WO2021002342A1 - 複層フィルム - Google Patents
複層フィルム Download PDFInfo
- Publication number
- WO2021002342A1 WO2021002342A1 PCT/JP2020/025615 JP2020025615W WO2021002342A1 WO 2021002342 A1 WO2021002342 A1 WO 2021002342A1 JP 2020025615 W JP2020025615 W JP 2020025615W WO 2021002342 A1 WO2021002342 A1 WO 2021002342A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane resin
- group
- active hydrogen
- component
- carbon atoms
- Prior art date
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Classifications
-
- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
Definitions
- the present invention relates to a multilayer film.
- a hard-coated film has been used as a surface protective film for an optical member such as a liquid crystal panel.
- an optical member such as a liquid crystal panel.
- a material having self-repairing property has been studied, and a film in which a polyester-based urethane resin is laminated on a transparent base material such as polyamide, polycarbonate and polyimide has been proposed (see, for example, Patent Document 1).
- the conventional technique including the multilayer film described in Patent Document 1 has a problem that the scratch recovery time is long and the scratch resistance is not sufficient under the condition that fine scratches are likely to occur. Further, there is a problem that the bending resistance is not sufficient in the conventional technique.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a film having excellent scratch resistance and also excellent bending resistance.
- the present invention is a multi-layer film having a base layer and a surface layer formed on the base layer, and the active hydrogen containing the compound (a1) in which the surface layer has a polyorganosiloxane group and an active hydrogen group as essential components. It contains a polyurethane resin (U1) composed of a component (A1) and an isocyanate component (B1), and the elastic recovery rate of the polyurethane resin (U1) at 100% elongation is 50 to 100%, and the base layer is active.
- It contains a polyurethane resin (U2) composed of a hydrogen component (A2) and an isocyanate component (B2), and the active hydrogen component (A2) does not contain a compound (a1) having a polyorganosiloxane group and an active hydrogen group.
- It is an active hydrogen component containing a high molecular weight polyol (a2) as an essential component, and is a multilayer film in which the elastic recovery rate of the polyurethane resin (U2) at 100% elongation is 80 to 100%.
- the multi-layer film of the present invention has excellent scratch resistance and also excellent bending resistance.
- the multi-layer film of the present invention is a multi-layer film having a base layer and a surface layer formed on the base layer.
- the surface layer contains a polyurethane resin (U1) composed of an active hydrogen component (A1) and an isocyanate component (B1) containing a compound (a1) having a polyorganosiloxane group and an active hydrogen group as an essential component.
- the elastic recovery rate of the polyurethane resin (U1) at 100% elongation is 50 to 100%
- the base layer contains a polyurethane resin (U2) composed of an active hydrogen component (A2) and an isocyanate component (B2).
- the active hydrogen component (A2) is an active hydrogen component that does not contain a polyorganosiloxane group and a compound (a1) having an active hydrogen group, but contains a high molecular weight polyol (a2) as an essential component, and is a polyurethane resin (U2). ) Is a multi-layer film having an elastic recovery rate of 80 to 100% when stretched at 100%.
- the polyurethane resin (U1) composed of an active hydrogen component (A1) and an isocyanate component (B1) containing a compound (a1) having a polyorganosiloxane group and an active hydrogen group as an essential component on the surface layer is contained, and the above polyurethane resin ( When the elastic recovery rate of U1) at 100% elongation is 50 to 100%, scratch resistance is improved. Further, a compound in which the base layer contains a polyurethane resin (U2) composed of an active hydrogen component (A2) and an isocyanate component (B2), and the active hydrogen component (A2) has the polyorganosiloxane group and the active hydrogen group.
- the polyurethane resin (U2) or the like used for the base layer in the present invention is excellent in scratch resistance and bending resistance, but often causes tack on the surface, and in the present invention, by providing a surface layer, a plurality of layers are provided. It is possible to suppress the occurrence of tack on the surface of the film.
- the polyurethane resin (U1) which is the main constituent component of the surface layer, reacts the active hydrogen component (A1) containing the compound (a1) having a polyorganosiloxane group and the active hydrogen group as an essential component with the isocyanate component (B1). It is a polyurethane resin obtained by
- the active hydrogen component (A1) in the polyurethane resin (U1) includes a polyorganosiloxane group as an essential component and a compound (a1) having an active hydrogen group, a polymer polyol (a2) as an optional component, and a chain extender (a3). ) And the reaction terminator (a4) and the like.
- a compound having a polyorganosiloxane group represented by the general formula (1) is preferable from the viewpoint of scratch resistance and haze.
- R 1 to R 6 in the general formula (1) independently represent hydrocarbon groups having 1 to 6 carbon atoms.
- R 1 to R 6 are preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
- N in the general formula (1) is an integer of 1 to 100, preferably 10 to 70, and more preferably 15 to 50 from the viewpoint of scratch resistance and haze.
- Examples of the active hydrogen group contained in the compound (a1) having a polyorganosiloxane group and an active hydrogen group [hereinafter abbreviated as (a1)] include a hydroxyl group, an amino group and a carboxyl group. Since (a1) generally has low compatibility with other constituent monomers of the polyurethane resin (U1), (a1) is uniformly introduced into the polyurethane resin (U1) to increase the haze of (U1). From the viewpoint of suppression, it is preferable to use (a1) having a hydroxyl group and an amino group as the active hydrogen group. In (a1), one type may be used alone or two or more types may be used in combination.
- (a1) as the compound (a11) having a hydroxyl group, a commercially available product can be used.
- KF-6001 functional group equivalent 900 g / mol
- KF-6002 having a hydroxyl group at both ends
- (a1) as the compound (a13) having a carboxyl group, a commercially available product can be used, for example, "X-22-162C” having a carboxyl group at both ends (functional group equivalent of 2,300 g / mol). ), “X-22-3710” having a carboxyl group at one end (functional group equivalent 1,450 g / mol) and “X-22-3701E” having a carboxyl group in the side chain (functional group equivalent 4,000 g / mol). mol) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
- the weight of the compound (a1) having a polyorganosiloxane group and an active hydrogen group in the polyurethane resin (U1) is based on the weight of the polyurethane resin (U1) as a constituent component from the viewpoints of scratch resistance, tack-free property and haze. It is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight.
- the polymer polyol (a2) is preferably a polymer polyol having a number average molecular weight (hereinafter abbreviated as Mn) of 500 or more, and specifically, a polyester polyol (a21), a polyether polyol (a22) and a polyether. Examples thereof include ester polyol (a23).
- Mn number average molecular weight
- the polymer polyol (a2) may be used alone or in combination of two or more.
- polyester polyol (a21) examples include a condensed polyester polyol, a polylactone polyol, a polycarbonate polyol, and the like.
