WO2018021350A1 - Composition pour former un film protecteur facilement enlevé par pelage - Google Patents

Composition pour former un film protecteur facilement enlevé par pelage Download PDF

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Publication number
WO2018021350A1
WO2018021350A1 PCT/JP2017/026929 JP2017026929W WO2018021350A1 WO 2018021350 A1 WO2018021350 A1 WO 2018021350A1 JP 2017026929 W JP2017026929 W JP 2017026929W WO 2018021350 A1 WO2018021350 A1 WO 2018021350A1
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meth
acrylate
composition
protective film
monofunctional
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PCT/JP2017/026929
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English (en)
Japanese (ja)
Inventor
佐藤　哲夫
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日産化学工業株式会社
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Priority to CN201780043906.3A priority Critical patent/CN109476950A/zh
Priority to JP2018530311A priority patent/JPWO2018021350A1/ja
Publication of WO2018021350A1 publication Critical patent/WO2018021350A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a composition for forming an easily peelable protective film, an easily peelable protective film, and a method for protecting the surface of an object to be coated.
  • a paint that can be applied to the surface of the article to form a film and can be peeled off without damaging the article when the required period has passed is generally In particular, it is called strippable paint.
  • paints in which synthetic rubber or chlorinated rubber is dissolved in an organic solvent paints in which a vinyl chloride-vinyl acetate copolymer is mixed with a plasticizer and dissolved in an organic solvent are mainly known. Yes.
  • this type of solvent-containing paint requires a long time for drying after application (5 to 10 minutes by heat drying). Further, when this paint is applied to an article made of synthetic resin, the surface of the article may swell or dissolve with an organic solvent. Furthermore, an acrylic emulsion or the like in which an acrylic resin is dispersed in water is also used as a strippable paint, but this paint also requires a long time for drying after application (see, for example, Patent Documents 1 and 2).
  • JP 2014-105314 A JP 2000-226539 A Japanese Patent Laid-Open No. 04-041190 JP 2005-15594 A Japanese Patent Laid-Open No. 05-301935
  • the present inventors have paid attention to a radical curable resin composition and have repeatedly studied to develop a new strippable paint.
  • a composition suitable as a strippable paint It came to the knowledge that it could become a resin thin film.
  • the coating film is cured by short-time light irradiation and / or heating (forms a cured film).
  • the cured film adheres well to the surface of various articles such as glass and resin.
  • the surface tack of the cured film is low.
  • the cured film has toughness and can be easily peeled without tearing during peeling.
  • the cured film can be easily peeled from the surface of various articles such as glass and resin.
  • An object of the present invention is to provide a composition that provides a resin film that can be easily peeled, suitable as a strippable paint that satisfies the above conditions, and a method for protecting the surface of an object to be coated using such a resin film. That is.
  • the present inventor has at least a monofunctional (meth) acrylate having a predetermined ratio of a urethane (meth) acrylate compound having a polycaprolactone skeleton as a main skeleton (meta). It was found that a uniform composition can be easily prepared by mixing together with acrylate) or a predetermined proportion of monofunctional (meth) acrylate and polyfunctional (meth) acrylate, and a radical polymerization initiator. In addition, when the composition is used, a tough and flexible cured film in which not only excellent adhesion to glass or resin, but also surface tack is suppressed by light irradiation and / or heating for a short time. The obtained cured film was found to be easily peelable by hand from the coated body such as glass or resin. The present invention has been completed based on these findings.
  • the composition for forming an easily peelable protective film characterized in that the composition is 50% by mass or more based on the total amount of the (meth) acrylate, 2.
  • the monofunctional (meth) acrylate comprises a monofunctional (meth) acrylate having a cyclic structure, 1 or 2 composition for easily peelable protective film formation, 4).
  • the content of the urethane (meth) acrylate compound having the polycaprolactone skeleton as a main skeleton in the easily peelable protective film forming composition is less than 80% by mass, any one of 1 to 3 An easily peelable protective film forming composition, 5.
