WO2014162942A1 - Film à base de résine et son procédé de production - Google Patents

Film à base de résine et son procédé de production Download PDF

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Publication number
WO2014162942A1
WO2014162942A1 PCT/JP2014/058475 JP2014058475W WO2014162942A1 WO 2014162942 A1 WO2014162942 A1 WO 2014162942A1 JP 2014058475 W JP2014058475 W JP 2014058475W WO 2014162942 A1 WO2014162942 A1 WO 2014162942A1
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Prior art keywords
meth
acrylate
resin film
urethane
active energy
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PCT/JP2014/058475
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English (en)
Japanese (ja)
Inventor
伊藤大祐
菊地慎二
田靡文大
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株式会社ダイセル
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Publication of WO2014162942A1 publication Critical patent/WO2014162942A1/fr

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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates

Definitions

  • the present invention relates to a resin film useful as an optical substrate such as a liquid crystal display, an organic EL display, a touch panel, a display substrate such as a color filter, an optical member, and the like, and a method for producing the same.
  • This application claims the priority of Japanese Patent Application No. 2013-079128 for which it applied to Japan on April 5, 2013, and uses the content here.
  • a glass substrate has been used as a display substrate for a liquid crystal display or the like, but in recent years, a display using a plastic substrate has been proposed from the viewpoint of lightness, thinning, resistance to cracking, mass productivity, manufacturing cost, and the like. It attracts attention.
  • a hard coat film in which a hard coat layer is coated on a plastic substrate such as a polyethylene terephthalate film (PET film) is known.
  • PET film polyethylene terephthalate film
  • such a hard coat film not only has low pencil hardness, but when it is thickened, the hard coat layer curls or cracks in the hard coat layer due to curing shrinkage of the resin constituting the hard coat layer. There was a problem such as entering.
  • Japanese Patent Application Laid-Open No. 2002-302517 discloses a resin molded article having excellent heat resistance and low birefringence when a polymerizable composition containing 75 wt% or more of a tri- to 8-functional aliphatic polyfunctional methacrylate is cured. It is described that JP-A-2003-292545 discloses a resin molded article having excellent heat resistance and a small linear expansion coefficient when a polymerizable composition containing an aliphatic difunctional methacrylate and a trifunctional or higher aliphatic polyfunctional methacrylate is cured. It is described that it is obtained.
  • Japanese Patent No. 4690053 discloses (A) a polyfunctional urethane (meth) acrylate having an alicyclic structure obtained by reacting a polyisocyanate compound having an alicyclic structure with a hydroxyl group-containing (meth) acrylate, and (B When a (meth) acrylate photopolymerizable composition containing a bifunctional (meth) acrylate having an alicyclic structure is photocured, a resin molded product having a thickness of 50 to 400 ⁇ m and a pencil hardness of 4H or more is obtained. It is described.
  • the conventional resin molded body tends to cause cracks and curls due to curing shrinkage of the resin, and it is difficult to increase the film thickness. Therefore, a resin film having a high surface hardness such as a pencil hardness of about 9H has not been obtained.
  • the present inventors have found that when a curable composition containing a specific amount of a 4- to 12-functional urethane (meth) acrylate having a tricyclodecane skeleton is cured, curing shrinkage occurs.
  • the inventors have found that the generation of cracks and curls is remarkably suppressed, the film thickness can be increased, and a resin film having a very high surface hardness can be obtained, and the present invention has been completed.
  • this invention is a resin film obtained by hardening
  • the said active energy ray curable composition is following formula (1).
  • a resin film comprising 10 to 10% by weight or more of a 4- to 12-functional urethane (meth) acrylate (A) having a tricyclodecane skeleton group represented by provide.
  • the thickness preferably exceeds 25 ⁇ m, and more preferably 500 ⁇ m or more.
  • the active energy ray-curable composition includes a 4- to 12-functional urethane (meth) acrylate (A) having a group containing a tricyclodecane skeleton represented by the formula (1) in the molecule, and other curing agents.
