JP6755153B2 - Cosmetic film - Google Patents

Description

The present invention relates to a decorative film.

A decorative film (decorative film) on which characters and figures are printed may be used for decoration and wrapping of building materials, vehicles, signs, etc. (for example, Patent Document 1). Such a decorative film generally includes a colored layer and a protective layer for protecting the colored layer on the base material, and the protective layer is usually required to be transparent.

The protective layer is also required to be flexible so that it can be easily installed on a curved surface and cracks are unlikely to occur even if the weather changes. Further, the protective layer is preferably resistant to chemicals so that it can be cleaned with chemicals.

Japanese Unexamined Patent Publication No. 2006-306020

An inkjet printing method is known as one of the printing methods. Of these, an inkjet printing printer using an ultraviolet curable ink can also form a relatively thick print or a three-dimensional print layer having irregularities. In a decorative film having a protective layer on a print layer formed by an inkjet printing method, the unevenness of the print layer may be large, and the protective layer required for flattening the surfaces thereof tends to be thick. The thicker the protective layer, the less flexible it is and the more noticeable yellowing is. Further, if an attempt is made to improve the flexibility of the protective layer, the chemical resistance tends to be reduced, so that it is difficult to achieve both the flexibility of the protective layer and the chemical resistance in such a decorative film. ..

Therefore, an object of the present invention is to provide a decorative film which is transparent and has a protective layer having both flexibility and chemical resistance.

The decorative film according to one aspect of the present invention is a decorative film in which an inkjet printing layer and a transparent protective layer are provided in this order on a flexible base material, and the transparent protective layer is a acylphosphine oxide-based photopolymerization initiator. Photopolymerization initiator containing phenylglioxylic acid ester photopolymerization initiator, photostabilizer containing hindered amine light stabilizer and ultraviolet absorber, fluorinated (meth) acrylic monomer, monofunctional (meth) acrylic monomer, polyfunctional ( It is an ultraviolet curable product of a monomer composition containing a meta) acrylic monomer and a urethane (meth) acrylate. Note that (meth) acrylic means acrylic or methacrylic, and the same applies to similar skeletons such as (meth) acrylate.

According to the above-mentioned decorative film, the transparent protective layer exhibits a high elongation rate and has flexibility, so that the decorative film provided with the protective layer and the flexible base material can have high flexibility. In addition, the transparent protective layer has high chemical resistance (for example, isopropanol (IPA)), and the decorative film can have high chemical resistance. Here, the fact that the protective layer is transparent means that characters and figures of the inkjet printing layer can be visually recognized through the protective layer.

The fluorinated (meth) acrylic monomer is a fluorinated (meth) acrylic monomer containing a fluoroalkyl group or a fluoroalkyl ether group and having a siloxane bond, and / or a siloxane bond containing a fluoroalkyl group or a fluoroalkyl ether group. It may be a fluorinated (meth) acrylic monomer having no.

Further, in the decorative film, the hindered amine light stabilizer may contain a high molecular weight hindered amine light stabilizer and a low molecular weight hindered amine light stabilizer, and the urethane (meth) acrylate is an aliphatic urethane polyfunctional (meth). It may be an acrylate. Further, the light stabilizer may include a high molecular weight hindered amine type light stabilizer and a low molecular weight hindered amine type light stabilizer.

By using the fluorinated (meth) acrylic monomer and urethane (meth) acrylate as described above, the transparency, flexibility and chemical resistance of the protective layer of the decorative film are further improved. By using a hindered amine-based light stabilizer, the weather resistance and curability will be further improved.

In the decorative film of another aspect of the present application, the pressure-sensitive adhesive layer may be provided on the surface of the flexible base material opposite to the surface on which the inkjet printing layer is provided. The decorative film of such an aspect can be easily attached to the adherend, and particularly exhibits good adhesive force to the adherend having irregularities or curved surfaces.

According to the present invention, it is possible to provide a decorative film having a protective layer having transparency, flexibility and chemical resistance.

It is sectional drawing which shows an example of the decorative film which concerns on embodiment.

Hereinafter, embodiments of the decorative film will be described in detail with reference to the drawings. In this description, the same code will be used for the same element, and duplicate description will be omitted.

FIG. 1 is a cross-sectional view showing a decorative film according to an embodiment of the present invention. The decorative film 1 shown in FIG. 1 includes a flexible base material 10, an inkjet printing layer 20, and a transparent protective layer 30, with an inkjet printing layer 20 on the flexible base material 10 and a transparent protective layer 30 on the inkjet printing layer 20. However, each is provided. The transparent protective layer 30 has a function of protecting the inkjet printing layer 20 from scratches and stains.

The flexible base material 10 is a film base material having flexibility, and for example, a polyvinyl chloride film base material, a (meth) acrylic film base material, a polyolefin base material, a metal foil (aluminum foil, etc.) and the like are used. The thickness of the flexible base material 10 can be appropriately determined according to the material and application of the base material, and can be, for example, 5 to 100 μm (further, 10 to 50 μm). Examples of the polyvinyl chloride film base material used as the flexible base material 10 include Scotchcal graphic film IJ180-10 (manufactured by 3M). This flexible base material is a white film made of polyvinyl chloride, and has an acrylic pressure-sensitive adhesive layer on a surface opposite to the surface on which the inkjet printing layer 20 is provided. Since this flexible base material has flexibility and has an adhesive layer, it can be attached to various surfaces such as a gentle quadric surface and a cubic curved surface. The thickness of the polyvinyl chloride film base material constituting the Scotchcal graphic film IJ180-10 is 50 μm, and the thickness including the pressure-sensitive adhesive layer is 90 μm.