  • the content of the urethane (meth) acrylate compound having the polycaprolactone skeleton as a main skeleton in the easily peelable protective film-forming composition is 10% by mass or more, any one of 1 to 4 An easily peelable protective film forming composition, 6.
  • An easily peelable protective film comprising a cured product of the easily peelable protective film forming composition according to any one of 1 to 5; Provided is a method for protecting the surface of an object to be coated using the easily peelable protective film of 7.6.
  • the surface tack is suppressed as well as excellent adhesion to glass or resin by light irradiation and / or heating for a short time.
  • a flexible resin film can be obtained.
  • the resin film can be easily peeled from the coated body by hand. Since the resin film has such characteristics, the surface of the article made of steel, glass, synthetic resin, etc. is corroded, worn, soiled, etc., such as when polishing / cutting the article or storing the product. It is expected to be used for temporary protection.
  • composition for forming an easily peelable protective film of the present invention (hereinafter sometimes simply referred to as “composition”) contains a urethane (meth) acrylate compound having a polycaprolactone skeleton as a main skeleton.
  • the urethane (meth) acrylate compound is not particularly limited as long as it has a polycaprolactone skeleton, which is a ring-opening polymer of caprolactone, as a main skeleton, and a commercially available product may be used. You may use what was manufactured.
  • a urethane (meth) acrylate compound for example, a reaction product of polycaprolactone polyol (such as Placel cell series manufactured by Daicel Corporation), a polyisocyanate compound, and a (meth) acrylate compound having a hydroxyl group is used.
  • polycaprolactone polyol such as Placel cell series manufactured by Daicel Corporation
  • polyisocyanate compound such as Placel cell series manufactured by Daicel Corporation
  • a (meth) acrylate compound having a hydroxyl group is used.
  • Examples of commercially available products include Art Resin UN-352 [manufactured by Negami Kogyo Co., Ltd.], but are not limited thereto.
  • the weight average molecular weight of the urethane (meth) acrylate compound used in the present invention is usually about 500 to 100,000. From the viewpoint of the toughness of the resulting film, it is preferably 1,000 or more, and much more. Preferably it is 2,000 or more. Further, from the viewpoint of suppressing an excessive increase in the viscosity of the composition and ensuring coating properties, it is preferably 50,000 or less, more preferably 10,000 or less, even more preferably 8,000 or less, and even more preferably 5 , 000 or less.
  • a weight average molecular weight is a polystyrene conversion measured value by gel permeation chromatography (GPC) (hereinafter the same).
  • content of the said urethane (meth) acrylate compound with respect to the whole composition becomes like this.
  • it is less than 80 mass% 10 mass% or more, More preferably, it is less than 70 mass% 10 mass% or more, More preferably, it is less than 70 mass%. It is 20% by mass or more, particularly preferably less than 60% by mass and 30% by mass or more.
  • the composition of the present invention is a (meth) acrylate containing at least a monofunctional (meth) acrylate as an ethylenically unsaturated monomer for the purpose of improving the adhesion of the resulting resin film, reducing the viscosity of the composition, and the like.
  • the (meth) acrylate may include monofunctional (meth) acrylate and polyfunctional (meth) acrylate.
  • the ethylenically unsaturated monomer is a compound having at least one ethylenically unsaturated double bond.
  • acrylate As the monofunctional (meth) acrylate, an alkyl (meth) acrylate is preferable, and an alkyl (meth) acrylate having 6 or more carbon atoms in the alkyl group is more preferable.
  • the alkyl group may be linear, branched, or cyclic.
  • a linear or branched alkyl group having 1 to 20 carbon atoms such as a group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group;
  • the monofunctional (meth) acrylate those having a ring structure in the molecule are preferable from the viewpoint of improving the toughness of the resin film.
  • a polymer of (meth) acrylate having a ring structure has a glass transition temperature (Tg) higher than that having a linear substituent, and a hard film is easily obtained.
