CN108350204A - Cyclic olefin resin film - Google Patents
Cyclic olefin resin film Download PDFInfo
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- CN108350204A CN108350204A CN201680065130.0A CN201680065130A CN108350204A CN 108350204 A CN108350204 A CN 108350204A CN 201680065130 A CN201680065130 A CN 201680065130A CN 108350204 A CN108350204 A CN 108350204A
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- methyl
- acrylate
- cyclic olefin
- olefin resin
- resin film
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
Abstract
The present invention provides a kind of cyclic olefin resin film, it is characterized in that in, in the cured coating film of the active energy ray-curable composition at least one surface of cyclic olefin resin film base material, the Actinic-radiation curable composition contains active energy ray-curable compound (A) and the amine system light stabilizer (B) that is obstructed is as required ingredient, which is selected from be obstructed amine system light stabilizer (B1) and at least one of the amine system light stabilizer (B2) that is obstructed with the phenolic group that is obstructed with polymerizable functional group.The present invention provides a kind of cyclic olefin resin film, has：High marresistance can be assigned to cyclic olefin resin film base material surface, can be formed in base coat the cured coating film for the Actinic-radiation curable composition that the cured coating film with excellent adaptation and then its adaptation will not still decline after being exposed to strong light between cyclic olefin resin film base material surface.
Description
Technical field
The present invention relates to it is high with marresistance and with the active-energy of the excellent adhesion of cyclic olefin resin film base material
The cyclic olefin resin film of the cured coating film of ray-curable composition.
Background technology
The transparency, low-birefringence, agent of low hygroscopicity, heat resistance, electrical insulating property, chemical-resistant of cyclic olefin resin film etc.
It is excellent, it is widely used in optical component, medical treatment, packaging film, automobile, semiconductor applications etc..In particular, in optical component, just
It is inquiring into：Corresponding to the diversification in liquid crystal display or the unit of touch panel on the way, replace previous used poly- pair
The plastic foils such as ethylene terephthalate (PET), triacetyl cellulose (TAC) and use the high and low hygroscopicity of the transparency excellent
Cyclic olefin resin film.
Also, cyclic olefin resin film has the risk being damaged because case hardness is insufficient in processing, in order to
Abrasion performance, marresistance are improved, is inquiring into and is being applied by the solidification of Actinic-radiation curable composition in the setting of its surface
The protective layers such as the hard conating that film is constituted.But cyclic olefin resin film is alicyclic structure, therefore the pole of film surface because of its main structure
Low, up to 90 ° or so of the water contact angle of property, therefore in the case where Actinic-radiation curable composition to be coated, deposit
Material is spreadable being difficult to will to apply, the low this problem of the adaptation between cyclic olefin resin film base material surface and hard conating.
As the method for improving the adaptation between cyclic olefin resin film base material surface and hard conating, it is proposed that in ring-type
After olefin resin film base material surface is arranged using the modified olefin system resin with polar group as the priming coat of principal component, coating electricity
From radiation curable resin and make its cured method (for example, referring to patent document 1.).For the method, it can be improved
Adaptation between cyclic olefin resin film base material surface and hard conating, but the process for increasing coated and dried priming coat, also
There are problems that yield rate reduction, cost increase.
In addition, as the method for being not provided with priming coat and hard conating being made to be sealed at cyclic olefin resin film base material surface, carry
Hard conating (example will be used as containing (methyl) acrylate with alicyclic structure, solidification compound cured coating film by having gone out
Such as, with reference to patent document 2.).Using the solidification compound, in order to make itself and cyclic olefin resin film base material
The adaptation on surface is abundant, needs the ratio for improving (methyl) acrylate with alicyclic structure.But if improving has fat
The ratio of (methyl) acrylate of ring structure, the then crosslink density that there is cured coating film reduce, the anti-scratch on cured coating film surface
The problem of wound property becomes inadequate.
In turn, the solidification that Actinic-radiation curable composition is just formed on cyclic olefin resin film base material surface applies
Adaptation (initial adaptation) after film though height, thereafter in the case where being exposed to strong light, adaptation (fast light adaptation)
Reduction become problem.
Therefore, seek following cyclic olefin resin films, have：Cyclic olefin resin film base material surface can be assigned high resistance to
It is scratch resistance, can be formed in base coat between cyclic olefin resin film base material surface with excellent adaptation solidification apply
The cured coating film for the Actinic-radiation curable composition that film and then its adaptation will not reduce after being exposed to strong light.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-284158 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2010-89458 bulletins
Invention content
Problem to be solved by the invention
Problem to be solved by this invention is to provide a kind of cyclic olefin resin film, has：It can be to cyclic olefin resin
Film base material surface assigns high marresistance, can be formed in base coat between cyclic olefin resin film base material surface with excellent
The active energy ray-curable group that the cured coating film of different adaptation and then its adaptation will not reduce after being exposed to strong light
Close the cured coating film of object.
The means used to solve the problem
The inventors of the present invention are concentrated on studies to solve the above-mentioned problems, as a result, it has been found that：By being formed in being used as
The material of the cured coating film on cyclic olefin resin film base material surface, in Actinic-radiation curable composition using specific
Light stabilizer, so as to assign high marresistance to cyclic olefin resin film base material surface, can be formed in base coat and ring
There is the cured coating film of excellent adaptation between shape olefin resin film base material surface and then its adaptation is after being exposed to strong light
It will not reduce, so as to complete the present invention.