- the condensed polyester polyol includes Mn or a polyol having a chemical formula of less than 500, a polyvalent carboxylic acid having 2 to 20 carbon atoms, or an ester-forming derivative thereof [acid anhydride, lower (1 to 4 carbon atoms) alkyl ester. And acid halide, etc.], and the like obtained by condensation with.
- Examples of the Mn or the polyol having a chemical formula of less than 500 include a polyhydric alcohol having 2 to 20 carbon atoms; an alkylene oxide (hereinafter abbreviated as AO) adduct having 2 to 12 carbon atoms in the polyhydric alcohol having 2 to 20 carbon atoms.
- Mn or chemical formula less than 500 bisphenol (bisphenol A, bisphenol S, bisphenol F, etc.) AO adduct having 2 to 12 carbon atoms and Mn or chemical formula less than 500; bis ( Examples thereof include 2-hydroxyethyl) terephthalate and an AO adduct having 2 to 12 carbon atoms having Mn or a chemical formula of less than 500.
- Examples of the AO having 2 to 12 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, and the like. Examples thereof include styrene oxide, ⁇ -olefin oxide and epichlorohydrin.
- polyhydric alcohol having 2 to 20 carbon atoms examples include linear or branched aliphatic dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5. -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.
- Examples of the polyvalent carboxylic acid having 2 to 20 carbon atoms or an ester-forming derivative thereof include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, and fumaric acid.
- alicyclic dicarboxylic acid dimeric acid, etc.
- aromatic dicarboxylic acid terephthalic acid, isophthalic acid, phthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'- Biphenyldicarboxylic acid, etc.
- trivalent or higher polyvalent carboxylic acid trimellitic acid, pyromellitic acid, etc.
- their anhydrides succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.
- These acid halides diichloroide of adipate, etc.
- these low molecular weight alkyl esters dimethyl succinate, dimethyl phthalate, etc.
- the polylactone polyol includes a lactone monomer having 3 to 12 carbon atoms ( ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ ) using the polyhydric alcohol having 2 to 20 carbon atoms as an initiator.
- -Caprolactone, 11-undecanolactone, 12-tridecanoid, etc. are ring-opened and polymerized.
- One type of lactone monomer may be used alone, or two or more types may be used in combination.
- the polycarbonate polyol is one or more (preferably) of the polyhydric alcohol having 2 to 20 carbon atoms (preferably an aliphatic dihydric alcohol having 3 to 9 carbon atoms, more preferably 4 to 6 carbon atoms). 2 to 4 types) and low molecular weight carbonate compounds (for example, dialkyl carbonate having 1 to 6 carbon atoms of an alkyl group, alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and diaryl having an aryl group having 6 to 9 carbon atoms. Examples thereof include a polycarbonate polyol produced by condensing while dealcoholizing (carbonate).
- Examples of the polyether polyol (a22) include a compound obtained by adding AO having 2 to 12 carbon atoms to the above Mn or a polyol having a chemical formula of less than 500.
- One type of AO may be used alone or two or more types may be used in combination, and in the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a combination system thereof may be used.
- Addition of AO to the Mn or polyol having a chemical formula less than 500 is always carried out, for example, in the absence of a catalyst or in the presence of a catalyst (alkaline catalyst, amine-based catalyst, acidic catalyst, etc.) (especially in the latter half of AO addition). It is performed in one step or multiple steps under pressure or pressure.
- polyether polyol (a22) examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (oxy-3-methyltetramethylene) glycol, tetrahydrofuran / ethylene oxide copolymer diol, and tetrahydrofuran / 3-methyltetrachloride.
- examples include polymerized diols.
- the polyether ester polyol (a23) includes one or more of the above-mentioned polyether polyols and one or more of the polyvalent carboxylic acids having 2 to 20 carbon atoms or their ester-forming derivatives exemplified as the raw materials of the above-mentioned condensed polyester polyols. Examples thereof include those obtained by polycondensing.
- the polycarbonate polyol is particularly preferable from the viewpoint of scratch resistance, tack-free property and chemical resistance.
- the Mn of the polymer polyol (a2) is preferably 500 or more, more preferably 500 to 5000, and particularly preferably 800 to 3000.
- the Mn of the polymer polyol (a2) in the present invention can be measured by gel permeation chromatography under the following conditions, for example.
- Equipment "Waters Alliance 2695" [manufactured by Waters] Column: "Guardcolum Super HL” (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together”
- Sample solution 0.25 wt% tetrahydrofuran solution
- Injection volume 10 ⁇ l
- Flow rate 0.6 ml / min Measurement temperature: 40 ° C
- Detector Refractive index detector
- Reference material Standard polyethylene glycol
- the weight of the polymer polyol (a2) in the polyurethane resin (U1) is preferably 50 to 90% by weight based on the weight of the polyurethane resin (U1) as a constituent component from the viewpoint of scratch resistance and tack-free property. More preferably, it is 60 to 80% by weight.
- Examples of the chain extender (a3) include water, the above-mentioned Mn or a polyol having a chemical formula of less than 500, and a Mn or a polyamine compound having a chemical formula of less than 500.
- Examples of the Mn or the polyol having a chemical formula amount of less than 500 include the same Mn or a polyol having a chemical formula amount of less than 500 constituting the condensed polyester polyol.
- Examples of the Mn or polyamine compound having a chemical formula amount of less than 500 include aliphatic polyamines having 2 to 36 carbon atoms [alkylenediamines such as ethylenediamine and hexamethylenediamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylene.
- chain extenders (a3) water, ethylene glycol, 1,4-butanediol and trimethylolpropane are preferable from the viewpoint of scratch resistance and tack-free property.
- the weight of the chain extender (a3) in the polyurethane resin (U1) is preferably 0.5 to 10 weight as a constituent component based on the weight of the polyurethane resin (U1) from the viewpoint of scratch resistance and tack-free property. %, More preferably 1 to 5% by weight.
- reaction terminator (a4) examples include monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.) and monoamines having 1 to 20 carbon atoms.
- monoalcohols having 1 to 20 carbon atoms methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.
- monoamines having 1 to 20 carbon atoms monoamines having 1 to 20 carbon atoms.
- Mono or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, and mono or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine
- reaction terminators (a4) monoethanolamine and diethanolamine are preferable from the viewpoint of scratch resistance and tack-free property.
- polyisocyanate component (B1) an aromatic polyisocyanate (b1) having 2 to 3 or more isocyanate groups and having 8 to 26 carbon atoms, an aliphatic polyisocyanate having 4 to 22 carbon atoms (b2), and carbon.
- aromatic polyisocyanate (b1) having 2 to 3 or more isocyanate groups and having 8 to 26 carbon atoms
- an aliphatic polyisocyanate having 4 to 22 carbon atoms (b2) examples thereof include an alicyclic polyisocyanate (b3) having the number 8 to 18, an aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms, and a modified product (b5) of these organic polyisocyanates.
- Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate.
