KR102097625B1 - Method of manufacturing decoration film with excellent adhesion to curved surface - Google Patents

Abstract

The present invention relates to a method for manufacturing a decoration film in a structure that a main body of a film comprising a printing layer is directly attached on a bonding target without a base film and a protective layer is arranged on the uppermost layer of the film. A base film layer is not formed in the film such that flexibility of the film is improved and contact properties of the film with respect to a curved part is improved.

Description

Manufacturing method of decoration film with excellent adhesion to curved surfaces {METHOD OF MANUFACTURING DECORATION FILM WITH EXCELLENT ADHESION TO CURVED SURFACE}

The present invention relates to a method of manufacturing a decoration film that is printable and has excellent adhesion to curved surfaces.

In general, a decoration film is used for the purpose of forming an exterior by providing a printing or UV molding pattern on the outer surface of an electronic device such as a camera, notebook, smartphone, tablet PC, and preventing scattering of glass in the event of an impact.

Since consumers place importance on the design according to the purpose of the display, various designs of displays have been developed, and designs using metal materials are in the spotlight, but metal materials have disadvantages such as heavy weight and increased manufacturing cost.

In order to compensate for this, displays using tempered glass instead of metallic materials have been developed, and UV is applied to the shatterproof film used on the back side of tempered glass as tempered glass shaped as a 2D or 3D curved surface is applied to portable electronic products as described above. BACKGROUND OF THE INVENTION The use of decoration films laminating on tempered glass shaped as curved surfaces by patterning or printing is increasing.

As in Korean Registered Patent No. 10-0773456, in general, a decoration film is a structure in which an adhesive layer and a release film layer are formed on one side of a transparent PET film as a base film, and a coating layer for decoration is formed on the opposite side. .

In general, the base film is made of PET or the like, but due to the rigidity of the PET material, it is difficult to apply to a product having a curved surface design having a small curvature radius, and there is a problem that the base film may be damaged in a repeated bending environment.

Korean Registered Patent No. 10-0773456

The present invention has been devised to solve the above problems, and has an object to provide a method of manufacturing a decoration film excellent in adhesion to a curved surface and excellent in bending resistance.

The manufacturing method of the decoration film according to the present invention comprises the steps of sequentially disposing a printing layer, a UV pattern layer, a deposition layer, and a shielding printing layer on one surface of the base film (S10);

Forming a protective layer over the shielding printed layer (S20);

Removing the base film (S30); And

And laminating the release film coated with the adhesive layer under the printing layer (S40).

The protective layer is one selected from the group comprising urethane acrylate oligomers, polyurethane resins, silicone resins, and mixtures thereof.

The polyurethane resin may be selected from the group consisting of polyester-based polyurethane and polycarbonate-based polyurethane.

The silicone resin may be a mixture containing an alkenyl polyorganosiloxane, a polyorganohydrogensiloxane, and a hydrosilylation reaction catalyst.

The thickness of the protective layer is 0.5 to 50㎛.

The pressure-sensitive adhesive layer may include an acrylic resin.

The decoration film according to the present invention does not use a base film of a PET material for supporting a printing layer or the like, and a protective layer is formed on the printing layer, thereby improving adhesion to a curved surface and having excellent durability in repeated bending. Can provide

1 is a cross-sectional view of a decoration film according to an embodiment of the present invention.
2 is a flowchart showing a method of manufacturing a decoration film according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily practice. The present invention can be implemented in many different forms and is not limited to the embodiments described herein.

Hereinafter, the fact that an arbitrary configuration is formed on the “top (or bottom)” of the substrate means not only that an arbitrary configuration is formed in contact with the top surface (or bottom surface) of the substrate, but also on the substrate and the substrate (or It is not limited to not including other components between any components formed.

Hereinafter, the present invention will be described in detail.

1 is a cross-sectional view of a decoration film according to an embodiment of the present invention, and FIG. 2 is a flowchart showing a method of manufacturing a decoration film according to an embodiment of the present invention.

Referring to Figure 1, the decoration film 100 is a release film layer 110; Adhesive layer 120; Print layer 130; A UV pattern layer 140 on which a predetermined pattern is formed; Deposition layer 150; A shielding print layer 160 including a light blocking material; And a protective layer 170; Includes this sequential layered structure.

In the decoration film, the tensile strength when removing the release film may be 3 to 10 kgf / mm ² when measured according to ASTM D 638. That is, since the tensile strength of the decoration film according to the present invention is lower than the tensile strength (15 to 40 kgf / mm ² ) of a decoration film using conventional PET, excitation does not occur even when attaching a curved portion. When the tensile strength of the decoration film is less than 3 kgf / mm ² , the film is fragile, and when it exceeds 15 kgf / mm2, elasticity may cause excitation of the curved portion.

In addition, when removing the release film, the elongation of the decoration film may be 20 to 40% when measured according to ASTM D 638. When the elongation is less than 20%, the film is brittle, and when it exceeds 40%, excitation may occur in the adhesive portion of the curved surface.

In the conventional decoration film, a base film for supporting a printing layer or the like was laminated between the adhesive layer and the printing layer. The base film mainly uses PET or the like as a base material, and the flexibility of the decoration film is reduced due to the base film, so that the adhesive force is reduced with respect to the adhesion object having a small curvature radius, and thus the decoration film is lifted from the adhesion object.