  • a polyfunctional (meth) acrylate may be included as the functional compound (B).
  • the active energy ray-curable composition includes a 4- to 12-functional urethane (meth) acrylate (A) having a group containing a tricyclodecane skeleton represented by the formula (1) in the molecule, and the like.
  • a polyfunctional (meth) acrylate having 4 or more functional groups may be contained.
  • This invention is a manufacturing method of the said resin film, Comprising: following formula (1) From an active energy ray-curable composition containing 10 to 10% by weight or more of a 4- to 12-functional urethane (meth) acrylate (A) having a group containing a tricyclodecane skeleton represented by A method for producing a resin film is provided, wherein the thin film layer is irradiated with active energy rays to be cured.
  • the resin film of the present invention is a resin film obtained by curing an active energy ray-curable composition containing a specific amount or more of a 4- to 12-functional urethane (meth) acrylate having a tricyclodecane skeleton.
  • the occurrence of cracks and curls is remarkably suppressed, the film can be made thick, and the surface hardness can be very high.
  • the resin film of the present invention can obtain the high surface hardness as described above without adding a filler such as fine particle silica.
  • the resin film of the present invention is excellent in optical properties such as transparency, thermal properties, and mechanical properties.
  • the resin film of the present invention has a 4- to 12-functional group having in its molecule a group containing a tricyclodecane skeleton represented by the above formula (1) (a group obtained by removing two hydrogen atoms of a hydroxyl group from tricyclodecane dimethanol).
  • Urethane (meth) acrylate (A) [hereinafter sometimes simply referred to as “4- to 12-functional urethane (meth) acrylate (A)” or “urethane (meth) acrylate (A)”) It is the resin film obtained by hardening
  • the amount of urethane (meth) acrylate (A) is preferably 15% by weight or more, more preferably 20% by weight or more, based on the entire curable compound in the active energy ray-curable composition.
  • Urethane (meth) acrylate (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the number of functional groups of urethane (meth) acrylate means the number of (meth) acryloyl groups in one molecule.
  • the number of functional groups of the urethane (meth) acrylate (A) is 3 or less, the surface hardness of the resin film tends to decrease.
  • the number of functional groups of urethane (meth) acrylate (A) is 13 or more, the effect of suppressing the occurrence of cracks and curls due to curing shrinkage is reduced, and the impact resistance and accelerated weather resistance of the resin film are lowered. It becomes a trend.
  • the number of functional groups of the urethane (meth) acrylate (A) is preferably 6 to 10, and more preferably 6 to 8.
  • Urethane (meth) acrylate (A) is, for example, tricyclodecane dimethanol (X) [a compound in which hydrogen atoms are bonded to both ends of a group containing a tricyclodecane skeleton represented by the above formula (1)] and poly It can be produced by reacting isocyanate (Y) with hydroxy group-containing (meth) acrylate (Z).
  • X tricyclodecane dimethanol
  • Z hydroxy group-containing (meth) acrylate
  • urethane (meth) acrylate (A) is simply “(A)” or “A”
  • tricyclodecane dimethanol (X) is simply “(X)” or “X”
  • polyisocyanate (Y) is The “(Y)” or “Y” may be simply referred to, and the hydroxy group-containing (meth) acrylate (Z) may be simply referred to as “(Z)” or “Z”.
  • the number of functional groups of polyisocyanate means the number of isocyanate groups in one molecule
  • the number of functional groups of hydroxy group-containing (meth) acrylate means the number of (meth) acryloyl groups in one molecule. Means.
  • diisocyanate (bifunctional polyisocyanate) is used as polyisocyanate (Y)
  • bifunctional (meth) acrylate compound is used as hydroxy group-containing (meth) acrylate (Z)
  • tricyclodecane dimethanol (X)
  • molar ratio of polyisocyanate (Y) and hydroxy group-containing (meth) acrylate (Z) is reacted at 1: 2: 2, tetrafunctional urethane (meth) acrylate (A) can be obtained.