- tolylene diisocyanate is abbreviated as TDI
- crude TDI 4,4'-or 2,4'-diphenylmethane diisocyanate
- MDI diphenylmethane diisocyanate
- polyarylpolyisocyanate 4,4 '-Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4 , 4', 4 "-triphenylmethane triisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.
- Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1, 6,11-Undecantryisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) ) Carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.
- ethylene diisocyanate tetramethylene diisocyanate
- hexamethylene diisocyanate hereinafter abbreviated as HDI
- dodecamethylene diisocyanate 1, 6,11-Undecantryis
- Examples of the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI) and 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated).
- IPDI isophorone diisocyanate
- hydrogenated 4,4′-dicyclohexylmethane diisocyanate
- MDI abbreviated
- cyclohexylene diisocyanate methylcyclohexylene diisocyanate
- bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate 2,5- or 2,6-norbornandiisocyanate.
- aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene. Isocyanate can be mentioned.
- modified organic polyisocyanate (b5) of (b1) to (b4) examples include urethane group, carbodiimide group, alohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone of the polyisocyanate.
- Group-containing modified products for example, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI, biuret modified HDI, isocyanurate modified HDI and isocyanurate modified IPDI] can be mentioned.
- an aromatic polyisocyanate (b1) having 8 to 26 carbon atoms is preferable from the viewpoint of scratch resistance, and an aromatic polyisocyanate (b1) having 8 to 26 carbon atoms is more preferable.
- Diisocyanates, particularly preferred are MDIs.
- the isocyanate component (B1) may be used alone or in combination of two or more.
- the weight of the isocyanate component (B1) in the polyurethane resin (U1) is preferably 10 to 50% by weight, more preferably 10 to 50% by weight, based on the weight of the polyurethane resin (U1) as a constituent component from the viewpoint of scratch resistance and tack-free property. It is preferably 20 to 40% by weight.
- the elastic recovery rate of the polyurethane resin (U1) can be set within a predetermined range.
- the Tg of the polymer polyol (a2) used in the polyurethane resin (U1) is preferably ⁇ 20 ° C. or lower, the concentration of the cross-linking point of the polyurethane resin (U1) is preferably 0.03 to 0.25 mmol / g, and the polyurethane resin (U1).
- the urethane group concentration (the total concentration of the urethane group and the urea group when the urea group is present) is preferably 1.5 to 2.5 mmol / g.
- the concentration (unit: mmol / g) of the cross-linking point of the polyurethane resin (U1) in the present invention is trifunctional, where F is the number of functional groups of the trifunctional or higher functional monomer used in the polyurethane resin (U1).
- F the number of functional groups of the trifunctional or higher functional monomer used in the polyurethane resin (U1).
- the method for producing the polyurethane resin (U1) in the present invention is not particularly limited, and a urethane prepolymer is produced in advance using an active hydrogen component (A1), an isocyanate component (B1) and, if necessary, an organic solvent to obtain a urethane prepolymer.
- active hydrogen component (A1) an isocyanate component (B1)
- organic solvent a urethane prepolymer.
- Examples thereof include a method of reacting with a chain extender, a method of collectively charging an active hydrogen component (A1), an isocyanate component (B1) and, if necessary, an organic solvent in a batch type reaction vessel, and heating to react.
- the method for producing the urethane prepolymer is not particularly limited, but for example, a method in which an active hydrogen component (A1) and an isocyanate component (B1) are mixed in a kneader under no solvent and heated to react, or in a batch type reaction tank equipped with a stirrer. Examples thereof include a method in which an active hydrogen component (A1) and an isocyanate component (B1) are mixed in the presence or absence of an organic solvent and heated for reaction.
- an organic solvent can be used in any of the production steps.
- the organic solvent is not particularly limited, and a ketone solvent having 3 to 10 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and an ester solvent having 2 to 10 carbon atoms (ethyl acetate, butyl acetate, ⁇ -butyrolactone, etc.) , Ether solvent with 4 to 10 carbon atoms (dioxane, tetrahydrofuran, ethyl cellosolve, diethylene glycol dimethyl ether, etc.), amide solvent with 3 to 10 carbon atoms (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl, etc.) -2-Pyrrolidone and N-methylcaprolactam, etc.), sulfoxide-based solvent with 2 to 10 carbon atoms (dimethyl
- methyl ethyl ketone and toluene are preferable from the viewpoint of solubility.
- the amount used is preferably such that the concentration of the polyurethane resin (U1) is 10 to 70% by weight, and more preferably 15 to 50% by weight.
- a catalyst can be contained if necessary to promote the reaction.
- the catalyst include organic metal compounds (dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate, bismuth alkoxide, chelate compounds of bismuth with compounds having a dicarbonyl group, etc.), inorganic metal compounds (bismuth oxide, hydroxylation). Bismuth, bismuth halide, etc.); Amines (triethylamine, triethylenediamine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc.) and a combination of two or more thereof can be mentioned.
- the surface layer contains polyurethane resin (U1) as an essential component, but if necessary, additives such as antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, adsorbents, fillers, mold release agents and flame retardants ( D) can be contained.
- additives such as antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, adsorbents, fillers, mold release agents and flame retardants ( D) can be contained.
- Antioxidants include hindered phenol compounds [pentaerystyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t). -Butyl-4-hydroxyphenyl) propionate, etc.], phosphorus compound [tris (2,4-di-t-butylphenyl) phosphite, etc.], sulfur compound [pentaerystyl-tetrakis (3-laurylthiopropionate), etc.] , Dilauryl-3,3'-thiodipropionate, etc.] and the like.
- ultraviolet absorber examples include benzotriazole compounds [2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc.]. Be done.
- Examples of the light stabilizer include hindered amine compounds [(bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc.].
- plasticizer examples include phthalic acid esters (dibutyl phthalate, dioctyl phthalate, dibutyl benzyl phthalate, diisodecyl phthalate, etc.); aliphatic dibasic acid esters (di-2-ethylhexyl adipate, -2-ethylhexyl sebacate, etc.) ); Trimeritic acid ester (tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.); Fatty acid ester (butyl oleate, etc.); aliphatic phosphate ester (trimethylphosphate, triethyl phosphate, tributylphosphate, tri- 2-Ethylhexyl phosphate and tributoxyphosphate, etc.); Aromatic phosphates [triphenylphosphate, tricresyl phosphate, trixylenyl phosphate, cresil
- adsorbent examples include alumina, silica gel, and molecular sieve.
- Fillers include kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fiber, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate. , Alumina, magnesia, wollastonite, zonotrite, whisker, metal powder and the like.