In contrast, the decoration film according to the present invention is a structure in which a body of a film including a printing layer is attached directly onto an object to be adhered without a base film, and a protective layer is disposed on the top layer of the film. The decoration film according to the present invention has the advantage of exhibiting low tensile strength and elongation when removing the release film, so that it has excellent adhesion to a curved surface and excellent durability in repeated bending.

The release film layer 110 is formed on one surface of the adhesive layer 120 serves to protect the adhesive layer 120. The release film 110 may use a variety of films, such as PET film, the release force may be 15 ~ 75 gf / inch to facilitate the release, specifically 20 ~ 60 gf / inch, thickness May be 20 to 200 μm, more specifically 50 to 100 μm.

The release film of the present invention can be formed of polyester films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutyrene terephthalate and / or polypropylene naphthalate.

The adhesive layer 120 is an optical clear adhesive (OCA) layer formed of an optically transparent adhesive material. The adhesive layer maintains interlayer interfacial adhesion, but removes an air layer that may be formed at the interface, and maintains visibility of the decoration film. The adhesive layer is applied, for example, between the decoration film and the back cover of a mobile display formed of glass.

The adhesive layer 120 may include a polymer resin and a curing agent. The polymer resin includes at least one selected from the group consisting of polyester resin, acrylic resin, alkyd resin, and amino resin. The polymer resin may be used alone, or two or more types of copolymers or mixtures may be used. Among them, acrylic resins having excellent optical properties, weather resistance, adhesion to substrates, and the like are most preferred. In this case, the refractive index of the acrylic resin may be 1.40 to 1.60, and more specifically 1.45 to 1.50.

The acrylic resin may be formed by polymerizing one or more acrylic monomers and carboxyl group-containing unsaturated monomers, respectively. Specifically, the acrylic monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydrofurryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate , Propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate , Methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1 , 1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl (meth) acrylate, dish At least one selected from the group containing clofentanil (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate You can.

More specifically, the acrylic monomer may be methyl (meth) acrylate, butyl (meth) acrylate, or a mixture thereof. Specifically, the carboxyl group-containing unsaturated monomer is acrylic acid, methacrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid , Acrylic acid duplex, itaconic acid, maleic acid, and maleic anhydride. More specifically, the carboxyl group-containing unsaturated monomer may be methacrylic acid or acrylic acid monomer.

Hereinafter, the resin composition of the adhesive layer 120 of the present invention will be described in more detail.

The pressure-sensitive resin constituting the pressure-sensitive adhesive layer 120 of the present invention may be prepared according to a conventional method of manufacturing an adhesive. The adhesive resin is generally formed by polymerization of monomers. Specifically, a monomer and a photoinitiator and an additive for forming the adhesive polymer resin may be mixed, and a filler may be added and polymerized thereafter, if necessary. Of course, a polymerization initiator and a crosslinking agent may be added in the manufacturing process of the pressure-sensitive adhesive composition. Preferably, in order to ensure that the filler and other additives are uniformly dispersed in the pressure-sensitive adhesive composition, the monomer for forming the pressure-sensitive polymer resin is first pre-polymerized to form a syrup, and thereafter the filler and other additives, etc. After adding and stirring uniformly, polymerization is carried out.

In addition, the pressure-sensitive adhesive composition according to the present invention may be subjected to a curing step, and a curing method may be a thermal curing method or a photo curing method, but thermal curing is more preferable.

The adhesive layer composition of the present invention may include a photoinitiator together with the above monomers. Such a photoinitiator reacts by irradiation of ultraviolet light or the like in the process of manufacturing the adhesive layer to initiate a curing reaction of the adhesive composition.

The type of photoinitiator that can be used in the invention is not particularly limited, and examples thereof include α-hydroxyketone-based chemicals, phenylglyoxylate-based compounds, benzyldimethylketal-based compounds, and α-aminoketone-based compounds. It is not limited thereto. The weight ratio of the photoinitiator may be 0.01 to 10, specifically 0.01 to 5. By controlling the weight ratio of the initiator in the above range, excellent physical properties and productivity can be secured.

The pressure-sensitive adhesive composition of the present invention may further include a silane coupling agent if necessary. The silane coupling agent can increase the adhesive strength of the adhesive film prepared from the adhesive composition. Silane coupling agents may include conventional adhesives known to those skilled in the art. Specifically, silane coupling agents include epoxy group-containing silane compounds such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane vinyltrimethoxysilane, (meth) acryloyloxypropyltrime Polymeric unsaturated group-containing silane compounds such as oxysilane 3-aminopropyltrimethoxysilane, amino group-containing silane compounds 3-mercaptopropyltrime such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane And one or more of mercapto group-containing silane compounds such as oxysilane.

The pressure-sensitive adhesive composition of the present invention may further include a conventional additive included in the pressure-sensitive adhesive composition. The additive may include an antifoaming agent, a leveling agent, an antistatic agent, and the like, but is not limited thereto. The additive may be included in 0.0001 parts by weight to 5 parts by weight, specifically 0.001 parts by weight to 1 part by weight, based on 100 parts by weight of the mixture of the (meth) acrylic copolymer and the (meth) acrylic monomer. In the above range, the adhesive film prepared with the adhesive composition may have good adhesive strength

The adhesive layer 120 may have an adhesive force of 10 N / inch or more to the glass to prevent scattering of the glass when the glass is broken. Specifically, the adhesive layer may have an adhesive strength of 10 to 20 N / inch to glass. When the adhesive strength of the adhesive layer is within the above range, there is an advantage of easy scattering prevention effect and easy rework process for recycling of glass when the process is defective.