  • triisocyanate trifunctional polyisocyanate such as nurate polyisocyanate
  • polyisocyanate (Y) polyisocyanate
  • monofunctional (meth) acrylate compound is used as hydroxy group-containing (meth) acrylate (Z).
  • X decanedimethanol
  • polyisocyanate (Y) polyisocyanate
  • hydroxy group-containing (meth) acrylate (Z) is 1: 2: 4
  • a tetrafunctional urethane (meth) acrylate (A ) Can be obtained.
  • the urethane (meth) acrylate (A) can be schematically represented by (Z) m —Y—XY— (Z) m (m is an integer of 1 or more, preferably 1 or 2). “-” In the above formula indicates that the components on both sides are reacted (hereinafter the same).
  • Method 1 A method in which (X), (Y), and (Z) are mixed and reacted.
  • Method 2 A method in which (X) and (Y) are reacted to form a urethane isocyanate prepolymer containing an isocyanate group, and then the prepolymer and (Z) are reacted.
  • Method 3 A method of reacting (Y) and (Z) to form a urethane isocyanate prepolymer containing an isocyanate group, and then reacting the prepolymer with (X).
  • urethane (meth) acrylate (A) increases the amount of urethane isocyanate prepolymer produced by repeating tricyclodecane dimethanol (X) and polyisocyanate (Y), ) Intramolecular density of the acryloyl group may decrease, and the surface hardness of the target resin film may decrease. Moreover, since various complicated compounds are irregularly generated, quality control may be difficult when the product is used as an active energy ray-curable resin composition.
  • [Method 2] the following method may be mentioned as a method for synthesizing the urethane isocyanate prepolymer.
  • [Method 2-1] A method in which (X) and (Y) are mixed and reacted.
  • [Method 2-2] A method in which (Y) is dropped into (X) for reaction.
  • [Method 2-3] A method in which (X) is dropped into (Y) for reaction.
  • polyisocyanate (Y) is dropped into a large amount of tricyclodecane dimethanol (X).
  • X tricyclodecane dimethanol
  • a urethane isocyanate prepolymer having hydroxyl groups at both ends of the XYX type is formed, and this is further reacted with 2 moles of polyisocyanate (Y).
  • Y- [XY] n -XY (n is an integer of 1 or more)
  • the urethanization reaction proceeds in a non-uniform state of tricyclodecane dimethanol (X) and polyisocyanate (Y) at the stage of charging the polyisocyanate (Y).
  • the molecular weight and viscosity of the resulting urethane isocyanate prepolymer change, and the reaction may be terminated in a state where unreacted polyisocyanate (Y) remains in the system.
  • a by-product is generated due to the reaction of the hydroxy group-containing (meth) acrylate (Z) and the remaining polyisocyanate (Y) to be used later, which may cause a decrease in the surface hardness of the resin film. is there.
  • the content of such a by-product is preferably less than 15% by weight based on the urethane (meth) acrylate (A) having a skeleton derived from the target tricyclodecane dimethanol (X).
  • X tricyclodecane dimethanol
  • a polyisocyanate (Y), a urethanization catalyst, and, if necessary, a diluting solvent are charged into a reactor and stirred until uniform. While stirring, the temperature is raised as necessary, and tricyclodecane dimethanol (X) is added dropwise.
  • [Method 2-3] is preferable in that the following products described in [Method 2-2] are the least generated.
  • urethane isocyanate prepolymer when synthesized by reaction of tricyclodecane dimethanol (X) and polyisocyanate (Y), tricyclodecane dimethanol (X) and polyisocyanate (Y) are combined.
  • the reaction is preferably carried out until the isocyanate group concentration in the reaction solution is equal to or lower than the end-point isocyanate group concentration.
  • the isocyanate group concentration in the reaction solution may be referred to as “NCO group concentration”.
  • End-point isocyanate group concentration means the theoretical isocyanate group concentration (hereinafter, sometimes referred to as “theoretical end-point isocyanate group concentration”) assuming that all of the hydroxyl groups charged into the system have been urethanized. It means the higher isocyanate group concentration of the isocyanate group concentration when the isocyanate group concentration no longer changes.