- a known release agent or the like can be used as the release agent, and a fluorine compound type release agent [triperfluoroalkyl phosphate (8 to 20 carbon atoms) ester (triperfluorooctyl phosphate, triperfluorododecyl phosphate, etc.) ]; Silicone compound type release agent (dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethylpolysiloxane, etc.); Stearic acid ester type release agent [mono or polyvalent alcohol ester of fatty acid having 10 to 24 carbon atoms (butyl) Stearate, hardened castor oil, ethylene glycol monostearate, etc.)]; Aliase acid amide type release agent [mono or bisamide of fatty acid having 8 to 24 carbon atoms (oleic acid amide, palmitate amide, stearic acid amide and ethylenediamine) Etc.), etc.]
- Examples of the flame retardant include halogen-containing flame retardants, phosphorus-containing flame retardants, antimony-containing flame retardants, and metal hydroxide-containing flame retardants.
- the elastic recovery rate of the polyurethane resin (U1) used for the surface layer which is measured by the method described later, is 50 to 100%, more preferably 60 to 100%. If the elastic recovery rate of the polyurethane resin (U1) is less than 50%, the scratch resistance and the bending resistance are inferior. With such a configuration, the polyurethane resin (U1) can be adjusted to a predetermined elastic recovery rate, and scratch resistance and bending resistance can be imparted.
- the base layer contains a polyurethane resin (U2) composed of an active hydrogen component (A2) and an isocyanate component (B2), and the active hydrogen component (A2) is a compound having a polyorganosiloxane group and an active hydrogen group. It is an active hydrogen component that does not contain (a1) but contains a high molecular weight polyol (a2) as an essential component, and the elastic recovery rate of the polyurethane resin (U2) at 100% elongation is 80 to 100%.
- the active hydrogen component (A2) in the polyurethane resin (U2) does not contain the compound (a1) having a polyorganosiloxane group and an active hydrogen group, but contains a polymer polyol (a2) as an essential component. Since the polyurethane resin (U2) does not contain the compound (a1) having an active hydrogen group, it has excellent transparency, and by containing the polymer polyol (a2) as an essential component, the elastic recovery rate can be adjusted to a predetermined value. It is possible to impart scratch resistance and bending resistance.
- the compound (a1) having a polyorganosiloxane group and an active hydrogen group and the polymer polyol (a2) are the compounds (a1) having a polyorganosiloxane group and an active hydrogen group described in the polyurethane resin (U1). It means a molecular polyol (a2).
- the polymer polyol (a2) preferably contains a polyether polyol (a22), preferably polytetramethylene glycol, from the viewpoint of adjusting the elastic recovery rate within a predetermined range and preferably imparting scratch resistance and bending resistance.
- a polyether polyol (a22) preferably polytetramethylene glycol
- Poly (oxy-3-methyltetramethylene) glycol and tetrahydrofuran / 3-methyltetrahydrofuran copolymer diol are more preferable, and polytetramethylene glycol is particularly preferable.
- the Mn of the polymer polyol (a2) is preferably 500 or more, more preferably 500 to 5000, and particularly preferably 800 to 4000.
- the weight of the polymer polyol (a2) in the polyurethane resin (U2) is preferably 60 to 90% by weight based on the weight of the polyurethane resin (U2) as a constituent component from the viewpoint of scratch resistance and bending resistance. More preferably, it is 70 to 85% by weight.
- the active hydrogen component (A2) may contain a chain extender and a reaction terminator as optional components.
- the chain extender the chain extender (a3) described in the polyurethane resin (U1) can be appropriately selected and used.
- the reaction terminator the reaction terminator (a4) described in the polyurethane resin (U1) can be appropriately selected and used.
- the weight of the chain extender (a3) in the polyurethane resin (U2) is preferably 0.5 to 20 weight as a constituent component based on the weight of the polyurethane resin (U2) from the viewpoint of scratch resistance and bending resistance. %, More preferably 1-10% by weight.
- the polyisocyanate component (B2) the polyisocyanate component (B1) described in the polyurethane resin (U1) can be appropriately selected and used.
- aromatic polyisocyanate (b1) having 8 to 26 carbon atoms is preferable from the viewpoint of scratch resistance, aromatic diisocyanate having 8 to 26 carbon atoms is more preferable, and MDI is particularly preferable.
- the weight of the polyisocyanate component (B2) in the polyurethane resin (U2) is preferably 5 to 40% by weight based on the weight of the polyurethane resin (U2) as a constituent component from the viewpoint of scratch resistance and bending resistance. More preferably, it is 10 to 30% by weight.
- the elastic recovery rate of the polyurethane resin (U2) can be set within a predetermined range.
- the Tg of the polymer polyol (a2) used in the polyurethane resin (U2) is preferably ⁇ 20 ° C. or lower
- the concentration of the cross-linking point of the polyurethane resin (U2) is preferably 0.05 to 0.25 mmol / g
- the polyurethane resin (U2) is preferably 0.05 to 0.25 mmol / g
- the urethane group concentration (the total concentration of the urethane group and the urea group when the urea group is present) is preferably 1.0 to 2.0 mmol / g.
- the concentration (unit: mmol / g) of the cross-linking point of the polyurethane resin (U2) in the present invention is trifunctional, where F is the number of functional groups of the trifunctional or higher functional monomer used in the polyurethane resin (U2).
- F is the number of functional groups of the trifunctional or higher functional monomer used in the polyurethane resin (U2).
- the method for producing the polyurethane resin (U2) in the present invention is not particularly limited, and the same method as the method for producing the polyurethane resin (U1) is used except that it contains an active hydrogen component (A2) and an isocyanate component (B2). Can be done.
- the catalyst used in the method for producing the polyurethane resin (U1) can be contained, if necessary, in order to promote the reaction.
- the base layer contains a polyurethane resin (U2) as an essential component, but if necessary, the above additive (D) used in the method for producing the polyurethane resin (U1) can be contained.
- the elastic recovery rate at 100% elongation is 80 to 80 to Must be 100%.
- the elastic recovery rate of the polyurethane resin (U2) is preferably 85 to 100%, more preferably 90 to 100%, and particularly preferably 95 to 100%. If the elastic recovery rate at 100% elongation is less than 80%, scratch resistance and flexibility are not sufficiently imparted.
- the elastic recovery rate at 100% elongation in the present invention is measured by the following method.
- ⁇ Measurement method of elastic recovery rate at 100% elongation> (1) A strip-shaped test piece having a length of 100 mm and a width of 5 mm is cut out from a sheet having a film thickness of about 2 mm and marked so that the distance between the marked lines is 50 mm. (2) Set this test piece on the chuck of an Instron type tensile tester (Autograph manufactured by Shimadzu Corporation), and set the distance between the marked lines to 100% at a constant speed of 500 mm / min in an atmosphere of 25 ° C. Immediately after stretching until it becomes, the operation of returning to the distance between the chucks before stretching is performed at the same speed.
- the multilayer film of the present invention has a base layer and a surface layer formed on the base layer.
- the film thickness of the surface layer is preferably 1 to 50 ⁇ m, more preferably 5 to 25, from the viewpoint of scratch resistance and tack suppression.
