CN110294950A - Active energy ray curable hard conating resin combination, cured film, laminated body - Google Patents
Active energy ray curable hard conating resin combination, cured film, laminated body Download PDFInfo
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- CN110294950A CN110294950A CN201910220758.9A CN201910220758A CN110294950A CN 110294950 A CN110294950 A CN 110294950A CN 201910220758 A CN201910220758 A CN 201910220758A CN 110294950 A CN110294950 A CN 110294950A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
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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
- C09D7/63—Additives non-macromolecular organic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention, which provides, to be formed closely sealed substrate especially difficult to untreated cyclic olefin resin film etc. and has excellent adaptation and the active energy ray curable hard conating resin combination of the cured film that can also maintain high rigidity, cured film, laminated body.A kind of active energy ray curable hard conating resin combination contains multifunctional (methyl) acrylate (A) and alkylbenzophenones (B).
Description
Technical field
The present invention relates to active energy ray curable hard conating resin combinations, cured film, laminated body.
Background technique
The surface of plastic sheet, plastic foil etc. is softer, is easy to produce scar, and pencil hardness is also low, therefore, by this
The surface setting hard conating of a little substrates improves surface hardness to be improved.
In addition, flat-panel monitor, touch panel etc. are on the way, tri acetyl cellulose membrane (hereinafter also referred to TAC) is mainstream,
But with the filming of smart phone, plate in recent years, the high moisture-inhibiting of the film is considered as problem, alternatively product, tool
There is the cyclic olefin resin film of excellent optical characteristics and low-moisture permeability to attract attention.But cyclic olefin resin film and TAC phase
Than, it is poor with the adaptation of hard conating etc., hard conating resin combination is required to the difficult closely sealed substrate such as cyclic olefin resin film
Adaptation.
As the technology for improving adaptation, for example, the applicant, which discloses, has (methyl) acryloyl containing specific quantity
The active energy ray curable group of the oligomer of base, polypentaerythritol skeleton and isocyanurate group and/or biuret groups
It closes object (patent document 1).But the technology is that have in the case where implementing the pretreated situation using corona etc. to difficult closely sealed substrate
The technology of excellent adaptation.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2017-179368 bulletin
Summary of the invention
Problem to be solved by the invention
The present invention provide to be formed closely sealed substrate especially difficult to untreated cyclic olefin resin film etc. have it is excellent close
The active energy ray curable hard conating resin combination of conjunction property and the cured film that can also maintain high rigidity.
The method for solving problem
Present inventor has performed further investigations, as a result, it has been found that, it is combined in multifunctional (methyl) acrylate specific
The active energy ray curable hard conating resin combination of curing agent can solve the above problems, so as to complete the present invention.
That is, the present invention relates to active energy ray curable hard conating resin combinations below, cured film, laminated body.
1. a kind of active energy ray curable hard conating resin combination, contains multifunctional (methyl) acrylate
(A) and alkylbenzophenones (B).
2. the active energy ray curable hard conating resin combination as described in preceding paragraph 1, wherein (B) ingredient contains
Selected from by 2 methyl benzophenone, 3- methyl benzophenone, 4- methyl benzophenone, 2,4,6- tri-methyl benzophenone and 2,3,
At least one of the group of 4- tri-methyl benzophenone composition.
3. the active energy ray curable hard conating resin combination as described in preceding paragraph 1 or 2, wherein (B) ingredient
Content is 1~30 parts by weight relative to 100 parts by weight of (A) ingredient in terms of solids by weight.
4. the active energy ray curable hard conating resin combination as described in any one of preceding paragraph 1~3, wherein
Without containing simple function (methyl) acrylate (C).
5. a kind of cured film is active energy ray curable hard conating resin described in any one of preceding paragraph 1~4
The cured film of composition.
6. a kind of laminated body has cured film described in preceding paragraph 5 in at least single side of substrate.
Invention effect
Active energy ray curable hard conating resin combination according to the present invention, by using alkyl diphenyl first
Ketone can form firm cured film, with having excellent adaptation and hardness also excellent feature to difficult closely sealed substrate.
Specific embodiment
Active energy ray curable hard conating resin combination of the invention contains multifunctional (methyl) acrylate
(A) (hereinafter referred to as (A) ingredient) and alkylbenzophenones (B) (hereinafter referred to as (B) ingredient).
