WO2018021350A1 - Composition for forming easily-peeled protective film - Google Patents

Composition for forming easily-peeled protective film 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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Prior art keywords
meth
acrylate
composition
protective film
monofunctional
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PCT/JP2017/026929
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French (fr)
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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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2018530311A priority Critical patent/JPWO2018021350A1/en
Priority to CN201780043906.3A priority patent/CN109476950A/en
Publication of WO2018021350A1 publication Critical patent/WO2018021350A1/en

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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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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

This composition for forming an easily-peeled protective film is characterized by including: a urethane (meth)acrylate compound having a polycaprolactone skeleton as a main skeleton; a (meth)acrylate including at least a monofunctional (meth)acrylate; and a radical polymerization initiator. The composition is further characterized in that the content of the monofunctional (meth)acrylate is at least 50 mass% of the total amount of the (meth)acrylate.

Description

易剥離性保護膜形成用組成物Composition for forming easily peelable protective film
　本発明は、易剥離性保護膜形成用組成物、易剥離性保護膜及び被塗布体表面の保護方法に関する。 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.
　物品の表面を磨耗や腐食から一時的に保護するために、物品の表面に塗布して膜を形成し、必要期間が過ぎたときに物品を損傷させずに剥ぎ取ることができる塗料は、一般的に、ストリッパブルペイントと呼ばれる。 In order to temporarily protect the surface of an article from abrasion and corrosion, 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.
　このようなストリッパブルペイントとしては、主に、合成ゴムや塩化ゴムを有機溶剤に溶解した塗料、塩化ビニル－酢酸ビニル共重合体に可塑剤を配合し有機溶剤に溶解した塗料等が知られている。 As such strippable paints, 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.
　しかしながら、この種の含溶剤塗料は、塗布後の乾燥に長時間（加熱乾燥で５～１０分間）が必要である。また、この塗料を合成樹脂製の物品に塗布すると、この物品の表面が有機溶剤により膨潤したり溶解したりすることがある。
　さらに、アクリル樹脂を水中に分散させたアクリルエマルジョン等もストリッパブルペイントとして使用されているが、この塗料も、やはり塗布後の乾燥に長時間が必要である（例えば特許文献１，２参照）。 However, 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).
特開２０１４－１０５３１４号公報JP 2014-105314 A 特開２０００－２２６５３９号公報JP 2000-226539 A 特開平０４－０４１１９０号公報Japanese Patent Laid-Open No. 04-041190 特開２００５－１５５９４号公報JP 2005-15594 A 特開平０５－３０１９３５号公報Japanese Patent Laid-Open No. 05-301935
　上述の事情の下、物品（以下、被塗布体ともいう）の表面に一時的な保護塗膜を形成するための組成物として、（メタ）アクリル酸と（メタ）アクリル酸エステルとの共重合体と、重合可能な二重結合を有する不飽和化合物、例えばフェニルグリシジルエーテルのアクリル酸付加物と、光重合開始剤とを含む光硬化型樹脂組成物が提案されている（例えば特許文献３～５参照）。
　このようなラジカル硬化系の樹脂組成物は、塗工後に短時間（１～５分間程度）の光照射及び／又は加熱により硬化し、強靭な被膜を形成する。このため、ラジカル硬化系の樹脂組成物によれば、作業性の向上が期待できる上、有機溶剤を用いずに組成物の調製が可能であるため、被塗布体表面の侵食の抑制も期待される。 Under the circumstances described above, as a composition for forming a temporary protective coating on the surface of an article (hereinafter also referred to as an article to be coated), co-weight of (meth) acrylic acid and (meth) acrylic ester Photocurable resin compositions comprising a polymer, an unsaturated compound having a polymerizable double bond, for example, an acrylic acid adduct of phenylglycidyl ether, and a photopolymerization initiator have been proposed (for example, Patent Documents 3 to 4). 5).
Such a radical curable resin composition is cured by light irradiation and / or heating for a short time (about 1 to 5 minutes) after coating to form a tough film. For this reason, according to the radical curable resin composition, workability can be improved, and the composition can be prepared without using an organic solvent. The
　そこで、本発明者らは、ラジカル硬化系の樹脂組成物に着目し、新規ストリッパブルペイントを開発するべく検討を重ねたところ、以下の条件を満たす場合に、ストリッパブルペイントとして好適な組成物や樹脂薄膜となり得るという知見に至った。
（１）塗膜が短時間の光照射及び／又は加熱により硬化する（硬化膜を形成する）。
（２）硬化膜がガラスや樹脂等の様々な物品表面に良好に密着する。
（３）硬化膜の表面タックが低い。
（４）硬化膜に靭性があり、剥離時にちぎれることなく容易に剥離できる。
（５）硬化膜がガラスや樹脂等の様々な物品表面から容易に剥離できる。 Therefore, the present inventors have paid attention to a radical curable resin composition and have repeatedly studied to develop a new strippable paint. When the following conditions are satisfied, a composition suitable as a strippable paint, It came to the knowledge that it could become a resin thin film.
(1) The coating film is cured by short-time light irradiation and / or heating (forms a cured film).
(2) The cured film adheres well to the surface of various articles such as glass and resin.
(3) The surface tack of the cured film is low.
(4) The cured film has toughness and can be easily peeled without tearing during peeling.
(5) The cured film can be easily peeled from the surface of various articles such as glass and resin.
　近年、ガラス基板の一部分を樹脂で被覆した複合基板と呼ばれる物品の、一時的な保護が求められている。しかしながら、一般的にガラス基板は親水性であり、樹脂膜は疎水性であるため、両者でストリッパブルペイントの密着性が異なる。このため、ガラス表面と樹脂表面の混在する複合基板からも容易に剥離できる実用可能なストリッパブルペイントは未だなく、その開発が望まれている。
　本発明の目的は、上記条件を満たすストリッパブルペイントとして好適な、容易に剥離できる樹脂膜を与える組成物、そのような樹脂膜及びこの樹脂膜を用いた被塗布体表面の保護方法を提供することである。 In recent years, there has been a demand for temporary protection of an article called a composite substrate in which a part of a glass substrate is coated with a resin. However, since the glass substrate is generally hydrophilic and the resin film is hydrophobic, the adhesiveness of the strippable paint differs between them. For this reason, there is still no practical strippable paint that can be easily peeled off even from a composite substrate in which the glass surface and the resin surface coexist, and the development thereof is desired.