- the film thickness of the base layer is preferably 100 to 1,000 ⁇ m, more preferably 300 to 600 ⁇ m, from the viewpoint of scratch resistance and bending resistance.
- the multilayer film of the present invention is preferably used as a surface protective film for optical members.
- An adhesive layer can be provided on the base layer side, if necessary, in order to impart adhesiveness to the optical member.
- As the adhesive layer a known one can be appropriately selected and used.
- the method for producing the multilayer film of the present invention is not particularly limited, and for example, it can be produced by the following method.
- a compound (a1) having a polyorganosiloxane group and an active hydrogen group, a polymer polyol (a2), and an isocyanate component (B1) are required as an organic solvent.
- a urethane prepolymer for a polyurethane resin (U1) having an isocyanate group at the terminal is produced by reacting in the process.
- Base layer forming step A urethane prepolymer for polyurethane resin (U2) or an organic solvent solution thereof is mixed with a chain extender (a3) to obtain a predetermined film thickness on the surface layer obtained in (3). It is coated and heat-cured to form a base layer. When an organic solvent is used, it is cured and dried.
- a multi-layer film having a surface layer and a base layer is formed on the release film.
- the temperature of the urethane prepolymerization reaction in the above steps (1) and (2) is not particularly limited, but is preferably 50 to 140 ° C, more preferably 70 to 100 ° C, and the reaction time is not particularly limited. However, it is preferably 1 to 10 hours, more preferably 2 to 8 hours.
- the drying temperature in the step (3) is not particularly limited, but is preferably 30 to 80 ° C., more preferably 40 to 60 ° C., and the drying time is not particularly limited, but is preferably 10 seconds to 5 minutes, more preferably. Is 20 to 60 seconds.
- the curing temperature in the step (4) is not particularly limited, but is preferably 60 to 150 ° C., more preferably 80 to 120 ° C., and the curing time is not particularly limited, but is preferably 1 to 8 hours, more preferably 1 to 8 hours. 2 to 6 hours.
- the drying of the organic solvent in the step (4) described above, which is performed as needed, is performed together with the curing.
- the part represents the weight part.
- urethane prepolymer for polyurethane resin (U1-1) used for surface layer A compound (a1) having a polyorganosiloxane group and active hydrogen of the type and amount (parts by weight) shown in Table 1 in a container equipped with a stirrer and a temperature control device, a polymer polyol (a2), and an aromatic polyisocyanate (b1). , A modified product of organic polyisocyanate (b5) and an organic solvent were charged and reacted at 80 ° C. for 3 hours to obtain a urethane prepolymer for polyurethane resin (U1-1). The NCO content of the obtained urethane prepolymer was 1.46%.
- Table 2 shows the concentration of the cross-linking point and the urethane group concentration of the polyurethane resin (U2-1). Using this sheet, the elastic recovery rate was measured based on the above-mentioned method for measuring the elastic recovery rate at 100% elongation. The results are shown in Table 2.
- Table 2 shows the concentrations of the cross-linking points and the urethane group concentrations of the polyurethane resins (U2-2) to (U2-8) and the comparative polyurethane resins (U2'-1) to (U2'-2). Using these sheets, the elastic recovery rate was measured based on the above-mentioned method for measuring the elastic recovery rate at 100% elongation. The results are shown in Table 2.
- Example 1 [Manufacturing of multi-layer film] 496.1 parts of urethane prepolymer for surface polyurethane resin (U1-1) obtained in Production Example 1 (total amount of urethane prepolymer materials shown in Table 1) and the corresponding urethane shown in Table 1. 7.6 parts of 1,4-butanediol and 496.3 parts of methyl ethyl ketone as a material for the chain extension reaction of the prepolymer are mixed and coated on a release film so that the thickness after drying is 10 ⁇ m. It was dried in a circulating air dryer at 50 ° C. for 30 seconds to volatilize the solvent to prepare a surface polyurethane resin.
- the urethane prepolymer for polyurethane resin (U2-1) and the chain extender (a3) obtained in Production Example 7 are blended according to the formulation shown in Table 2, and the film thickness is 400 ⁇ m on the surface polyurethane resin. After curing at 120 ° C. for 2 hours, the release film was peeled off to obtain a multi-layer film in which the surface layer was a polyurethane resin (U1-1) and the base layer was a polyurethane resin (U2-1).
- Examples 2 to 19 and Comparative Examples 1 to 4 The multilayer films of Examples 2 to 19 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the polyurethane resin for the surface layer and the polyurethane resin for the base layer were changed to the combinations shown in Table 3. ..
- ⁇ Comparative example 5> A urethane prepolymer for a surface layer polyurethane resin (U1-1) obtained in the same manner as in Example 1 was used as a 400 ⁇ m-thick polyurethane resin (U2'-3) obtained in the same manner as in Comparative Test Example 5. The sheet was coated so that the film thickness after drying was 10 ⁇ m, dried in a circulation dryer at 50 ° C. for 30 seconds, and further cured at 120 ° C. for 2 hours to obtain the multilayer film of Comparative Example 5. Obtained.
- Table 3 shows the results of evaluating the scratch resistance of the obtained multi-layer film by the following evaluation method.
- the polyurethane resin of the present invention has excellent scratch resistance and also excellent bending resistance, it is suitable for a surface protective film for optical members, particularly a surface protective film for touch-type devices.