That is, the present invention relates to a kind of cyclic olefin resin films, which is characterized in that cyclic olefin resin film base material at least
The cured coating film of active energy ray-curable composition, the Actinic-radiation curable composition contain on one surface
As required ingredient, the amine system light that is obstructed is steady for active energy ray-curable compound (A) and the amine system light stabilizer (B) that is obstructed
It is selected from the amine system light stabilizer (B1) and with the amine system of being obstructed for the phenolic group that is obstructed of being obstructed with polymerizable functional group to determine agent (B)
At least one of light stabilizer (B2).
Invention effect
The cyclic olefin resin film of the present invention on its surface by being formed by Actinic-radiation curable composition
Cured coating film and with high scratch resistance, and the adaptation of the cured coating film and the cyclic olefin resin as base material is high, sudden and violent
After dew to strong light, high adhesion will not reduce.Therefore, cyclic olefin resin film of the invention can be used as in liquid crystal display
Device, the touch panel optical film used on the way.
Specific implementation mode
At least one surface active energy of the cyclic olefin resin film of the present invention in cyclic olefin resin film base material
The cured coating film of ray-curable composition, the Actinic-radiation curable composition contain active energy ray-curable
Object (A) and the amine system light stabilizer (B) that is obstructed are closed as required ingredient, which is selected from polymerization
Be obstructed amine system light stabilizer (B1) and at least one to be obstructed in amine system light stabilizer (B2) with the phenolic group that is obstructed of property functional group
Kind.
As above-mentioned active energy ray-curable compound (A), such as multifunctional (methyl) acrylate can be enumerated
(A1), carbamate (methyl) acrylate (A2) etc..One kind can be used in these substances, also can and with two or more.
It should be noted that in the present invention, so-called " (methyl) acrylate " refers to acrylate and methacrylic acid
One or both of ester, so-called " (methyl) acryloyl group " refers to one of acryloyl group and methylacryloyl or two
Person.
Above-mentioned multifunctional (methyl) acrylate (A1) is that have more than two (methyl) acryloyl groups in a molecule
Compound.As the concrete example of the multifunctional (methyl) acrylate (A1), 1,4-butanediol two (methyl) acrylic acid can be enumerated
Ester, 3- methyl-1s, 5- pentanediols two (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, two (first of neopentyl glycol
Base) acrylate, 2- methyl-1s, 8- ethohexadiols two (methyl) acrylate, 2- butyl -2- ethyls-two (first of 1,3-PD
Base) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two
(methyl) acrylate, triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two
Two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, the polypropylene glycol two of the dihydric alcohols such as (methyl) acrylate
(methyl) acrylate, two (methyl) acrylate of three (2- ethoxys) isocyanuric acid esters, to 1 mole of neopentyl glycol addition 4
Mole or more ethylene oxide or propylene oxide obtained by glycol two (methyl) acrylate, rub to 1 moles of bisphenol A additions 2
Two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid of glycol obtained by your ethylene oxide or propylene oxide
Ester, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl)
Acrylate, double trimethylolpropane three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, three (2-
(methyl) acryloyl-oxyethyl) isocyanuric acid ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) propylene
Acid esters, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl)
Acrylate, dipentaerythritol six (methyl) acrylate etc..One kind can be used in these multifunctional (methyl) acrylates (A1),
Also can and with two or more.Also, among these multifunctional (methyl) acrylates (A1), from raising work used in the present invention
It sets out in terms of the marresistance of the cured coating film of property energy ray-curable composition, preferably dipentaerythritol six (methyl)
Acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl)
Acrylate more preferably combines dipentaerythritol six (methyl) acrylate with dipentaerythritol five (methyl) acrylate
It uses.Also, make as dipentaerythritol six (methyl) acrylate is combined with dipentaerythritol five (methyl) acrylate
With the case where mass ratio, from improve cured coating film marresistance aspect, preferably 40/60~80/20 range,
More preferably 50/50~75/25 range, further preferably 60/40~70/30 range.
Above-mentioned carbamate (methyl) acrylate (A2) is to make polyisocyanates (a2-1) and have hydroxyl (first
Base) acrylate (a2-2) reaction obtained from.
As above-mentioned polyisocyanates (a2-1), aliphatic polyisocyante and aromatic polyisocyanate can be enumerated, but
Be from can further lower the coloring of cured coating film of Actinic-radiation curable composition used in the present invention in terms of
It sets out, preferably aliphatic polyisocyante.
Above-mentioned aliphatic polyisocyante is the compound that the position other than isocyanate group is made of aliphatic hydrocarbon.
As the concrete example of the aliphatic polyisocyante, hexamethylene diisocyanate can be enumerated, lysine diisocyanate, rely ammonia
The aliphatic polyisocyantes such as sour triisocyanate；Norbornene alkyl diisocyanate, isophorone diisocyanate, di-2-ethylhexylphosphine oxide
Bis- (isocyanatomethyl) hexamethylenes of (4- cyclohexyl isocyanates), 1,3-, 2- methyl-1s, the cyclization of 3- diisocyanate roots oneself
Alkane, 2- methyl-1s, ester ring types polyisocyanates such as 5- diisocyanate root trimethylcyclohexanes etc..Also, by above-mentioned aliphatic polyisocyanate cyanogen
Tripolymer also is used as above-mentioned aliphatic polyisocyante obtained by acid esters or ester ring type polyisocyanates trimerizing.Also, this
One kind can be used in a little aliphatic polyisocyantes, also can and with two or more.