  • Tg glass transition temperature
  • a substituent having a ring structure has a smaller free volume than a linear substituent, and is difficult to inhibit entanglement between (meth) acrylate main chains necessary for the toughness of the resin film. Therefore, a resin film containing a monofunctional (meth) acrylate having a ring structure is considered to be a hard but tough film.
  • alkyl (meth) acrylate having 6 or more carbon atoms in the alkyl group include hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 6-methylheptyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, 7-methyloctyl (meth) acrylate, decyl (meth) acrylate, 8-methylnonyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 16-methylheptadecyl (meth) acrylate, and the
  • (meth) acrylate other than alkyl (meth) acrylate having 6 or more carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth).
  • Monofunctional (meth) acrylates include cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 8-methylnonyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, 16-methylheptadecyl (meth) ) Acrylate is preferred.
  • Monofunctional (meth) acrylates can be used singly or in combination of two or more.
  • Multifunctional (meth) acrylate examples include bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and the like.
  • bifunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate.
  • Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Examples include pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerin polyglycidyl ether (meth) acrylic acid adduct.
  • polyfunctional (meth) acrylate bifunctional (meth) acrylate or trifunctional (meth) acrylate is preferable, and bifunctional (meth) acrylate is more preferable.
  • Polyfunctional (meth) acrylates can be used singly or in combination of two or more.
  • the content of (meth) acrylate, that is, monofunctional (meth) acrylate and polyfunctional (meth) acrylate with respect to the entire composition is usually 10 mass from the viewpoint of reducing the viscosity of the composition and improving workability. % Or more, preferably 20% by mass or more, more preferably 30% by mass or more, and from the viewpoint of controlling the toughness and adhesion of the cured product, preferably 35% by mass or more, more preferably 40% by mass. That's it.
  • the content of monofunctional (meth) acrylate is polyfunctional (meta) from the viewpoint of ensuring the toughness of the resin film that can be used by stripping paint. ) More than acrylate content.
  • the content of the polyfunctional (meth) acrylate is higher than the content of the monofunctional (meth) acrylate, the resin film becomes hard, but becomes brittle and the toughness decreases.
  • the content ratio of the monofunctional (meth) acrylate content (W s ) and the polyfunctional (meth) acrylate content (W m ) is W m / (W s + W m ) ⁇ 50 mass. % (In other words, W s / (W s + W m ) ⁇ 50 mass%).
  • the content is preferably 40% by mass or less, more preferably 30% by mass or less, and from the viewpoint of improving the water resistance of the resulting resin film, preferably 1% by mass or more. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, More preferably, it is 15 mass% or more.
  • the composition of the present invention is a polar group-containing monomer that can be copolymerized with the above-mentioned monofunctional (meth) acrylate and polyfunctional (meth) acrylate for the purpose of improving the adhesion of the resin film to the substrate, heat resistance, etc. May be included.
  • the polar group-containing monomer include (meth) acrylic acid, (meth) acrylamide, (meth) acryloylmorpholine, (meth) acrylonitrile, and the like.
  • composition of the present invention contains a polar group-containing monomer
  • the content does not exceed the content of (meth) acrylate, that is, the total content of monofunctional (meth) acrylate and polyfunctional (meth) acrylate.
  • the ratio of the polar group-containing monomer is increased, the water resistance of the resulting resin film is lowered, and as a result, peelability and the like may be lowered.
  • the composition of the present invention contains a radical polymerization initiator.
  • the radical polymerization initiator include a radiation radical polymerization initiator and a thermal radical polymerization initiator.
  • radiation radical polymerization initiators include ⁇ -diketones such as diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; thioxanthone, 2,4-diethyl Benzophenones such as thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, ⁇ -acetoxy- ⁇ , ⁇ -dimethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- (4
  • Examples of commercially available radiation radical polymerization initiators include IRGACURE (registered trademark) 651, 184, 2959, 127, 907, 369, 379EG, 819, TPO, DAROCUR (registered trademark) 1173, MBF [above, manufactured by BASF Japan Ltd.], KAYACURE DETX-S, EPA [above, produced by Nippon Kayaku Co., Ltd.] and the like are exemplified, but not limited thereto.
