JP7277182B2 - makeup film - Google Patents

Description

The present invention relates to decorative films.

2. Description of the Related Art Conventionally, a decorative material having a design is produced by attaching a decorative film to a substrate (adherend). Decorative films are used as interior materials such as floors, walls, and ceilings of buildings, surface decorative materials for furniture and various cabinets, surface decorative materials for fittings, and surface decorative materials for vehicle interiors, etc. Wearability is required. Documents disclosing prior arts related to such decorative materials or decorative films include, for example, Patent Documents 1 to 4.

Patent Document 1 discloses a decorative board having a surface protective layer having excellent surface oil repellency and excellent scratch resistance. and the carbon element content ratio of the surface is 28 to 48%, so that excellent oil repellency is exhibited, and the surface protective layer contains inorganic particles as a wear-resistant filler to improve scratch resistance. disclosed to improve.

Patent Document 2 discloses a decorative sheet excellent in scratch resistance, adhesion between surface protective layers, and impact resistance. , a primer layer, a first surface protective layer and a second surface protective layer in this order. In addition, the second surface protective layer may contain inorganic particles such as α-alumina for the purpose of further enhancing scratch resistance or scratch resistance, and may contain silica as a matting agent. is disclosed.

Patent Document 3 discloses a decorative sheet having excellent scratch resistance, abrasion resistance, and post-processability while ensuring high transparency in the surface protective layer. A configuration with a surface protective layer is disclosed. Since the resin composition, which is the main component of the surface protective layer, is a curable resin, the cross-linking of the resin composition that constitutes the surface protective layer provides high scratch resistance and optimum flexibility for post-processing. It is disclosed that it is possible to provide a decorative sheet having a surface protective layer with a

In Patent Document 4, a wear-resistant decorative material, which is an ionizing radiation-curable resin containing spherical alumina and inorganic or organic spherical fillers, is used to form a protective layer on the surface, thereby improving the conventional corners. It is disclosed that the abrasion resistance can be further improved and the touch feeling can be made very soft as compared with the case of using a pointed polygonal powder filler.

JP 2016-190436 A JP 2014-065283 A JP 2017-177815 A JP-A-1998-286932

Thus, resins and fillers to be used in the surface protective layer have been studied in order to produce a decorative sheet or decorative material having excellent scratch resistance, abrasion resistance, and abrasion resistance. However, it was not possible to obtain sufficient scratch resistance, scratch resistance and abrasion resistance only by examining the type of resin used in the surface protective layer and the filler used.

The present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide a decorative film excellent in scratch resistance, abrasion resistance and abrasion resistance.

The inventors of the present invention focused on the hardness of the thermoplastic resin layer of a decorative film having a base film, a thermoplastic resin layer, and a top coat in that order. Various studies have been made on methods for improving scratch resistance and abrasion resistance. As a result, the present inventors have found that the scratch resistance, abrasion resistance, and wear resistance of the topcoat can be improved by setting the hardness of the thermoplastic resin layer to a specific value or more, and completed the present invention.

The decorative film of the present invention is a decorative film having a base film, a thermoplastic resin layer and a topcoat layer in that order, wherein the topcoat layer contains an ultraviolet curable resin, silica and alumina, and has a thickness of 5 μm or more. and the thickness of the thermoplastic resin layer is 40 to 200 μm, and the hardness of the thermoplastic resin layer is 62 (JIS K6253-3 type D durometer) or more at a thickness of 2 mm or more and 2.5 mm or less. Characterized by

The content of alumina is preferably 5 to 15 parts by weight with respect to 100 parts by weight of the resin solid content of the top coat layer.

The ultraviolet curable resin is preferably a urethane (meth)acrylate resin.

It is preferable to have a design layer between the base film and the thermoplastic resin layer.

The thermoplastic resin layer is preferably embossed.

ADVANTAGE OF THE INVENTION According to this invention, the decorative film excellent in scratch resistance, abrasion resistance, and abrasion resistance can be implement|achieved.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed typically an example of the decorative material of this invention.

The decorative film of the present invention comprises a base film, a thermoplastic resin layer and a topcoat in that order, wherein the topcoat contains an ultraviolet curable resin, silica and alumina and has a thickness of 5 μm or more. , The thickness of the thermoplastic resin layer is 40 to 200 μm, and the hardness of the thermoplastic resin layer is 62 (JIS K6253-3 type D durometer) or more at a thickness of 2 mm or more and 2.5 mm or less. do. In this specification, "film" is synonymous with "sheet", and the two are not distinguished by thickness.