The adhesive layer 120 may be in the range of 5 to 50㎛ thickness. Specifically, the adhesive layer 120 may have a thickness of 10 to 30㎛, more specifically 10 to 20㎛, or 10 to 15㎛. When the thickness of the adhesive layer is within the above range, occurrence of defects due to pressing can be prevented and the adhesive strength of the adhesive layer can be properly maintained.

On the other hand, in the decoration film according to the present invention, the printing layer 130 is a layer that can be printed on the surface, and is for expressing characters, patterns, etc. having various colors as a base, and can be used to express photos, patterns, and Colors, patterns, etc. can be displayed freely in any desired form.

These may include inks, dyes and pigments, and specifically, the dyes and pigments include SiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , BST {(Ba, Sr) TiO ₃ }, PZT {Pb (Zr, Ti) O ₃ }, Al ₂ O ₃ , HfO ₂ , ZrO ₂ , La ₂ O ₃ , In, TiO ₂ , Ti ₃ O ₅ , aluminate, and silicates. The printed layer exhibits excellent adhesion to the substrate, heat resistance, durability (high temperature, high pressure, high humidity) and protective properties of the underlying film, and can maintain high transmittance even after high temperature treatment.

The thickness of the printing layer 130 may be 5 to 50 μm, preferably 10 to 20 μm, and more preferably 10 to 15 μm.

In one example, the UV pattern layer 140 is a layer on which a plurality of patterns for displaying a three-dimensional effect of color is formed, and is disposed with the printing layer 130 and the deposition layer 150 interposed therebetween.

The UV pattern layer 140 may be composed of a photo-curable resin, a diluent, a photoinitiator, and various additives. For example, among the additives used in the UV pattern layer 140, the photocurable resin (oligomer) is an important component that determines the resin properties, and a polymer bond may be formed by a polymerization reaction to form a cured film. The photo-curable resin may be classified into acrylates such as polyester-based, epoxy-based, urethane-based, polyether-based, and polyacrylic-based resins according to the structure of the skeleton molecule. As another example, a diluent (monomer) among additives used in the UV pattern layer serves as a crosslinking agent and a diluent for the reactive oligomer, and can be polymerized to form a cured film. As another example, among the additives used in the UV pattern layer 140, the photopolymerization initiator is the most basic raw material of the UV curing resin, and the photopolymerization initiator absorbs ultraviolet rays to generate radicals or cations to initiate polymerization. It can be used alone or by adding two or three kinds of substances. As another example, photosensitizers, colorants, thickeners, polymerization inhibitors, etc. may be added depending on the use as other additives used in the UV pattern layer.

The thickness of the UV pattern layer 140 may be 5 to 30 μm, specifically 10 to 20 μm, or 10 to 15 μm.

In one example, the deposition layer 150 is to implement the necessary gloss, color, and maintain the pattern formed on the UV pattern layer. The deposition layer 150 is formed by depositing a material necessary to obtain the required gloss and color. For example, when the material is a metal, a metallic pattern can be used to scatter the curved light to realize a shiny pattern. There will be.

The thickness of the evaporation layer 150 may be 0.01 to 0.05 μm, and an appropriate level of metallic luster can be obtained without deteriorating adhesion when within the above range.

In one example, the shielding printed layer 160 is formed on the deposition layer, it is characterized in that it comprises a light-shielding material. The shading material is preferably a colored pigment or dye. The shielding print layer prevents light leakage and the like, and only when light is supplied, the light transmission effect by the evaporation layer is expressed, thereby improving aesthetics and visibility. In addition, the composition constituting the shielding printing layer may further include a binder and a curing agent in addition to the light blocking material.

The thickness of the shielding printed layer may be 5 to 30 μm, specifically 10 to 20 μm, or 10 to 15 μm.

In one example, a protective layer 170 is formed on top of the shielding printed layer 160. The protective layer prevents the printed layer and the deposition layer from being damaged by external physical impact, and improves the flexibility of the decoration film to improve adhesion to a curved surface.

The protective layer 170 of the present invention may be one selected from the group comprising urethane acrylate resins, polyurethane resins, silicone resins, and mixtures thereof.

The urethane acrylate is a resin containing a urethane unit and an acrylic unit, and may be prepared by further copolymerizing an acrylic monomer component with the polyurethane resin. In the case of the urethane acrylate resin as described above, solvent resistance and transparency may be further improved.

Here, the acrylic monomers that can be used include, for example, alkyl (meth) acrylate, alkyl acrylate, epoxy (meth) acrylate, hydroxy alkyl acrylate, alkyl (meth) acrylic acid containing a carbonyl group, alkyl acrylic acid, sulfonic acid It may be one or more selected from the group consisting of acrylate containing salt. In this case, the acrylate containing sulfonate is, for example, acrylate containing sodium 2-methyl-2-propene-1-sulfonate, acrylate containing sodium arylsulfonate, 2-propene-1 -It may be an acrylate containing sulfonate.

Further, the urethane acrylate oligomer may be copolymerized with other monomers in addition to the acrylic monomer component, if necessary. In this case, the other monomers include unsaturated nitriles such as (meth) acrylonitrile; Unsaturated amides such as (meth) acrylic imide; Olefins such as ethylene and propylene; Β-unsaturated aliphatic monomers such as halogenated vinyl chloride and vinylidene chloride; Β-unsaturated aromatic monomers such as styrene and methylstyrene may be used. These can be used alone or in combination of two or more.