As (A) ingredient, as long as having at least two (methyl) acryloyl group to be not particularly limited, can make
With various well known substances.It can enumerate for example: 1,4- butanediol two (methyl) acrylate, neopentyl glycol two (methyl) propylene
Acid esters, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, two (first of trimethylolpropane
Base) acrylate, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, two (first of cyclohexanedimethanol
Base) acrylate, tristane two (methyl) acrylate, bisphenol-A epoxy oxide-modified two (methyl) acrylate, Bisphenol F
Two functions (methyl) acrylate such as ethylene-oxide-modified two (methyl) acrylate；Trimethylolpropane tris (methyl) acrylic acid
Ester, tetramethylol methane three (methyl) acrylate, isocyanuric acid ethylene-oxide-modified three (methyl) acrylate, pentaerythrite
Three (methyl) acrylate etc. trifunctionals (methyl) acrylate；Pentaerythritol tetraacrylate, dipentaerythritol four (methyl)
Tetrafunctionals (methyl) acrylate such as acrylate, double trimethylolpropane four (methyl) acrylate；Five (first of dipentaerythritol
Base) acrylate, dipentaerythritol six (methyl) acrylate, it is more than such five function of tripentaerythritol (methyl) acrylate
(methyl) acrylate etc..These substances can be two or more alone or in combination.Wherein, from the high rigidity for maintaining cured film
Viewpoint considers, preferably comprises (methyl) acrylate (trifunctional (methyl) acrylate, tetrafunctional (methyl) of trifunctional or more
(methyl) acrylate more than acrylate, five functions), further preferably selected from by pentaerythritol triacrylate, season penta
Tetra-acrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate and tripentaerythritol acrylate
One of group of composition.It should be noted that (methyl) acryloyl group refers to times in methylacryloyl or acryloyl group
It anticipates one kind, in addition, (methyl) acrylate is any one in methacrylate or acrylate.(methyl) below
Similarly.
In addition, " ビ ス コ ー ト #230 ", " ビ ス コ ー ト #260 ", " ビ ス コ ー ト # can be enumerated as commercially available product
300 ", " ビ ス コ ー ト #295 ", " ビ ス コ ー ト #802 " (the above are Osaka Organic Chemical Industry Co., Ltd.'s manufactures), " NK
Ester A-HD-N ", " NK ester HD-N ", " NK ester A-NOD-N ", " NK ester NOD-N ", " NK ester A-TMM-3 ", " NK ester A-TMM-3L ",
" NK ester A-TMMT ", " NK ester A-9550 " (the above are the manufactures of chemical industry Co., Ltd., the village Xin Zhong), " ア ロ ニ ッ Network ス M-
305”、“アロニックスM-450”、“アロニックスM-309”、“アロニックスM-400”、“アロニックスM-
402 " (the above are Toagosei Co., Ltd's manufactures) etc..
In addition, such as polyurethane (methyl) acrylate, polyester (first can also be used in addition to this as (A) ingredient
Base) acrylate, poly- (methyl) acrylate of epoxy etc..These substances can be two or more alone or in combination.Furthermore, it is also possible to
With above-mentioned two functions (methyl) acrylate, trifunctional (methyl) acrylate, tetrafunctional (methyl) acrylate, five functions
Above (methyl) acrylate is applied in combination.
It as urethane acrylate, can enumerate: by making various well known polyalcohols and polyisocyanates carry out ammonia
Isocyanate-terminated prepolymer obtained from carbamateization reaction is further carried out with (methyl) acrylate of hydroxyl
Acrylate oligomer obtained from urethane reaction keeps polyalcohol and polyisocyanates progress urethane anti-
Acrylate obtained from hydroxy-end capped prepolymer obtained from answering and list (methyl) acrylate reactions containing isocyanate group
Oligomer etc..
It as polyalcohol, is not particularly limited, it is more that such as polyether polyol, polyester polyol, polycarbonate can be enumerated
First alcohol, acrylic polyol, polyolefin polyhydric alcohol etc..These substances can be two or more alone or in combination.