FIG. 1 is a cross-sectional view schematically showing an example of the decorative film of the present invention. The decorative film 10 shown in FIG. 1 has a structure in which a topcoat layer 1, a primer layer 2, a thermoplastic resin layer 3, a design layer 4, a base film 5 and an adhesive layer 6 are laminated in order. Since the top coat layer 1 is attached to the base film 5 via the thermoplastic resin layer 3 and the primer layer 2, the member has an appearance different from that of the base film 5 and has a high design property. . Moreover, the top coat layer 1 constitutes the surface in contact with the space.

[Top coat layer]
The top coat layer 1 is positioned on the outermost surface of the decorative film 10 and contains silica and alumina in an ultraviolet curable resin. Inclusion of silica and alumina can impart scratch resistance, scratch resistance, and abrasion resistance.

In the topcoat layer 1, the alumina content is preferably 5 to 15 parts by weight per 100 parts by weight of the solid content of the resin. If the content of alumina is less than 5 parts by weight with respect to 100 parts by weight of the resin solid content, scratch resistance and abrasion resistance may be insufficient. This is because there is a possibility that the performance will decrease. If the transparency of the topcoat layer 1 is excessively lowered, the visibility of the pattern imparted by the design layer 4 is lowered, and the design of the decorative film 10 is impaired. Even if the decorative film is not provided with the design layer 4, the visibility of the colored thermoplastic resin layer 3 is lowered, and the design of the decorative film 10 is impaired. More preferably, the alumina content is 11 parts by weight or less per 100 parts by weight of the resin solid content.

The shape of the alumina is not particularly limited as long as it is granular, and is preferably 0.7 to 20 μm (particle size at 50% cumulative height). If the particle size of alumina is less than 0.7 μm, the scratch resistance and scratch resistance of the decorative film of the present invention may be deteriorated. There is a possibility that the loss of the alumina will increase and there will be a concern that the alumina will fall off.

The silica may be silica particles composed of silicon dioxide, and the shape and average particle size thereof are not particularly limited, but from the viewpoint of increasing the strength of the topcoat layer, the average particle size is preferably 1 nm or more and 1 μm or less. . Since the average particle diameter of silica contained in the topcoat layer is within the above particle diameter range, the transparency of the topcoat layer can be improved even if the silica content relative to the resin solid content forming the topcoat layer increases. can keep. More preferably, the average particle size of silica is 1 nm or more and 0.1 μm or less.

The content of the silica particles in the top coat layer 1 is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, relative to 100 parts by weight of the resin solid content, from the viewpoint of imparting abrasion resistance. , 100 parts by weight or more. In addition, the content of silica particles is preferably 250 parts by weight or less with respect to 100 parts by weight of the resin solid content, from the viewpoint of preventing a decrease in transparency of the topcoat layer 1 and an excessive increase in haze. It is more preferably 210 parts by weight or less.

The UV-curable resin includes a resin having a group polymerized by UV rays (UV-curable resin), and preferably includes a urethane (meth)acrylate resin having a group polymerized by UV rays. By including a urethane (meth)acrylate resin having a group polymerizable by ultraviolet rays, the scratch resistance and scratch resistance of the topcoat layer can be improved. In addition, in this specification, "urethane (meth)acrylate" represents "at least one of urethane acrylate and urethane methacrylate".

The urethane (meth)acrylate resin is not particularly limited, but includes, for example, pentaerythritol triacrylate hexamethylene diisocyanate urethane polymer, pentaerythritol triacrylate toluene diisocyanate urethane polymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane polymer, etc. These can be preferably used. This is because the number of functional groups is large and the number of chemical cross-linking points increases due to the reaction, resulting in a dense structure, which makes it hard and strong. In addition, three-dimensional entanglement can be expected from the structure, and it can be used more preferably.

The topcoat layer 1 can be formed, for example, by applying a composition for forming a topcoat layer. The composition for forming a topcoat layer may further contain a cross-linking agent (curing agent) in addition to the ultraviolet-curable resin, silica and alumina. As the cross-linking agent, known cross-linking agents such as isocyanate-based curing agents and epoxy-based curing agents can be used. Moreover, various additives such as ultraviolet absorbers and stabilizers may be added.

The thickness of the topcoat layer 1 may be 5 μm or more, preferably 15 μm or less, and more preferably 10 μm or less. If the thickness of the topcoat layer 1 is less than 5 μm, there is a possibility that sufficient scratch resistance and scratch resistance cannot be obtained. Further, when the thickness of the topcoat layer 1 is 15 μm or less, the decorative film of the present invention can obtain excellent scratch resistance, scratch resistance and abrasion resistance while maintaining good flexibility and foldability. That is, it is possible to achieve both film properties such as flexibility and foldability, and excellent scratch resistance, scratch resistance, and abrasion resistance.