  • This reaction is preferably performed in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazine for the purpose of preventing polymerization.
  • a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazine for the purpose of preventing polymerization.
  • the addition amount of these polymerization inhibitors is preferably 1 to 10,000 ppm (weight basis), more preferably 100 to 1000 ppm, and still more preferably 400 to 500 ppm with respect to the urethane (meth) acrylate (A) to be produced. If the addition amount of the polymerization inhibitor is less than 1 ppm relative to the urethane (meth) acrylate (A), a sufficient polymerization inhibition effect may not be obtained. If it exceeds 10000 ppm, the physical properties of the product may be adversely affected. There is.
  • this reaction is preferably performed in a molecular oxygen-containing gas atmosphere.
  • the oxygen concentration is appropriately selected in consideration of safety.
  • the reaction may be performed using a catalyst (urethanization catalyst) in order to obtain a sufficient reaction rate.
  • a catalyst urethanization catalyst
  • dibutyltin dilaurate, tin octylate, tin chloride or the like can be used, but dibutyltin dilaurate is preferable from the viewpoint of reaction rate.
  • the amount of these catalysts added is usually 1 to 3000 ppm (weight basis), preferably 50 to 1000 ppm. When the addition amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained. When the addition amount is more than 3000 ppm, the physical properties of the target product may be adversely affected, such as a decrease in the surface hardness of the resin film.
  • the reaction can be performed in the presence of a known volatile organic solvent.
  • the volatile organic solvent include, but are not limited to, esters such as ethyl acetate, butyl acetate, and isobutyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ethylene glycol monomethyl ether and the like Ethers; glycol monoether acetates such as diethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate; hydrocarbons such as xylene and toluene; and mixtures thereof.
  • ketones such as methyl isobutyl ketone and esters such as butyl acetate are preferable.
  • the reaction is preferably carried out at a temperature of 130 ° C. or less, more preferably 40 to 130 ° C. When the temperature is lower than 40 ° C., a practically sufficient reaction rate may not be obtained. When the temperature is higher than 130 ° C., the double bond portion may be cross-linked by radical polymerization due to heat, and a gelled product may be generated.
  • the reaction is usually carried out until the residual isocyanate group is 0.1% by weight or less.
  • the residual isocyanate group concentration is analyzed by gas chromatography, titration method or the like.
  • Tricyclodecane dimethanol (X) Tricyclodecane dimethanol (X) is not particularly limited, and a commercially available product may be used. Examples of commercially available products include “TCD alcohol DM” (manufactured by Oxea) (tricyclo [5.2.1.0 2,6 ] decanedimethanol).
  • the polyisocyanate (Y) is not particularly limited, but aliphatic polyisocyanates (including those having an alicyclic skeleton) are preferable. Examples of such polyisocyanate (Y) include isophorone diisocyanate, 1,6-hexane diisocyanate (1,6-hexamethylene diisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl.
  • Hexamethylene diisocyanate, diisocyanate compounds obtained by hydrogenating aromatic diisocyanates for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate
  • trimers of these diisocyanates (biuret, nurate, or adducts); Trifunctional polyisocyanate) and the like.
  • trimer of the diisocyanate compound nurate polyisocyanate is particularly preferable.
  • Polyisocyanate (Y) may be used individually by 1 type, and may be used in combination of 2 or more.
  • the hydroxy group-containing (meth) acrylate (Z) is not particularly limited.
  • the active energy ray-curable composition in the present invention includes the urethane (meth) acrylate (A) and other curable compounds (B) [hereinafter sometimes referred to simply as “curable compounds (B)”]. May be included.
  • the curable compound (B) may be any compound (a monomer or oligomer having a polymerizable group) that is cured by irradiation with active energy rays.
  • a single compound having one (meth) acryloyl group in the molecule For example, a single compound having one (meth) acryloyl group in the molecule.
  • Functional (meth) acrylates, polyfunctional (meth) acrylates having two or more (meth) acryloyl groups in the molecule can be used.