It as polyether polyol, is not particularly limited, can enumerate such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol
Polyalkylene glycol and ethylene oxide-propylene oxide copolymer etc. contain (epoxy of multiple epoxyalkane as monomer component
Alkane-other epoxyalkane) copolymer etc., these substances can be two or more alone or in combination.As commercially available product, can enumerate
アデカポリエーテルP-400、アデカポリエーテルG-400、アデカポリエーテルT-400、アデカポ
リ エ ー テ Le AM-302 (the above are Asahi Denka Co., Ltd.'s manufactures) etc..
It as polyester polyol, is not particularly limited, can enumerate for example: the condensation polymer of polyalcohol and polybasic carboxylic acid；Ring
The ring-opening polymerization polymer of shape ester (lactone)；Polyalcohol, reaction product of polybasic carboxylic acid and cyclic ester these three substances etc..
As polyalcohol, be not particularly limited, can enumerate for example: diethylene glycol, 1,2-PD, 1,3-PD,
1,4- butanediol, 2- methyl-1,3-propanediol, 1,5- pentanediol, neopentyl glycol, 1,6-HD, 1,9- nonanediol, 1,10-
The aliphatic diols such as decanediol；The aliphatic triol such as glycerine, trimethylolpropane, trimethylolethane；1,2- cyclohexanediol,
The alicyclic diols such as 1,4- cyclohexanediol, 1,4 cyclohexane dimethanol；The bisphenols such as bisphenol-A, Bisphenol F；Xylitol, D-sorbite
Equal glycitols etc., these substances can be two or more alone or in combination.It, can be in addition, be not particularly limited as polybasic carboxylic acid
It enumerates for example: the aliphatic such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid
Dicarboxylic acids；The alicyclic dicarboxylic acids such as 1,4- cyclohexane dicarboxylic acid；Terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,6- naphthalene
The aromatic dicarboxylic acids such as dicarboxylic acids；The aliphatic tricarboxylic acids such as propane -1,2,3- tricarboxylic acids；The fragrance such as trimellitic acid, trimesic acid
Race's tricarboxylic acids etc., these substances can be two or more alone or in combination.In addition, being not particularly limited as cyclic ester, Ke Yilie
Citing such as propiolactone, Beta-methyl-δ-valerolactone, 6-caprolactone, these substances can be two or more alone or in combination.As poly-
The commercially available product of ester polyol, can enumerate that Network ラ レ Port リ オ ー Le P-510, (the above are strain formulas by Network ラ レ Port リ オ ー Le F-510
The manufacture of commercial firm's Kuraray), プ ラ Network セ Le 205 (manufacture of Co., Ltd.'s Daicel) etc..
It as polycarbonate polyol, is not particularly limited, the reaction product of such as polyalcohol and phosgene can be enumerated；Ring
The ring-opening polymerization polymer etc. of shape carbonic ester (alkylene carbonates etc.).As polyalcohol, above-mentioned polyalcohol can be enumerated.As carbon
Sour alkylene ester, is not particularly limited, can enumerate such as ethylene carbonate, propylene carbonate, butylene carbonate, carbonic acid it is sub- oneself
Ester etc., these substances can be two or more alone or in combination.As the commercially available product of polycarbonate polyol, Network ラ レ can be enumerated
Port リ オ ー Le C-590 (Kuraray Co., Ltd.'s manufacture) etc..
It as acrylic polyol, is not particularly limited, the hydroxyl in such as 1 molecule with 1 or more can be enumerated
Acrylic monomer homopolymer or copolymer or substance obtained from being copolymerized other monomers and above-mentioned copolymer, this
A little substances can be two or more alone or in combination.As the commercially available product of acrylic polyol, ARUFON UH- can be enumerated
2041 (Toagosei Co., Ltd's manufactures) etc..
It as polyolefin polyhydric alcohol, is not particularly limited, polybutadiene, hydrogen with 2 or more hydroxyls can be enumerated
Change polybutadiene, polyisoprene, hydrogenated polyisoprene, their chloride etc., these substances can be with alone or in combination two
Kind or more.As commercially available product, NISSO-PB GI-1000 (Tso Tat Co., Ltd., Japan's manufacture) etc. can be enumerated.
