial condensate (A2)～(A6) in the same manner as example 1
With partial condensate liquid (A2-1)～(A6-1).
[example 7: the manufacture of partial condensate (A7)]
The cooperation of raw material is changed into as shown in table 1.After reaction terminates, separate out white grease.By white grease-like
Thing filter, with ion exchange water clean to pH be 6～7, under decompression in 60 DEG C be dried 3 hours, somewhat had sticking in vain
Color solid, shaped resin.Using the resin that obtains as partial condensate (A7).
[example 8: partial condensate (A8) and the manufacture of partial condensate liquid (A8-1)]
In being equipped with the four-hole boiling flask of 300mL of blender and cooling tube, add the tetrabutyl titanate of 80mg, 100g
C3F7(OCF2CF2CF2)20O(CF2)2CH2OH (Daikin Ind Ltd (ダ イ キ ンGong society) system, goods name: デ system
Na system SA, number-average molecular weight (Mn): 4000) and the 6-caprolactone of 10g, heat 5 hours in 150 DEG C.Obtain at C3F7
(OCF2CF2CF2)20O(CF2)2CH2White waxy compound obtained by one end of OH and 6-caprolactone open loop addition.This change
The number-average molecular weight (Mn) of compound is 4400, and the polymerization number of degrees of caprolactone are about 3.5.
Then, this compound is cooled to room temperature, adds two (trifluoromethyl) benzene and the 2 of 60mg between 50g, the tertiary fourth of 6-bis-
Base paracresol, stirs 30 minutes.Add the 2-methacryloxyethyl isocyanates of 6.0g, be stirred for 24 in room temperature little
Time, obtain between the partial condensate (A8) that end has been modified by methylacryloyl two (trifluoromethyl) benzole soln (containing 70
The partial condensate (A8) of quality %), i.e. partial condensate liquid (A8-1).Table 1 shows partial condensate liquid (A8-1)
Composition and the fluorine atom containing ratio of partial condensate (A8), number-average molecular weight (Mn).
[table 1]
[example 9: hard coat compositions and there is the manufacture of base material of hard coat]
Put in being equipped with the four-hole boiling flask of 300mL of blender and cooling tube manufactured by example 1 10g (A1-1) liquid,
80g photopolymerizable compound (B-1), 4g Photoepolymerizationinitiater initiater (C-1), 100g organic solvent (D-1), at room temperature and the shape of shading
Stir 1 hour under state.Then, stir and be slowly added 75g silica sol (E-1), then in room temperature and shading
Stir 1 hour under state, obtain hard coat compositions 1.
Then, it is coated with hard coat compositions example 1 by stick coating method on the surface of pet substrate, with the heating plate of 50 DEG C
It is dried 1 minute, forms film on the surface of substrate.Then, high voltage mercury lamp (light quantity: 300mJ/cm is used2, the ultraviolet of wavelength 365nm
Line cumlative energy) carry out light irradiation.Its result is the cured film obtaining thickness 5 μm on the surface of substrate.By above-mentioned method
This cured film (hard coat) is evaluated.Result is shown in together with the composition of hard coat compositions table 2.
[example 10～17: hard coat compositions and there is the manufacture of base material of hard coat]
Except by the partial condensate liquid (A1-1) obtained by example 1～6 and 8～(A6-1), (A8-1), being obtained by example 7
Partial condensate (A7), photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C), organic solvent (D) and silica sol (E)
Change into beyond as shown in table 2, manufacture hard coat compositions 2～9 in the same manner as example 9.Use these compositionss respectively, with example
9 similarly form cured film (hard coat) on pet substrate, are evaluated.Group by result Yu hard coat compositions
Become to be shown in table 2 together.
[table 2]
[example 18: partial condensate (A9) and the manufacture of partial condensate liquid (A9-1)]
The 3.3g CF as above-claimed cpd (a-1) is put in the 2 liters of flasks possess blender3O(CF2CF2O)8CF2C
(=O) NHCH2CH2CH2Si(OCH3)3(example 2 based on International Publication the 2009/008380th manufactures), 62.1g are as above-mentionedization
Si (the OC of compound (a-2)2H5)4(COLCOAT Co., Ltd. system), 34.6g are as the CH of above-claimed cpd (a-3)2=CHCOO
(CH2)3Si(OCH3)3(Tokyo HuaCheng Industry Co., Ltd's system).Then, two (trifluoromethyl) benzene and 227g between 530g are put into
2-propanol, obtains mixture.