Among above-mentioned aliphatic polyisocyante, in order to make the marresistance of film improve, in aliphatic polyisocyante
Among, preferably as the hexamethylene diisocyanate of the diisocyanate of straight-chain aliphatic hydrocarbon, as ester ring type diisocyanate
The norbornene alkyl diisocyanate of ester, isophorone diisocyanate.
Above-mentioned (methyl) acrylate (a2-2) is the compound for having hydroxyl and (methyl) acryloyl group.As (the first
Base) acrylate (a2-2) concrete example, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (first can be enumerated
Base) acrylic acid 2- hydroxy butyl esters, (methyl) acrylic acid 4- hydroxy butyl esters, 1,5-PD list (methyl) acrylate, 1,6- hexylene glycols
Single (methyl) acrylate, neopentyl glycol single (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol single (methyl) acrylate
List (methyl) acrylate of equal dihydric alcohols；Trimethylolpropane two (methyl) acrylate, ethylene oxide (EO) are modified three hydroxyls
Two (methyl) acrylate of the modified trimethylolpropane of methylpropane (methyl) acrylate, propylene oxide (PO), two (first of glycerine
Base) list of trihydroxylic alcohols or two (methyl) such as acrylate, bis- (2- (methyl) acryloyl-oxyethyl) hydroxyethylisocyanurates
Acrylate, or there is the list and two of hydroxyl obtained by a part for these alcohol hydroxyl groups is modified with 6-caprolactone
(methyl) acrylate；Pentaerythrite three (methyl) acrylate, double trimethylolpropane three (methyl) acrylate, two seasons penta
Tetrol five (methyl) acrylate etc. has the compound of the hydroxyl and (methyl) acryloyl groups more than 3 functions of 1 function, or
Multifunctional (methyl) acrylate with hydroxyl obtained by the compound is further modified using 6-caprolactone；Dipropyl
Glycol list (methyl) acrylate, diethylene glycol list (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, poly- second two
Alcohol list (methyl) acrylate etc. has (methyl) acrylate of oxyalkylene chain；Polyethylene glycol propylene glycol list (methyl) third
Olefin(e) acid ester, polyoxybutylene-polypropylene oxide list (methyl) acrylate etc. has (methyl) of the oxyalkylene chain of block structure
Propylene acid esters；Poly- (ethylene glycol-tetramethylene glycol) single (methyl) acrylate, poly- (propylene glycol-tetramethylene glycol) single (first
Base) (methyl) acrylate of oxyalkylene chain etc. with disordered structure such as acrylate.These (methyl) acrylate (a2-
2) one kind can be used, also can and with two or more.
Among above-mentioned carbamate (methyl) acrylate (A2), in order to improve active energy used in the present invention
The marresistance for measuring the cured coating film of ray-curable composition, tool (methyl) propylene there are four more than preferably in a molecule
Carbamate (methyl) acrylate of acyl group.In order to make above-mentioned carbamate (methyl) acrylate (A2) become one
There are four carbamate (methyl) acrylate of above (methyl) acryloyl group for tool in molecule, as above-mentioned (methyl) propylene
Acid esters (a2-2), it is however preferred to have carbamate (methyl) acrylate of more than two (methyl) acryloyl groups.As this
Kind (methyl) acrylate (a2-2), can enumerate such as trimethylolpropane two (methyl) acrylate, ethylene-oxide-modified three
Hydroxymethyl-propane two (methyl) acrylate, epoxy pronane modification trimethylolpropane two (methyl) acrylate, two (first of glycerine
Base) acrylate, bis- (2- (methyl) acryloyl-oxyethyl) hydroxyethylisocyanurates, pentaerythrite three (methyl) acrylic acid
Ester, double trimethylolpropane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc..These (methyl) propylene
Acid esters (a2-2) relative to a kind of above-mentioned aliphatic polyisocyante, can be used it is a kind of also can and with two or more.Also, at this
A bit among (methyl) acrylate (a2-2), pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid
Ester is preferred because that can improve marresistance.
Above-mentioned polyisocyanates (a2-1) is reacted with above-mentioned (methyl) acrylate (a2-2's), can pass through conventional amino
Formic acid esterification reacts to carry out.Also, for the progress for promoting urethane to react, preferably it is catalyzed in urethane
Urethane reaction is carried out in the presence of agent.As above-mentioned urethanation catalyst, such as pyridine, pyrrole can be enumerated
It coughs up, the amine compounds such as triethylamine, diethylamine, dibutyl amine；The phosphorus compounds such as triphenylphosphine, triethyl phosphine；Di lauric dibutyl
Organo-tin compounds, the zinc octoates such as tin, trilauryl tin octylate, octyltin diacetate, dibutyltin diacetate, tin octoate etc. have
Machine zinc compound etc..
Also, as needed, as except above-mentioned multifunctional (methyl) acrylate (A1), carbamate (methyl) third
Epoxy (methyl) acrylate, polyester (first can be used in active energy ray-curable compound (A) other than olefin(e) acid ester (A2)
Base) higher molecular weights such as acrylate, polyethers (methyl) acrylate (methyl) acrylate (A3).As above-mentioned epoxy
(methyl) acrylate can be enumerated for example by by bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, polymethylacrylic acid
Ethylene oxidic ester etc. is reacted with (methyl) acrylic acid and is esterified gained person.Also, as above-mentioned polyester (methyl) acrylic acid
Ester can be enumerated for example by the way that polycarboxylic acid and polyalcohol will be made to carry out the polyester and (methyl) third that two ends obtained by polycondensation are hydroxyl
Olefin(e) acid reacted and be esterified gained person or will to polycarboxylic acid addition alkylene oxide and winner is reacted with (methyl) acrylic acid
And it is esterified gained person.In turn, it as above-mentioned polyethers (methyl) acrylate, can enumerate for example by by polyether polyol and (first
Base) acrylic acid reacted and is esterified gained person.Also, above-mentioned (methyl) acrylate (A3) can be used alone, and can also be used in combination
It is two or more.