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.
　本発明者は、上記課題を解決するために鋭意検討を重ねた結果、ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物を、所定の割合の単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレート又は所定の割合の単官能（メタ）アクリレート及び多官能（メタ）アクリレート、並びにラジカル重合開始剤とともに混合することで、均一な組成物を容易に調製することができることを見出した。また、当該組成物を用いた場合に、光照射及び／又は短時間の加熱によって、ガラスや樹脂等への優れた密着性だけでなく、表面タックが抑制された、強靱で柔軟な硬化膜が得られ、この硬化膜が、ガラスや樹脂等の被塗布体から手で容易に剥離できることを見出した。そして、これらの知見により本発明を完成させた。 As a result of intensive studies in order to solve the above problems, 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.
　なお、ウレタン（メタ）アクリレート化合物を用いたストリッパブルペイントに関する報告はなされているが（例えば特許文献５参照）、ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレートとともに、所定の割合の単官能（メタ）アクリレート及び必要に応じて多官能（メタ）アクリレートを用いることで、本発明特有の特徴を有する組成物や樹脂膜が得られることを教示する文献は見当たらない。 In addition, although the report regarding the strippable paint using a urethane (meth) acrylate compound is made | formed (for example, refer patent document 5), with the urethane (meth) acrylate which has a polycaprolactone skeleton as the main skeleton, it is a monofunctional of a predetermined ratio. There is no document that teaches that a composition or a resin film having characteristics peculiar to the present invention can be obtained by using (meth) acrylate and optionally polyfunctional (meth) acrylate.
　すなわち、本発明は、
１．ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、ラジカル重合開始剤とを含み、前記単官能（メタ）アクリレートの含有量が、前記（メタ）アクリレートの全量に対して５０質量％以上であることを特徴とする、易剥離性保護膜形成用組成物、
２．前記（メタ）アクリレートが、前記単官能（メタ）アクリレートと、多官能（メタ）アクリレートとを含むことを特徴とする、１の易剥離性保護膜形成用組成物、
３．前記単官能（メタ）アクリレートが、環状構造を有する単官能（メタ）アクリレートを含むことを特徴とする、１又は２の易剥離性保護膜形成用組成物、
４．前記易剥離性保護膜形成用組成物中の前記ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物の含有量が、８０質量％未満であることを特徴とする、１～３の何れかの易剥離性保護膜形成用組成物、
５．前記易剥離性保護膜形成用組成物中の前記ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物の含有量が、１０質量％以上であることを特徴とする、１～４の何れかの易剥離性保護膜形成用組成物、
６．１～５の何れかの易剥離性保護膜形成用組成物の硬化物からなることを特徴とする、易剥離性保護膜、
７．６の易剥離性保護膜を用いた、被塗布体表面の保護方法
を提供する。 That is, the present invention
1. A urethane (meth) acrylate compound having a polycaprolactone skeleton as a main skeleton, a (meth) acrylate containing at least a monofunctional (meth) acrylate, and a radical polymerization initiator, wherein the content of the monofunctional (meth) acrylate is 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 composition for forming an easily peelable protective film according to 1, wherein the (meth) acrylate includes the monofunctional (meth) acrylate and a polyfunctional (meth) acrylate,
3. 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.
　本発明の易剥離性保護膜形成用組成物を用いることで、光照射及び／又は短時間の加熱によって、ガラスや樹脂等への優れた密着性だけでなく、表面タックが抑制された、強靱で柔軟な樹脂膜を得ることができる。更に、当該樹脂膜は、手で容易に被塗布体から剥離できる。当該樹脂膜は、このような特徴を備えることから、物品を研磨・切断する場合や、製品を保管する場合など、鉄鋼、ガラス、合成樹脂等からなる物品の表面を腐食、磨耗、汚れ等から一時的に保護するために使用されることが期待される。 By using the composition for forming an easily peelable protective film according to the present invention, 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. Furthermore, 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.
＜ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物＞
　本発明の易剥離性保護膜形成用組成物（以下、単に「組成物」ということがある。）は、ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物を含む。
　上記ウレタン（メタ）アクリレート化合物は、カプロラクトンの開環重合体であるポリカプロラクトン骨格を主骨格として有するものであれば特に限定されるものではなく、市販品を用いてもよいし、公知の方法によって製造したものを用いてもよい。
　このようなウレタン（メタ）アクリレート化合物としては、例えば、ポリカプロラクトンポリオール（（株）ダイセル製プラクセルシリーズ等）と、ポリイソシアネート化合物と、水酸基を有する（メタ）アクリレート化合物との反応物を用いることができる。
　また、市販品としては、アートレジンＵＮ－３５２［根上工業（株）製］等が挙げられるが、これらに限定されない。 <Urethane (meth) acrylate compound with polycaprolactone skeleton as main skeleton>
The 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.
As such 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. Can do.
Examples of commercially available products include Art Resin UN-352 [manufactured by Negami Kogyo Co., Ltd.], but are not limited thereto.
　本発明で用いられる前記ウレタン（メタ）アクリレート化合物の重量平均分子量は、通常、５００～１００，０００程度であるが、得られる膜の強靭性等の観点から、好ましくは１，０００以上、より一層好ましくは２，０００以上である。また、組成物の過度の粘度の増加を抑制し塗工性を確保する観点から、好ましくは５０，０００以下、より好ましくは１０，０００以下、より一層好ましくは８，０００以下、さらに好ましくは５，０００以下である。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算測定値である（以下、同様）。 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. In addition, a weight average molecular weight is a polystyrene conversion measured value by gel permeation chromatography (GPC) (hereinafter the same).