  • thermal radical polymerization initiator examples include hydrogen peroxides, azo compounds, and redox initiators.
  • hydrogen peroxides include tert-butyl (3,5,5-trimethylhexanoyl) peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, peroxy Tert-butyl octanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyisobutyrate, lauroyl peroxide, tert-amyl peroxypivalate, tert-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, persulfate Examples include potassium and ammonium persulfate.
  • azo compound examples include 2,2′-azobis (2-methylpropionic acid) dimethyl, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-butanenitrile), 4 , 4′-azobis (4-pentanoic acid), 1,1′-azobis (cyclohexanecarbonitrile), 2- (tert-butylazo) -2-cyanopropane, 2,2′-azobis (N, N′-di) Methyleneisobutylamidine) dichloride, 2,2′-azobis (2-amidinopropane) dichloride, 2,2′-azobis (N, N-dimethyleneisobutyramide), 2,2′-azobis (2-methyl-N—) (1,1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide), 2,2′-azobis (2-methyl-N- (1,1-bis (hydroxy) Methyl) ethyl) propionamide), 2,2'-azobis (2-methyl-N
  • redox initiators include hydrogen peroxide, alkyl peroxides, peroxide esters, percarbonates, etc., and iron salts, first titanium salts, zinc formaldehyde sulfoxylate, sodium formaldehyde sulfoxylate, etc.
  • alkali metal salts such as persulfuric acid, perboric acid, perchloric acid, ammonium salt of perchloric acid, and bisulfite alkali metal salts, such as sodium metabisulfite
  • a mixture of an alkali metal persulfate and other similar acids such as arylphosphonic acid such as benzenephosphonic acid can be exemplified.
  • thermal radical polymerization initiators examples include Perhexa (registered trademark) HC (manufactured by NOF Corporation), MAIB (manufactured by Otsuka Chemical Co., Ltd.), and the like.
  • the radical polymerization initiator can be used alone or in combination of two or more.
  • the content of the radical polymerization initiator with respect to the entire composition of the present invention is a urethane (meth) acrylate having polycaprolactone as the main skeleton from the viewpoint of suppressing the effect of radical deactivation due to oxygen, ensuring the storage stability, and the like.
  • the total amount of the compound and (meth) acrylate (monofunctional (meth) acrylate or monofunctional (meth) acrylate and polyfunctional (meth) acrylate) is 100 parts by mass, preferably 0.1 to 50 parts by mass, more preferably Is 1 to 30 parts by mass, and more preferably 2 to 30 parts by mass.
  • composition of the present invention may contain a hydrogen-donating compound such as mercaptobenzothiazole or mercaptobenzoxazole, or a radiosensitizer together with a radical polymerization initiator.
  • a hydrogen-donating compound such as mercaptobenzothiazole or mercaptobenzoxazole
  • radiosensitizer together with a radical polymerization initiator.
  • composition of the present invention may contain a solvent.
  • a solvent will not be specifically limited if each component of the composition of this invention can be dissolved uniformly, and it does not react with these.
  • the solvent include carbonates such as ethylene carbonate and propylene carbonate; fatty acids such as caproic acid and caprylic acid; alcohols such as 1-octanol, 1-nonanol and benzyl alcohol; ethylene glycol monoethyl ether, diethylene glycol monomethyl Alkyl ethers of polyhydric alcohols such as ether and propylene glycol monomethyl ether (PGME); alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol monomethyl ether acetate (PGMEA); and many such as phenyl cellosolve acetate Aryl ether acetates of dihydric alcohols; methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxypropion Ethyl, ethyl lactate, esters such as ⁇ - butyrolactone; and ketols diacetone alcohol and the like.
  • carbonates
  • composition of the present invention contains a solvent
  • content thereof is about 5 to 30% by mass with respect to the whole composition.
  • the composition of the present invention may contain a surfactant for the purpose of improving coating properties, antifoaming properties, leveling properties and the like.
  • a surfactant for the purpose of improving coating properties, antifoaming properties, leveling properties and the like.