In turn, in Actinic-radiation curable composition used in the present invention, in addition to as above-mentioned active-energy
Other than (A1)~(A3) illustrated by ray-curable compound (A), if (methyl) acrylate of cooperation with phosphate
(A4), then from can further improve to the adaptation aspect of base material and it is preferred that.Above-mentioned (methyl) third with phosphate
Olefin(e) acid ester (A4) is that at least there are one phosphate (methyl) acrylate for tool in a molecule.As this with phosphate
(methyl) acrylate (A4) can enumerate such as phosphoric acid (methyl) acryloyloxyethyl ester, di(2-ethylhexyl)phosphate (methyl) acryloxy
Ethyl ester, tricresyl phosphate (methyl) acryloyloxyethyl ester, caprolactone modification phosphoric acid (methyl) acryloyloxyethyl ester etc., it is possible to use
There is the compound of more than two (methyl) acryloyl groups in one molecule.Also, these (methyl) acrylic acid with phosphate
One kind can be used in ester (A4), also can and with two or more.
Coordinate in Actinic-radiation curable composition used in the present invention above-mentioned (methyl) with phosphate
Its use level in the case of acrylate (A4) is consolidated from can further improve the adaptation to base material and also can further improve
Set out in terms of the marresistance for changing film coated surface, preferably in above-mentioned active energy ray-curable compound (A) for 0.1~
30 mass %, more preferably 0.5~20 mass %.
Actinic-radiation curable composition used in the present invention as must ingredient contain above-mentioned active-energy
Ray-curable compound (A) and the amine system light stabilizer (B) that is obstructed, it is described be obstructed amine system light stabilizer (B) be selected from
Be obstructed amine system light stabilizer (B1) and being obstructed in amine system light stabilizer (B2) extremely with the phenolic group that is obstructed of polymerizable functional group
Few one kind.
As above-mentioned light stabilizer (B1), can enumerate such as with polymerism function (methyl) acryloyl group, vinyl
The amine system light stabilizer that is obstructed of group.More specifically, can enumerate 2,2,6,6- tetramethyl -4- piperidyls (methyl) acrylate,
1,2,2,6,6- pentamethyl -4- piperidyls (methyl) acrylate etc..One kind can be used in these above-mentioned light stabilizers (B1), also may be used
It is used in combination two or more.Among those, from the adaptation that can further improve with cyclic olefin resin, can also inhibit be exposed to
Adaptation (hreinafter referred to as " fast light adaptation " after strong light.) aspect that further decreases sets out, it is preferable to use 2,2,6,6-
Tetramethyl -4- piperidyls (methyl) acrylate.
As above-mentioned light stabilizer (B2), can enumerate for example with phenolic group that is obstructed such as 3,5- di-t-butyl -4- hydroxyphenyls
Amine system of being obstructed light stabilizer.More specifically, the compound etc. represented by following formula (1) can be enumerated.The light stabilizer (B2)
It can be used in combination with above-mentioned light stabilizer (B1).
Above-mentioned in Actinic-radiation curable composition used in the present invention is obstructed the matching of amine system light stabilizer (B)
Resultant, from the reduction aspect with the initial adaptation of cyclic olefin resin and fast light adaptation, phase can be further suppressed
For above-mentioned 100 mass parts of active energy ray-curable compound (A), preferably 0.05~5 mass parts, more preferably
0.1~2 mass %, further preferably 0.3~1.5 mass %.
In addition, Actinic-radiation curable composition used in the present invention after being coated on cyclic annular base material by irradiating
Active energy beam and cured coating film can be made.The so-called active energy beam refers to that ultraviolet light, electron ray, α are penetrated
The ionization radial lines such as line, β rays, Γ rays.Ultraviolet light is irradiated as active energy beam and in the case of cured coating film is made,
It is preferred that adding aftermentioned Photoepolymerizationinitiater initiater (C) in the Actinic-radiation curable composition of the present invention and improving solidification
Property.Also, photosensitizer (D) if necessary, also can be further added to improve curability.On the other hand, using electron ray,
In the case of the ionization radial lines such as alpha ray, β rays, Γ rays, because even without using Photoepolymerizationinitiater initiater (C), photosensitizer
(D) also can rapidly cure, so not being especially added with necessity of Photoepolymerizationinitiater initiater (C), photosensitizer (D).
As above-mentioned Photoepolymerizationinitiater initiater (C), such as diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl can be enumerated
Propane -1- ketone, oligomeric { 2- hydroxy-2-methyls -1- [4- (l- methyl ethylenes) phenyl] acetone }, benzil dimethyl ketal,
1- (4- isopropyl phenyls) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl)
Ketone, 1- hydroxycyclohexylphenylketones, 2- methyl -2- morpholinyl (4- thiomethylphenyls) propane -1- ketone, 2- benzyl -2- methyl
The acetophenones based compounds such as amino -1- (4- beautiful jades are for phenyl)-butanone；The benzene such as benzoin, benzoin methylether, benzoin iso-propylether
Acyloin based compound；2,4,6- trimethylbenzene acyloin diphenyl phosphine oxides, the oxidation of bis- (2,4,6- trimethylbenzoyl)-phenyl
The acylphosphine oxide compounds such as phosphine；Benzil (dibenzoyl), methyl phenyl glyoxylate ester, hydroxyl phenylacetic acid 2- (2- hydroxyls
Ethyoxyl) the benzils based compound such as ethyl ester, hydroxyl phenylacetic acid 2- (2- oxo -2- phenylacetyl oxygroups ethyoxyl) ethyl ester；Two
Benzophenone, o-benzoyl yl benzoic acid methyl esters -4- phenyl benzophenones, 4,4 '-dichloro benzophenones, dihydroxy benaophenonel, 4-
Benzoyl -4 '-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) hexichol
Ketone, 3, the hexichol first such as 3 '-dimethyl -4- methoxy benzophenones, 2,4,6- tri-methyl benzophenones, 4- methyl benzophenones
Ketone based compound；2-isopropylthioxanthone, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, 2,4-, bis- clopenthixal ketones etc.