Abstract
Description
そこで自己修復性を有する材料が検討されており、例えばポリアミド、ポリカーボネート及びポリイミド等の透明基材にポリエステル系ウレタン樹脂を積層したフィルムが提案されている(例えば、特許文献1参照)。
しかしながら、特許文献1記載の複層フィルムを含めて従来の技術では傷の回復時間が長く、微細な傷が付きやすい条件下での耐擦傷性が十分ではないと言う問題がある。また、従来の技術では、耐屈曲性が十分ではないという問題もある。
即ち本発明は、基層と上記基層上に形成された表層とを有する複層フィルムであって、上記表層がポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を必須成分として含有する活性水素成分(A1)とイソシアネート成分(B1)とからなるポリウレタン樹脂(U1)を含有し、上記ポリウレタン樹脂(U1)の100%伸長時の弾性回復率が50~100%であり、上記基層が、活性水素成分(A2)とイソシアネート成分(B2)からなるポリウレタン樹脂(U2)を含有し、上記活性水素成分(A2)が、ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を含有せず、高分子ポリオール(a2)を必須成分として含有する活性水素成分であり、上記ポリウレタン樹脂(U2)の100%伸長時の弾性回復率が80~100%である複層フィルムである。
そして、上記表層がポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を必須成分として含有する活性水素成分(A1)とイソシアネート成分(B1)とからなるポリウレタン樹脂(U1)を含有し、上記ポリウレタン樹脂(U1)の100%伸長時の弾性回復率が50~100%であり、上記基層が、活性水素成分(A2)とイソシアネート成分(B2)とからなるポリウレタン樹脂(U2)を含有し、上記活性水素成分(A2)がポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を含有せず、高分子ポリオール(a2)を必須成分として含有する活性水素成分であり、上記ポリウレタン樹脂(U2)の100%伸長時の弾性回復率が80~100%である複層フィルムである。
また、上記基層が、活性水素成分(A2)とイソシアネート成分(B2)からなるポリウレタン樹脂(U2)を含有し、上記活性水素成分(A2)が上記ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を含有せず、高分子ポリオール(a2)を必須成分として含有する活性水素成分であり、上記ポリウレタン樹脂(U2)の100%伸長時の弾性回復率が80~100%であることにより、耐擦傷性及び耐屈曲性に優れるフィルムとすることができる。
また、一般的に本発明における基層に用いるポリウレタン樹脂(U2)等は耐擦傷性及び耐屈曲性に優れるが、表面にタックを生じることが多く、本発明においては表層を設けることにより、複層フィルムの表面のタックの発生を抑えることが可能となる。
表層の主要構成成分であるポリウレタン樹脂(U1)は、ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を必須成分として含有する活性水素成分(A1)とイソシアネート成分(B1)とを反応させて得られるポリウレタン樹脂である。
(a1)は、一般的にポリウレタン樹脂(U1)の他の構成単量体と相溶性が低いため、ポリウレタン樹脂(U1)に均質に(a1)を導入して(U1)のヘイズの上昇を抑制する観点から、活性水素基として水酸基及びアミノ基を有する(a1)を用いることが好ましい。(a1)は1種を単独で用いても2種以上を併用してもよい。
装置:「Waters Alliance 2695」[Waters社製]
カラム:「Guardcolumn Super H-L」(1本)、「TSKgel SuperH2000、TSKgel SuperH3000、TSKgel SuperH4000(いずれも東ソー株式会社製)を各1本連結したもの」
試料溶液:0.25重量%のテトラヒドロフラン溶液
溶液注入量:10μl
流量:0.6ml/分
測定温度:40℃
検出装置:屈折率検出器
基準物質:標準ポリエチレングリコール
イソシアネート成分(B1)は、1種を単独で用いても2種以上を併用してもよい。
ポリウレタン樹脂(U1)に用いる高分子ポリオール(a2)のTgは-20℃以下が好ましく、ポリウレタン樹脂(U1)の架橋点の濃度は0.03~0.25mmol/gが好ましく、ポリウレタン樹脂(U1)中のウレタン基濃度(ウレア基が存在する場合はウレタン基とウレア基の合計濃度)は1.5~2.5mmol/gが好ましい。
尚、本発明におけるポリウレタン樹脂(U1)の架橋点の濃度(単位:mmol/g)は、ポリウレタン樹脂(U1)に用いる3官能以上の構成単量体の官能基数をFとした場合、3官能以上の構成単量体それぞれについて、(F-2)×{3官能以上の構成単量体のポリウレタン樹脂(U2)1g中のミリモル数}を計算してその総和をとることにより算出された値である。
ウレタンプレポリマーの製造方法は特に限定されないが、例えば無溶剤下、ニーダー中で活性水素成分(A1)及びイソシアネート成分(B1)を混合し、加熱して反応させる方法や攪拌機付きバッチ式反応槽中で有機溶剤の存在下又は非存在下に、活性水素成分(A1)及びイソシアネート成分(B1)を混合し、加熱して反応させる方法が挙げられる。
ポリウレタン樹脂(U1)では、このような構成とすることにより、所定の弾性回復率に調整することができ、耐擦傷性及び耐屈曲性を付与することができる。
本発明において、基層は、活性水素成分(A2)とイソシアネート成分(B2)とからなるポリウレタン樹脂(U2)を含有し、上記活性水素成分(A2)がポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を含有せず、高分子ポリオール(a2)を必須成分として含有する活性水素成分であり、ポリウレタン樹脂(U2)の100%伸長時の弾性回復率が80~100%である。
ポリウレタン樹脂(U2)では、活性水素基を有する化合物(a1)を含有しないので透明性に優れ、高分子ポリオール(a2)を必須成分として含有することにより、所定の弾性回復率に調整することができ、耐擦傷性及び耐屈曲性を付与することができる。
なお、上記ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)、高分子ポリオール(a2)は、ポリウレタン樹脂(U1)で記載したポリオルガノシロキサン基及び活性水素基を有する化合物(a1)、高分子ポリオール(a2)を意味する。
上記鎖伸長剤としては、ポリウレタン樹脂(U1)で記載した鎖伸長剤(a3)を適宜選択して用いることができる。
また、上記反応停止剤としては、ポリウレタン樹脂(U1)で記載した反応停止剤(a4)を適宜選択して用いることができる。
なかでも、耐擦傷性の観点から好ましいのは、炭素数8~26の芳香族ポリイソシアネート(b1)、更に好ましいのは炭素数8~26の芳香族ジイソシアネート、特に好ましいのはMDIである。