  • Examples of the monofunctional (meth) acrylate include (meth) acrylate having an aromatic carbon ring such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclo (Meth) acrylates having an alicyclic skeleton such as pentenyloxyethyl (meth) acrylate; lactone-modified hydroxyalkyl (meth) acrylates such as polycaprolactone-modified hydroxyethyl (meth) acrylate; heterocycles such as acryloylmorpholine (meta ) Acrylate and the like.
  • aromatic carbon ring such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate
  • cyclohexyl (meth) acrylate isobornyl (meth) acrylate
  • polyfunctional (meth) acrylate examples include 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Of polyhydric alcohols (aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, etc.) such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate ) Polyfunctional monomers such as acrylate; Urethane (meth) acrylate [excluding the urethane (meth) acrylate (A)], epoxy (meth) acrylate, polyester (meth) acrylate and other polyfunctional oligomers It is.
  • polyhydric alcohols aliphatic polyhydric alcohols, alicyclic
  • the curable compound (B) is preferably a polyfunctional (meth) acrylate, particularly a polyfunctional (functional 4 or more, preferably 6 to 15, preferably 6 to 12, more preferably 8 to 12 functional). (Meth) acrylate is preferred.
  • polyfunctional (meth) acrylates polyfunctional urethane (meth) acrylate (B1) is preferable.
  • the number of functional groups of the polyfunctional urethane (meth) acrylate is preferably 4 or more (for example, 4 to 15 functions, preferably 6 to 15 functions, more preferably 8 to 12 functions).
  • Polyfunctional urethane (meth) acrylate (B1) can be produced by a known method. For example, (i) a method of reacting a polyisocyanate (Y ′) with a hydroxy group-containing (meth) acrylate (Z ′), (ii) a polyol (X ′), a polyisocyanate (Y ′), and a hydroxy group-containing (meta ) It can be produced by a method of reacting with acrylate (Z ′).
  • polyol (X ′) examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl.
  • Diols such as -1,5-pentanediol and tricyclodecane dimethanol; trivalent or higher polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol can be used.
  • Polyol (X ') may be used individually by 1 type, and may be used in combination of 2 or more.
  • polyisocyanate (Y ′) examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5 -Aromatic diisocyanates such as naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate; isophorone diisocyanate, 1,6-hexane diisocyanate (1,6-hexamethylene diisocyanate), 2,2,4-trimethylhexa Diisocyanate compounds obtained by hydrogenating methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aromatic diisocyanate (for example, hydrogenated) Aliphatic polyisocyanates (including those having an alicyclic skeleton) such as silylene di
  • aliphatic polyisocyanates including those having an alicyclic skeleton
  • the nurate type polyisocyanate is also preferable.
  • Polyisocyanate (Y ′) may be used alone or in combination of two or more.
  • Examples of the hydroxy group-containing (meth) acrylate (Z ′) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3- Monofunctional (meth) acrylate compounds having a hydroxyl group such as methoxypropyl (meth) acrylate and these lactone adducts (caprolactone adduct, etc.); pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Polyfunctional (meth) acrylate compounds having hydroxyl groups such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and these lactone adducts (caprolactone adducts, etc.) Such as things.
  • the tetrafunctional or higher functional group containing the 4- to 12-functional urethane (meth) acrylate (A) is used.
  • the total amount of polyfunctional (meth) acrylates (especially polyfunctional urethane (meth) acrylates having 4 or more functionalities) is 30% by weight or more based on the entire curable compound in the active energy ray-curable composition. It is preferably 50% by weight or more, more preferably 60% by weight or more.
  • the active energy ray-curable composition in the present invention may contain a solvent, a photopolymerization initiator, an additive and the like as required in addition to the curable compound.
  • the solvent can be appropriately selected in consideration of the solubility of the curable compound and is not particularly limited.
  • esters such as ethyl acetate, butyl acetate, and isobutyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
  • Ketones such as ethylene glycol monomethyl ether; glycol monoether acetates such as diethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate; hydrocarbons such as xylene and toluene; and mixtures thereof.