While being stirred at room temperature this mixture, the 1% aqueous solution of nitric acid water of dropping 59.7g.After completion of dropwise addition, then
Stir 5 hours.Using the solution containing 5 mass % partial condensates (A9) that obtains as partial condensate liquid (A9-1).Part
The fluorine atom containing ratio of condensation substance (A9) is 3.9 mass %, and number-average molecular weight (Mn) is 1160.
[example 19: partial condensate (A10) and the manufacture of partial condensate liquid (A10-1)]
5.2g KY-108 (trade name, letter as above-claimed cpd (a-1) is put in the 2 liters of flasks possess blender
More chemical industry Co., Ltd. system), 60.7g is as the Si (OC of above-claimed cpd (a-2)2H5)4(COLCOAT Co., Ltd. system),
34.1g is as the CH of above-claimed cpd (a-3)2=CHCOO (CH2)3Si(OCH3)3(Tokyo HuaCheng Industry Co., Ltd's system).Connect
, put into two (trifluoromethyl) benzene and the 2-propanol of 230g between 537g, obtain mixture.
While being stirred at room temperature this mixture, the 1% aqueous solution of nitric acid water of dropping 57.6g.After completion of dropwise addition, then
Stir 5 hours.Using the solution containing 7 mass % partial condensates (A10) that obtains as partial condensate liquid (A10-1).Portion
The fluorine atom containing ratio dividing condensation substance (A10) is 7.4 mass %, and number-average molecular weight (Mn) is 1230.
[example 20: partial condensate (X1) and the manufacture of partial condensate liquid (X1-1)]
The 1.7g CF as above-claimed cpd (a-1) is put in the 2 liters of flasks possess blender3O(CF2CF2O)8CF2C
(=O) NHCH2CH2CH2Si(OCH3)3(example 2 based on International Publication the 2009/008380th manufactures), 62.8g are as above-mentionedization
Si (the OC of compound (a-2)2H5)4(COLCOAT Co., Ltd. system), 35.5g are as the CH of above-claimed cpd (a-3)2=CHCOO
(CH2)3Si(OCH3)3(Tokyo HuaCheng Industry Co., Ltd's system).Then, two (trifluoromethyl) benzene and 226g between 526g are put into
2-propanol, obtains mixture.
While being stirred at room temperature this mixture, the 1% aqueous solution of nitric acid water of dropping 61.3g.After completion of dropwise addition, then
Stir 5 hours.Using the solution containing 5 mass % partial condensates (X1) that obtains as partial condensate liquid (X1-1).Part
The fluorine atom containing ratio of condensation substance (X1) is 2.1 mass %, and number-average molecular weight (Mn) is 1150.
[example 21: partial condensate (A11) and the manufacture of partial condensate liquid (A11-1)]
In the 2 liters of flasks possessing blender, put into the F (CF of 88.0g under nitrogen atmosphere2)6CH2CH2OC (=O) C (CH3)
=CH2, the HSCH of 40.0g2CH2CH2Si(OCH3)3, the 2,2 '-azobis isobutyronitrile (AIBN) of 0.33g.Then, 710g is put into
Between two (trifluoromethyl) benzene and the 2-propanol of 304g, obtain mixture.
While stirring this mixture in 70 DEG C, making it react 12 hours, obtaining containing 10 mass %F (CF2)6CH2CH2OC (=O) CH (CH3)CH2SCH2CH2CH2Si(OCH3)3The solution of (compound (a-1-11)).
The 162g compound (a-1-11) as above-claimed cpd (a-1) is put in the 1 liter of flask possess blender
10% solution, 53.6g are as the Si (OC of above-claimed cpd (a-2)2H5)4(COLCOAT Co., Ltd. system), 30.2g are as above-mentioned
The CH of compound (a-3)2=CHCOO (CH2)3Si(OCH3)3(Tokyo HuaCheng Industry Co., Ltd's system).Then, put between 149g
Two (trifluoromethyl) benzene and the 2-propanol of 64g, obtain mixture.
While being stirred at room temperature this mixture, the 1% aqueous solution of nitric acid water of dropping 53.8g.After completion of dropwise addition, then
Stir 5 hours.Using the solution containing 10 mass % partial condensates (A11) that obtains as partial condensate liquid (A11-1).Portion
The fluorine atom containing ratio dividing condensation substance (A11) is 12.4 mass %, and number-average molecular weight (Mn) is 990.