ポリウレタン樹脂(U2)に用いる高分子ポリオール(a2)のTgは-20℃以下が好ましく、ポリウレタン樹脂(U2)の架橋点の濃度は0.05~0.25mmol/gが好ましく、ポリウレタン樹脂(U2)中のウレタン基濃度(ウレア基が存在する場合はウレタン基とウレア基の合計濃度)は1.0~2.0mmol/gが好ましい。
尚、本発明におけるポリウレタン樹脂(U2)の架橋点の濃度(単位:mmol/g)は、ポリウレタン樹脂(U2)に用いる3官能以上の構成単量体の官能基数をFとした場合、3官能以上の構成単量体それぞれについて、(F-2)×{3官能以上の構成単量体のポリウレタン樹脂(U2)1g中のミリモル数}を計算してその総和をとることにより算出された値である。
<100%伸長時の弾性回復率の測定方法>
(1)膜厚が約2mmのシートから、縦100mm×横5mmの短冊状の試験片を切り出して標線間距離が50mmとなるように標線を付ける。
(2)この試験片をインストロン型引張り試験機(島津製作所社製オートグラフ)のチャックにセットして、25℃の雰囲気下、500mm/分の一定速度で標線間の距離が100%になるまで伸長後、直ちに同じ速度で伸長前のチャック間の距離まで戻す操作を行う。
(3)この操作時の伸長過程における50%伸長時の応力(M1)と戻り過程における50%伸長時の応力(M2)を測定し、次式から弾性回復率を求める。
弾性回復率(%)=M2/M1×100
本発明の複層フィルムは、基層と基層上に形成された表層とを有する。
表層の膜厚は、耐擦傷性及びタック抑制の観点から、好ましくは1~50μm、更に好ましくは5~25である。
基層の膜厚は、耐擦傷性及び耐屈曲性の観点から、好ましくは100~1,000μm、更に好ましくは300~600μmである。
(1)表層に用いるポリウレタン樹脂(U1)用ウレタンプレポリマーの製造工程
ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)と高分子ポリオール(a2)とイソシアネート成分(B1)を必要により有機溶剤中で反応させて末端にイソシアネート基を有するポリウレタン樹脂(U1)用ウレタンプレポリマーを製造する。
(2)基層に用いるポリウレタン樹脂(U2)用ウレタンプレポリマーの製造工程
高分子ポリオール(a2)とイソシアネート成分(B2)を必要により有機溶剤中で反応させて末端にイソシアネート基を有するポリウレタン樹脂(U2)用ウレタンプレポリマーを製造する。
(3)表層の形成工程
ポリウレタン樹脂(U1)用ウレタンプレポリマー又はその有機溶剤溶液と、必要に応じて高分子ポリオール(a2)及び/又は鎖伸長剤(a3)とを混合して、離型フィルム上に所定の膜厚となる様に塗工する。尚、有機溶剤を用いた場合は有機溶剤の乾燥を行う。
(4)基層の形成工程
ポリウレタン樹脂(U2)用ウレタンプレポリマー又はその有機溶剤溶液と、鎖伸長剤(a3)とを混合して、(3)で得られた表層上に所定の膜厚に塗工して加熱硬化させて基層を形成させる。尚、有機溶剤を用いた場合は硬化と共に乾燥を行う。
上記(1)~(4)の工程により、離型フィルム上に表層と基層を有する複層フィルムが形成される。
上記(4)の工程における硬化温度は特に限定されないが、好ましくは60~150℃、更に好ましくは80~120℃であり、硬化時間は特に限定されないが、好ましくは1~8時間、更に好ましくは2~6時間である。尚、必要に応じて行われる上記(4)の工程での有機溶剤の乾燥は上記硬化と共に行われる。
撹拌装置及び温度制御装置付きの容器に表1に示す種類及び量(重量部)のポリオルガノシロキサン基と活性水素を有する化合物(a1)、高分子ポリオール(a2)、芳香族ポリイソシアネート(b1)、有機ポリイソシアネートの変性物(b5)及び有機溶剤を仕込み、80℃で3時間反応させてポリウレタン樹脂(U1-1)用ウレタンプレポリマーを得た。得られたウレタンプレポリマーのNCO含量は1.46%であった。
使用原料とその使用量(重量部)を表1に記載のものに変更すること以外は製造例1と同様にして、表層に用いるポリウレタン樹脂(U1-2)~(U1-6)用ウレタンプレポリマー及び比較用のポリウレタン樹脂(U1’-1)~(U1’-2)用ウレタンプレポリマーを得た。
ポリプロピレン製のビーカーに製造例1で得られた(U1-1)用ウレタンプレポリマーと鎖伸長剤(a3)を表1に記載の処方にて配合した。得られた配合液を11×17.5cmのポリプロピレン製のトレイに、乾燥後の厚さが200μmとなるように流し込み、室温で一晩乾燥した。乾燥後、120℃で2時間硬化して表層に用いるポリウレタン樹脂(U1-1)のシートを得た。
このシートを用いて上述の100%伸長時の弾性回復率の測定方法に基づいて弾性回復率を測定した。その結果を表1に示す。
使用するウレタンプレポリマー及び鎖伸長剤(a3)とその使用量(重量部)を表1に記載のものに変更すること以外は試験例1と同様にして、表層に用いるポリウレタン樹脂(U1-2)~(U1-6)及び比較用のポリウレタン樹脂(U1’-1)~(U1’-2)のシートを得た。
このシートを用いて上述の100%伸長時の弾性回復率の測定方法に基づいて弾性回復率を測定した。その結果を表1に示す。
<ポリウレタン樹脂用ウレタンプレポリマーの材料>
[ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)]
・X-22-161A:信越化学株式会社製アミノ基変性シリコーンオイル[Mn=1600、一般式(1)におけるR1~R6=メチル基、n=22]
・KF-6003:信越化学株式会社製水酸基変性シリコーンオイル[Mn=5100、一般式(1)におけるR1~R6=メチル基、n=68]
[高分子ポリオール(a2)]
・クラレポリオールC1090:クラレ株式会社製ポリカーボネートポリオール(Mn:1000)
[芳香族ポリイソシアネート(b1)]
・4,4’-MDI:東ソー株式会社製「ミリオネートMT」
[有機ポリイソシアネートの変性物(b5)]
・コロネート2793:東ソー株式会社製アロファネート基含有ポリイソシアネート(平均官能基数=5.1)
[有機溶剤]
・トルエン
<ウレタンプレポリマーの鎖伸長反応用材料>
[鎖伸長剤(a3)]
・1,4-ブタンジオール
・トリメチロールプロパン
[有機溶剤]
・メチルエチルケトン
また、表1の「ウレタンプレポリマーの鎖伸長反応用材料」の欄には後述の実施例で使用する各プレポリマーを鎖伸長する際に用いる材料とその使用量を記載した。
撹拌装置及び温度制御装置付きの容器に表2に示す種類及び量(重量部)の高分子ポリオール(a2)、芳香族ポリイソシアネート(b1)を仕込み、80℃で3時間反応させてポリウレタン樹脂(U2-1)用ウレタンプレポリマーを得た。得られたウレタンプレポリマーのNCO含量は3.36%であった。
使用するウレタンプレポリマー及びとその使用量(重量部)を表2に記載のものに変更すること以外は製造例7と同様にして、表層に用いるポリウレタン樹脂(U2-2)~(U2-8)用ウレタンプレポリマー及び比較用のポリウレタン樹脂(U2’-1)~(U2’-2)用ウレタンプレポリマーを得た。
<ポリウレタン樹脂用ウレタンプレポリマーの材料>
[高分子ポリオール(a2)]
・PTMG-1000:三菱ケミカル株式会社製ポリテトラメチレングリコール(Mn=1000)
・PTMG-2000:三菱ケミカル株式会社製ポリテトラメチレングリコール(Mn=2000)
・PTMG-3000:三菱ケミカル株式会社製ポリテトラメチレングリコール(Mn=3000)