  • the content of the solvent in the active energy ray-curable composition is, for example, 0 to 95% by weight, preferably 5 to 90% by weight, and more preferably 10 to 80% by weight.
  • a known radical photopolymerization initiator can be used, and is not particularly limited.
  • ⁇ -hydroxyalkylphenone polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and ⁇ -aminoalkyl such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • a phenone-based polymerization initiator When used in combination with a phenone-based polymerization initiator, it can be uniformly cured from the surface to the inside of the thin film layer made of the active energy ray-curable composition, and a homogeneous resin film can be obtained.
  • the amount of the photopolymerization initiator used is, for example, 1 to 20 parts by weight, preferably 1.5 to 10 parts by weight with respect to 100 parts by weight of the curable compound in the active energy ray-curable composition. If it is less than 1 part by weight, there is a risk of causing poor curing. Conversely, if it exceeds 20 parts by weight, an odor derived from the photoinitiator may remain from the cured coating film.
  • additives examples include fillers (particulate silica, etc.), dyes and pigments, leveling agents, ultraviolet absorbers, light stabilizers, antifoaming agents, dispersants, thixotropic agents, and the like.
  • the amount of these additives to be added is, for example, 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the curable compound in the active energy ray-curable composition.
  • a resin film having a high surface hardness can be obtained without adding fine particle silica (or without adding filler such as fine particle silica). .
  • the resin film of the present invention comprises a tetra- to 12-functional urethane (meth) acrylate (A) having a group containing a tricyclodecane skeleton represented by the above formula (1) in the molecule, in an amount of 10 to the entire curable compound. It can manufacture by irradiating an active energy ray to the thin film layer which consists of an active energy ray curable composition containing weight% or more and making it harden
  • the active energy ray-curable composition is cast on a substrate or in a mold to form a thin film and dried as necessary (after removing the solvent)
  • the resin film of the present invention can be produced by curing by irradiation.
  • the substrate is not particularly limited, and examples thereof include polyester resins, polyolefin resins, cellulose resins, polystyrene resins, methacrylic resins, polycarbonate resins, polymethylpentels, polysulfones, polyether ketones, and polyethers. Examples thereof include plastic base materials such as sulfone, polyetherimide, polyimide, and fluorine resin, glass base materials, metal base materials, and the like.
  • the surface of the substrate is preferably subjected to a release treatment with a release agent (release agent).
  • the material of the mold can be the same as that of the substrate, and the surface thereof is preferably subjected to a release treatment (fluorine resin coating or the like) with a release agent (release agent).
  • the resin film of this invention can be obtained by irradiating the surface of the thinned active energy ray-curable composition with active energy rays such as ultraviolet rays or electron beams to cure the curable compound.
  • active energy rays such as ultraviolet rays or electron beams
  • a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like is used as a light source for ultraviolet irradiation.
  • an irradiation source with a lamp output of about 80 to 300 W / cm is used.
  • curing may be promoted by heating as necessary.
  • the thickness of the resin film of the present invention is preferably more than 25 ⁇ m, more preferably 100 ⁇ m or more, further preferably 200 ⁇ m or more, and particularly preferably 500 ⁇ m or more in order to ensure high pencil hardness.
  • the upper limit of the thickness of the resin film is not particularly limited, but is, for example, 4 mm, preferably 2 mm.
  • the resin film of the present invention has a high surface hardness, for example, a pencil hardness of 4H or more when the film thickness is 100 ⁇ m or more, and a pencil hardness of 9H or more when the film thickness is 500 ⁇ m or more.
  • the resin film of the present invention thus obtained can be used as an optical substrate such as a display substrate such as a liquid crystal display, an organic EL display, a touch panel, and a color filter, and an optical member.
  • the isocyanate group concentration was measured as follows. In addition, the measurement was performed under stirring with a stirrer in a 100 mL glass flask.