As polyisocyanates, be not particularly limited, can enumerate: 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene two are different
Cyanate, 1,3- xylene diisocyanate, diphenyl methane -4,4- diisocyanate, two isocyanide of 3- Dimethyl diphenylmethane
The aromatic diisocyanates such as acid esters, 1,5- naphthalene diisocyanate；Dicyclohexyl methyl hydride diisocyanate, two isocyanide of isophorone
The aliphatic diisocyanates such as acid esters, hexamethylene diisocyanate；Their two~hexamer etc., these substances can be independent
Or combination is two or more.
It as list (methyl) acrylate of hydroxyl, is not particularly limited, (methyl) acrylic acid 1- hydroxyl can be enumerated
Methyl esters, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (first
Base) acrylic acid 4- hydroxybutyl, (methyl) dihydroxypropyl cyclohexyl, (methyl) acrylic acid 4- (hydroxymethyl) cyclohexyl first
Ester, 2 hydroxy propanoic acid 4- (hydroxymethyl) cyclohexylmethyl, (methyl) crylic acid hydroxylphenyl ester etc., these substances can individually or
It combines two or more.
It as (methyl) acrylate containing isocyanate group, is not particularly limited, (methyl) acrylic acid 2- can be enumerated
Isocyanato ethyl and 1,1- (double acryloyloxymethyls) ethyl isocyanate etc., these substances can be with alone or in combination two
Kind or more.
It as polyester (methyl) acrylate, is not particularly limited, can enumerate makes above-mentioned dicarboxylic acids (aliphatic dicarboxyl
Acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid) and low-molecular-weight diol carry out hydroxy-terminated polyester obtained from esterification into one
Step carries out (methyl) acrylate oligomer obtained from esterification with unsaturated carboxyl, makes above-mentioned dicarboxylic acids and glycol chemical combination
Object reaction obtained from carboxy-terminated polyester further with the list of above-mentioned hydroxyl (methyl) acrylate carry out esterification and
Obtained (methyl) acrylate oligomer etc..
It as unsaturated carboxyl, is not particularly limited, such as acrylic acid, methacrylic acid, itaconic acid, (nothing can be enumerated
Water) maleic acid, fumaric acid, crotonic acid etc., these substances can be two or more alone or in combination.
As poly- (methyl) acrylate of epoxy, can enumerate for example make above-mentioned carboxylic list (methyl) acrylate with
Epoxy resin in one molecule at least two epoxy group carries out acrylate oligomer obtained from addition reaction.
It as epoxy resin, is not particularly limited, can enumerate for example: bisphenol A type epoxy resin, bisphenol F type epoxy tree
Rouge, united phenol-type epoxy resin, phenol novolak type epoxy, cresol novolak type epoxy resin, bisphenol A-type phenolic epoxy tree
Rouge, naphthalene diol type epoxy resin, phenol dicyclopentadiene phenolic aldehyde type ring oxygen resin and their hydride；3,4- epoxycyclohexyl
Methyl -3 ', 4 '-epoxycyclohexane carboxylates, 1,2- oxireme cyclohexene, bis- (3,4- epoxycyclohexyl-methyl) adipic acids
Ester, 1- epoxy ethyl -3,4- 7-oxa-bicyclo[4.1.0,3,4- epoxycyclohexyl methanol, dicyclopentadiene dicyclic oxide, 2,2- are bis-
Cycloaliphatic epoxy resins such as 1,2- epoxy -4- (2- Oxyranyle) hexamethylene addition product of (hydroxymethyl)-n-butyl alcohol etc., this
A little substances can combine two or more.It should be noted that the epoxy resin as oligomer types in cycloaliphatic epoxy resin,
Such as epoxidation butane tetracarboxylic acid four (3- cyclohexenyl group methyl esters) can be enumerated and modify 6-caprolactone (for example, trade name " エ Port リ
ー De GT401 ", the manufacture of Co., Ltd.'s Daicel) etc. so that alicyclic olefin is carried out epoxy resin etc. obtained from epoxidation.
It as the physical property of (A) ingredient, is not particularly limited, from the viewpoint of the high rigidity for maintaining cured film, for example, weight
Average molecular weight (the polystyrene scaled value obtained based on gel permeation chromatography) is preferably from about 150~about 100000, more preferably
About 180~about 80000.