Thioxanthones based compound；Michler's keton, 4, the aminobenzophenones based compound such as 4 '-diethylamino benzophenone；10- butyl-
2- chloro-acridines ketone, 2- ethyl hydrazine, 9,10- phenanthrenequione, camphorquinone, 1- [4- (4- benzoylphenyls sulfhydryl) phenyl] -2- first
Base -2- (4- methylphenylsulfonyls) propane -1- ketone etc..One kind can be used in these Photoepolymerizationinitiater initiaters (C), can also and with two
Kind or more.
In addition, as above-mentioned photosensitizer (D), the uncle such as diethanol amine, N methyldiethanol amine, tri-butylamine can be enumerated
Carbamide compounds, diethyldithioposphoric acid sodium, the s- benzylisothioureas-tosilate such as amine compounds, adjacent toluene thiocarbamide
Equal sulphur compounds etc..
The usage amount of above-mentioned Photoepolymerizationinitiater initiater (C) and photosensitizer (D), the active energy beam relative to the present invention are solid
Total 100 mass parts of above-mentioned active energy ray-curable compound (A) and above compound (B) in the property changed composition,
Preferably each 0.05~20 mass parts, more preferably 0.5~10 mass %.
In the Actinic-radiation curable composition of the present invention, in addition to above-mentioned active energy ray-curable chemical combination
Other than object (A), amine system of being obstructed light stabilizer (B) etc., according to purposes, characteristic is required, organic solvent, polymerization inhibitor, surface can be coordinated
Conditioning agent, antistatic agent, antifoaming agent, viscosity modifier, resistance to light stabilizer, weathering stabilizers, heat-resisting stabilizing agent, ultraviolet radiation absorption
The additives such as agent, antioxidant, levelling agent, organic pigment, inorganic pigment, pigment dispersing agent, organic microbead；Silica (dioxy
SiClx particle), aluminium oxide, titanium oxide, zirconium oxide, inorganic fillers such as antimony pentaoxide etc..These other complexs can be used
One kind, also can and with two or more.
Among above-mentioned inorganic filler, by coordinating silicon dioxide granule, work used in the present invention can further improve
The marresistance on the cured coating film surface of property energy ray-curable composition, also can further improve the adaptation to base material.
Can be particle of its surface after organic group is surface modified, or without surface as above-mentioned silicon dioxide granule
The particle of modification.In addition, above-mentioned silicon dioxide granule, from further increasing active energy ray-curable used in the present invention
It sets out in terms of the transparency of the cured coating film of composition and the marresistance on surface, preferably the silica of nano-grade size
Particle, more preferably colloidal silicon dioxide.As the average grain diameter of above-mentioned silicon dioxide microparticle, the preferably model of 5~200nm
It encloses, more preferably the range of 5~100nm.It should be noted that the average grain diameter is measured by dynamic light scattering method
Value.
Coordinate its use level in the case of above-mentioned inorganic filler, from can further improve activity used in the present invention
The marresistance on the cured coating film surface of energy ray-curable composition, also can further improve the side to the adaptation of base material
Face is set out, and relative to above-mentioned 100 mass parts of active energy ray-curable compound (A), preferably 1~150 mass parts are more excellent
It is selected as 5~100 mass parts.
Above-mentioned organic solvent is viscous from the solution for suitably adjusting Actinic-radiation curable composition used in the present invention
It is useful from the aspect of degree, especially for film coated is carried out, adjustment film thickness becomes easy.As workable herein
Organic solvent can enumerate the aromatic hydrocarbon such as toluene, dimethylbenzene；The alcohols such as methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol；Acetic acid second
The esters such as ester, butyl acetate, propylene glycol methyl ether acetate；The ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone
Class etc..One kind can be used in these solvents, also can and with two or more.
Cyclic olefin resin film base material used in cyclic olefin resin film as the present invention, as long as by cyclic olefin
The person of being polymerized then is not particularly limited, and homopolymer can be used, it is possible to use copolymer.As the commercially available product of cyclic olefin resin,
" ZEONOR (registered trademark) ", " ZEONEX (registered trademark) " of such as Japan's ZEON Co. Ltd. systems can be enumerated；JSR plants of formula meetings
" ARTON (registered trademark) " of society；" TOPAS (registered trademark) " of Polyplastics plastics Co. Ltd. system etc..
Above-mentioned cyclic olefin resin film base material is to form in cyclic olefin resin on film and winner.Also, in order to improve
With the adaptation of the cured coating film of Actinic-radiation curable composition used in the present invention, cyclic olefin resin film base material
Surface preferably by the further provided for contouring processing on the surface based on sand-blast, solvent treatment method etc., electric treatment (at corona discharge
Reason, atmospheric plasma treatment), chromic acid processing, flame treatment, hot wind handle, at ozone/ultraviolet light/electronbeam irradiation
Reason, oxidation processes etc. and carry out processor, among these, more preferably carry out Corona discharge Treatment, at atmospheric pressure plasma
The electric treatment persons such as reason.