The inkjet printing layer 20 is a layer printed by an inkjet method, and is provided on the flexible base material 10 by an inkjet printer (for example, UJV500 manufactured by Mimaki Engineering Co., Ltd.) using an ultraviolet curable ink. An LED (light emitting diode) is an example of a light source for curing ink with ultraviolet rays. In the inkjet printing layer 20, characters and figures are formed by, for example, ultraviolet curable cyan pigment ink, magenta pigment ink, yellow pigment ink, and black pigment ink. The thickness of the inkjet printing layer 20 using the ultraviolet curable ink can be 0.1 μm or more, 5 μm or more, 10 μm or more, or 50 μm or more.

The transparent protective layer 30 covers the inkjet printing layer 20. For example, the transparent protective layer 30 is formed by applying a composition for forming a transparent protective layer (monomer composition) before curing onto the inkjet printing layer 20 and curing it with ultraviolet rays. It is possible. As described above, this monomer composition contains a photopolymerization initiator, a fluorinated (meth) acrylic monomer, a monofunctional (meth) acrylic monomer, a polyfunctional (meth) acrylic monomer, a urethane (meth) acrylate, and a light stabilizer. To do. The monomer composition may contain an additive component as described later, if necessary. The thickness of the transparent protective layer 30 after being cured by ultraviolet rays can be about 10 μm.

Hereinafter, each component of the monomer composition that forms the transparent protective layer 30 by ultraviolet curing will be described in detail.

The monomer composition contains a photopolymerization initiator. The photopolymerization initiator is a material that initiates a polymerization reaction by generating radicals or the like at least by ultraviolet rays, and in the present embodiment, it contains an acylphosphine oxide-based photopolymerization initiator and a phenylglioxylate ester-based photopolymerization initiator. .. As described above, by including the two types of photopolymerization initiators, curing on the surface and inside of the protective layer can be promoted more uniformly. It suffices to contain the above-mentioned two types of polymerization initiators, and may contain other types of photopolymerization initiators. The content of the photopolymerization initiator is preferably 1 to 10% by mass or 3 to 8% by mass based on the total amount of the monomer composition. The total amount of the acylphosphine oxide-based photopolymerization initiator and the phenylglioxylic acid ester-based photopolymerization initiator in the total amount of the photopolymerization initiator can be, for example, 80% by mass or more, and 90% by mass or more. Is preferable, and 100% by mass is preferable.

As the acylphosphine oxide-based photopolymerization initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (MAPO) (BASF, IrgacureTPO), bis (2,4,6-trimethylbenzoyl) -phenyl Examples thereof include phosphine oxide (BAPO) (manufactured by BASF, Irgacure 819) and 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide. The acylphosphine oxide-based photopolymerization initiator belongs to the intramolecular cleavage type photopolymerization initiator. These photopolymerization initiators mainly contribute to the internal curing of the protective layer. That is, it contributes to the curability of the lower layer of the protective layer, and can improve the adhesion to the printing layer of the lower layer, for example.

Examples of the phenylglycoxylic acid ester-based photopolymerization initiator include benzophenylacetic acid 2- [2-oxo-2-], which is a methyl benzoyllate acid-based photopolymerization initiator such as phenylglycylic acid methyl ester (BASF, Irgacare MBF). Examples thereof include a mixture of a phenylacetoxyethoxy] ethyl ester and a 2- (2-hydroxyethoxy) ethyl ester of oxophenylacetic acid (Irgacure 754 manufactured by BASF), and a 2- (2-hydroxyethoxy) ethyl ester of oxophenylacetic acid. The phenylglyoxylic acid ester-based photopolymerization initiator is a hydrogen abstraction type photopolymerization initiator and is classified into an intramolecular hydrogen abstraction type. These photopolymerization initiators mainly contribute to surface hardening and have the effect of improving the surface chemical resistance of the protective layer. As described above, by using two kinds of photopolymerization initiators, uniform curing is possible in the thickness direction of the protective layer.

Among the intramolecular cleavage type photopolymerization initiators, benzylketal-based photopolymerization initiators and α-hydroxyalkylphenone, which are classified as alkylphenone-based photopolymerization initiators, can be used as photopolymerization initiators in addition to the above. There are system photopolymerization initiators and α-aminoalkylphenone system photopolymerization initiators. Examples of the benzyl ketal-based photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651 manufactured by BASF), and examples of the α-hydroxyalkylphenone-based photopolymerization initiator include α-hydroxyalkylphenone-based photopolymerization initiators. 1-Hydroxy-cyclohexyl-phenyl-ketone (BASF, Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (BASF, Irgacure 1173), 1- [4- ( 2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (BASF, Irgacure 2959), 2-hydroxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one (BASF, Irgacure 127) can be mentioned.

Examples of the α-aminoalkylphenone-based photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (BASF, Irgacure 907) and 2-benzyl-2-. Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF, Irgacure 369E), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( 4-Morphorinyl) phenyl] -1-butanone (BASF, Irgacure 379EG) can be mentioned.

As the photopolymerization initiator, an oxime ester-based photopolymerization initiator and a titanosen-based photopolymerization initiator, which are intramolecular cleavage type photopolymerization initiators, can also be used. Examples of the oxime ester-based photopolymerization initiator include 1,2-octanedione 1,4- (4-phenylthio) -2- (O-benzoyl oxime) (IrgacureOXE01 manufactured by BASF).

Further, as the photopolymerization initiator, an intermolecular hydrogen abstraction type photopolymerization initiator, which is a kind of hydrogen abstraction type photopolymerization initiator, can also be used. Examples of the intermolecular hydrogen abstraction type photopolymerization initiator include benzophenone / amine, 4,4'-bis (dimethylamino) benzophenone / benzophenone, and thioxanthone / amine. In addition to these, bifunctional (intramolecular cleavage and hydrogen abstraction) photopolymerization initiators can also be used. Bifunctional photopolymerization initiators for intramolecular cleavage and intermolecular hydrogen abstraction include 1-propanone, 1- [4- [4-benzoylphenyl] thio] phenyl] -2-methyl-2-[(4-methyl). Phenyl) sulfonyl] (Esacure 1001M, manufactured by Lamberti).