The partial condensate (A9), (A10), (X1) and (A11) represented with quality (g) shown in table 3 raw material composition with
And the amount of each composition used by manufacturing.Additionally, form for raw material, illustrate time compound (a-1) is denoted as 100 moles simultaneously
Molal quantity.For the amount of each composition used in manufacturing, illustrate simultaneously and the total amount of compound (a-1)～(a-3) is denoted as 100
Mass parts during mass parts.Additionally, illustrate fluorine atom containing ratio, number-average molecular weight (Mn) simultaneously.
[table 3]
[example 22～26: hard coat compositions and there is the manufacture of base material of hard coat]
Add the partial condensate liquid (A9-1), (A10-1), (X1-1) and (A11-1) obtained by example 18～21 to table 4
In the resin combination (Y) that shown commercially available hard coat is formed so that partial condensate (A9), (A10), (X1) and
(A11) ratio reaches the ratio shown in table 4 relative to the total solid composition of resin combination (Y) and the gross mass of partial condensate
Example (quality %), prepares hard coat compositions 10～14.It addition, as the Photocurable resin composition (Y) in each example,
Use hard coat agent HC162 (trade name, Heng Bang rubber Co., Ltd. system) and hard coat agent combined complete 575 (CB) (business
The name of an article, Arakawa Chemical Industries, Ltd.'s system) in any one.Use these compositionss respectively, at PET base in the same manner as example 11
Form cured film (hard coat) on plate, be evaluated.Result is shown in together with the composition of hard coat compositions table 4.
[table 4]
The hard coat of the example 9,10 using the partial condensate (A1) of the present invention and (A2) respectively and formed, is with water repellent
Oil repellent and refuse anti-fingerprint tack that ink represents, light resistance, cured film outward appearance, hard coat that pencil hardness is good.
The hard coat of the example 11 using the partial condensate (A3) of the present invention and formed is to have anti-fingerprint tack, Gu
Change the hard coat that film outward appearance is good.
The example 22 using the partial condensate (A9), (A10) and (A11) of the present invention respectively and formed～the hard of 24 and 26
Coating is with water and oil repellant and to refuse anti-fingerprint tack that ink represents and the good hard coat of cured film outward appearance.
The hard of the example 12 employing the fluorine atom containing ratio of the partial condensate partial condensate (A4) more than 40% is coated with
The cured film appearance property of layer is insufficient.
Employ the example 13 of the partial condensate (A5) without compound (a-2) unit hard coat refuse ink not
Fully.Can speculate this is because cause the film property of partial hydrolysis condensate to suffer damage without compound (a-2) unit
Result.
Employ the example 14 of the partial condensate (A6) without compound (a-3) unit hard coat refuse ink not
Fully.Can speculate this is because cause the partial hydrolysis condensate can not be with optical polymerism chemical combination without compound (a-3) unit
Thing (B) is polymerized, it is difficult to concentrate the result being present in coating, particularly surface.
Use and use partial condensate obtained by the hydrolysable silanes compound with the perfluoroalkyl that carbon number is 8
(A7) hard coat of example 15, its carrying capacity of environment is big.Additionally, cured film appearance property is insufficient.Its reason can speculate be because of
Number-average molecular weight for partial hydrolysis condensate is big, and the compatibility with photopolymerizable compound (B) is insufficient.
The light resistance of the hard coat of the example 16 of the partial condensate (A8) that use main chain is made up of hydrocarbon is insufficient.Can speculate
It is because main chain to be made up of hydrocarbon, so ultraviolet causes deterioration.
In example 17, use the partial hydrolysis condensate of the embodiment obtained by example 1 to manufacture hard coat compositions, make
There is the base material of hard coat with this hard coat compositions manufacture.Wherein, it is condensed with the partial hydrolysis in total solid composition
The content of thing more than 20 mass % composition manufacture hard coat compositions, so the hard coat of example 17 refuse ink not
Fully.The partial hydrolysis condensate of low-surface-energy has the characteristic at surface segregation.The hard coat being because example 17 can be speculated
Can the layer that concentrates of forming part hydrolytic condensate, partial condensate (A) and photopolymerizable compound (B) cannot be full cross-linked.
In the case of the partial hydrolysis condensate of the present invention is contained in compositions use, according to the model of the characteristic required by said composition
Enclose, suitably adjust and use after preferably forming.