Meanwhile, the urethane acrylate oligomer is not limited thereto, and the weight ratio of the polyurethane resin and the acrylic monomer may be about 1: 9 to 9: 1, more preferably about 2: 8 to 8: 2. When the weight ratio of the polyurethane resin and the acrylic monomer satisfies the above numerical range, it is because there is an advantage that it is easy to secure transparency and to form a coating layer because of excellent coating properties.

The urethane acrylate resin may have a weight average molecular weight of 5000 to 30,000 or less, and more specifically 10000 to 20000. If the weight average molecular weight is less than 5000, scratch resistance and the like are excellent, but since curing shrinkage increases, wrinkles may occur after coating. When a urethane acrylate resin having a weight average molecular weight exceeding 30,000 is used, viscosity may be excessively increased, resulting in tack after curing, and the coating function of the film is deteriorated, and scratch resistance and film strength are not excellent.

The polyurethane resin may be selected from the group consisting of polyester-based polyurethane and polycarbonate-based polyurethane.

Polyurethane (PU) is a urethane bond in a molecule which is generally obtained by reacting a polyisocyanate such as a high molecular weight polyol or diisocyanate with a chain extender, if necessary, using a catalyst such as dibutyltin dilaurate, and polyaddition reaction. It is a polymer having. It softens upon heating and exhibits fluidity. The hard segment is formed by the reaction of the chain extender and the polyisocyanate, while the soft segment is formed by the reaction of the high molecular weight polyol and the polyisocyanate.

Examples of high molecular weight polyols include polyester polyols, polycarbonate polyols having two or more hydroxyl groups and having a number average molecular weight of 400 or more, and combinations thereof. Polyester polyols form polyester-based polyurethanes, and polycarbonate polyols form polycarbonate-based polyurethanes. In the present disclosure, polyols having both ester bonds and carbonate bonds in the molecule are classified as polycarbonate polyols. Polyurethanes formed by polyols containing both polyester polyols and polycarbonate polyols are classified as polycarbonate-based polyurethanes. The polyester polyol is preferably a polyester diol, and the polycarbonate polyol is preferably a polycarbonate diol, because the thermoplastic may be deteriorated when excessive crosslinking structure is introduced into the polyurethane.

Polyester polyols are obtained, for example, by condensation reactions or transesterification reactions of short-chain polyols having two or more hydroxyl groups and a number average molecular weight of 400 or more with polybasic acids or alkyl esters, acid anhydrides, or acid halides thereof. You can. In addition to short-chain polyols, short-chain polyamines having two or more amino groups and having a number average molecular weight of less than 400 may be involved in the condensation reaction or transesterification reaction.

Examples of short chain polyols include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol , 1,6-hexanediol, 2,6-dimethyl-1-octene-3,8-diol, C7-C22 alkane diol, cyclohexanediol, cyclohexane dimethanol, bisphenol A, hydrogenated bisphenol A , 1,4-dihydroxy-2-butene, bishydroxy ethoxy benzene, xylene glycol, bishydroxy ethylene terephthalate, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, Hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, and hex Saoxypropylene glycol; Trihydric alcohols such as glycerol, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethyl pentane, 1,2,6-hexanetri Ole, trimethylol propane, and 2,2-bis (hydroxymethyl) -3-butanol; Tetrahydric alcohols such as pentaerythritol and diglycerol; Pentahydric alcohols, such as xylitol; And hexavalent alcohols, such as sorbitol, mannitol, alinitol, iditol, dulcitol, atritol, inositol, and dipentaerythritol, and the like. Short chain polyols also include polyoxyalkylene polyols obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to such short chain polyols. Short chain polyols may be used alone or in combination of two or more. Since excessive thermoplastic cross-linking structure may be introduced into the polyurethane, the divalent alcohol is preferably used as a short chain polyol.

Examples of polybasic acids include saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane , 3-methyl-3-ethyl glutaric acid, azelaic acid, and sebacic acid; Unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; Aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, and naphthalene dicarboxylic acid; Alicyclic dicarboxylic acids such as hexahydrophthalic acid; And other polyvalent carboxylic acids such as dimer acid, hydrogenated dimer acid, and HET acid. Examples of the alkyl ester, acid anhydride, and acid halide of the polybasic acid include methyl ester and ethyl ester of the polybasic acid; Oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-C12-C18 alkyl succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and the like; Oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride, and the like. The polybasic acid may be used alone or in combination of two or more. Since excessive thermoplastic cross-linking structure may be introduced into the polyurethane, the dicarboxylic acid or its alkyl ester, acid anhydride or acid halide is preferably used as a polybasic acid.

Examples of short chain polyamines include short chain diamines, such as ethylene diamine, 1,3-propane diamine, 1,3-butane diamine, 1,4-butane diamine, 1,6-hexamethylene diamine, 1 , 4-cyclohexane diamine, 3-aminomethyl-3,5,5-trimethyl cyclohexylamine, 4,4'-dicyclohexylmethane diamine, 2,5 (2,6) -bis (aminomethyl) ) Bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, and o-, m-, or p-tolylene diamine; Short chain triamines such as diethylene triamine; And short chain polyamines having 4 or more amino groups, such as triethylene tetramine and tetraethylene pentamine. Short chain polyamines may be used alone or in combination of two or more. Short-chain diamines are preferably used as short-chain polyamines, because thermoplastics may be deteriorated when excessive cross-linking structures are introduced into the polyurethane.