　本発明において、組成物全体に対する前記ウレタン（メタ）アクリレート化合物の含有量は、好ましくは８０質量％未満１０質量％以上、より好ましくは７０質量％未満１０質量％以上、さらに好ましくは７０質量％未満２０質量％以上、特に好ましくは６０質量％未満３０質量％以上である。当該化合物の含有量を上述した８０質量％未満とすることで、組成物の粘度の過度な上昇を抑制し組成物の塗工性を維持し易くなるだけでなく、相対的に後述するエチレン性不飽和単量体の量が多くなり、基板密着力等の調整が容易になる。また、当該化合物の含有量を上述した１０質量％以上とすることで、樹脂膜の剥離性を確保し易くなる。 In this invention, content of the said urethane (meth) acrylate compound with respect to the whole composition becomes like this. Preferably 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. By setting the content of the compound to less than 80% by mass as described above, it is not only easy to suppress an excessive increase in the viscosity of the composition and maintain the coating property of the composition, but also relatively later described as ethylenic. The amount of the unsaturated monomer increases, and the adjustment of the substrate adhesion force and the like becomes easy. Moreover, it becomes easy to ensure the peelability of a resin film because content of the said compound shall be 10 mass% or more mentioned above.
＜単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレート＞
　本発明の組成物は、得られる樹脂膜の密着性の改善、組成物の低粘度化等を目的に、エチレン性不飽和単量体として、少なくとも単官能（メタ）アクリレートを含む（メタ）アクリレートを含む。上記（メタ）アクリレートは、単官能（メタ）アクリレートと多官能（メタ）アクリレートとを含んでもよい。なお、エチレン性不飽和単量体とは、少なくとも１つのエチレン性不飽和二重結合を有する化合物である。 <(Meth) acrylate containing at least monofunctional (meth) acrylate>
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. including. 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.
［単官能（メタ）アクリレート］
　前記単官能（メタ）アクリレートとしては、アルキル（メタ）アクリレートが好適であり、そのアルキル基の炭素数が６以上のアルキル（メタ）アクリレートがより好適である。
　アルキル基としては、直鎖状、分岐状、環状の何れでもよく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の炭素数１～２０の直鎖状又は分岐状アルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等の炭素数３～２０の環状アルキル基等が挙げられる。 [Monofunctional (meth) 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. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl 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; Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclo Examples thereof include cyclic alkyl groups having 3 to 20 carbon atoms such as decyl group.
　また、単官能（メタ）アクリレートとしては、樹脂膜の靱性向上の観点から、分子内に環構造を有しているものが好ましい。環構造を有する（メタ）アクリレートの重合物は、直鎖状の置換基を有するものよりガラス転移温度（Ｔｇ）が高く、硬い膜が得られやすい。一方で環構造の置換基は、直鎖状の置換基より自由体積が小さく、樹脂膜の靭性に必要な（メタ）アクリレート主鎖同士の絡み合いを阻害しにくい。そのため環構造を有している単官能（メタ）アクリレートを配合した樹脂膜は、硬いながらも靭性がある膜になると考えられる。 Further, as 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. On the other hand, 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.
　アルキル基の炭素数が６以上のアルキル（メタ）アクリレートの具体例としては、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、６－メチルヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、７－メチルオクチル（メタ）アクリレート、デシル（メタ）アクリレート、８－メチルノニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、１６－メチルヘプタデシル（メタ）アクリレート等が挙げられる。 Specific examples of the 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 like.
　また、このようなアルキル基の炭素数が６以上のアルキル（メタ）アクリレート以外の（メタ）アクリレートの具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、アリル（メタ）アクリレート、グリシジル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フルフリル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、エチレンオキシド変性（ｎ＝２）フェノール（メタ）アクリレート、２－ヒドロキシ－２－フェノキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、プロピレンオキシド変性（ｎ＝２．５）４－ノニルフェノール（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート等が挙げられる。中でも、ヒドロキシ基を含有しないものが好ましく、また、分子量は１００～３００程度が好ましい。 Specific examples of (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). Acrylate, 2-butoxyethyl (meth) acrylate, carbitol (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 3-chloro- 2-hydroxypropyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, Ren oxide modified (n = 2) phenol (meth) acrylate, 2-hydroxy-2-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, propylene oxide modified (n = 2.5) 4 -Nonylphenol (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate and the like. Among them, those not containing a hydroxy group are preferable, and the molecular weight is preferably about 100 to 300.
　単官能（メタ）アクリレートとしては、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、８－メチルノニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ラウリル（メタ）アクリレート、１６－メチルヘプタデシル（メタ）アクリレートが好ましい。 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.
　単官能（メタ）アクリレートは、１種単独で又は２種以上組合わせて使用できる。 Monofunctional (meth) acrylates can be used singly or in combination of two or more.
［多官能（メタ）アクリレート］
　前記多官能（メタ）アクリレートとしては、２官能（メタ）アクリレート、３官能以上の（メタ）アクリレート等が挙げられる。 [Multifunctional (meth) acrylate]
Examples of the polyfunctional (meth) acrylate include bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and the like.
　２官能（メタ）アクリレートとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレンオキシド変性ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド変性ビスフェノールＡジ（メタ）アクリレート、エチレングリコールジグリシジルエーテル（メタ）アクリル酸付加物、ジエチレングリコールジグリシジルエーテル（メタ）アクリル酸付加物、フタル酸ジグリシジル（メタ）アクリル酸付加物等が挙げられる。 Examples of the bifunctional (meth) acrylate 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. , Dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythrito Rudi (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, ethylene glycol diglycidyl ether (meth) acrylic acid adduct, diethylene glycol diglycidyl ether (meth) acrylic acid addition Products, diglycidyl phthalate (meth) acrylic acid adducts, and the like.
　３官能以上の（メタ）アクリレートとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセリンポリグリシジルエーテル（メタ）アクリル酸付加物等が挙げられる。 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.
　前記多官能（メタ）アクリレートとしては、２官能（メタ）アクリレート又は３官能（メタ）アクリレートが好ましく、２官能（メタ）アクリレートがより好ましい。 As the polyfunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional (meth) acrylate is preferable, and bifunctional (meth) acrylate is more preferable.
　多官能（メタ）アクリレートは、１種単独で又は２種以上組合わせて使用できる。 Polyfunctional (meth) acrylates can be used singly or in combination of two or more.
　本発明において、組成物全体に対する（メタ）アクリレート、すなわち単官能（メタ）アクリレートと多官能（メタ）アクリレートの含有量は、組成物を低粘度化し、作業性を高める観点から、通常、１０質量％以上であるが、好ましくは２０質量％以上、より一層好ましくは３０質量％以上であり、硬化物の靭性および密着力を制御する観点から、好ましくは３５質量％以上、より好ましくは４０質量％以上である。 In the present invention, 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.