In addition to the photopolymerization initiator described above, the monomer composition contains a light stabilizer. The light stabilizer is a material that prevents deterioration due to light such as ultraviolet rays by acting such as blocking ultraviolet rays, absorbing ultraviolet rays, extinguishing light, and preventing radical chains, and contributes to improving the weather resistance of the protective layer. It is roughly classified into a scavenger and a peroxide decomposing agent, and an ultraviolet absorber is included as a radical chain initiation inhibitor, and a hindered amine-based light stabilizer (HALS) is included as a radical scavenger. In this embodiment, a hindered amine-based light stabilizer and an ultraviolet absorber are included. The light stabilizer may contain the above two types of light stabilizers, and may contain other types of light stabilizers. The content of the light stabilizer is preferably 1 to 10% by mass or 3 to 8% by mass based on the total amount of the monomer composition. The total amount of the hindered amine-based light stabilizer and the ultraviolet absorber to the total amount of the light stabilizer can be, for example, 80% by mass or more, preferably 90% by mass or more, and preferably 100% by mass.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and oxalic acid anilide-based ultraviolet absorbers. These ultraviolet absorbers can be used alone or in a plurality of types, but preferably contain at least a triazine-based ultraviolet absorber.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole (manufactured by BASF, TINUVINPS) and 2- (2H-benzotriazole-2-yl) -4. , 6-Bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF, TINUVIN 900), 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl)- Examples thereof include 4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN928 manufactured by BASF), and examples of the triazine-based ultraviolet absorber include 2- (4,6-bis (2,4-dimethyl)). Phenyl) -1,3,5-triazine-2-yl) -5-Hydroxyphenyl reaction product with oxylan (TINUVIN400, manufactured by BASF), 2- (2,4-dihydroxyphenyl) -4,6- Reaction product of bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate (BASF, TINUVIN 405), 2,4-bis [2-hydroxy -4-Butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (TINUVIN 460, manufactured by BASF).

Examples of the salicylate-based UV absorber include phenyl salicylate and 4-t-butylphenyl salicylate, and examples of the cyanoacrylate-based UV absorber include ethyl-2-cyano-3,3-diphenylacrylate and 2-ethylhexyl-2-. Examples thereof include cyano-3,3-diphenylacrylate, and examples of the oxalic acid anilide-based ultraviolet absorber include 2-ethyl-2'-ethoxy-oxalarinide.

Another component of the light stabilizer is a hindered amine light stabilizer. The hindered amine light stabilizer refers to a light stabilizer having a 2,2,6,6-tetramethylpiperidine skeleton, and in the present embodiment, a high molecular weight hindered amine light stabilizer and a low molecular weight hindered amine light stabilizer are used. It is preferable to use them together. Here, the low molecular weight means a molecular weight of less than 1000, and the high molecular weight means a molecular weight of 1000 or more. The low molecular weight hindered amine light stabilizer traps radicals, prevents deterioration due to light such as ultraviolet rays, and contributes to improvement of weather resistance of the protective layer. However, if the amount is too large, it becomes difficult to cure the protective layer itself. It is preferable to increase the amount of the high molecular weight hindered amine light stabilizer to enhance the curability of the protective layer. In consideration of this point, the ratio of the mass of the low molecular weight hindered amine light stabilizer (LowMHA) to the mass of the high molecular weight hindered amine light stabilizer (HighMHA), that is, (LowMHA) :( HighMHA) is 1: 50 to 1. : 200 (further, 1:50 to 1: 100) is preferable.

Examples of low molecular weight hindered amine-based light stabilizers include 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine (BASF, Linostab 1198) and sebacate-bis- [2,2,6,6. -Tetramethyl-4-piperidyl] (ADEKA, Adecastab LA-77), sebacate-bis- [N-methyl-2,2,6,6-tetramethyl-4-piperidyl] (BASF, TINUVIN765) ), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] Butylmalonate (manufactured by BASF) , TINUVIN144), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (Adekastab LA-52, manufactured by ADEKA).

As the high molecular weight hindered amine-based light stabilizer, for example, a polymer-type light stabilizer having a 2,2,6,6-tetramethylpiperidine skeleton in the side chain can be used. High-molecular-weight hindered amine-based photostabilizers include N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexanediamine and morpholin-2,4,6-trichloro-1. , 3,5-Triazine polymer (Cytec, CyberUV-3259), succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (BASF, TINUVIN622) ), {2,2,6,6-tetramethyl-4-piperidyl / β, β, β', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,) 5) Undecane] Dimethyl} -1,2,3,4-butanetetracarboxylate (Adekastab LA-68 manufactured by ADEKA) can be mentioned.

The monomer composition further contains a fluorinated (meth) acrylic monomer. Here, the fluorinated (meth) acrylic monomer has a (meth) acryloyl group, and a part or all of hydrogen atoms other than the hydrogen atom in the acryloyl group are substituted with fluorine atoms. The solid content of the fluorinated (meth) acrylic monomer agent is preferably about 0.01% by mass or more and about 0.05% by mass or more based on the total amount of the monomer composition. The solvent resistance of the protective layer can be improved by using a fluorinated (meth) acrylic monomer agent. On the other hand, when the content of the fluorinated (meth) acrylic monomer agent increases, it becomes difficult for the adhesive to adhere to the surface of the protective layer. Therefore, in the case of layering, the solid fluorinated (meth) acrylic monomer agent is solidified. The content is preferably about 1% by mass or less, about 0.5% by mass or less, or about 0.2% by mass or less based on the total amount of the monomer composition.

Examples of the fluorinated (meth) acrylic monomer include a fluorinated (meth) acrylic monomer having a fluorinated portion and a siloxane bond, and a fluorinated (meth) acrylic monomer having a fluorinated portion and not having a siloxane bond. In the present embodiment, it is preferable to include at least one of these. Examples of the former include a fluorinated (meth) acrylic monomer containing a fluoroalkyl group or a fluoroalkyl ether group and having a siloxane bond, and the latter includes a fluoroalkyl group or a fluoroalkyl ether group and having a siloxane bond. A non-fluorinated (meth) acrylic monomer can be exemplified.