Polyester polyols that can be used include hydroxycarboxylic acids, for example, vegetable oil-based polyester polyols obtained by condensation reaction of hydroxyl group-containing vegetable oil aliphatic acids; And polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone and lactides such as L-lactide and D-lactide.

Examples of polycarbonate polyols include ring-opening polymers of ethylene carbonate using short-chain polyols as initiators; And the short chain divalent alcohol, for example, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, or 1,6-hexanediol is phosgene or And polycarbonate obtained by reacting with diphenyl carbonate, the short-chain divalent alcohol, and amorphous polycarbonate polyol obtained by copolymerizing the ring-opening polymer.

Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, aromatic aliphatic polyisocyanates, and the like, and multimers of these polyisocyanates (dimers, trimers, etc.), burette-modified products, allophanates- Modified products, oxadiazine trion-modified products, and carbodiimide-modified products. The polyisocyanate may be used alone or in combination of two or more. Diisocyanates are preferably used as polyisocyanates, since excessive thermoplastic cross-linking structures may be introduced into the polyurethane, which may lower the thermoplasticity.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2,2 ' -Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexa Methylene diisocyanate, 1,6,11-undecamethylene triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5,7- Trimethyl-1,8-diisocyanate-5-isocyanatome Thioloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine isocyanatomethyl ester, lysine Triisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate, 2-isocyanatopropyl-2,6-diisocyanate hexanoate, bis (4-isocyanate-n-butylidene ) Pentaerythritol, and 2,6-diisocyanate methylcaproate.

Examples of alicyclic polyisocyanates include isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trans, trans-, trans, cis- and cis, cis-dicyclohexylmethane-4,4'- Diisocyanates and mixtures thereof (hydrogenated MDI), 1,3- or 1,4-cyclohexane diisocyanates and mixtures thereof, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, methyl Cyclohexane diisocyanate, 2,2'-dimethyl dicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethyl bicyclo [2.2.1] -heptane, 2,6-diisocyanato Methyl bicyclo [2.2.1] -heptane (NBDI), 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl bicyclo- [2.2.1] -heptane, 2 -Isocyanatomethyl-2- (3-eye Cyanatopropyl) -6-isocyanatomethyl bicyclo- [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -Bicyclo- [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2.2.1]- Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2.2.1] -heptane, and 2-isocyanatomethyl- 2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2.2.1] -heptane.

Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (TDI), 4,4'-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate, and isomer mixtures of these diphenylmethane diisocyanates (MDI), toluidine diisocyanates (TODI), paraphenylene diisocyanates and naphthalene dias Isocyanates (NDI).

Examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI), and 1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI ) Is included.

Examples of chain extenders include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol , 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol All, 1,6-hexanediol, 2,6-dimethyl-1-octene-3,8-diol, C7-C22 alkane diol, cyclohexanediol, cyclohexane dimethanol, bisphenol A, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, bishydroxy ethoxy benzene, xylene glycol, bishydroxy ethylene terephthalate, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol , Hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, and hex Saoxypropylene glycol; Trihydric alcohols such as glycerol, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethyl pentane, 1,2,6-hexanetri Ole, trimethylol propane and 2,2-bis (hydroxymethyl) -3-butanol; Tetrahydric alcohols such as pentaerythritol and diglycerol; Pentahydric alcohols, such as xylitol; And hexavalent alcohols, such as sorbitol, mannitol, alinitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol. Chain extenders also include polyoxyalkylene polyols obtained by adding alkylene oxides such as ethylene oxide or propylene oxide to these short chain polyols. Chain extenders may be used alone or in combination of two or more. Since excessive thermoplastic cross-linking structure may be introduced into the polyurethane, the divalent alcohol is preferably used as a chain extender.

The silicone resin is a mixture containing an alkenyl polyorganosiloxane, a polyorganohydrogensiloxane and a hydrosilylation reaction catalyst.

The alkenyl polyorganosiloxane is a compound in which a substituent having a carbon-carbon double bond is bonded to a silicon atom of a polyorganosiloxane in which the main chain is formed of a diorganosiloxane repeating unit. The polyorganosiloxane may be linear, cyclic or branched. It is preferably straight chain.

The substituent having a carbon-carbon double bond of the alkenyl polyorganosiloxane is a C1 to C10 linear alkenyl group, preferably a substituent selected from the group consisting of a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group to be. More preferably, the alkenyl group is a vinyl group.

The substituent having the carbon-carbon double bond is an average of one or more, preferably two or more alkenyl groups in one molecule of polyorganosiloxane. If one substituent per molecule of polyorganosiloxane does not reach, it may not be cured sufficiently.

On the other hand, as being bonded to the silicon atom of the polyorganosiloxane, in addition to the substituent having the above-described carbon-carbon double bond, an organic substituent may be bonded, and the organic substituent may be, for example, methyl group, ethyl group, propyl group, butyl Group, pentyl group, hexyl group, cyclohexyl group, heptyl group, phenyl group, tolyl group, xylyl group, naphthyl group, chloromethyl group, 3-chloropropyl group, 3,3,3, -trifluoropropyl group It may be a substituent selected. Preferably it is a methyl or phenyl group, More preferably, it is a methyl group.