(B) ingredient be for excellent adaptation is also played to the difficult closely sealed substrate such as cyclic olefin resin film and use at
Point.It as (B) ingredient, is not particularly limited, can enumerate for example: 2 methyl benzophenone, 3- methyl benzophenone, 4- methyl
The monoalkyls benzophenone such as benzophenone；The trialkyls two such as 2,4,6- tri-methyl benzophenone, 2,3,4- tri-methyl benzophenone
Benzophenone etc..These substances can be two or more alone or in combination.Wherein, it preferably comprises selected from by 2 methyl benzophenone, 3-
What methyl benzophenone, 4- methyl benzophenone, 2,4,6- tri-methyl benzophenone and 2,3,4- tri-methyl benzophenone formed
At least one of group, more preferable 4- methyl benzophenone.
It as the content of (B) ingredient, is not particularly limited, from the viewpoint of the high rigidity for maintaining cured film, with solid
Ingredients Weight meter is preferably from about 1 parts by weight~about 30 parts by weight, even more preferably about 1 parts by weight relative to 100 parts by weight of (A) ingredient
~about 5 parts by weight.
In active energy ray curable hard conating resin combination of the invention, it can further contain (B) ingredient
Other curing agent (becoming " other curing agent " below) in addition.It as other curing agent, is not particularly limited, example can be enumerated
Such as 1- hydroxycyclohexyl phenyl ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1- cyclohexyl phenyl ketone, 2- hydroxyl
Base-2- methyl-1-phenyl-propane-1- ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl]-2- hydroxy-2-methyl-1- propane-1-
Ketone, 2- methyl-1-[4- (methylsulfany) phenyl]-2- morpholino propane-1- ketone, 2- benzyl-2- dimethylamino-1- (4-
Quinoline is for phenyl) -1- butanone, bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, 2,4,6- trimethyl benzoyl diphenyl
Base phosphine oxide etc..In addition, being also not particularly limited as its content, relative to 100 parts by weight of (A) ingredient, usually less than 10 weights
Measure part, preferably shorter than 5 parts by weight.
Active energy ray curable hard conating resin combination of the invention can further contain simple function (first
Base) acrylate (C) (hereinafter referred to as (C) ingredient), but from the viewpoint of the high rigidity for maintaining cured film, be more preferably free of
Have.As (C) ingredient, be not particularly limited, can enumerate for example: (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate,
(methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) n-octyl,
(methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid,
(methyl) isodecyl acrylate, (methyl) acrylic acid n-undecane ester, the different hendecane ester of (methyl) acrylic acid, (methyl) acrylic acid
N-dodecane ester, (methyl) acrylic acid Permethyl 99A ester, the positive lauryl of (methyl) acrylic acid, the positive nutmeg of (methyl) acrylic acid
Ester, the different myristin of (methyl) acrylic acid, the positive cetyl of (methyl) acrylic acid, the positive stearyl ester of (methyl) acrylic acid, (methyl) third
Olefin(e) acid 2- ethylhexyl etc. aliphatic list (methyl) acrylate；Alicyclic (methyl) propylene such as (methyl) acrylate alkyl ester
Acid esters；(methyl) phenyl acrylate etc. aromatic series list (methyl) acrylate etc..These substances can with two kinds alone or in combination with
On.
Active energy ray curable hard conating resin combination of the invention can further contain organic solvent.Make
It for organic solvent, is not particularly limited, can enumerate for example: the ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Toluene, benzene etc.
Aromatic hydrocarbon；The esters such as butyl acetate, propyl acetate, ethyl acetate, propylene glycol methyl ether acetate；The alcohol such as ethyl alcohol, 2- propyl alcohol；Just
The aliphatic hydrocarbons such as hexane, hexamethylene, hexahydrotoluene, normal heptane；Isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4- dioxy
The ethers such as azacyclohexane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate；
Chloroform, dimethylformamide etc., these substances can be two or more alone or in combination.As the content of organic solvent, without spy
It does not limit, is adjusted in the way of 40~80 weight % are preferably reached in terms of the solid component concentration by resin combination.
Active energy ray curable hard conating resin combination of the invention can further contain surface conditioner,
Surfactant, photosensitizer, light stabilizer, antioxidant, levelling agent, pigment, inorganic filler, silane coupling agent, colloidal state two
The various well known additives such as silica, defoaming agent, wetting agent, antirust agent, ultraviolet absorbing agent, antistatic agent.