　本発明においては、多官能（メタ）アクリレートを併用する場合、ストリッパブルペイントして使用できる程度の樹脂膜の靭性を確保する観点から、単官能（メタ）アクリレートの含有量が、多官能（メタ）アクリレートの含有量より多い。多官能（メタ）アクリレートの含有量が単官能（メタ）アクリレートの含有量よりも多くなると、樹脂膜は硬くなる一方、脆くなり、靭性が低下する。 In the present invention, when polyfunctional (meth) acrylate is used in combination, 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. When 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.
　本発明においては、単官能（メタ）アクリレートの含有量（Ｗｓ）と多官能（メタ）アクリレートの含有量（Ｗｍ）との含有割合は、Ｗｍ／（Ｗｓ＋Ｗｍ）＜５０質量％（言い換えると、Ｗｓ／（Ｗｓ＋Ｗｍ）≧５０質量％）を満たす。樹脂膜の靭性の観点から、これらの含有割合は、好ましくは４０質量％以下、より好ましくは３０質量％以下であり、得られる樹脂膜の耐水性を向上させる観点から、好ましくは１質量％以上、より好ましくは５質量％以上、より一層好ましくは、１０質量％以上、さらに好ましくは１５質量％以上である。 In the present invention, 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%). From the viewpoint of the toughness of the resin film, 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.
　本発明の組成物は、樹脂膜の基材への密着性、耐熱性等の向上等を目的として、上述の単官能（メタ）アクリレート及び多官能（メタ）アクリレートと共重合できる極性基含有モノマーを含んでいてもよい。
　極性基含有モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、（メタ）アクリロニトリル等が挙げられる。 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.
Examples of the polar group-containing monomer include (meth) acrylic acid, (meth) acrylamide, (meth) acryloylmorpholine, (meth) acrylonitrile, and the like.
　本発明の組成物が極性基含有モノマーを含む場合、その含有量は、（メタ）アクリレートの含有量、すなわち単官能（メタ）アクリレートと多官能（メタ）アクリレートの合計含有量を超えない。極性基含有モノマーの比率が高くなると、得られる樹脂膜の耐水性が低下し、その結果、剥離性等が低下することがある。 When the 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. When 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.
＜ラジカル重合開始剤＞
　本発明の組成物は、ラジカル重合開始剤を含む。
　ラジカル重合開始剤としては、放射線ラジカル重合開始剤、熱ラジカル重合開始剤などが挙げられる。 <Radical polymerization initiator>
The composition of the present invention contains a radical polymerization initiator.
Examples of the radical polymerization initiator include a radiation radical polymerization initiator and a thermal radical polymerization initiator.
［放射線ラジカル重合開始剤］
　放射線ラジカル重合開始剤の具体例としては、ジアセチル等のα－ジケトン類；ベンゾイン等のアシロイン類；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のアシロインエーテル類；チオキサントン、２，４－ジエチルチオキサントン、チオキサントン－４－スルホン酸、ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等のベンゾフェノン類；アセトフェノン、ｐ－ジメチルアミノアセトフェノン、α－アセトキシ－α，α－ジメトキシアセトフェノン、α，α－ジメトキシ－α－フェニルアセトフェノン、ｐ－メトキシアセトフェノン、２－メチル－１－（４－メチルチオフェニル）－２－モルホリノプロパン－１－オン、１－（２－メチル－４－メチルチオフェニル）－２－モルホリノプロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシル＝フェニル＝ケトン、α，α－ジメトキシ－α－（４－モルホリノメチルチオフェニル）アセトフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－（ｐ－トリルメチル）ブタン－１－オン等のアセトフェノン類；アントラキノン、１，４－ナフトキノン等のキノン類；フェナシルクロリド、トリブロモメチルフェニルスルホン、トリス（トリクロロメチル）－ｓ－トリアジン等のハロゲン化合物；［１，２’－ビスイミダゾール］－３，３’，４，４’－テトラフェニル、［１，２’－ビスイミダゾール］－１，２’－ジクロロフェニル－３，３’，４，４’－テトラフェニル等のビスイミダゾール類；ジ－ｔｅｒｔ－ブチルパ－オキシド等の過酸化物；ジフェニル（２，４，６－トリメチルベンゾイル）ホスフィンオキシド等のアシルホスフィンオキシド類；ｐ－ジメチルアミノ安息香酸エチル等のｐ－ジメチルアミノ安息香酸エステルなどが挙げられる。 [Radiation radical polymerization initiator]
Specific examples of radiation radical polymerization initiators include α-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, α-acetoxy- α, α-dimethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- (2-methyl-4-methylthiophenyl) -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl = phenyl ketone, α, α-Dimethoxy-α- (4-morpholinomethylthiophenyl) acetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-acetphenones such as 2- (p-tolylmethyl) butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine Halogen compounds such as [1,2'-bisimidazole] -3,3 ', 4 Bisimidazoles such as '-tetraphenyl, [1,2'-bisimidazole] -1,2'-dichlorophenyl-3,3', 4,4'-tetraphenyl; peroxides such as di-tert-butyl peroxide Oxides; acylphosphine oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; p-dimethylaminobenzoic acid esters such as ethyl p-dimethylaminobenzoate and the like.
　放射線ラジカル重合開始剤の市販品としては、ＩＲＧＡＣＵＲＥ（登録商標）６５１、同１８４、同２９５９、同１２７、同９０７、同３６９、同３７９ＥＧ、同８１９、同ＴＰＯ、ＤＡＲＯＣＵＲ（登録商標）１１７３、同ＭＢＦ［以上、ＢＡＳＦジャパン（株）製］、ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ、同ＥＰＡ［以上、日本化薬（株）製］等が挙げられるが、これらに限定されない。 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.
［熱ラジカル重合開始剤］
　熱ラジカル重合開始剤としては、過酸化水素類、アゾ化合物、レドックス系開始剤等が挙げられる。 [Thermal radical polymerization initiator]
Examples of the thermal radical polymerization initiator include hydrogen peroxides, azo compounds, and redox initiators.