Also, the thickness of above-mentioned cyclic olefin resin film base material is preferably 1~200 μm of range, more preferably 5~100 μ
The range of m, further preferably 10~50 μm of range.By the way that the thickness of film base material is set as the range, even if in ring
The case where cured coating film of Actinic-radiation curable composition used in the present invention is arranged in the single side of shape olefin resin film
Under also be easy inhibit curling.
The cyclic olefin resin film of the present invention is that activity is coated at least one surface of cyclic olefin resin film base material
Energy ray-curable composition irradiates active energy beam thereafter and cured coating film gained person is made.As by active-energy
The method that ray-curable composition is coated on cyclic olefin resin film can enumerate such as die coating cloth, micro- intaglio plate coating, intaglio plate and apply
Cloth, roller coating cloth, comma coating, airblade coating, kiss-coating, spraying coating, suspension coating, dip coated, rotary coating, wheel apply
Cloth, utilizes the solid coating, bar coating, flow coat etc. of silk screen at bristle coating.
In addition, using ultraviolet light as active energy beam to make Actinic-radiation curable composition cure
In the case of, as the device of irradiation ultraviolet light, such as low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide can be enumerated
Object lamp electrodeless lamp (fusion lamp), chemical lamp, black light lamp, mercury-xenon lamp, short-arc lamp, He-Cd laser, argon laser, sunlight, LED
Deng.
For the cyclic olefin resin film of the present invention, due to excellent optical properties of its base material, dimensional stability, resistance to
Hot, transparent and its surface excellent scratch resistance, therefore it is applicable to various uses, especially as liquid crystal
It is useful for the optical films of the image displaying part of image display devices such as display (LCD), organic el display (OLED).
Especially, there is excellent marresistance to be slim, therefore such as electronic notebook, mobile phone, intelligence can be suitable as
Type mobile phone, portable audio player, removable computer, tablet terminal equipment etc. minimize or high portable of requirement of slimming
The optical film of the image displaying part of the image display device of electric terminal equipment.In addition, as optical film, can use
Make the base material of protective film, touch panel used in the most surface of the image displaying part of image display.In turn, with going bail for
In the case of cuticula, such as protect the image aobvious for being provided on the top of the image displays such as LCD module, OLED module
For the image display for showing this composition of the transparent panel of module, by be attached at surface or the back side of the transparent panel come
It uses, to be effectively prevented scratch, prevent dispersing when transparent panel breakage.
Embodiment
Hereinafter, further illustrating the present invention by embodiment.
(preparation example 1)
By dipentaerythritol hexaacrylate (hreinafter referred to as " DPHA ".) and Dipentaerythritol Pentaacrylate (with
Under, referred to as " DPPA ".) mixture (DPHA/DPPA=65/35 (mass ratio)) 100 mass parts, silicon dioxide microparticle (day
Production chemical industry Co. Ltd. system " MEK-ST40 ", 10~20nm of average grain diameter, the 40 of organic silicon sol (colloidal silicon dioxide)
Quality % methyl ethyl ketone dispersions) 25 mass parts (for silicon dioxide microparticle be 10 mass parts), there is methacryl
The amine system light stabilizer that is obstructed (ADEKA Corp.'s system " ADK STAB (registered trademark) LA-87 " of base；2,2,6,6- tetramethyls-
4- piperidino methyls acrylate) 1 mass parts and 1- hydroxycyclohexylphenylketones (BASF JAPAN Co. Ltd. systems
" IRGACURE (registered trademark) 184 ") after 6 mass parts equably stir, it is diluted, is prepared non-volatile using methyl ethyl ketone
The Actinic-radiation curable composition (1) of 50 mass % of ingredient.
(preparation example 2)
In addition to by the use level of ADK STAB LA-87 from other than 1 mass parts are changed to 0.1 mass parts, it is same with preparation example 1
It carries out to sample, prepares Actinic-radiation curable composition (2).
(preparation example 3)
In addition to by the use level of ADK STAB LA-87 from other than 1 mass parts are changed to 0.5 mass parts, it is same with preparation example 1
It carries out to sample, prepares Actinic-radiation curable composition (3).
(preparation example 4)
In addition to by the use level of ADK STAB LA-87 from other than 1 mass parts are changed to 2 mass parts, it is same as preparation example 1
Ground carries out, and prepares Actinic-radiation curable composition (4).
(preparation example 5)
In addition to the amine system light that is obstructed for being changed to ADK STAB LA-87 used in preparation example 1 that there is methylacryloyl
Stabilizer (ADEKA Corp.'s system " ADK STAB (registered trademark) LA-82 "；1,2,2,6,6- pentamethyl -4- piperidino methyls
Acrylate) other than, it is carried out similarly with preparation example 1, prepares Actinic-radiation curable composition (5).
(preparation example 6)
Stablize in addition to ADK STAB LA-87 used in preparation example 1 are changed to the amine system light that is obstructed with the phenolic group that is obstructed
Agent (BASF JAPAN Co. Ltd. systems " TINUVIN (registered trademark) PA144 "；Compound represented by following formula (1)) other than,
It is carried out similarly with preparation example 1, prepares Actinic-radiation curable composition (6).