Active energy ray curable hard conating resin combination of the invention can by by (A) ingredient and (B) at
Divide, the mixing of solvent as needed, additive is to obtain.Mixed media and order by merging are not particularly limited.
Cured film of the invention be make active energy ray curable hard conating resin combination of the invention solidify and
Obtained film.
As the thickness of cured film of the invention, it is not particularly limited, typically about 1 μm~about 40 μm, preferably from about 3 μm
~about 20 μm.
Laminated body of the invention has above-mentioned cured film as its method in at least single side of substrate and is not particularly limited,
Such as it can be by being coated with active energy ray curable hard conating resin combination of the invention on substrate and irradiating work
Property energy-ray obtains.
It as substrate, is not particularly limited, such as polyethylene terephthalate film (PET film), ring-type can be enumerated
Olefin resin film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer
Film, poly (ethylene naphthalate) film, polybutylene terephthalate (PBT) film, polyurethane film, ethane-acetic acid ethyenyl ester film, from
Copolymer resin film, ethylene-(methyl) acrylic copolymer film, ethylene-(methyl) acrylate copolymer film, polystyrene film,
Polycarbonate membrane, polyimide film, fluororesin film etc..Alternatively, it is also possible to use their cross linking membrane or stacked film.These films can
With any one in the film that uses untreated film, implement the light~film that re-releases that treated or have easy adhesive layer.
In addition, being not particularly limited as coating method, such as spreader, bar coater, roll coater, scraper can be enumerated
Coating machine, gravure coater etc..
For laminated body of the invention, active energy ray curable hard conating resin combination preferably is coated in substrate
Afterwards, advancing with heat source makes its predrying and removes organic solvent.It as heat source, is not particularly limited, hot wind can be enumerated and followed
Ring drying machine, electric furnace, steam stove etc..It as drying condition, is not particularly limited, typical temperature is about 40 DEG C~about 150 DEG C, preferably
It is about 50 DEG C~about 120 DEG C, the time is about 15 seconds~about 5 minutes, is preferably from about 30 seconds~about 3 minutes.
Then, it irradiates active energy beam and solidifies coating layer.As active energy beam, it is not particularly limited, it can
To enumerate such as ultraviolet light, visible light, electron ray, ionizing radiation.In the present invention, from the viewpoint of the curability of coating layer
Consider, it is preferable to use ultraviolet light.
It as the light source of ultraviolet light, is not particularly limited, such as ultrahigh pressure mercury lamp, high-pressure sodium lamp, low-pressure mercury can be enumerated
Lamp, carbon arc, xenon lamp, metal halide lamp etc..In addition, as irradiation condition, it is different according to used light source, usually accumulate
Light quantity is about 1mJ/cm2~about 1000mJ/cm2, in addition, exposure intensity is about 1mW/cm2~about 1000mW/cm2。
The thickness of laminated body as the resulting, is not particularly limited, and is about 100 μm~about 140 μm, only with cured film
(hard coat resin layer) is calculated as about 1 μm~about 40 μm.
[embodiment]
Hereinafter, enumerating, examples illustrate the present invention, but the present invention is not limited thereto.It should be noted that implementing
Part and % of example and comparative example are then weight basis unless otherwise specified.
(weight average molecular weight)
By gel permeation chromatography (GPC method), weight average molecular weight is measured under the following conditions.
Molecular weight apparatus (ProductName " HLC-8220GPC ", TOSOH Co., Ltd's manufacture)
Column (ProductName " TSKgel G1000H ", " TSKgel G2000H ", TOSOH Co., Ltd's manufacture)
Developing solvent: tetrahydrofuran
Flow velocity: 0.35mL/ minutes
Sample solution concentration: 0.5g/L
Standard substance: polystyrene (standard polystyren suit, PStQuickA, B, C, TOSOH Co., Ltd's manufacture)
Production Example 1 (manufacture of urethane acrylate)
ビ ス コ ー ト # is put into the reaction vessel for having agitating device, condenser pipe, dropping funel and nitrogen ingress pipe
300 95 parts of (the acrylic acid condensation product of pentaerythritol triacrylate and pentaerythritol tetraacrylate), two isocyanide of isophorone
5 parts of acid esters, with 0.1 part of 4- metoxyphenol and as after 0.04 part of tin octoate of catalyst, making temperature be warming up to 80 DEG C, are protected
Temperature 2 hours.It is cooled down, obtains the urethane acrylate of solid component concentration 100%, weight average molecular weight 900.