Preferable examples of the fluorinated (meth) acrylic monomer are KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.) and RS-76-NS (manufactured by DIC Corporation). KY-1203 is composed of a fluorinated (meth) acrylic monomer (20% by mass), methyl isobutyl ketone (60% by mass) and methyl ethyl ketone (20% by mass). RS-76-NS is composed of a fluorinated (meth) acrylic monomer (20% by mass) and dipropylene glycol diacrylate (80% by mass). The fluorinated (meth) acrylic monomer contained in KY-1203 corresponds to a fluorinated (meth) acrylic monomer having a fluorinated portion and a siloxane bond, and is fluorinated (meth) contained in RS-76-NS. The acrylic monomer corresponds to a fluorinated (meth) acrylic monomer having a fluorinated moiety and no siloxane bond.

Examples of the fluorinated (meth) acrylic monomer containing a fluoroalkyl group or a fluoroalkyl ether group and having a siloxane bond include compounds represented by the following general formula (1).
{CH ₂ = CR ^0- CO-X- (R ¹ ) _n- Y-} _m- R _f0 ... (1)
In the formula, R ⁰ is a hydrogen atom or a methyl group, X is a single bond, -O-, -NH- or -NR ^2- (R ² is a monovalent organic group), R ¹ is a linear, cyclic or cyclic group. A branched divalent organic group (the divalent organic group may be a hydrocarbon group or an organic group having a bonding group such as a urethane bond, an amide bond, or an ether bond), Y is , A divalent group derived from a linear or cyclic organosiloxane, R _f0 is a perfluoroalkane, a partial fluoroalcan, a perfluoroalkyl ether or an m-valent group derived from a partial fluoroalkyl ether, n is 0 or 1 , M is 1 to 10 (preferably 1 to 6). Y is bonded to R ¹ or R _f0 by a silicon atom or an oxygen atom in Y. Examples of the organosiloxane include dimethylsiloxane, methylphenylsiloxane, and diphenylsiloxane. Among the compounds represented by the general formula (1), those having m of 2 or more (those having the functional number of (meth) acryloyl group of 2 or more), that is, polyfunctional fluorinated (meth) acrylic monomers can be used. Preferably, the use of such a monomer improves chemical resistance.

The polyfunctional fluorinated (meth) acrylic monomer containing a siloxane bond is, for example, a linear or cyclic oligosiloxane or polysiloxane (hydrogensiloxane) containing 3 or more Si—H bonds, and one or an ethylenically unsaturated group. A perfluoro compound such as a perfluoropolyether compound having 2 or more is added (hydrosilylated) in the presence of a platinum catalyst or the like in an amount less than 1 equivalent to the Si—H bond, and a hydroxyl group is contained in the remaining Si—H bond. It can also be synthesized by adding (hydrosilylating) an ethylenically unsaturated compound in the presence of a platinum catalyst or the like, and then reacting the hydroxyl group with an epoxy (meth) acrylate, a urethane (meth) acrylate or the like. The partial molecular weight of the perfluoro moiety calculated from the chemical formula can be 500 to 30,000.

When Y is derived from a cyclic organosiloxane, the cyclic organosiloxane is preferably a cyclic organosiloxane having 3 to 7 silicon atoms, such as tetramethylcyclotetrasiloxane and pentamethylcyclopentasiloxane.

Among the compounds represented by the general formula (1), those in which Y is a linear organosiloxane include, for example, those represented by the following (1a).
_{CH 2 = CH-COO-C} p H 2p -NHCOO-C q H 2q - (Si (CH 3) 2 -O) r -Si (CH 3) 2 -C t H 2t -C l F 2l -C t _{H 2t -Si (CH 3) 2} - (O-Si (CH 3) 2) r -OOCNH-C p H 2p -OCO-CH = CH 2 ··· (1a)
In the formula, t, p, q and l independently represent 1 to 6, and r represents 1 to 1000, respectively.

Among the compounds represented by the general formula (1), those in which Y is a cyclic organosiloxane include, for example, those represented by the following (1b) and (1c).

In the above formula, R _f is a divalent group derived from a perfluoroalkane, a partial fluoroalkane, a perfluoroalkyl ether or a partially fluoroalkyl ether. Examples of R _f include −CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2- (p / q = 0.9, p + q≈45), which is a divalent perfluoropolyether group. ..

Examples of the fluorinated (meth) acrylic monomer containing a fluoroalkyl group or a fluoroalkyl ether group and having no siloxane bond include compounds represented by the following general formula (2).
{CH ₂ = CR ^0- CO-X- (R ¹ ) _n- } _m- R _f0 ... (2)
In the formula, R ⁰ , X, R ¹ , R _f0 , n and m are synonymous with the above. In addition, it is preferable to use one having m of 2 or more, that is, a polyfunctional fluorinated (meth) acrylic monomer, and by using such a monomer, chemical resistance is improved.

As the fluorinated (meth) acrylic monomer containing a fluoroalkyl group or a fluoroalkyl ether group and not having a siloxane bond, a polyfunctional perfluoroether (meth) acrylate as shown below can be adopted.