  • the blank value was measured as follows. First, 15 mL of a THF solution (0.1N) of dibutylamine was added to 15 mL of THF (tetrahydrofuran). Further, after adding 3 drops of bromophenol blue (diluted in 1% by weight of methanol) to give a blue color, titration was performed with an aqueous HCl solution having a normality of 0.1N. The titration amount of the aqueous HCl solution when the color change was observed was defined as V b (mL).
  • the measured isocyanate group concentration was measured as follows. First, a sample of W s (g) was weighed and dissolved in 15 mL of THF, and 15 mL of dibutylamine in THF (0.1 N) was added. After confirming that the solution was formed, 3 drops of bromophenol blue (diluted in 1% by weight of methanol) were added to give a blue color, followed by titration with an aqueous HCl solution having a normality of 0.1N. The titer of the aqueous HCl solution when the color change was observed was defined as V s (mL).
  • TCDDM Tricyclodecane dimethanol used in the synthesis example
  • TCDDM Product name "TCD alcohol DM” (Oxea)
  • HMDI trimer Product name “Sumijour N3300” (manufactured by Sumitomo Bayer Urethane Co., Ltd .; 1,6-hexamethylene diisocyanate-derived nurate compound)
  • IPDI Product name “VESTANAT IPDI” (Evonik; isophorone diisocyanate)
  • HEA Hydrophilicity group-containing (meth) acrylate used in synthesis example
  • BHEA Product name “BHEA” (manufactured by Nippon Shokubai Co., Ltd .; 2-hydroxyethyl acrylate)
  • PETIA Product name “PETRA” (manufactured by Cytec; mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate having a hydroxyl value of 120 mg KOH / g)
  • M-403 Product name “Aronix M-403” (manufactured by Toagosei Co., Ltd .; mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
  • the completion of the reaction was confirmed by confirming that the isocyanate group concentration in the reaction solution was not more than the theoretical end-point isocyanate group concentration (the same applies to other synthesis examples).
  • the procedure shifted to the next operation.
  • the internal temperature was raised to 70 ° C.
  • 0.08 g of dibutyltin laurate was added, and 474.3 g of PETIA was added dropwise over 2 hours while maintaining the reaction temperature at 70 ° C. After completion of the dropping, stirring was continued at 70 ° C. for 1 hour.
  • the reaction was terminated, and the backbone had an organic group obtained by removing two hydrogen atoms of a hydroxyl group from tricyclodecane dimethanol, and the number of functional groups was 2.
  • the urethane (meth) acrylate containing material (UA3) was obtained.
  • Examples and Comparative Examples The urethane (meth) acrylate-containing material prepared in the synthesis example, the photopolymerization initiator, and methyl isobutyl ketone (MIBK) are mixed in a light-shielding bottle so as to have the composition shown in Table 1 (numbers are parts by weight) An energy ray curable composition was prepared.
  • photopolymerization initiator 1 is 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, product name “IRGACURE184”)
  • photopolymerization initiator 2 is 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one (product name “IRGACURE907” manufactured by BASF).
  • the number in parentheses below “UA1” in the urethane (meth) acrylate column indicates the number of functional groups of the (meth) acryloyl group in one molecule.
  • a resin film was produced by the following film production method 1 or 2.
  • Film production method 1 An active energy ray-curable composition is flowed on a polyethylene terephthalate (PET) film (base material: thickness 125 ⁇ m, trade name “O321E”, manufactured by Mitsubishi Plastics) using a wire bar # 38. After extending, the solvent was removed by drying with a dryer at 80 ° C. After irradiating ultraviolet rays from a high pressure mercury lamp in a nitrogen atmosphere, the resin film having a predetermined thickness (20 ⁇ m, 100 ⁇ m) was obtained by peeling from the base material.
  • PET polyethylene terephthalate
  • Film production method 2 The active energy ray-curable composition was cast on a Teflon (registered trademark) petri dish, and then the solvent was removed by drying with a dryer at 80 ° C. After irradiating ultraviolet rays from a high pressure mercury lamp in a nitrogen atmosphere, the resin film having a predetermined thickness (200 ⁇ m, 1000 ⁇ m) was obtained by peeling from the teflon petri dish.