Production Example 2 (manufacture of epoxy polyacrylate)
Methacrylic acid is put into the reaction vessel for having agitating device, condenser pipe, dropping funel and nitrogen ingress pipe
250 parts of ethylene oxidic ester, 1.3 parts of lauryl mercaptan, 1000 parts of methyl iso-butyl ketone (MIBK) and 2,2 '-azodiisobutyronitriles are (hereinafter referred to as
After 7.5 parts of AIBN), with being warming up within about 1 hour until temperature reaches 90 DEG C under stream of nitrogen gas, 1 hour is kept the temperature.Then, to
It is put into advance in dropping funel by 3.7 parts and AIBN22.5 portions GMA750 parts, lauryl mercaptan mixed liquors constituted, in nitrogen gas
It flows down and was added drop-wise in system with about 2 hours, after keeping the temperature 3 hours at such a temperature, be further added AIBN10 parts, keep the temperature 1 hour.
Then, so that temperature is warming up to 130 DEG C, keep the temperature 2 hours.After being cooled to 60 DEG C, nitrogen ingress pipe is replaced with into air leading-in conduit, is thrown
Enter 507 parts of acrylic acid (hereinafter referred to as AA), 2.3 parts of 4- metoxyphenol and 6.0 parts of triphenylphosphine, after mixing, is bubbled in air
Under be warming up to 110 DEG C.After keeping the temperature 8 hours at such a temperature, 1.6 parts of 4- metoxyphenol are put into, is cooled down, it is different that methyl is added
Butyl ketone so that solid component concentration be 60%, obtain the epoxy polyacrylate of weight average molecular weight 22000.
Embodiment 1
By mixture (trade name " the ビ ス コ ー ト # of pentaerythritol triacrylate and pentaerythritol tetraacrylate
300 ", organic industry Co., Ltd. in Osaka manufactures) 100 parts, 5 parts of 4- methyl benzophenone and 105 parts of toluene mixing, obtain solid
The active energy ray curable hard conating resin combination of constituent concentration 50%.
Embodiment 2~15, comparative example 1~2
By composition shown in table 1 and toluene cooperation, the active energy ray-curable of solid component concentration 50% is respectively obtained
Type hard conating resin combination.
The production > of < laminated body
On the cyclic olefin resin film (untreated) with a thickness of 100 μm, using bar coater so that the thickness of coating layer reaches
It is 1 point dry at 80 DEG C to the active energy ray curable hard conating resin combination of 10 μm of mode coating Examples 1
Clock.Then, make it from high-pressure sodium lamp (accumulated light: 100mJ/cm in an atmosphere2, exposure intensity: 100mW/cm2) under by (removing
Running speed degree 10m/ minutes), make its solidification, thus obtains laminated body.The active-energy of embodiment 2~15, Comparative Examples 1 and 2 is penetrated
Line curing type hard conating is similarly operated with resin combination, respectively obtains laminated body.
< adaptation >
The cut mark for reaching substrate is engraved with the interval 1mm to the surface of each laminated body, carries out the gridiron pattern cellophane tape of 100 lattice
Initial stage adaptation is evaluated in disbonded test.Result is shown in table 1.It is opposite with the number (molecule) of unstripped grid
It is indicated in 100 lattice (denominator), 100/100 indicates most good adaptation (similarly hereinafter).
< pencil hardness >
It is measured according to JIS K5600-5-4.B or more is set as good.
[table 1]
< (A) ingredient >
A-1: mixture (trade name " the ビ ス コ ー of pentaerythritol triacrylate and pentaerythritol tetraacrylate
ト #300 ", the manufacture of Osaka organic industry Co., Ltd.)