・プラクセル220:株式会社ダイセル製ポリカプロラクトンジオール(Mn=2000)
[Mn500未満のポリオール]
・サンニックスPP-400:三洋化成工業株式会社製ポリプロピレングリコール(Mn=400)
[芳香族ポリイソシアネート(b1)]
・4,4’-MDI:東ソー株式会社製「ミリオネートMT」
<ウレタンプレポリマーの鎖伸長反応用材料>
[鎖伸長剤(a3)]
・1,4-ブタンジオール
・トリメチロールプロパン
また、表2の「ウレタンプレポリマーの鎖伸長反応用材料」の欄には後述の試験例及び実施例で使用する各プレポリマーを鎖伸長する際に用いる材料とその使用量を記載した。
ポリプロピレン製のビーカーに予め80℃に温調しておいた製造例7で得られたポリウレタン樹脂(U2)用ウレタンプレポリマーと鎖伸長剤(a3)を表2に記載の処方にて配合し、アジターで1分間撹拌混合した後、減圧下で2分間脱泡を行った。得られた混合物を隙間が2mmのSUS製の金型に注型し、120℃で2時間硬化して基層に用いるポリウレタン樹脂(U2-1)のシートを得た。
ポリウレタン樹脂(U2-1)の架橋点の濃度及びウレタン基濃度を表2に示す。
このシートを用いて上述の100%伸長時の弾性回復率の測定方法に基づいて弾性回復率を測定した。その結果を表2に示す。
使用するウレタンプレポリマー及び鎖伸長剤(a3)とその使用量(重量部)を表2に記載のものに変更すること以外は試験例7と同様にして、基層に用いるポリウレタン樹脂(U2-2)~(U2-8)及び比較用のポリウレタン樹脂(U2’-1)~(U2’-2)のシートを得た。
ポリウレタン樹脂(U2-2)~(U2-8)及び比較用のポリウレタン樹脂(U2’-1)~(U2’-2)の架橋点の濃度及びウレタン基濃度を表2に示す。
これらのシートを用いて上述の100%伸長時の弾性回復率の測定方法に基づいて弾性回復率を測定した。その結果を表2に示す。
トルエン350部を仕込んだ撹拌装置及び温度制御装置付きの容器に、撹拌下で、ポリエーテル系熱可塑性ウレタンエラストマー「エラストラン1180A」(BASFジャパン株式会社製)150部を仕込み、80℃に昇温して溶解させた。得られた配合液を11×17.5cmのポリプロピレン製のトレイに、乾燥後の厚さが400μmとなるように流し込み、室温で一晩乾燥した。さらに100℃の減圧乾燥機で2時間乾燥して基層に用いる比較用のポリウレタン樹脂(U2’-3)のシートを得た。
このシートを用いて上述の100%伸長時の弾性回復率の測定方法に基づいて弾性回復率を測定した。その結果を表2に示す。
製造例1で得られた表層用のポリウレタン樹脂(U1-1)用のウレタンプレポリマー496.1部(表1に記載のウレタンプレポリマー材料の合計量)と、対応する表1に記載のウレタンプレポリマーの鎖伸長反応用材料としての1,4-ブタンジオール7.6部及びメチルエチルケトン496.3部を混合して離型フィルム上に乾燥後の膜厚が10μmになるように塗工し、50℃の循風乾燥機で30秒乾燥し、溶剤を揮発させて表層用ポリウレタン樹脂を作製した。
製造例7で得られたポリウレタン樹脂(U2-1)用ウレタンプレポリマーと鎖伸長剤(a3)を表2に記載の処方にて配合し、表層用ポリウレタン樹脂の上に膜厚が400μmとなるように塗工し、120℃で2時間硬化後に、離型フィルムを剥離して表層がポリウレタン樹脂(U1-1)で基層がポリウレタン樹脂(U2-1)である複層フィルムを得た。
表層用のポリウレタン樹脂と基層用のポリウレタン樹脂を表3に記載の組み合わせに変更したこと以外は実施例1と同様にして、実施例2~19及び比較例1~4の複層フィルムを得た。
実施例1と同様にして得られた表層用のポリウレタン樹脂(U1-1)用のウレタンプレポリマーを、比較試験例5と同様にして得られた厚さ400μmのポリウレタン樹脂(U2’-3)のシート上に、乾燥後の膜厚が10μmになるように塗工し、50℃の循風乾燥機で30秒乾燥し、さらに120℃で2時間硬化させて比較例5の複層フィルムを得た。
新東科学株式会社製「トライボギア TYPE:40」のスチールウール固定治具に日本スチールウール社製のスチールウール(No.0000)を取り付け、1cm2あたり100gの荷重をかけて、実施例及び比較例で得られた複層フィルムの表層側を5cmの長さを繰り返し摩擦した際に、何往復で傷が発生したかを観察して、下記基準に基づいて評価した。その結果を表3に示した。
<評価基準>
◎:500往復以上で傷が発生しない。
○:300往復以上500往復未満で傷が発生した。
×:300往復未満で傷が発生した。
実施例及び比較例で得られた複層フィルムについて、幅方向(折りたたみ部の方向)50mm×流れ方向(屈曲方向)100mmの大きさのサンプルを用意する。無負荷U字伸縮試験機(ユアサシステム機器社製、DLDMLH-FS)を用いて、屈曲半径3mmを設定し、1回/秒の速度で、5万回屈曲させた。その際、サンプルは長辺側両端部10mmの位置を固定して、屈曲する部位は50mm×80mmとした。屈曲処理終了後、サンプルの屈曲内側を下にして平面に置き、目視検査を行った。
<評価基準>
◎:サンプルの変形がないか又は変形があっても、水平に置いた際、浮き上がり最大高さが3mm未満。
○:サンプルの変形があり、水平に置いた際、浮き上がり最大高さが3mm以上5mm未満。
×:サンプルに折跡があるか、水平に置いた際、浮き上がり最大高さが5mm以上。
Claims (7)
- 基層と前記基層上に形成された表層とを有する複層フィルムであって、
前記表層が、ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を必須成分として含有する活性水素成分(A1)とイソシアネート成分(B1)とからなるポリウレタン樹脂(U1)を含有し、前記ポリウレタン樹脂(U1)の100%伸長時の弾性回復率が50~100%であり、
前記基層が、活性水素成分(A2)とイソシアネート成分(B2)とからなるポリウレタン樹脂(U2)を含有し、前記活性水素成分(A2)が、前記ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)を含有せず、高分子ポリオール(a2)を必須成分として含有する活性水素成分であり、前記ポリウレタン樹脂(U2)の100%伸長時の弾性回復率が80~100%である複層フィルム。 - 前記ポリオルガノシロキサン基及び活性水素基を有する化合物(a1)の重量が、構成成分として、前記ポリウレタン樹脂(U1)の重量を基準として、0.5~5重量%である請求項1又は2記載の複層フィルム。
- 前記高分子ポリオール(a2)が、ポリテトラメチレングリコールを含む高分子ポリオールである請求項1~3のいずれか記載の複層フィルム。
- 前記ポリウレタン樹脂(U2)の架橋点の濃度が、0.05~0.25mmol/gであり、前記ポリウレタン樹脂(U2)のウレタン基濃度(ウレア基が存在する場合はウレタン基とウレア基の合計濃度)が、1.0~2.0mmol/gである請求項1~4のいずれか記載の複層フィルム。
- 前記表層の膜厚が1~50μmであり、前記基層の膜厚が100~1,000μmである請求項1~5のいずれか記載の複層フィルム。
- 光学部材の表面保護フィルム用である請求項1~6のいずれか記載の複層フィルム。
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