HFPO-C (O) N (H) CH (CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) N (H) C (CH ₂ CH ₃ ) (CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) NHC (CH ₂ OC (O) CH = CH ₂ ) ₃ ;
HFPO-C (O) N (CH ₂ CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) NHCH ₂ CH ₂ N (C (O) CH = CH ₂ ) CH ₂ OC (O) CH = CH ₂ ;
HFPO-C (O) NHCH (CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) NHC (CH ₃ ) (CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) NHC (CH ₂ CH ₃ ) (CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) NHCH ₂ CH (OC (O) CH = CH ₂ ) CH ₂ OC (O) CH = CH ₂ ;
HFPO-C (O) NHCH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ OC (O) CH = CH ₂ ) ₂ ;
HFPO-C (O) OCH ₂ C (CH ₂ OC (O) CH = CH ₂ ) ₃ ;
HFPO-C (O) NH (CH ₂ CH ₂ N (C (O) CH = CH ₂ )) ₄ CH ₂ CH ₂ NC (O) -HFPO;
CH ₂ = CHC (O) OCH ₂ CH (OC (O) HFPO) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OC (O) HFPO) CH ₂ OCOCH = CH ₂ ;
HFPO-CH ₂ O-CH ₂ CH (OC (O) CH = CH ₂ ) CH ₂ OC (O) CH = CH ₂

In the above formula, HFPO is a compound containing a perfluoroether moiety represented by F (CF (CF ₃ ) CF ₂ O) _n CF (CF ₃ ) − (n is 2 to 15) and such a perfluoroether moiety. Means.

The polyfunctional perfluoropolyether (meth) acrylate includes, for example, a poly (hexafluoropropylene oxide) ester such as HFPOC (O) OCH _3n or a poly (hexafluoropropylene oxide) acid halide HFPO-C (O) F, and at least 3 of them. Reaction with one alcohol or a material containing a primary or secondary amino group to produce an HFPO-amide polyol or polyamine, an HFPO-ester polyol or polyamine, an HFPO-amide, or a mixed amine and an HFPO-ester having an alcohol group. It can be synthesized through a first step, a second step of (meth) acrylicizing an alcohol group and / or an amine group with (meth) acryloyl halide, (meth) acrylic acid anhydride, or (meth) acrylic acid. Alternatively, reactive perfluoroethers and poly (meth) acrylates, such as an adduct of HFPO-C (O) N (H) CH ₂ CH ₂ CH ₂ N (H) CH ₃ with trimethylolpropane triacrylate (TMPTA). It can also be synthesized using the Michael-type addition reaction with.

In addition to the above, the monomer composition can contain a monofunctional (meth) acrylic monomer. The use of a monofunctional (meth) acrylic monomer can impart flexibility to the protective layer. Here, the monofunctional (meth) acrylic monomer means that the functional number of the (meth) acryloyl group is 1. The content of the monofunctional (meth) acrylic monomer is preferably 50 to 90% by mass or 60 to 80% by mass based on the total amount of the monomer composition.

Examples of the monofunctional (meth) acrylic monomer include (meth) acrylic acid alkyl esters in which the alkyl group is linear or branched and the number of carbon atoms is 1 to 22 (preferably 1 to 18 and further 1 to 12). Can be mentioned. Other monofunctional (meth) acrylic monomers include IBOA (isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), EEEA (ethylcarbitol acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), PEA (phenoxyethyl acrylate, Osaka). Examples include CTFA (Cyclic Trimethylol Propaneformal Acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and THFA (Tetrahydrofurfuryl Acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The monomer composition can also contain a polyfunctional (meth) acrylic monomer. Here, the polyfunctional (meth) acrylic monomer means that the number of functional numbers of the (meth) acryloyl group is 2 or more. The use of the polyfunctional (meth) acrylic monomer can impart appropriate hardness to the protective layer softened by the use of the monofunctional (meth) acrylic monomer, and can impart blocking resistance. The content of the polyfunctional (meth) acrylic monomer is preferably 1 to 20% by mass or 5 to 15% by mass based on the total amount of the monomer composition.

Preferable examples of the polyfunctional (meth) acrylic monomer are HDDA (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and PETTA (pentaerythritol tetraacrylate, manufactured by Sartomer, USA). As the polyfunctional (meth) acrylic monomer, an amine-modified diacrylate (CN371, manufactured by Sartmer, amine value: 136 mgKOH / g) can also be adopted.

By further containing urethane (meth) acrylate in the monomer composition, the protective layer can be imparted with extensibility. Urethane (meth) acrylate is a (meth) acrylate having a urethane polymer or urethane oligomer skeleton, and may be monofunctional or polyfunctional, but from the viewpoint of chemical resistance, polyfunctional urethane (meth) acrylate. Is preferable. The content of urethane (meth) acrylate is preferably 1 to 30% by mass or 10 to 25% by mass based on the total amount of the monomer composition. Here, the polyfunctional urethane (meth) acrylate means that the number of functional numbers of the (meth) acryloyl group is 2 or more.

Urethane (meth) acrylate is a (meth) acrylic obtained by synthesizing an isocyanate-terminated urethane polymer or oligomer from, for example, polyisocyanate and polyol, and having an isocyanate group-reactive functional group (for example, a hydroxyl group, an amino group, or a carboxy group). It can be obtained by reacting with a compound. Urethane (meth) acrylate is composed of a hydroxyl group-terminated urethane polymer or oligomer synthesized from polyisocyanate and polyol, and a (meth) acrylic compound having a hydroxyl group-reactive functional group (for example, isocyanate group, amino group, carboxy group). It can also be obtained by reacting. Monofunctional urethane (meth) acrylates and polyfunctional urethane (meth) acrylates having various functional groups can be obtained depending on the type of polyisocyanate or polyol and the type of terminal group of the urethane polymer or oligomer obtained.

As the polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate or the like can be used, and as the polyol, a polyester-based polyol or a polyether-based polyol can be used. As the urethane (meth) acrylate, it is preferable to use an aliphatic urethane polyfunctional (meth) acrylate, particularly an aliphatic urethane di (meth) acrylate. Examples of the aliphatic urethane di (meth) acrylate include CN981 (aliphatic urethane acrylate oligomer, manufactured by Sartmer).