  • the surfactant include BM-1000, BM-1100 [above, manufactured by BM Chemie], MegaFace (registered trademark) F142D, F172, F173, F183, F183, and F570 [above, DIC Corporation )], FLORARD FC-135, FC-170C, FC-430, FC-431 [above, manufactured by 3M Japan Ltd.], Surflon S-112, S-113, S-131, S-141, S-145 [above, manufactured by AGC Seimi Chemical Co., Ltd.], SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 [above, manufactured by Toray Dow Corning Co., Ltd. And the like, and commercially available fluorine-based surfactants and silicone-
  • composition of the present invention contains a surfactant
  • its content is preferably 5% by mass or less of the entire composition from the viewpoint of preventing precipitation from the resin film.
  • the composition of the present invention may contain a thermal polymerization inhibitor.
  • thermal polymerization inhibitors include phenol, n-butylphenol, hydroquinone, methylhydroquinone, tert-butylhydroquinone, di-tert-amylhydroquinone, amyloxyhydroquinone, hydroquinone monopropyl ether, hydroquinone monobenzyl ether, tert-butyl.
  • the content thereof is preferably 5% by mass or less of the entire composition from the viewpoint of preventing an excessive decrease in radical polymerizability and ensuring appropriate radical polymerizability. .
  • the composition of the present invention may contain a release agent for the purpose of improving peeling peelability.
  • a release agent any of wax compounds, silicone compounds, and fluorine compounds can be used.
  • silicone compounds silicone compounds (silicones having a siloxane bond as the main skeleton from the viewpoints of heat resistance, moisture resistance, and stability over time) Oils, emulsions, etc.) are preferred.
  • release agent examples include Shin-Etsu Silicone (registered trademark) KF-96-10CS, KF-6012, X-22-2426, X-22-164E [above, manufactured by Shin-Etsu Chemical Co., Ltd.] TEGO (registered trademark) RAD 2200N, 2700 [above, manufactured by Evonik Japan Co., Ltd.], BYK (registered trademark) -333 [above, manufactured by Big Chemie Japan Co., Ltd.], etc. Can be mentioned.
  • the content thereof is preferably 5% by mass or less of the entire composition from the viewpoint of preventing precipitation from the resin film.
  • composition of the present invention may contain other components such as a leveling agent and an antifoaming agent.
  • the composition of the present invention is prepared by mixing components such as a urethane (meth) acrylate compound having polycaprolactone as a main skeleton, a monofunctional (meth) acrylate, and a polyfunctional (meth) acrylate as necessary. can do.
  • a predetermined amount of each component is put into a SUS preparation tank having stirring blades, and stirred at room temperature (approximately 23 ° C.) or under heating until uniform.
  • a certain component which comprises a composition has the function of another component, it is necessary to determine the quantity of each component in consideration of the point.
  • the protective film (resin film) of the present invention can be formed by applying the composition of the present invention described above to a glass substrate, a resin-coated substrate, a metal substrate or the like and curing it by light irradiation and / or heating. it can. That is, the protective film of the present invention comprises a cured product of the composition of the present invention.
  • the coating method examples include, but are not limited to, spin coating, slit coating, roll coating, screen printing, applicator, and dispenser.
  • the thickness of the resin film is preferably 5 to 250 ⁇ m, more preferably 5 to 150 ⁇ m, and still more preferably 10 to 50 ⁇ m from the viewpoint of realizing each characteristic such as peelability with good reproducibility.
  • As a method for changing the film thickness for example, there is a method of changing the solid content concentration in the composition or changing the coating amount on the substrate.
  • Blade coating Doctor blade Baker applicator YBA-3 type, manufactured by Yoshimitsu Seiki Co., Ltd., wet film thickness 125 ⁇ m setting Coating speed: about 20 cm / sec
  • UV exposure equipment QRE4016, manufactured by Oak Manufacturing Co., Ltd.