　過酸化水素類の具体例としては、ｔｅｒｔ－ブチル（３，５，５－トリメチルヘキサノイル）ペルオキシド、ｔｅｒｔ－ブチルヒドロペルオキシド、クメンヒドロペルオキシド、ペルオキシ酢酸ｔｅｒｔ－ブチル、ペルオキシ安息香酸ｔｅｒｔ－ブチル、ペルオキシオクタン酸ｔｅｒｔ－ブチル、ペルオキシネオデカン酸ｔｅｒｔ－ブチル、ペルオキシイソ酪酸ｔｅｒｔ－ブチル、過酸化ラウロイル、ペルオキシピバル酸ｔｅｒｔ－アミル、ペルオキシピバル酸ｔｅｒｔ－ブチル、過酸化ジクミル、過酸化ベンゾイル、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。 Specific examples of 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.
　アゾ化合物の具体例としては、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－ブタンニトリル）、４，４’－アゾビス（４－ペンタン酸）、１，１’－アゾビス（シクロヘキサンカルボニトリル）、２－（ｔｅｒｔ－ブチルアゾ）－２－シアノプロパン、２，２’－アゾビス（Ｎ，Ｎ’－ジメチレンイソブチルアミジン）ジクロリド、２，２’－アゾビス（２－アミジノプロパン）ジクロリド、２，２’－アゾビス（Ｎ，Ｎ－ジメチレンイソブチルアミド）、２，２’－アゾビス（２－メチル－Ｎ－（１，１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル）プロピオンアミド）、２，２’－アゾビス（２－メチル－Ｎ－（１，１－ビス（ヒドロキシメチル）エチル）プロピオンアミド）、２，２’－アゾビス（２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド）、２，２’－アゾビス（イソブチルアミド）二水和物等が挙げられる。 Specific examples of the azo compound 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-(2-hydroxyethyl) propionamide), 2,2'-azobis (isobutyramide) dihydrate and the like.
　レドックス系開始剤の具体例としては、過酸化水素、過酸化アルキル、過酸化エステル、過炭酸塩等と、鉄塩、第１チタン塩、亜鉛ホルムアルデヒドスルホキシレート、ナトリウムホルムアルデヒドスルホキシレート等との混合物が挙げられる。また、過硫酸、過ホウ酸、過塩素酸等のアルカリ金属塩、過塩素酸のアンモニウム塩と、メタ重亜硫酸ナトリウムのような重亜硫酸アルカリ金属塩等との混合物が挙げられる。さらに、過硫酸アルカリ金属塩と、ベンゼンホスホン酸等のアリールホスホン酸のような他の同様の酸等との混合物等を挙げることができる。 Specific examples of redox initiators include hydrogen peroxide, alkyl peroxides, peroxide esters, percarbonates, etc., and iron salts, first titanium salts, zinc formaldehyde sulfoxylate, sodium formaldehyde sulfoxylate, etc. A mixture is mentioned. Moreover, the mixture of 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, is mentioned. Furthermore, a mixture of an alkali metal persulfate and other similar acids such as arylphosphonic acid such as benzenephosphonic acid can be exemplified.
　熱ラジカル重合開始剤の市販品としては、パーヘキサ（登録商標）ＨＣ［日油（株）製］、ＭＡＩＢ［大塚化学（株）製］等が挙げられる。 Examples of commercially available thermal radical polymerization initiators include Perhexa (registered trademark) HC (manufactured by NOF Corporation), MAIB (manufactured by Otsuka Chemical Co., Ltd.), and the like.
　ラジカル重合開始剤は、１種単独で又は２種以上組み合わせて使用できる。 The radical polymerization initiator can be used alone or in combination of two or more.
　本発明の組成物全体に対するラジカル重合開始剤の含有量は、酸素によるラジカルの失活の影響を抑制する観点、保存安定性確保の観点等から、ポリカプロラクトンを主骨格とするウレタン（メタ）アクリレート化合物、及び（メタ）アクリレート（単官能（メタ）アクリレート又は単官能（メタ）アクリレート及び多官能（メタ）アクリレート）の総量１００質量部に対して、好ましくは０．１～５０質量部、より好ましくは１～３０質量部、より一層好ましくは２～３０質量部である。 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.
　本発明の組成物は、メルカプトベンゾチアゾール、メルカプトベンゾオキサゾールのような水素供与性を有する化合物や、放射線増感剤をラジカル重合開始剤とともに含んでいてもよい。 The 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.
＜溶媒＞
　本発明の組成物は、溶媒を含んでいてもよい。
　溶媒は、本発明の組成物の各成分を均一に溶解させることができ、これらと反応しないものであれば特に限定されない。 <Solvent>
The 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.
　溶媒の具体例としては、炭酸エチレン、炭酸プロピレン等の炭酸エステル類；カプロン酸、カプリル酸等の脂肪酸；１－オクタノール、１－ノナノール、ベンジルアルコール等のアルコール類；エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）等の多価アルコールのアルキルエーテル類；エチレングリコールエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）等の多価アルコールのアルキルエーテルアセテート類；フェニルセロソルブアセテート等の多価アルコールのアリールエーテルアセテート類；３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、２－ヒドロキシプロピオン酸エチル、乳酸エチル、γ－ブチロラクトン等のエステル類；ジアセトンアルコール等のケトール類などが挙げられる。なお、溶媒は、１種単独で又は２種以上組み合わせて使用できる。 Specific examples of 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 γ- butyrolactone; and ketols diacetone alcohol and the like. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.
　本発明の組成物が溶媒を含む場合、その含有量は、組成物全体に対して、５～３０質量％程度である。 When the composition of the present invention contains a solvent, the content thereof is about 5 to 30% by mass with respect to the whole composition.
＜その他の添加剤＞
［界面活性剤］
　本発明の組成物は、塗布性、消泡性、レベリング性等を向上させる目的で、界面活性剤を含んでいてもよい。
　界面活性剤の具体例としては、ＢＭ－１０００、ＢＭ－１１００［以上、ＢＭケミー社製］、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７２、同Ｆ１７３、同Ｆ１８３、同Ｆ５７０［以上、ＤＩＣ（株）製］、フロラードＦＣ－１３５、同ＦＣ－１７０Ｃ、同ＦＣ－４３０、同ＦＣ－４３１［以上、スリーエムジャパン（株）製］、サーフロンＳ－１１２、同Ｓ－１１３、同Ｓ－１３１、同Ｓ－１４１、同Ｓ－１４５［以上、ＡＧＣセイミケミカル（株）製］、ＳＨ－２８ＰＡ、ＳＨ－１９０、ＳＨ－１９３、ＳＺ－６０３２、ＳＦ－８４２８［以上、東レ・ダウコーニング（株）製］等の商品名で市販されているフッ素系界面活性剤、シリコーン系界面活性剤などが挙げられる。 <Other additives>
[Surfactant]
The composition of the present invention may contain a surfactant for the purpose of improving coating properties, antifoaming properties, leveling properties and the like.