A-2:A-1 and the urethane acrylate of Production Example 1 mixture (A-1/ Production Example 1=50/50 (and solid at
Divide weight))
A-3:A-1 and the epoxy polyacrylate of Production Example 2 mixture (A-1/ Production Example 2=50/50 (and solid at
Divide weight))
The mixture of A-4:A-1, the urethane acrylate of Production Example 1 and 1,6 hexanediol diacrylate (HDDA)
(A-1/ Production Example 1/HDDA=45/45/10 (solids by weight))
A-5: mixture (trade name " the ア ロ of Dipentaerythritol Pentaacrylate and dipentaerythritol hexaacrylate
ニ ッ Network ス M-400 ", Toagosei Co., Ltd's manufacture)
A-6: tripentaerythritol acrylate (trade name " ビ ス コ ー ト #802 ", Osaka Organic Chemical Industry strain formula meeting
Society manufactures, also referring to following chemical formulas)
Need to illustrate when, " ビ ス コ ー ト #802 " (Osaka Organic Chemical Industry Co., Ltd.'s manufacture) of A-6 is by following
Chemical formula indicate.
< (B) ingredient >
4-MBP:4- methyl benzophenone
2-MBP:2- methyl benzophenone
TMBP:2,3,4- tri-methyl benzophenone
Other curing agent of < >
TPO:2,4,6- trimethyl benzoyl diphenyl base phosphine oxide (trade name " Speedcure TPO ", Lambson
Group Ltd. company manufacture)
Irg184:1- hydroxycyclohexyl phenyl ketone (trade name " イ Le ガ キ ュ ア 184 ", BASF Japanese strain formula meeting
Society's manufacture)
Irg907:2- methyl-1-[4- (methylsulfany) phenyl]-2- morpholino propane-1- ketone (trade name " イ Le ガ
キ ュ ア 907 ", the manufacture of BASF Amada Co., Ltd.)
Claims (6)
1. a kind of active energy ray curable hard conating resin combination contains multifunctional (methyl) acrylate (A)
With alkylbenzophenones (B).
2. active energy ray curable hard conating resin combination as described in claim 1, wherein (B) ingredient contains
Selected from by 2 methyl benzophenone, 3- methyl benzophenone, 4- methyl benzophenone, 2,4,6- tri-methyl benzophenone and 2,3,
At least one of the group of 4- tri-methyl benzophenone composition.
3. active energy ray curable hard conating resin combination as claimed in claim 1 or 2, wherein (B) ingredient
Content is 1~30 parts by weight relative to 100 parts by weight of (A) ingredient in terms of solids by weight.
4. active energy ray curable hard conating resin combination according to any one of claims 1 to 3, wherein
Without containing simple function (methyl) acrylate (C).
5. a kind of cured film is active energy ray curable hard conating resin according to any one of claims 1 to 4
The cured film of composition.
6. a kind of laminated body has cured film described in claim 5 in at least single side of substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018057101 | 2018-03-23 | ||
| JP2018-057101 | 2018-03-23 |
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| JP (1) | JP7044087B2 (en) |
| KR (1) | KR102535069B1 (en) |
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| JP6658184B2 (en) | 2016-03-24 | 2020-03-04 | 東洋インキＳｃホールディングス株式会社 | UV curable coating composition and laminate |
| KR102285267B1 (en) | 2016-03-29 | 2021-08-02 | 아라까와 가가꾸 고교 가부시끼가이샤 | Composition curable with active energy ray and coating film |
| JP6294999B1 (en) | 2017-06-05 | 2018-03-14 | 日本化工塗料株式会社 | Active energy ray-curable composition for forming a cured film on a cyclic olefin-based resin substrate, and method for producing a hard coat film |
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2019
- 2019-03-15 JP JP2019048325A patent/JP7044087B2/en active Active
- 2019-03-21 KR KR1020190032369A patent/KR102535069B1/en active IP Right Grant
- 2019-03-22 TW TW108109986A patent/TWI768192B/en active
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| JP2004043662A (en) * | 2002-07-12 | 2004-02-12 | Dainippon Ink & Chem Inc | Surface treatment method of film and method for producing laminated film |
| CN101061192A (en) * | 2004-12-17 | 2007-10-24 | 瓦尔斯帕供应公司 | Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods |
| KR20090039345A (en) * | 2007-10-18 | 2009-04-22 | 동우 화인켐 주식회사 | Hard coating composition, hard coating film, polarizing plate and image display device |
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| TW201940604A (en) | 2019-10-16 |
| TWI768192B (en) | 2022-06-21 |
| KR20190111809A (en) | 2019-10-02 |
| KR102535069B1 (en) | 2023-05-19 |
| JP7044087B2 (en) | 2022-03-30 |
| JP2019167524A (en) | 2019-10-03 |
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