  • Lamp HSL-300 / B-FM
  • Equipment Desktop precision universal testing machine Autograph AGS-500NX, manufactured by Shimadzu Corporation
  • UV7000B Polytetramethylene glycol-based urethane acrylate [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light (registered trademark) UV-7000B]
  • IBA Isobornyl acrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • TMPTA trimethylolpropane triacrylate [Shin Nakamura Chemical Co., Ltd.
  • NK Ester A-TMPT 2,4-diethylthioxanthone [KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.]
  • I907 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [IRGACURE (registered trademark) 907 manufactured by BASF Japan Ltd.]
  • composition (the composition for forming an easily peelable protective film) was prepared by blending each raw material with the composition described in Table 1 below and stirring the mixture at about 50 ° C. until uniform using a magnetic stirrer. .
  • UN352 has a polycaprolactone skeleton as a main skeleton, a urethane moiety at both ends thereof, a cyclohexyl ring in the molecule, and two acrylate groups in the molecule by structural analysis. It was recognized that there was.
  • UV7000B has a polytetramethylene glycol skeleton as a main skeleton by structural analysis, has urethane moieties at both ends thereof, has a cyclohexyl ring in the molecule, and has two acrylate groups in the molecule. It was recognized as a thing.
  • Adhesion to substrate The substrate was held so that the cured film produced on the substrate faced downward, the state of the cured film was visually confirmed, and evaluated according to the following criteria.
  • the cured film was cut into strips having a length of 10 cm and a width of 3 cm without peeling from the substrate.
  • the substrate was fixed horizontally to a testing machine, and one end in the length direction of the cured film cut into strips was slightly peeled off and held by a chuck.
  • the chuck was moved upward at a speed of 1 cm / second, and the resistance [N] when peeling the cured film at a peeling angle of 90 ° was measured.
  • the peeling resistance [N / cm] was calculated by dividing the resistance force by the width (3 cm) of the cured film.
  • the cured film (protective film) obtained from the composition of the present invention was easily peelable from both the resin-coated substrate and the glass substrate.
  • the cured film of the comparative example could be easily peeled from the resin-coated substrate, it could not be easily peeled from the glass substrate, and the peel resistance was large.
  • the difference between the composition of Example 1 and the composition of Comparative Example 1 is only the structure of the urethane (meth) acrylate compound, and the physical properties derived from this structure are peelable substrates. It is thought that the dependency is affected.
  • the composition of Example 1 has a lower breaking strength (toughness) than the composition of Comparative Example 1, but 0.8 mN / ⁇ m, which is another practical criterion for tear strength, which is an evaluation standard for toughness. It can be said that the strength is considered to be practically endurable as an easily peelable protective film. Further, as shown in the composition of Example 2, it is possible to improve the breaking strength by increasing the content of polyfunctional (meth) acrylate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition pour former un film protecteur facilement enlevé par pelage, caractérisée en ce qu'elle comprend : un composé de type uréthane-(méth)acrylate présentant un squelette de type polycaprolactone en tant que squelette principal ; un (méth)acrylate comprenant au moins un (méth)acrylate monofonctionnel ; et un initiateur de polymérisation radicalaire. La composition est en outre caractérisée en ce que la teneur en (méth)acrylate monofonctionnel est d'au moins 50 % en masse de la quantité totale du (méth)acrylate.
PCT/JP2017/026929 2016-07-26 2017-07-25 Composition pour former un film protecteur facilement enlevé par pelage WO2018021350A1 (fr)

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CN201780043906.3A CN109476950A (zh) 2016-07-26 2017-07-25 易剥离性保护膜形成用组合物
JP2018530311A JPWO2018021350A1 (ja) 2016-07-26 2017-07-25 易剥離性保護膜形成用組成物

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CN110643315A (zh) * 2019-10-16 2020-01-03 中国工程物理研究院化工材料研究所 一种梯度温敏型强粘接热熔胶及制备方法

Citations (8)

* Cited by examiner, † Cited by third party
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JPH05301935A (ja) * 1992-04-28 1993-11-16 Sekisui Chem Co Ltd 光硬化型樹脂組成物
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