Specific examples of 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-based surfactants.
　本発明の組成物が界面活性剤を含む場合、その含有量は、樹脂膜からの析出を防ぐ観点から、組成物全体の５質量％以下が好ましい。 When the 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.
［熱重合禁止剤］
　本発明の組成物は、熱重合禁止剤を含んでいてもよい。
　熱重合禁止剤の具体例としては、フェノール、ｎ－ブチルフェノール、ヒドロキノン、メチルヒドロキノン、ｔｅｒｔ－ブチルヒドロキノン、ジ－ｔｅｒｔ－アミルヒドロキノン、アミルオキシヒドロキノン、ヒドロキノンモノプロピルエーテル、ヒドロキノンモノベンジルエーテル、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、ピロガロール、４，４’－（１－メチルエチリデン）ビス（２－メチルフェノール）、４，４’－（１－メチルエチリデン）ビス（２，６－ジメチルフェノール）、４，４’－（１－（４－（１－（４－ヒドロキシフェニル）－１－メチルエチル）フェニル）エチリデン）ビスフェノール、４，４’，４’’－エチリデントリスフェノール、４，４’，４’’－エチリデントリス（２－メチルフェノール）、１，１，３－トリス（２，５－ジメチル－４－ヒドロキシフェニル）－３－フェニルプロパン、メチレンブルー等を挙げることができる。 [Thermal polymerization inhibitor]
The composition of the present invention may contain a thermal polymerization inhibitor.
Specific examples of thermal polymerization inhibitors include phenol, n-butylphenol, hydroquinone, methylhydroquinone, tert-butylhydroquinone, di-tert-amylhydroquinone, amyloxyhydroquinone, hydroquinone monopropyl ether, hydroquinone monobenzyl ether, tert-butyl. Catechol, benzoquinone, pyrogallol, 4,4 '-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4 ' -(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, 4,4 ′, 4 ″ -ethylidenetrisphenol, 4,4 ′, 4 ″- Ethylidentris (2-methylphenol), 1,1,3-to Scan (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, it can be exemplified such as methylene blue.
　本発明の組成物が熱重合禁止剤を含む場合、その含有量は、ラジカル重合性の過度な低下を防ぎ、適切なラジカル重合性を確保する観点から、組成物全体の５質量％以下が好ましい。 When the composition of the present invention contains a thermal polymerization inhibitor, 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. .
［剥離剤］
　本発明の組成物は、ピーリング剥離性を向上させる目的で、剥離剤を含んでいてもよい。
　剥離剤としては、ワックス系化合物、シリコーン系化合物、フッ素系化合物の何れも使用できるが、中でも、耐熱性、耐湿性、経時安定性の観点から、シリコーン系化合物（シロキサン結合を主骨格とするシリコーンオイル、エマルジョン等）が好ましい。
　剥離剤の具体例としては、信越シリコーン（登録商標）ＫＦ－９６－１０ＣＳ、同ＫＦ－６０１２、同Ｘ－２２－２４２６、同Ｘ－２２－１６４Ｅ［以上、信越化学工業（株）製］、ＴＥＧＯ（登録商標）ＲＡＤ　２２００Ｎ、同２７００［以上、エボニックジャパン（株）製］、ＢＹＫ（登録商標）－３３３［以上、ビックケミー・ジャパン（株）製］等の商品名で市販されているものが挙げられる。 [paint remover]
The composition of the present invention may contain a release agent for the purpose of improving peeling peelability.
As the release agent, any of wax compounds, silicone compounds, and fluorine compounds can be used. Among them, 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.
Specific examples of the release agent 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.
　本発明の組成物が剥離剤を含む場合、その含有量は、樹脂膜からの析出を防ぐ観点から、組成物全体の５質量％以下が好ましい。 When the composition of the present invention contains a release agent, the content thereof is preferably 5% by mass or less of the entire composition from the viewpoint of preventing precipitation from the resin film.
　その他、本発明の組成物は、レベリング剤、消泡剤等その他の成分を含んでいてもよい。 In addition, the composition of the present invention may contain other components such as a leveling agent and an antifoaming agent.
＜組成物の調製＞
　本発明の組成物は、ポリカプロラクトンを主骨格とするウレタン（メタ）アクリレート化合物、単官能性（メタ）アクリレート、必要に応じて多官能（メタ）アクリレート等の各成分を混合することで、調製することができる。
　例えば、撹拌羽根を有するＳＵＳ製調製タンクに各成分を所定量投入し、室温（およそ２３℃）又は加温下で、均一になるまで撹拌する。
　また、必要に応じて、各成分を混合することで得られる組成物を、メッシュ、メンブレンフィルター等でろ過してもよい。
　なお、組成物を構成するある成分が、他の成分の機能を兼ね備える場合には、その点を考慮して、各成分の量を決める必要がある。 <Preparation of composition>
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.
For example, 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.
Moreover, you may filter the composition obtained by mixing each component with a mesh, a membrane filter, etc. as needed.
In addition, when 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.
＜保護膜＞
　以上説明した本発明の組成物を、ガラス基板、樹脂被覆基板、金属基板等に塗布し、光照射及び／又は加熱により硬化させることで、本発明の保護膜（樹脂膜）を形成することができる。即ち、本発明の保護膜は、本発明の組成物の硬化物からなっている。 <Protective film>
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.
　前記塗布方法としては、スピンコート法、スリットコート法、ロールコート法、スクリーン印刷法、アプリケーター法、ディスペンサー法等が挙げられるが、これらに限定されない。
　樹脂膜の厚さは、剥離性等の各特性を再現性よく実現する観点から、好ましくは５～２５０μｍ、より好ましくは５～１５０μｍ、さらに好ましくは１０～５０μｍである。
　膜厚を変化させる方法としては、例えば、組成物中の固形分濃度を変化させたり、基板上への塗布量を変化させたりする方法がある。 Examples of the coating method 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 μm, more preferably 5 to 150 μm, and still more preferably 10 to 50 μm 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.