Employ fluorine atom containing ratio less than 2.5% partial condensate (X1) example 25 hard coat refuse ink
Insufficient.Can speculate that being because surface is the most fully coated to Rf。
The probability utilized in industry
The hard coat compositions of the partial hydrolysis condensate containing the present invention can be formed on base material to be had sufficiently
Hardness and the soil resistance of excellence, the hard coat of particularly excellent anti-fingerprint tack.And, carrying capacity of environment is few.Additionally,
There is the mar proof of the base material of hard coat, the transparency excellent, and its surface has sufficient hardness, soil resistance, especially
The light resistance being anti-fingerprint tack is the most excellent.Therefore, the attachment that can be used as lipid dirt, particularly fingerprint becomes apparent
The structure of the touch screen of use, display glass, optical element, sanitary equipment etc. in the smart mobile phone of problem and panel computer etc.
Part.
It addition, the Japanese patent application 2012-017605 filed an application 2012 incorporated herein January 31 and
Description, claims and the summary of the Japanese patent application 2012-245498 that on November 7th, 2012 files an application
Full content is as the announcement of the description of the present invention.
Claims (21)
1. a manufacture method for anti-fingerprint adhesive agent, described anti-fingerprint adhesive agent is 2.5～40 matter by fluorine atom containing ratio
The partial hydrolysis condensate of amount % is constituted, and described partial hydrolysis condensate is to comprise the hydrolysable silanes represented with following formula (a-1)
Compound (a-1), the hydrolysable silanes compound (a-2) represented with following formula (a-2) and the water-disintegrable silicon represented with following formula (a-3)
The partial hydrolysis condensate of the mixture of hydride compounds (a-3)；In the presence of water, organic solvent and acid, make hydrolysable silanes
Compound mixture hydrolysis, partial condensates, manufacture the partial hydrolysis condensate that fluorine atom containing ratio is 2.5～40 mass %；Institute
State in hydrolysable silanes compound mixture, relative to the hydrolysable silanes compound represented with (a-1) described in 100 moles
(a-1), comprise the described hydrolysable silanes compound (a-2) represented with (a-2) with the mol ratio of 1～23000 mole, with 20～
The mol ratio of 11500 moles comprises the described hydrolysable silanes compound (a-3) represented with (a-3)；
[changing 1]
Rf-Q1-SiX1 3 ···(a-1)
RH1 p-SiX2 (4-p) …(a-2)
Symbol in formula (a-1), (a-2) and (a-3) is as follows:
Rf: F (CF2)4-、F(CF2)6-or with Rf1ORf21 valency group of the carbon number 2～100 of-expression, wherein, Rf1It is that carbon is former
The perfluoroalkyl of subnumber 1～6, Rf2It it is the perfluorinated alkylidene can between carbon-to-carbon atom with etheric oxygen atom；
Q1: the divalent organic group without fluorine atom of carbon number 1～10；
Y: there is the group of ethylene double bond；
Q2: the divalent organic group without fluorine atom of carbon number 1～6；
RH1、RH2: the alkyl of carbon number 1～6；
X1、X2、X3: hydrolization group；
The integer of p:0～3；
Q:1 or 2；
R:0 or 1；Q+r is the number of 1 or 2；
Wherein, the X in formula (a-1)1, and the X in formula (a-2) or formula (a-3)2、X3、RH1、Y-Q2When existing multiple, each other may be used
With similar and different.
2. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 1, it is characterised in that described partial hydrolysis condensate
Fluorine atom containing ratio is 20～40 mass %, the R in described formula (a-1)fIt is F (CF2)4-、F(CF2)6-or with Rf1ORf2-represent
1 valency group of carbon number 2～40, wherein, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It is can be former at carbon-to-carbon
There is between son the perfluorinated alkylidene of etheric oxygen atom.
3. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 1, it is characterised in that described partial hydrolysis condensate is
Make the hydrolysis of hydrolysable silanes compound mixture, partial condensates and the partial hydrolysis condensate that manufactures；Described hydrolysable silanes
In polymer mixtures, the described hydrolysable silanes compound (a-1) relative to 100 moles, with the mol ratio bag of 1～800 mole
Containing described hydrolysable silanes compound (a-2), comprise described hydrolysable silanes compound (a-with the mol ratio of 20～300 moles
3)。
4. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 1, it is characterised in that relative to described hydrolysable silanes
Compound mixture 100 mass parts, the addition of described water is 5～100 mass parts.
5. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 2, it is characterised in that relative to described hydrolysable silanes
Compound mixture 100 mass parts, the addition of described water is 5～100 mass parts.
6. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 3, it is characterised in that relative to described hydrolysable silanes
Compound mixture 100 mass parts, the addition of described water is 5～100 mass parts.
7. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 3, it is characterised in that relative to described hydrolysable silanes
Compound mixture 100 mass parts, the addition of described water is 5～40 mass parts.
8. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 1, it is characterised in that described organic solvent comprises and has
Hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
9. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 2, it is characterised in that described organic solvent comprises and has
Hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
10. the manufacture method of anti-fingerprint adhesive agent as claimed in claim 3, it is characterised in that described organic solvent comprises tool
There are hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
The manufacture method of 11. anti-fingerprint adhesive agents as claimed in claim 4, it is characterised in that described organic solvent comprises tool
There are hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
The manufacture method of 12. anti-fingerprint adhesive agents as claimed in claim 5, it is characterised in that described organic solvent comprises tool
There are hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
The manufacture method of 13. anti-fingerprint adhesive agents as claimed in claim 6, it is characterised in that described organic solvent comprises tool
There are hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
The manufacture method of 14. anti-fingerprint adhesive agents as claimed in claim 7, it is characterised in that described organic solvent comprises tool
There are hydroxyl, the compound that ratio dielectric constant is 5～20 at 25 DEG C.
The manufacture method of the 15. anti-fingerprint adhesive agents as according to any one of claim 1～14, it is characterised in that described acid
It is nitric acid.
16. 1 kinds of hard coat compositionss, it is that the hard containing following part hydrolytic condensate and optical polymerism composition is coated with
Layer compositions, it is characterised in that the content of the following part hydrolytic condensate in the total solid composition of described compositions is
0.01～20 mass %；
Partial hydrolysis condensate: comprise represent with following formula (a-1) hydrolysable silanes compound (a-1), represent with following formula (a-2)
Hydrolysable silanes compound (a-2) and the part of the mixture of hydrolysable silanes compound (a-3) that represents with following formula (a-3)
Hydrolytic condensate, and the fluorine atom containing ratio of this partial hydrolysis condensate is 2.5～40 mass %；This partial hydrolysis condensate is
By making hydrolysable silanes compound mixture hydrolyze in the presence of water, organic solvent and acid, partial condensates and the fluorine that manufactures
Atom containing ratio is the partial hydrolysis condensate of 2.5～40 mass %；In described hydrolysable silanes compound mixture, relative to
The described hydrolysable silanes compound (a-1) represented with (a-1) of 100 moles, comprises institute with the mol ratio of 1～23000 mole
State the hydrolysable silanes compound (a-2) represented with (a-2), comprise with the mol ratio of 20～11500 moles described with (a-3) table
The hydrolysable silanes compound (a-3) shown；
[changing 2]
Rf-Q1-SiX1 3 ···(a-1)
RH1 p-SiX2 (4-p) …(a-2)
Symbol in formula (a-1), (a-2) and (a-3) is as follows:
Rf: F (CF2)4-、F(CF2)6-or with Rf1ORf21 valency group of the carbon number 2～100 of-expression, wherein, Rf1It is that carbon is former
The perfluoroalkyl of subnumber 1～6, Rf2It it is the perfluorinated alkylidene can between carbon-to-carbon atom with etheric oxygen atom；
Q1: the divalent organic group without fluorine atom of carbon number 1～10；
Y: there is the group of ethylene double bond；
Q2: the divalent organic group without fluorine atom of carbon number 1～6；
RH1、RH2: the alkyl of carbon number 1～6；
X1、X2、X3: hydrolization group；
The integer of p:0～3；
Q:1 or 2；
R:0 or 1；Q+r is the number of 1 or 2；
Wherein, the X in formula (a-1)1, and the X in formula (a-2) or formula (a-3)2、X3、RH1、Y-Q2When existing multiple, each other may be used
With similar and different.
17. hard coat compositionss as claimed in claim 16, it is characterised in that the fluorine of described partial hydrolysis condensate is former
Sub-containing ratio is 20～40 mass %, the R in described formula (a-1)fIt is F (CF2)4-、F(CF2)6-or with Rf1ORf2The carbon of-expression
1 valency group of atomic number 2～40, wherein, Rf1It is the perfluoroalkyl of carbon number 1～6, Rf2It is can be between carbon-to-carbon atom
There is the perfluorinated alkylidene of etheric oxygen atom.
The 18. hard coat compositionss as described in claim 16 or 17, it is characterised in that described optical polymerism composition contains
Photopolymerizable compound and Photoepolymerizationinitiater initiater.