The monomer composition may contain additional components in addition to the above components. Examples of the additive component include fillers, plasticizers, silane coupling agents, surface conditioners, and the like, and suitable examples of the surface conditioners include Tego Flow 425 (polyether-modified polysiloxane copolymer, manufactured by Evonik Industries, Inc.) and Polyflow KL401. (Modified silicone, manufactured by Kyoeisha Chemical Co., Ltd.).

The ratio of fluorinated (meth) acrylic monomer, monofunctional (meth) acrylic monomer, polyfunctional (meth) acrylic monomer and urethane (meth) acrylate in the monomer composition is such that the transparent protective layer becomes transparent when cured by ultraviolet rays. It is preferable that the glass transition temperature (Tg), softening temperature, cross-linking density and the like are sufficiently high so as not to be in a sticky state or a flowing state. For example, from this point of view, Tg is 20 ° C to 60 ° C, more preferably 30 ° C to 50 ° C. In addition, Tg can be obtained from the following Fox formula.
1 / Tg = X ₁ / (Tg ₁ + 273.15) + X ₂ / (Tg ₂ + 273.15) + ... + X _n / (Tg _n + 273.15)
Here, Tg ₁ is the glass transition temperature (° C.) of the homopolymer of the component 1, Tg ₂ is the glass transition temperature (° C.) of the homopolymer of the component 2, and Tg _n is the glass transition temperature of the homopolymer of the component n. (° C.), X ₁ is the mass fraction of the monomer of the component 1 added during the polymerization, X ₂ is the mass fraction of the monomer of the component 2 added during the polymerization, and X _n is the mass fraction of the monomer of the component 2 added during the polymerization. The mass fraction of the monomer of the added component n and X ₁ + X ₂ + ... + X _n = 1.

The monomer composition of the case of UV curing, UV intensity is preferably 1000 mW / cm ² from 200 mW / cm ^2. Further, when curing with ultraviolet rays, it is preferable to carry out the curing in a state where oxygen is blocked in order to increase the degree of polymerization. For example, in a nitrogen purge environment.

A decorative film can be obtained by applying the above-mentioned monomer composition on an inkjet printing layer of a flexible base material on which an inkjet printing layer is formed, and curing the monomer composition with ultraviolet rays to form a transparent protective layer. The thickness of the flexible base material is 20 to 300 μm, and the thickness of the inkjet printing layer is 0.1 μm or more, 5 μm or more, 10 μm or more, or 50 μm or more by using an ultraviolet curable ink to express a three-dimensional effect. It is also possible. On the other hand, when nonflammability is required, it is preferably 200 μm or less, 100 μm or less, or 80 μm or less. The transparent protective layer is preferably thick enough to cover and protect the print layer, and is preferably 5 μm or more, 10 μm or more, or 30 μm or more depending on the shape and thickness of the print layer. On the other hand, when nonflammability is required, it is desirable to set it to 200 μm or less, 100 μm or less, or 50 μm or less.

An adhesive layer may be provided on the surface of the flexible base material opposite to the surface on which the inkjet printing layer is provided. This pressure-sensitive adhesive layer can be formed of, for example, a (meth) acrylic pressure-sensitive adhesive, a polyolefin-based pressure-sensitive adhesive, a styrene block copolymer-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like, and has a typical thickness of 10 to 50 μm.

Hereinafter, the decorative film will be further described with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to the following examples. The abbreviations, compound names, product names, sources, etc. of the materials used in Examples and Comparative Examples are as follows.
IBOA: Isobornyl acrylate (Osaka Organic Chemical Industry Co., Ltd.).
EEEA: Ethylcarbitol acrylate (Osaka Organic Chemical Industry Co., Ltd.).
PEA: Phenoxyethyl acrylate (Osaka Organic Chemical Industry).
CTFA: Cyclic trimethylolpropane formal acrylate (Osaka Organic Chemical Industry Co., Ltd.).
HDDA: 1,6 hexanediol diacrylate (Osaka Organic Chemical Industry Co., Ltd.).
PETTA: Pentaerythritol tetraacrylate (sertomer).
CN981: Urethane acrylate oligomer (sertmer).
TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (BASF).
Irgacure MBF: Phenylglycolic acid methyl ester (BASF).
Esacure 1001M: Ketosulfonic acid type photopolymerization initiator (Lamberti).
Linostab 1198: Light Stabilizer for Woodworking (BASF).
Cysorb UV3529: Hindered amine-based light stabilizer (Cytec).
Tinuvin 405: Hydroxyphenyltriazine-based ultraviolet absorber (BASF).
Polyflow KL401: Modified silicone (Kyoeisha Chemical Co., Ltd.).
KY-1203 (solid content 20 wt%): Fluoroacrylic compound (Shin-Etsu Chemical).
RS-76-NS: Fluorine-containing group, hydrophilic group, lipophilic group, ultraviolet reactive group-containing oligomer (DIC).

Tables 1 and 2 are tables showing the monomer composition components (mass%) contained in the protective layer constituting the decorative film according to Examples and Comparative Examples, respectively. The total of the monomer composition components shown in this table means the total of the material solid components of the protective layer before curing.

[Example 1]
Photopolymerization initiator (TPO, UVure MBF), monofunctional (meth) acrylic monomer (IBOA, EEEA, PEA, CTFA), polyfunctional (meth) acrylic monomer (PETTA), aliphatic urethane di (meth) acrylate (CN981), A stirring solution was prepared by stirring a hindered amine-based light stabilizer (Liginostab 1198, Catalyst UV3529) and an ultraviolet absorber (Tinuvin 405) for about 60 minutes using a mixer (TK Robomix, manufactured by Tokushu Kika Kogyo Co., Ltd.). To this stirred solution, 1% by mass of fluorinated (meth) acrylic monomer (KY-1203) and a surface conditioner (Polyflow KL401) are added, and the mixture is further stirred for about 5 minutes, and the solution for the transparent protective layer (monomer composition). The thing) was made.