　以下、実施例を挙げて本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
　なお、実施例において、試料の調製及び物性の分析に用いた装置及び条件は、以下のとおりである。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
（１）ブレードコート
　ドクターブレード：ヨシミツ精機（株）製　ベーカーアプリケーターＹＢＡ－３型、ウエット膜厚１２５μｍ設定
　塗布速度：およそ２０ｃｍ／秒
（２）ＵＶ露光
　装置：（株）オーク製作所製　ＱＲＥ４０１６
　ランプ：ＨＳＬ－３００／Ｂ－ＦＭ
（３）破断強度、引裂き強度、剥離抵抗
　装置：（株）島津製作所製　卓上形精密万能試験機オートグラフＡＧＳ－５００ＮＸ (1) Blade coating Doctor blade: Baker applicator YBA-3 type, manufactured by Yoshimitsu Seiki Co., Ltd., wet film thickness 125 μm setting Coating speed: about 20 cm / sec (2) UV exposure equipment: QRE4016, manufactured by Oak Manufacturing Co., Ltd.
Lamp: HSL-300 / B-FM
(3) Breaking strength, tear strength, peel resistance Equipment: Desktop precision universal testing machine Autograph AGS-500NX, manufactured by Shimadzu Corporation
　また、略記号は以下の意味を表す。 The abbreviations mean the following.
ＵＮ３５２：ポリカプロラクトン系ウレタンアクリレート［根上工業（株）製　アートレジンＵＮ－３５２］
ＵＶ７０００Ｂ：ポリテトラメチレングリコール系ウレタンアクリレート［日本合成化学工業（株）製　紫光（登録商標）ＵＶ－７０００Ｂ］
ＩＢＡ：イソボルニルアクリレート［東京化成工業（株）製］
ＴＭＰＴＡ：トリメチロールプロパントリアクリレート［新中村化学工業（株）製　ＮＫエステルＡ－ＴＭＰＴ］
ＤＥＴＸＳ：２，４－ジエチルチオキサントン［日本化薬（株）製　ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ］
Ｉ９０７：２－メチル－１－（４－メチルチオフェニル）－２－モルホリノプロパン－１－オン［ＢＡＳＦジャパン（株）製　ＩＲＧＡＣＵＲＥ（登録商標）９０７］ UN352: Polycaprolactone-based urethane acrylate [Negami Kogyo Art Resin UN-352]
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]
DETXS: 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.]
［実施例１～２、比較例１］
［組成物の調製］
　下記表１に記載の組成で各原料を配合し、およそ５０℃でマグネチックスターラーを用いて均一になるまで撹拌することで、各組成物（易剥離性保護膜形成用組成物）を調製した。
　なお、ＵＮ３５２は、構造解析により、ポリカプロラクトン骨格を主骨格として有するとともに、その両端にウレタン部位を有し、分子内にシクロヘキシル環を有し、且つ、分子内に２つのアクリレート基を有するものであると認められた。
　また、ＵＶ７０００Ｂは、構造解析により、ポリテトラメチレングリコール骨格を主骨格として有するとともに、その両端にウレタン部位を有し、分子内にシクロヘキシル環を有し、且つ、分子内に２つのアクリレート基を有するものであると認められた。 [Examples 1 and 2, Comparative Example 1]
[Preparation of composition]
Each 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.
Moreover, 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.
［硬化膜の作製と評価］
　得られた各組成物を、それぞれ樹脂被覆基板（予めオプトマー（登録商標）ＮＮ９０１［ＪＳＲ（株）製］を塗布、硬化させた樹脂で被覆されたガラス基板、以下同様）上、及びガラス基板上にブレードコートし塗膜を得た。この塗膜を、空気雰囲気下、露光量５００ｍＪ／ｃｍ２（ＵＶ照度５０ｍＷ／ｃｍ２×１０秒間）のＵＶ光を照射し露光することで、およそ１４０μｍの膜厚を有する硬化膜（易剥離性保護膜）を得た。
　得られた硬化膜の、基板との密着性、基板からの剥離性及び剥離抵抗、タックの有無、破断強度、引裂き強度を、以下の方法により評価した。結果を下記表１に併せて示す。 [Production and evaluation of cured film]
Each of the obtained compositions was placed on a resin-coated substrate (a glass substrate coated with a resin obtained by applying and curing Optomer (registered trademark) NN901 [manufactured by JSR Co., Ltd.] in advance), and on a glass substrate. A coating was obtained by blade coating. The coated film is exposed to UV light with an exposure amount of 500 mJ / cm 2 (UV illuminance of 50 mW / cm 2 × 10 seconds) in an air atmosphere to be a cured film having a film thickness of about 140 μm (easy peelability). A protective film) was obtained.
The obtained cured film was evaluated for adhesion to the substrate, peelability and peel resistance from the substrate, presence / absence of tack, break strength, and tear strength by the following methods. The results are also shown in Table 1 below.
［基板との密着性］
　基板上に作製した硬化膜が下向きになるように基板を持ち、硬化膜の様子を目視で確認し、以下の基準に従い評価した。
　Ａ：自然に脱落することなく密着している
　Ｃ：密着せずに自然に脱落する [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.
A: Adhering naturally without falling off C: Natural falling without adhering
［基板からの剥離性］
　硬化膜を手で基板から剥離する際の様子を、以下の基準に従い評価した。
　Ａ：容易に剥離できる
　Ｃ：容易に剥離できない、又は剥離できない [Peelability from substrate]
The state of peeling the cured film from the substrate by hand was evaluated according to the following criteria.
A: Can be easily peeled C: Cannot be easily peeled off or cannot be peeled off
［基板からの剥離抵抗］
　硬化膜を基板から剥離せずに、長さ１０ｃｍ、幅３ｃｍの短冊状に切り込んだ。基板を試験機に水平に固定し、短冊状に切り込んだ硬化膜の長さ方向の一端を少し剥離しチャックで保持した。このチャックを１ｃｍ／秒の速度で上方へ移動させ、硬化膜を剥離角度９０°で剥離する際の抵抗力［Ｎ］を測定した。抵抗力を剥離させた硬化膜の幅（３ｃｍ）で除して剥離抵抗［Ｎ／ｃｍ］を算出した。 [Peeling resistance from substrate]
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.