As a specific example of the alkenyl polyorganosiloxane, dimethylsiloxane · methylvinylsiloxane copolymer, methylvinylpolysiloxane, dimethylsiloxane · methylvinylsiloxane · methylphenylsiloxane copolymer having both ends of the molecular chain blocked with a trimethylsiloxy group; Dimethylpolysiloxane, methylvinylpolysiloxane, dimethylsiloxane · methylvinylsiloxane copolymer, dimethylsiloxane · methylvinylsiloxane · methylphenylsiloxane copolymer having both ends of the molecular chain blocked with dimethylvinylsiloxy groups; Dimethylpolysiloxane blocked at both ends of the molecular chain with a trivinylsiloxy group; And so on.

On the other hand, it is preferable to use the alkenyl polyorganosiloxane having a weight average molecular weight of 500 to 100,000. If the weight average molecular weight does not reach 500, there is a problem in that the strength of the coating layer decreases, and when it exceeds 100,000, the solubility in organic solvents such as benzene and toluene decreases, resulting in a decrease in workability during coating.

The polyorganohydrogensiloxane acts as a crosslinking agent that reacts with an alkenyl polyorganosiloxane. The polyorganohydrogensiloxane is also a polyorganosiloxane in which the main chain is formed of repeating diorganosiloxane units. Unlike the alkenyl polyorganosiloxane, the polyorganohydrogensiloxane is a hydrogen atom bonded to a silicon atom rather than a substituent having a carbon-carbon double bond, and contains a hydrosilyl group (Si-H) in the molecule. .

The polyorganohydrogensiloxane may be straight-chain, cyclic or branched, preferably straight-chain. A weight average molecular weight of 200 to 100,000 is used, and more preferably 300 to 30,000.

The number of hydrogen contained in the molecule of the polyorganohydrogensiloxane, that is, the hydrosilyl group (Si-H) is 2 or more, preferably 3 or more.

The amount of the polyorganohydrogensiloxane used is in the range of 0.1 to 10 hydrogens, preferably 1.0 to 3 hydrogens, of the polyorganohydrogensiloxane component per alkenyl substituent of the alkenyl polyorganosiloxane. . When the hydrogen ratio of the polyorganohydrogensiloxane component does not reach 0.1, the curing is insufficient, and the protective layer formed therefrom does not function as a primer coating layer. On the other hand, when the number exceeds 10, the possibility of change over time caused by unreacted materials increases.

As the hydrosilylation reaction catalyst, a known one can be used. Specifically, there are platinum-based, palladium-based, and rhodium-based catalysts. Preferably, platinum-based catalysts such as H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O (n is an integer from 1 to 6) are used. The amount of the catalyst is usually used in a weight ratio of 0.1 to 1000 ppm relative to the sum of the components of the alkenyl polyorgano siloxane and polyorganohydrogensiloxane.

In addition, the protective layer may be crosslinked, and in this case, the composition constituting the protective layer preferably includes a photoinitiator. In the case of thermal crosslinking, the deposition layer and the printing layer may be damaged, which is not preferable.

The photoinitiator is benzophenone (benzophenone), thioxanthone (thioxanthone), alpha hydroxy ketone (α-hydroxy ketone), ketone (ketone), phenyl glyoxylate (phenyl glyoxylate) and acrylic phosphine oxide It may be one or more selected from the group consisting of (acyl phosphine oxide).

In addition, additives such as reactive diluents, leveling agents, UV stabilizers, tackifiers, stabilizers, adhesion promoters, surface tension modifiers, antifoaming agents, flow modifiers, wetting agents, ionic strength modifiers, antioxidants, etc. It may further include, and according to the purpose, an aliphatic urethane acrylate oligomer having a molecular weight of 5000 to 10000 may be added.

The composition constituting the protective layer includes 30 to 80 parts by weight, preferably 40 to 70 parts by weight, and more preferably 35 to 65 parts by weight of a urethane acrylate oligomer, a polyurethane resin, a silicone resin, and a mixture thereof. You can. For the reactive diluent, 20 to 60 parts by weight, preferably 30 to 50 parts by weight, more preferably 35 to 45 parts by weight may be included. In the case of a photoinitiator, 0.1 to 5 parts by weight, preferably 1 to 4 parts by weight may be included, and other additives may be included in 0.5 to 1 part by weight.

The average thickness of the protective layer may be 0.5 to 50㎛. Specifically, the thickness of the protective layer may be 10 to 40㎛, more specifically 20 to 30㎛. When the thickness of the protective layer is less than 0.5 μm, the protective layer becomes too thin to reduce scattering prevention and protection functions. When the thickness of the protective layer exceeds 50 μm, the protective layer becomes too thick, so adhesion to the curved surface may decrease. have.

On the other hand, the decoration film of the present invention uses a diluting solvent in consideration of workability when coating the composition of the adhesive layer, the printing layer, and the protective layer, and the solvent used must be one capable of dissolving the composition, acetone, toluene, Xylene, ethanol, isobutanol, isopropanol, cyclohexanone, methethyl ketone, methyl isobutyl ketone, ethyl acetate, and the like, but these are exemplary, and are not limited thereto. The solvent may be used alone or in a mixture of two or more types, and any method may be used.

In addition, the present invention provides a method of manufacturing a decoration film.

2 is a flowchart showing a method of manufacturing a decoration film according to an embodiment of the present invention.