(comparing preparation example 1)
It other than not using ADK STAB LA-87 used in preparation example 1, is carried out similarly, prepares with preparation example 1
Actinic-radiation curable composition (R1).
(comparing preparation example 2)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (the BASF JAPAN that are obstructed
Co. Ltd. system " TINUVIN (registered trademark) 111FDL "；Dimethyl succinate and 4- hydroxyls -2,2,6,6- tetramethyl -1- piperazines
The polymer and N of pyridine ethyl alcohol, N ', N ", N " '-four-(4,6- bis--(butyl-(N- methyl -2,2,6,6- tetramethyl piperidine -4- bases)
Amino)-triazine -2- bases) -4,7- diaza decane -1,10- diamines mass ratio be 1: 1 mixture) other than, with preparation example 1
It is carried out similarly, prepares Actinic-radiation curable composition (R2).
(comparing preparation example 3)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (the BASF JAPAN that are obstructed
Co. Ltd. system " TINUVIN (registered trademark) 770DF "；Bis- (2,2,6,6- tetramethyl -4- piperidyls) sebacates) other than,
It is carried out similarly with preparation example 1, prepares Actinic-radiation curable composition (R3).
(comparing preparation example 4)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (ADEKA plants of formula meetings of being obstructed
Society's system " ADK STAB (registered trademark) LA-81 "；Bis- (1- hendecane epoxides -2,2,6,6- tetramethyl piperidine -4- bases) carbonic esters)
In addition, it is carried out similarly with preparation example 1, prepares Actinic-radiation curable composition (R4).
(comparing preparation example 5)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (the BASF JAPAN that are obstructed
Co. Ltd. system " TINUVIN (registered trademark) 123 "；Bis- { 2,2,6,6- tetramethyl -1- (octyloxy) piperidines -4- of decane diacid
Base ester }) other than, it is carried out similarly with preparation example 1, prepares Actinic-radiation curable composition (R5).
(comparing preparation example 6)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (the BASF JAPAN that are obstructed
Co. Ltd. system " TINUVIN (registered trademark) 5100 "；Bis- (2,2,6,6- tetramethyl -1- octyloxies piperidin-4-yls) -1,10-
Sebacate and 1, bis- [{ 2,2,6,6- tetramethyl -4- ((2,2,6,6- tetramethyl -1- octyloxies the piperidin-4-yl)-decane-of 8-
1,10- diyl) piperidin-1-yl oxygroup] octane mixture) other than, be carried out similarly with preparation example 1, prepare active-energy and penetrate
Line solidification compound (R6).
(comparing preparation example 7)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (the BASF JAPAN that are obstructed
Co. Ltd. system " TINUVIN (registered trademark) 292 "；Bis- (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates 70~80
Quality % and methyl-1, the mixture of 2,2,6,6- pentamethyl -4- piperidinyl sebacates, 20~30 mass %) other than, with system
Standby example 1 is carried out similarly, and prepares Actinic-radiation curable composition (R7).
(comparing preparation example 8)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to amine system light stabilizer (ADEKA plants of formula meetings of being obstructed
Society's system " ADK STAB (registered trademark) LA-52 "；Four (1,2,2,6,6- pentamethyl -4- piperidyls) butane -1,2,3,4- tetramethyls
Acid esters) other than, it is carried out similarly with preparation example 1, prepares Actinic-radiation curable composition (R8).
(comparing preparation example 9)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to ultra-violet absorber (JAPAN plants of formulas of BASF
Commercial firm's system " TINUVIN (registered trademark) 400 ") other than, it is carried out similarly with preparation example 1, prepares active energy ray-curable
Composition (R9).
(comparing preparation example 10)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to ultra-violet absorber (JAPAN plants of formulas of BASF
Commercial firm's system " TINUVIN (registered trademark) 384-2 ") other than, it is carried out similarly with preparation example 1, prepares active energy ray-curable
Property composition (R10).
(comparing preparation example 11)
In addition to ADK STAB LA-87 used in preparation example 1 are changed to antioxidant (BASF JAPAN Co., Ltd.
Make " IRGANOX (registered trademark) 1010 ") other than, it is carried out similarly with preparation example 1, prepares active energy ray-curable combination
Object (R11).
(embodiment 1)
Using bar (Wire Bar), will be coated on by the Actinic-radiation curable composition (1) of 1 gained of preparation example
Its surface electric treatment (Corona discharge Treatment has been subjected in advance；Export 100W, speed 1.0m/ minutes) cyclic olefin resin film
On base material (Japanese Zeon Co. Ltd. systems " ZEONOR (registered trademark) films ZF16-100 ", 100 μm of thickness), 90 are heated at 60 DEG C
After second, under air environment, using ultraviolet lamp (EYE GRAPHICS Co. Ltd. systems " MIDN-042-C1 ",
Lamp：120W/cm, high-pressure sodium lamp), with irradiate light quantity 0.4J/cm2Ultraviolet light is irradiated, the cured coating film with 2 μm of thickness is obtained
Cyclic olefin resin film (1).
[evaluation of marresistance]
For the surface of the cured coating film of the cyclic olefin resin film (1) by above-mentioned gained, Crockmeter type is used
Frictional testing machine (diameter 1.0cm circles friction, steel wool #0000, load 500g, 10 times it is reciprocal) tested, with mesh
Cured coating film surface after being tested depending on observation, passes through following benchmark evaluations marresistance.
A：There is no scar.
B：5 or less shallow scars.
C：5 or less scars.
D：A plurality of scar.
E：A plurality of apparent deep scar.