［タックの有無］
　硬化膜の表面を指で触り、その感触を以下の基準に従い評価した。
　Ａ：タック（粘着性）がない
　Ｃ：タック（粘着性）がある [Tack presence / absence]
The surface of the cured film was touched with a finger, and the touch was evaluated according to the following criteria.
A: No tack (adhesiveness) C: There is tack (adhesiveness)
［破断強度］
　硬化膜を基板から剥離し、長さ１０ｃｍ、幅２ｃｍの短冊状試験片を切り出した。試験片の長さ方向の両端を試験機のチャックで保持した。片方のチャックを１ｍｍ／秒の速度で移動させることで試験片を引っ張り、試験片が破断したときの抵抗力［Ｎ］を測定した。抵抗力を試験片の断面積［ｃｍ２］で除して破断強度［Ｎ／ｃｍ２］を算出した。
　この破断強度が高いほど、膜は切れにくく靭性があるといえる。 [Breaking strength]
The cured film was peeled off from the substrate, and a strip-shaped test piece having a length of 10 cm and a width of 2 cm was cut out. Both ends in the length direction of the test piece were held by a chuck of a testing machine. The test piece was pulled by moving one chuck at a speed of 1 mm / second, and the resistance [N] when the test piece was broken was measured. The breaking strength [N / cm 2 ] was calculated by dividing the resistance force by the cross-sectional area [cm 2 ] of the test piece.
It can be said that the higher the breaking strength, the harder the film is torn and the toughness.
［引裂き強度］
　硬化膜を基板から剥離し、長さ１０ｃｍ、幅２ｃｍの短冊状試験片を切り出した。試験片の片方の短辺中央から、長さ方向に３ｃｍの切り込みを入れた。切り込みで切断された短辺のそれぞれを試験機のチャックで保持した。片方のチャックを１ｍｍ／秒の速度で移動させ、試験片を引裂く際の抵抗力［Ｎ］を測定した。抵抗力を試験片の厚み［μｍ］で除して引裂き強度［ｍＮ／μｍ］を算出した。
　この引裂き強度が高いほど、膜は切れにくく靭性があるといえる。 [Tear strength]
The cured film was peeled off from the substrate, and a strip-shaped test piece having a length of 10 cm and a width of 2 cm was cut out. A 3 cm cut was made in the length direction from the center of the short side of one of the test pieces. Each of the short sides cut by cutting was held by a chuck of a testing machine. One chuck was moved at a speed of 1 mm / second, and the resistance [N] when tearing the test piece was measured. The tear strength [mN / μm] was calculated by dividing the resistance by the thickness [μm] of the test piece.
It can be said that the higher the tear strength, the harder the film is torn and the toughness.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、本発明の組成物から得られた硬化膜（保護膜）は、樹脂被覆基板及びガラス基板の何れからも容易に剥離可能であった。これに対し、比較例の硬化膜は、樹脂被覆基板からは容易に剥離できたものの、ガラス基板からは容易に剥離できず、また剥離抵抗も大きい結果となった。この理由については未だよく分かっていないが、実施例１の組成物と比較例１の組成物の違いがウレタン（メタ）アクリレート化合物の構造のみであるため、この構造由来の物性が剥離性の基板依存性に影響していると考えられる。
　なお、実施例１の組成物は比較例１の組成物と比べて破断強度（靭性）が低いが、もう一つの靭性の評価基準である引裂き強度が実用上の目安である０．８ｍＮ／μｍを上回っており、易剥離性保護膜として実用上耐えられると考えられる強度であるといえる。また、実施例２の組成物に示される通り、多官能（メタ）アクリレートの含有量を増加することで破断強度を向上させることが可能である。 As shown in Table 1, 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. On the other hand, although 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. Although the reason for this is not yet well understood, 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 / μm, 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.

Claims (7)

  1. ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物と、単官能（メタ）アクリレートを少なくとも含む（メタ）アクリレートと、ラジカル重合開始剤とを含み、前記単官能（メタ）アクリレートの含有量が、前記（メタ）アクリレートの全量に対して５０質量％以上であることを特徴とする、易剥離性保護膜形成用組成物。 A urethane (meth) acrylate compound having a polycaprolactone skeleton as a main skeleton, a (meth) acrylate containing at least a monofunctional (meth) acrylate, and a radical polymerization initiator, wherein the content of the monofunctional (meth) acrylate is The composition for forming an easily peelable protective film, which is 50% by mass or more based on the total amount of the (meth) acrylate.
  2. 前記（メタ）アクリレートが、前記単官能（メタ）アクリレートと、多官能（メタ）アクリレートとを含むことを特徴とする、請求項１記載の易剥離性保護膜形成用組成物。 The composition for forming an easily peelable protective film according to claim 1, wherein the (meth) acrylate contains the monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
  3. 前記単官能（メタ）アクリレートが、環状構造を有する単官能（メタ）アクリレートを含むことを特徴とする、請求項１又は２記載の易剥離性保護膜形成用組成物。 The composition for forming an easily peelable protective film according to claim 1 or 2, wherein the monofunctional (meth) acrylate contains a monofunctional (meth) acrylate having a cyclic structure.
  4. 前記易剥離性保護膜形成用組成物中の前記ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物の含有量が、８０質量％未満であることを特徴とする、請求項１～３の何れか一項記載の易剥離性保護膜形成用組成物。 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. The composition for easily peelable protective film formation as described in any one of Claims.
  5. 前記易剥離性保護膜形成用組成物中の前記ポリカプロラクトン骨格を主骨格とするウレタン（メタ）アクリレート化合物の含有量が、１０質量％以上であることを特徴とする、請求項１～４の何れか一項記載の易剥離性保護膜形成用組成物。 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, The composition for easily peelable protective film formation as described in any one of Claims.
  6. 請求項１～５の何れか一項記載の易剥離性保護膜形成用組成物の硬化物からなることを特徴とする、易剥離性保護膜。 An easily peelable protective film comprising a cured product of the easily peelable protective film forming composition according to any one of claims 1 to 5.
  7. 請求項６記載の易剥離性保護膜を用いた、被塗布体表面の保護方法。 A method for protecting the surface of an object to be coated using the easily peelable protective film according to claim 6.
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