Next, the above-mentioned monomer composition was applied onto the inkjet printing layer provided on the Scotchcal graphic film IJ180-10 using a wire bar (# 7). The inkjet printing layer was formed by an inkjet printer UJV500 (manufactured by Mimaki Engineering Co., Ltd.). The ink densities were 66.7% cyan pigment ink, 66.7% magenta pigment ink, 66.7% yellow pigment ink, and 100% black pigment ink.

Subsequently, the monomer composition was cured using a fusion ultraviolet lamp (Hbulb) to prepare a decorative film. The wavelength range of the ultraviolet lamp was set to UVA, and the solution was irradiated with ultraviolet rays in a nitrogen atmosphere. The illuminance of the ultraviolet lamp was 600 mW / cm ² , and the integrated irradiation amount was 500 mJ / cm ² . The thickness of the protective layer after irradiation with the ultraviolet lamp was about 10 μm.

[Example 2]
A stirring solution similar to that of Example 1 was prepared, and the fluorinated (meth) acrylic monomer (RS-76-NS) was added to the stirred solution instead of the fluorinated (meth) acrylic monomer (KY-1203) of Example 1. Was added together with a surface conditioner (Polyflow KL401) and stirred for an additional 5 minutes to prepare a solution of the protective layer. Subsequently, a decorative film was produced by the same production procedure as in Example 1.

[Example 3]
A decorative film was prepared by the same composition and preparation procedure as in Example 1 except that the composition of the fluorinated (meth) acrylic monomer (KY-1203) was changed.

[Example 4]
A decorative film was prepared by the same composition and preparation procedure as in Example 1 except that the composition of the fluorinated (meth) acrylic monomer (KY-1203) was changed.

[Example 5]
A decorative film was prepared by the same composition and preparation procedure as in Example 1 except that the compositions of the monofunctional (meth) acrylic monomer (PEA) and the fluorinated (meth) acrylic monomer (KY-1203) were changed.

[Example 6]
A decorative film was prepared by the same composition and preparation procedure as in Example 1 except that the compositions of the monofunctional (meth) acrylic monomer (PEA) and the fluorinated (meth) acrylic monomer (KY-1203) were changed.

[Comparative Example 1]
A decorative film was prepared by the same composition and preparation procedure as in Example 1 except that the fluorinated (meth) acrylic monomer was not used.

[Comparative Example 2]
The composition is the same as that of Example 1 except that the compositions of the polyfunctional (meth) acrylic monomer (PETTA) and the fluorinated (meth) acrylic monomer (KY-1203) are changed and urethane (meth) acrylate is not used. And the production procedure was used to produce a decorative film.

[Comparative Example 3]
Example 1 and Example 1 except that the compositions of the monofunctional (meth) acrylic monomer (IBOA) and the fluorinated (meth) acrylic monomer (KY-1203) were changed and the polyfunctional (meth) acrylic monomer (PETTA) was not used. A decorative film was prepared by the same composition and preparation procedure.

[Comparative Example 4]
The same composition and preparation as in Example 1 except that the compositions of the monofunctional (meth) acrylic monomer (CTFA) and the fluorinated (meth) acrylic monomer (KY-1203) were changed and urethane (meth) acrylate was not used. A decorative film was prepared by the procedure.

[Comparative Example 5]
The composition of the monofunctional (meth) acrylic monomer (IBOA, PEA) was changed, and the polyfunctional (meth) acrylic monomer (HDDA) was used instead of the polyfunctional (meth) acrylic monomer (PETTA), and photopolymerization was started. A decorative film was prepared by the same composition and preparation procedure as in Example 1 except that the agent (TPO) and the fluorinated (meth) acrylic monomer were not used.

[Comparative Example 6]
The composition of the monofunctional (meth) acrylic monomer (IBOA, PEA) was changed, and the polyfunctional (meth) acrylic monomer (HDDA) was used instead of the polyfunctional (meth) acrylic monomer (PETTA), and photopolymerization was started. A decorative film according to the same composition and preparation procedure as in Example 1 except that a photopolymerization initiator (Esacure 1001M) was used instead of the agent (TPO, IrgacureMBF) and a fluorinated (meth) acrylic monomer was not used. Was produced.

Tables 3 and 4 are tables showing the results of evaluating the characteristics of the decorative films of Examples and Comparative Examples, respectively. Tables 3 and 4 show the evaluation results obtained by performing four measurements: color difference measurement, gloss value measurement, elongation measurement, and IPA resistance test. All of these four measurements / tests obtained "A (good)" were comprehensively evaluated as "A (good)", and one of the four measurements gave "B (bad)". Those were comprehensively evaluated as "B (defective)".

In the color difference measurement, the L * a * b * value of the decorative film was measured using a spectrophotometer CM-3700d (manufactured by Konica Minolta). The light source for measurement was D65, and the observation angle was 10 degrees. A first decorative film sample having a protective layer on the inkjet printing layer and a second decorative film sample without a protective layer on the inkjet printing layer were prepared. For the first decorative film sample, the protective layer was irradiated with light to measure the L * a * b * value, and for the second decorative film sample, the inkjet printing layer was irradiated with light to L * a * b *. The value was measured.

In the calculation of the color difference ΔE *, the L * a * b * value of the first decorative film sample is expressed as L * 1, a * 1, b * 1, and the L * a * b * value of the second decorative film sample is expressed. Was expressed as L * 2, a * 2, b * 2, and the following formula was followed.
ΔE * = [(L * 2-L * 1) ² + (a * 2-a * 1) ² + (b * 2-b * 1) ² ] ^1/2

In the evaluation of the color difference measurement, "A (good)" is evaluated when a transparent protective layer with reduced color difference ΔE * is produced, and "B (defective)" is evaluated when a transparent protective layer is not produced. I evaluated it. Specifically, the evaluation criteria for color difference measurement are as follows.
A ... ΔE * is 1.5 or less.
B ... ΔE * is greater than 1.5.