  • the resin films of Examples 1 to 3 using a tetra- or hexafunctional urethane (meth) acrylate having a group containing a tricyclodecane skeleton represented by the formula (1) in the molecule Compared with a bifunctional urethane (meth) acrylate having a group containing a tricyclodecane skeleton represented by the formula (1) in the molecule, while the pencil hardness is “3H” even when the thickness is 20 ⁇ m.
  • the resin film of Example 1 has a thickness of 20 ⁇ m and a pencil hardness of “H”.
  • the resin films of Examples 5 to 11 using a tetra- or hexafunctional urethane (meth) acrylate having a group containing a tricyclodecane skeleton represented by the formula (1) in the molecule have a thickness of 200 ⁇ m or 1000 ⁇ m.
  • Comparative Examples 2 to 4 using a bifunctional urethane (meth) acrylate having a group containing a tricyclodecane skeleton represented by the formula (1) in the molecule The resin film has a thickness of 200 ⁇ m or 1000 ⁇ m and a pencil hardness of “5H” to “7H”.
  • the resin film of the present invention generation of cracks and curls due to curing shrinkage is remarkably suppressed, the film thickness can be increased, and the surface hardness can be very high. Further, high surface hardness can be obtained without adding a filler such as fine particle silica. Furthermore, the resin film of the present invention is excellent in optical properties such as transparency, thermal properties, and mechanical properties. Therefore, it is useful as an optical substrate such as a liquid crystal display, an organic EL display, a touch panel, a display substrate such as a color filter, an optical member, or the like.

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Abstract

Cette invention concerne un film à base de résine obtenu par durcissement d'une composition durcissable par des rayons d'énergie active, la composition durcissable par des rayons d'énergie active étant caractérisée en ce qu'elle contient 10 % en poids ou plus, par rapport à tous les composés durcissables, d'un (méth)acrylate d'uréthane (A) tétra- à dodécafonctionnel comportant dans sa molécule un groupe contenant un squelette tricyclodécane représenté par la formule (1). L'épaisseur du film à base de résine selon l'invention est de préférence supérieure à 25 µm, et est dans l'idéal de 500 µm ou plus.
PCT/JP2014/058475 2013-04-05 2014-03-26 Film à base de résine et son procédé de production WO2014162942A1 (fr)

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JP2016104859A (ja) * 2014-11-25 2016-06-09 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤

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JP2016190952A (ja) * 2015-03-31 2016-11-10 日油株式会社 活性エネルギー線硬化型樹脂組成物
CN107132940A (zh) 2016-02-26 2017-09-05 宸盛光电有限公司 使用三维打印制作的触控基板及其制作方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2005255979A (ja) * 2004-02-10 2005-09-22 Daicel Ucb Co Ltd 活性エネルギー線硬化型樹脂組成物の硬化物
JP2007204736A (ja) * 2006-01-05 2007-08-16 Nippon Synthetic Chem Ind Co Ltd:The 樹脂成形体、樹脂成形体の製造方法、及びその用途
WO2013114750A1 (fr) * 2012-01-31 2013-08-08 ダイセル・サイテック株式会社 Composition de résine vulcanisable par rayons d'énergie active

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WO2013022068A1 (fr) * 2011-08-10 2013-02-14 日立化成工業株式会社 Composition de résine photosensible, film photosensible, réserve permanente et procédé de production de réserve permanente

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255979A (ja) * 2004-02-10 2005-09-22 Daicel Ucb Co Ltd 活性エネルギー線硬化型樹脂組成物の硬化物
JP2007204736A (ja) * 2006-01-05 2007-08-16 Nippon Synthetic Chem Ind Co Ltd:The 樹脂成形体、樹脂成形体の製造方法、及びその用途
WO2013114750A1 (fr) * 2012-01-31 2013-08-08 ダイセル・サイテック株式会社 Composition de résine vulcanisable par rayons d'énergie active

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016104859A (ja) * 2014-11-25 2016-06-09 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物及びコーティング剤

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