The 19. hard coat compositionss as described in claim 16 or 17, it is characterised in that described hard coat compositions
The film of solidification is at least transparent relative to luminous ray.
20. 1 kinds of base materials with hard coat, it is characterised in that include base material；With at least part of surface at described base material
On the hard that constitutes of the cured film formed by the hard coat compositions according to any one of claim 16～18 be coated with
Layer.
21. 1 kinds of touch screens, it is characterised in that include the base material with hard coat described in claim 20.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012017605 | 2012-01-31 | ||
| JP2012-017605 | 2012-01-31 | ||
| JP2012245498 | 2012-11-07 | ||
| JP2012-245498 | 2012-11-07 | ||
| PCT/JP2013/051923 WO2013115191A1 (en) | 2012-01-31 | 2013-01-29 | Agent for preventing accumulation of fingerprints, method for producing same, composition for hard coats, base having hard coat layer, and touch panel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104080877A CN104080877A (en) | 2014-10-01 |
| CN104080877B true CN104080877B (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380007252.0A Expired - Fee Related CN104080877B (en) | 2012-01-31 | 2013-01-29 | Anti-fingerprint adhesive agent and manufacture method, hard coat compositions, the base material with hard coat and touch screen |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6206188B2 (en) |
| KR (1) | KR101969192B1 (en) |
| CN (1) | CN104080877B (en) |
| TW (1) | TWI598418B (en) |
| WO (1) | WO2013115191A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10675658B2 (en) | 2014-03-18 | 2020-06-09 | 3M Innovative Properties Company | Treated article and method of making the same |
| US10858540B2 (en) | 2015-09-23 | 2020-12-08 | 3M Innovative Properties Company | Composition including silanes and methods of making a treated article |
| CN109890896B (en) * | 2016-10-31 | 2021-09-17 | Ａｇｃ株式会社 | Fluorine-containing ether composition, coating liquid, and article |
| CN106927690B (en) * | 2017-02-21 | 2019-06-07 | 陕西科技大学 | A method of making touched panel glass surface soiling anti-fingerprint |
| KR20200070810A (en) | 2018-12-10 | 2020-06-18 | 삼성전자주식회사 | Composition, film comprising cured product of the same, stacked structure comprising the film and display device |
| JP2020180274A (en) * | 2019-04-23 | 2020-11-05 | 住友化学株式会社 | Mixed composition |
| US20230416483A1 (en) * | 2020-12-16 | 2023-12-28 | Sumitomo Electric Industries, Ltd. | Resin composition, secondary coating material for optical fiber, optical fiber, and method for manufacturing optical fiber |
| CN112940236A (en) * | 2021-02-01 | 2021-06-11 | 浙江巨化技术中心有限公司 | Preparation method of high-wear-resistance anti-fingerprint agent |
| WO2024166724A1 (en) * | 2023-02-07 | 2024-08-15 | 信越化学工業株式会社 | Fluorine-containing coating agent, article, and method for modifying surface of article |
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| JP3876961B2 (en) * | 2000-06-29 | 2007-02-07 | 信越化学工業株式会社 | Surface treatment agent and water / oil repellent article |
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- 2013-01-29 WO PCT/JP2013/051923 patent/WO2013115191A1/en active Application Filing
- 2013-01-29 CN CN201380007252.0A patent/CN104080877B/en not_active Expired - Fee Related
- 2013-01-29 JP JP2013556418A patent/JP6206188B2/en not_active Expired - Fee Related
- 2013-01-29 KR KR1020147019644A patent/KR101969192B1/en active IP Right Grant
- 2013-01-30 TW TW102103512A patent/TWI598418B/en active
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| JP2000275403A (en) * | 1999-03-19 | 2000-10-06 | Fuji Photo Film Co Ltd | Antireflection film and display device with antireflection film arranged thereon |
| TW200829661A (en) * | 2006-09-14 | 2008-07-16 | Toray Industries | Coating material, optical article using it and method for producing optical article |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN104080877A (en) | 2014-10-01 |
| KR101969192B1 (en) | 2019-04-15 |
| TWI598418B (en) | 2017-09-11 |
| JPWO2013115191A1 (en) | 2015-05-11 |
| WO2013115191A1 (en) | 2013-08-08 |
| TW201341483A (en) | 2013-10-16 |
| JP6206188B2 (en) | 2017-10-04 |
| KR20140119025A (en) | 2014-10-08 |
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