In the gloss value measurement, the gloss value of the protective layer was measured using a portable gloss meter GMX-202 (manufactured by Murakami Color Technology Research Institute). The measurement angle was 60 degrees and the number of measurements was three. The gloss value was calculated by averaging the three measured values.

In the evaluation of the gloss value measurement, when the protective layer had a high gloss value, it was evaluated as "A (good)", and when it did not have a high gloss value, it was evaluated as "B (poor)". Specifically, the evaluation criteria for measuring the gloss value are as follows.
A ... The gloss value is 70 or more.
B ... The gloss value is less than 70.

For elongation measurement, a decorative film sample having a size of 1 inch x 4 inch was prepared. The elongation at break of the film was measured using an elongation-tensile tester. The tensile speed was 300 mm / min, and the distance between the chucks holding the sample was 5 cm. The elongation-tensile test was performed three times, and the elongation rate was calculated by averaging the measured values of these three times.

In the evaluation of the elongation measurement, when the protective layer had a high elongation rate, it was evaluated as "A (good)", and when it did not have a high elongation rate, it was evaluated as "B (poor)". Specifically, the evaluation criteria for elongation measurement are as follows.
A ... The growth rate is 50 or more.
B ... The elongation rate is less than 50.

For the IPA resistance (isopropanol) test, a decorative film sample having a size of 1 inch × 12 inch was prepared. Using a Gakushin wear tester AB-301 (manufactured by Tester Sangyo Co., Ltd.), a gold width No. 3 impregnated with IPA was attached to the wearer, and the metal width No. 3 was reciprocated on the decorative film sample under a load of 500 g. Every time the gold width No. 3 was reciprocated 10 times, the presence or absence of peeling of the protective layer was observed. The test was conducted until the gold width No. 3 was reciprocated a total of 50 times. In the IPA resistance test, about 0.1 ml of IPA was impregnated into the gold width No. 3 every 10 round trips to replenish the IPA.

In the evaluation of the IPA resistance test, when the protective layer had high IPA resistance, it was evaluated as "A (good)", and when it did not have high IPA resistance, it was evaluated as "B (bad)". Specifically, the evaluation criteria for the IPA resistance test are as follows.
A ... The number of peelings is 0.
B ... The number of times of peeling is one or more.

In Example 1, the protective layer is a photopolymerization initiator (TPO, IrgacureMBF) containing an acylphosphine oxide-based photopolymerization initiator and a phenylglioxylic acid ester-based photopolymerization initiator, and 1% by mass of fluorination (meth). Acrylic monomer (KY-1203), monofunctional (meth) acrylic monomer (IBOA, EEEA, PEA, CTFA), polyfunctional (meth) acrylic monomer (PETTA), aliphatic urethane (meth) acrylate (CN981) , A hindered amine-based light stabilizer (Lignostab 1198, Catalyst UV3529) and an ultraviolet absorber (Tinuvin 405) are used.

According to the composition of the protective layer of Example 1, good evaluations were obtained in color difference measurement, gloss value measurement, elongation measurement, and IPA resistance test, and in addition to being transparent, both flexibility and chemical resistance were achieved. It becomes possible to produce a protective layer.

In Examples 2 to 5, the protective layer is also a photopolymerization initiator containing an acylphosphine oxide-based photopolymerization initiator and a phenylglioxylic acid ester-based photopolymerization initiator, a fluorinated (meth) acrylic monomer, and a monofunctional (meth). It has an acrylic monomer, a polyfunctional (meth) acrylic monomer, a urethane (meth) acrylate, a hindered amine-based light stabilizer, and an ultraviolet absorber. Therefore, it is possible to produce a protective layer that is transparent and has both flexibility and chemical resistance.

On the other hand, in Comparative Example 1, the fluorinated (meth) acrylic monomer was not used, and in Comparative Example 2 and Comparative Example 4, urethane (meth) acrylate was not used. In Comparative Example 3, a polyfunctional (meth) acrylic monomer is not used. In Comparative Example 5 and Comparative Example 6, only one kind of photopolymerization initiator was used, and the fluorinated (meth) acrylic monomer was not used. Therefore, in the protective layers of Comparative Examples 1 to 6, the evaluation in at least one of the color difference measurement, the gloss value measurement, the elongation measurement, and the IPA resistance test is "B (defective)". In addition to being transparent, the protective layers of Comparative Examples 1 to 6 have not been able to achieve both flexibility and chemical resistance.

1 ... decorative film, 10 ... flexible substrate, 20 ... inkjet printing layer, 30 ... transparent protective layer.

Claims (5)

A decorative film in which an inkjet printing layer and a transparent protective layer are provided in this order on a flexible base material.
The transparent protective layer is
Photopolymerization initiator containing acylphosphine oxide-based photopolymerization initiator and phenylglioxylic acid ester-based photopolymerization initiator, photostabilizer containing hindered amine-based photostabilizer and ultraviolet absorber, fluorinated (meth) acrylic monomer, simple A decorative film which is an ultraviolet curable product of a monomer composition containing a functional (meth) acrylic monomer, a polyfunctional (meth) acrylic monomer, and a urethane (meth) acrylate. The fluorinated (meth) acrylic monomer is
A fluorinated (meth) acrylic monomer containing a fluoroalkyl group or a fluoroalkyl ether group and having a siloxane bond, and / or a fluorinated (meth) acrylic containing a fluoroalkyl group or a fluoroalkyl ether group and having no siloxane bond. The decorative film according to claim 1, which is a monomer. The hindered amine-based light stabilizer is
The decorative film according to claim 1 or 2, which comprises a high molecular weight hindered amine light stabilizer and a low molecular weight hindered amine light stabilizer. The decorative film according to any one of claims 1 to 3, wherein the urethane (meth) acrylate is an aliphatic urethane polyfunctional (meth) acrylate. The decorative film according to any one of claims 1 to 4, wherein an adhesive layer is provided on a surface of the flexible base material opposite to the surface on which the inkjet printing layer is provided.

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