Referring to FIG. 2, the method of manufacturing the decoration film includes sequentially disposing a printing layer, a UV pattern layer, a deposition layer, and a shielding printing layer on one surface of the base film (S10); Forming a protective layer over the shielding printed layer (S20); Removing the base film (S30); And laminating the release film coated with the adhesive layer to the bottom of the printing layer (S40); It includes.

Specifically, the base film is preferably a polycarbonate or polyester material, and when dropping water droplets on the pattern forming panel, the contact angle between the water droplets and the pattern forming panel is preferably 30 degrees to 90 degrees.

A printing layer is formed on one surface of the base film. At this time, printing of the printing layer may be performed by digital printing, gravure printing, comma coating, reverse coating, or the like, but is not particularly limited to these methods.

In addition, by forming a rough surface such as sanding or hairline on the edge portion on the base film, it improves the adhesion between the printing layer and the UV pattern layer and the base film, and prevents the printing layer and the UV pattern layer from separating from the base film during post-processing. And, it is possible to prevent the shrinkage of the printed layer and the UV pattern layer.

In the case of the UV pattern layer, a composition including a photo-curable resin, a diluent, a photoinitiator, and various additives may be applied on the top of the printed layer and roll-pressed to form a pattern with a pattern forming panel, and then irradiated with UV to cure. . After curing, the pattern forming panel is removed. The pattern forming panel is preferably a polycarbonate or polyester material, and when dropping water droplets on the pattern forming panel, the contact angle between the water droplets and the pattern forming panel is preferably 100 degrees or more. In addition, the friction coefficient between the pattern forming panels is preferably larger than the friction coefficient of the base film, which is to easily fix the UV pattern layer.

The deposition layer is formed by depositing a material to be deposited on the UV pattern layer. The material to be deposited is as described above, and there is no particular limitation on the deposition method, but a vacuum thin film deposition method is preferred. Specifically, sputtering and E-BEAM deposition may be used as the vacuum thin film deposition method. By forming the deposition layer in this way, the pattern formed on the UV pattern layer is prevented from being filled by the deposition material, and the luminance of the UV pattern layer can be improved.

A shielding print layer may be formed on the deposition layer by printing a composition containing a light-shielding material, and the printing method is the same as the printing method of the above-described printing layer.

A protective layer may be formed on the shielding printed layer. The protective layer is preferably formed using a coating method for applying the composition as described above. When the protective layer is formed, the amount of the additive added to the composition can be freely controlled by using a coating method. As the coating method, an appropriate one can be selected from known methods such as nip coating, bar coating, gravure coating, slot die coating, and knife coating.

In addition, when cross-linking the resin constituting the protective layer, the light crosslinking amount is preferably 300 to 2000 mJ / cm2, and more preferably 500 to 1000 mJ / cm2.

When a printing layer, a UV pattern layer, a deposition layer, a shielding printing layer, and a protective layer are sequentially disposed on the base film, the base film is removed and then the release film coated with the adhesive layer is laminated, and the adhesive layer and Release films can be placed sequentially. The adhesive layer includes an acrylic resin, and may be cured after being applied to a release film. Both heat curing and photo curing are possible, but heat curing is preferable in terms of curing efficiency and cost reduction.

In addition, the present invention provides a substrate to which the decoration film is attached, and the substrate includes a glass cover or the like. The glass cover mediates the decoration film, and may be manufactured by removing the release film from the above-described decoration film and then attaching it to one surface of the glass cover. The decoration film is provided with a release film and an adhesive layer, so that the decoration film can be adhered to the glass cover after the release film is removed. At this time, the decoration film may be cut according to the shape of the target substrate to be adhered. The decoration film according to the present invention does not contain a base film made of PET or the like, so flexibility is improved, and even if it is attached on a substrate having a small radius of curvature, the decoration film does not float.

Specifically, the display device,

A rear cover material of a display device including a shape in which the edge portion is curved; And

It includes a decoration film formed on one or both sides of the back cover material,

The decoration film, an adhesive layer; Printed layer; A UV pattern layer on which a predetermined pattern is formed; Deposition layer; A shielding printed layer comprising a light-shielding material; And a protective layer; includes a sequential layered structure,

The decoration film is a structure in which the adhesive layer is attached to the rear cover material.

Hereinafter, the present invention will be described in detail through examples as follows. However, the following examples are only to illustrate the present invention, the present invention is not limited by the following examples.

[Example 1]

After the colored pigment was printed on the PET film as the base film, a urethane-based resin was applied and pressed as a photo-curable resin between the pattern forming panels of PET material. After curing the urethane-based resin by UV irradiation, titanium was deposited on the surface to form a deposition layer. A colored pigment was printed on top of the evaporation layer to arrange a shielding print layer.

Finally, 65 parts by weight of urethane acrylate oligomer having a molecular weight of 20000 on the top of the shielding printed layer (65:35 by weight of urethane monomer and acrylate monomer), 34.5 parts by weight of reactive diluent, 1 part by weight of initiator, and 0.5 parts by weight of additive The composition was applied so that the thickness after drying was 20 μm to form a protective layer.

Next, after removing the base film, a decorative film was prepared by attaching a release film made of a PET material coated with an acrylic adhesive resin at a thickness of 15 μm to the lower portion of the printed layer. At this time, the acrylic adhesive resin was attached to the lower portion of the printing layer.

[Example 2]

After the colored pigment was printed on the PET film as the base film, a urethane-based resin was applied and pressed as a photo-curable resin between the pattern forming panels of PET material. After curing the urethane-based resin by UV irradiation, titanium was deposited on the surface to form a deposition layer. A colored pigment was printed on top of the evaporation layer to arrange a shielding print layer.