[evaluation of initial adaptation]
On the cured coating film surface of the cyclic olefin resin film (1) by above-mentioned gained, longitudinal and transverse 11 are cut out with the intervals 1mm
Notch makes 100 grids.Next, making cellophane tape (NICHIBAN Co. Ltd. systems " Cellotape (registered trademark)
CT-18 ") be sealed at its surface after, peel without a break, be repeated twice this operation.Utilize unstripped and remaining revolution mark ratio
Rate evaluates initial adaptation by following benchmark.It should be noted that by being D~F person with following benchmark evaluations, sentence
It is set to unqualified.
A：Revolution mark ratio is 100%.
B：Revolution mark ratio is 95% or more and 99% or less.
C：Revolution mark ratio is 85% or more and 94% or less.
D：Revolution mark ratio is 50% or more and 84% or less.
E：Revolution mark ratio is 35% or more and 49% or less.
F：Revolution mark ratio is 34% or less.
[evaluation of the adaptation (fast light adaptation) after light fastness test]
For the cyclic olefin resin film (1) by above-mentioned gained, implement adding using Sunshine Weather Meter
(according to JIS L0891, experimental condition is for example following for fast atmospheric exposure test.), after experiment with the evaluation of above-mentioned initial adaptation
It is carried out similarly, has rated fast light adaptation.
Light source：Sun shine carbon arc lamp Continuous irradiation
Temperature：63℃
Relative humidity：50%RH
Irradiation time：48 hours
The period and time of rainfall：It does not set
(embodiment 2~6 and comparative example 1~11)
Active energy ray-curable group in addition to using by above-mentioned preparation example 2~6 and comparing 1~11 gained of preparation example
It closes other than object (2)~(6) and (R1)~(R11), similarly to Example 1, makes the cyclic annular alkene with respective cured coating film
Hydrocarbon resin film (2)~(6) and (R1)~(R11), it is evaluation marresistance, initial closely sealed for the cyclic olefin resin film of gained
Property and fast light adaptation.
By above-mentioned preparation example 1~6 and Actinic-radiation curable composition prepared by preparation example 1~11 will be compared
Composition and by above-mentioned gained cyclic olefin resin film evaluation result is shown in table 1~3.It should be noted that in table 1~3
Composition recorded with nonvolatile component amount.
[table 1]
[table 2]
[table 3]
Known to evaluation result as shown in Table 1：For the Examples 1 to 6 of the cyclic olefin resin film of the present invention,
The excellent scratch resistance on the cured coating film surface of Actinic-radiation curable composition possessed by film, with cyclic olefin resin
The initial adaptation of film base material is also high, and then fast light adaptation (adaptation after Light Resistance Test) is also excellent.
On the other hand, comparative example 1~11 shown in table 2 and 3 is with steady without the amine system light used in the present invention that is obstructed
Determine the cyclic olefin resin film of the cured coating film of the Actinic-radiation curable composition of agent.These cyclic olefin resin films
At least one in marresistance, initial adaptation and fast light adaptation is insufficient, and there are problems on practicability.
Claims (7)
1. a kind of cyclic olefin resin film, which is characterized in that have at least one surface of cyclic olefin resin film base material and live
The cured coating film of property energy ray-curable composition, the Actinic-radiation curable composition contain active energy beam
As required ingredient, the amine system light stabilizer (B) that is obstructed is choosing for curability compound (A) and the amine system light stabilizer (B) that is obstructed
From be obstructed amine system light stabilizer (B1) and the amine system light stabilizer (B2) that is obstructed with the phenolic group that is obstructed with polymerizable functional group
At least one of.
2. cyclic olefin resin film as described in claim 1, wherein the light stabilizer (B1) is selected from 2,2,6,6- tetramethyls
Base -4- piperidyls (methyl) acrylate and 1, at least one in 2,2,6,6- pentamethyl -4- piperidyls (methyl) acrylate
Kind.
3. cyclic olefin resin film as described in claim 1, wherein the light stabilizer (B2) is that following formula (1) is represented
Compound,
4. cyclic olefin resin film according to any one of claims 1 to 3, wherein relative to the active energy beam
100 mass parts of curability compound (A), the content of the amine system light stabilizer (B) that is obstructed are the range of 0.05~5 mass parts.
5. cyclic olefin resin film as described in any one of claims 1 to 4, wherein the active energy ray-curable
Compound (A) includes multifunctional (methyl) acrylate (A1).
6. cyclic olefin resin film as claimed in claim 5, wherein the multifunctional (methyl) acrylate (A1) be selected from
Dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylic acid
At least one of ester and pentaerythrite three (methyl) acrylate.
7. such as cyclic olefin resin film according to any one of claims 1 to 6, wherein the active energy ray-curable
Composition also contains inorganic filler.
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| KR (1) | KR102061586B1 (en) |
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2016
- 2016-10-25 KR KR1020187011074A patent/KR102061586B1/en active IP Right Grant
- 2016-10-25 CN CN201680065130.0A patent/CN108350204B/en active Active
- 2016-10-25 WO PCT/JP2016/081532 patent/WO2017082038A1/en active Application Filing
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| TW201723048A (en) | 2017-07-01 |
| JPWO2017082038A1 (en) | 2018-03-22 |
| CN108350204B (en) | 2021-09-07 |
| KR102061586B1 (en) | 2020-01-02 |
| TWI722040B (en) | 2021-03-21 |
| WO2017082038A1 (en) | 2017-05-18 |
| JP6331115B2 (en) | 2018-05-30 |
| KR20180056717A (en) | 2018-05-29 |
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