Finally, a composition comprising 65 parts by weight of a polyurethane resin, 34.5 parts by weight of a reactive diluent, 1 part by weight of an initiator, and 0.5 parts by weight of an additive was applied to the top of the shielding printed layer so that the thickness after drying was 20 μm to form a protective layer.

Next, next, after removing the base film, a release film made of a PET material coated with an acrylic adhesive resin to a thickness of 15 μm was attached to the lower portion of the printing layer to produce a decoration film. At this time, the acrylic adhesive resin was attached to the lower portion of the printing layer.

[Example 3]

After the colored pigment was printed on the PET film as the base film, a urethane-based resin was applied and pressed as a photo-curable resin between the pattern forming panels of PET material. After curing the urethane-based resin by UV irradiation, titanium was deposited on the surface to form a deposition layer. A colored pigment was printed on top of the evaporation layer to arrange a shielding print layer.

에서 20분간 추가 교반하여 실리콘 수지를 포함하는 조액을 준비하였다.Also, as an alkenyl polyorganosiloxane, 0.5 parts by weight of a polyorganohydrogensiloxane (Dow Corning, SL7028) as a curing agent, and a platinum catalyst (Dow Corning, Syl) relative to 100 parts by weight of PSA Primer (Dow Corning, 30% solids) -Off 4000 catalyst) 0.5 parts by weight, 500 parts by weight of toluene solvent was added in order, and then room temperature (25

The mixture was further stirred for 20 minutes to prepare a crude liquid containing silicone resin.

Finally, a protective layer was coated on the top of the shielding printed layer by applying a composition containing 65 parts by weight of the crude liquid containing the silicone resin, 34.5 parts by weight of the reactive diluent, 1 part by weight of the initiator, and 0.5 parts by weight of the additive so that the thickness after drying was 20 μm. Formed.

Next, next, after removing the base film, a release film made of a PET material coated with an acrylic adhesive resin to a thickness of 15 μm was attached to the lower portion of the printing layer to produce a decoration film. At this time, the acrylic adhesive resin was attached to the lower portion of the printing layer.

[Comparative Example 1]

On the base film made of 50 μm thick PET material, the same printing layer, UV pattern layer, vapor deposition layer, and shielding printing layer as in the example are sequentially stacked, and an adhesive layer and a release film layer are disposed on opposite sides to decorate the decoration film. It was produced.

[Comparative Example 2]

A decoration film without a PET base film was produced in the same manner as in Example 1, except that a protective layer was not formed on the top of the shielding printed layer.

[Experimental Example 1]

After removing the release film, tensile strength and elongation of the decoration films according to Examples and Comparative Examples were measured according to ASTM-D638 and the results are shown in Table 1. Specifically, it was measured using INSTRON's UTM, and the specimen was made in the form of a dog bone, and the specimen size was 10 mm x 50 mm, and the measurement speed was 300 mm / min.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile strength (kgf / mm ² ) 8 6 5 18 1.5 Elongation (%) 34 29 24 98 8

As can be seen in Table 1, the decoration film in the form of a protective layer formed on the top layer without the base film being disposed on the bottom of the printed layer as in the example is compared with Comparative Example 1 using a base film of PET material and tensile strength and Since the elongation is low, it can be seen that the flexibility is excellent and the adhesion to the curved surface is improved. In addition, in Comparative Example 2 in which the protective layer was not formed, the tensile strength and elongation were too low, making them unsuitable for use as a film.

Although described above with reference to preferred embodiments of the present invention, those skilled in the art or those of ordinary skill in the art will depart from the spirit and technical scope of the invention described in the claims below. It will be understood that various modifications and changes may be made to the present invention without departing from the scope.

Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

100: decoration film
110: release film
120: adhesive layer
130: printed layer
140: UV pattern layer
150: deposited layer
160: shielding printed layer
170: protective layer

Claims (6)

Step of sequentially placing a printed layer of 5 to 50 μm thick, a UV pattern layer of 5 to 30 μm thick, a deposition layer of 0.01 to 1 μm thick, and a shielding printed layer of 5 to 30 μm thick on one surface of the base film (S10) );
Forming a protective layer having a thickness of 0.5 to 50 µm by coating a composition comprising one selected from the group containing urethane acrylate oligomer, polyurethane resin, silicone resin, and mixtures thereof on the top of the shielding printed layer (S20);
Removing the base film (S30); And
Laminating a release film of 20 to 200 μm thickness coated with an adhesive layer of 5 to 50 μm thickness under the printing layer (S40); Including,
The polyurethane resin is selected from the group consisting of polyester-based polyurethane and polycarbonate-based polyurethane,
The silicone resin is a mixture containing an alkenyl polyorganosiloxane, a polyorganohydrogensiloxane and a hydrosilylation reaction catalyst,
The composition constituting the protective layer includes 35 to 65 parts by weight of a urethane acrylate oligomer, a silicone resin, a polyurethane resin or a mixture thereof, 35 to 45 parts by weight of a reactive diluent, and 1 to 4 parts by weight of a photoinitiator,
When removing the release film, the tensile strength is 3 ~ 10 kgf / mm ² and the elongation is 20 to 40%.
delete delete delete delete According to claim 1,
The adhesive layer is a method of manufacturing a decoration film comprising an acrylic resin.

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