The topcoat layer 1 preferably has high transparency in order to further enhance the design of the design layer 4. Specifically, the total light transmittance is preferably 80% or more, and is 90% or more. is more preferable. In addition, in this specification, a total light transmittance is a value based on JISK7375.

[Primer layer]
The primer layer 2 is a layer that enhances the adhesion between the top coat layer 1 and the thermoplastic resin layer 3, and is a layer that is formed as necessary when the adhesion between the layers is insufficient. The primer layer 2 is not particularly limited, and may contain, for example, polyester-based, acrylic, acrylic urethane-based, polyvinyl chloride-based, vinyl chloride/vinyl acetate copolymer-based, butyral-based resins.

Although the thickness of the primer layer 2 is not particularly limited, it is preferably 1 to 10 μm. A more preferable lower limit of the thickness of the primer layer 2 is 3 μm, and a more preferable upper limit thereof is 7 μm. The primer layer 2 preferably contains an acrylic resin and can be formed using an acrylic adhesive. An acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer. Acrylic pressure-sensitive adhesives are excellent in adhesiveness, workability, heat aging resistance, moisture aging resistance, and weather resistance, and are relatively inexpensive.

[Thermoplastic resin layer]
The type of thermoplastic resin used for the thermoplastic resin layer 3 is not particularly limited as long as the resin has a hardness of 62 (JIS K6253-3 type D durometer) or higher at a thickness of 2 mm or more and 2.5 mm or less. Highly transparent thermoplastic resins such as polyethylene terephthalate (PET) and vinyl chloride resins are preferably used, and vinyl chloride resins are more preferably used. The vinyl chloride resin may be generally called a polyvinyl chloride film (PVC film). The thermoplastic resin 3 has a role of protecting the surface of the design layer 4, and preferably has high transparency. The inventors have found that the hardness of the topcoat layer 1 is affected by the hardness of the thermoplastic resin layer 3 arranged below the topcoat layer 1 . This is the same when the layers are laminated via a primer layer. Therefore, the hardness of the thermoplastic resin layer 3 is 62 (JIS K6253-3 type D durometer) or more at a thickness of 2 mm or more and 2.5 mm or less, so that the top coat layer 1 of the decorative film 10 has excellent scratch resistance, Scratch resistance and abrasion resistance can be exhibited. In addition, from the viewpoint of the film properties such as flexibility and bendability of the decorative film of the present invention, the hardness of the thermoplastic resin layer 3 is 68 (JIS K6253-3 type D durometer) or less at a thickness of 2 mm or more and 2.5 mm or less. is preferred.

Examples of the vinyl chloride resin include homopolymers of vinyl chloride and copolymers of vinyl chloride and other monomers.

Examples of the other monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; and (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate. ; Maleic acid diesters such as dibutyl maleate and diethyl maleate; Fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; Vinyl cyanides such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinylidene chloride and vinyl bromide; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether can be mentioned. These may be used alone or in combination of two or more.

The content of the other monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. If it exceeds 50% by weight, the flexibility of the vinyl chloride resin layer 2 may deteriorate. Among the above vinyl chloride resins, vinyl chloride homopolymers are preferred from the viewpoint of obtaining dimensional stability.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, and is adjusted according to the desired hardness of the film and the amount of plasticizer used to adjust the hardness. . A preferable upper limit of the average degree of polymerization is 1,050. When the average degree of polymerization is within the range of 750 to 1,300, moldability at relatively low temperatures is particularly good. As used herein, the average degree of polymerization of vinyl chloride resin means the average degree of polymerization measured according to JIS K6721 "Testing methods for vinyl chloride resins".

The thermoplastic resin layer 3 may further contain a plasticizer. The plasticizer is not particularly limited, and those conventionally blended in thermoplastic resins can be used. Examples include octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, phthalic Phthalic acid diesters such as dinonyl and diisononyl phthalate (DINP); aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; phosphate triesters such as tricresyl phosphate and trioctyl phosphate; Epoxy plasticizers such as soybean oil and epoxy resin; polymer polyester plasticizers, and the like.

Examples of the polymeric polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diesters, polypropylene glycol diesters, and polyethylene glycol polypropylene glycol diesters of phthalic acid; polyethylene glycol diesters of aliphatic dibasic acids such as adipic acid and sebacic acid; , polypropylene glycol diester, polyethylene glycol polypropylene glycol diester, and other polyalkylene glycol diesters. These may be used alone or in combination of two or more. The number average molecular weight of the plasticizer is, for example, 350-3000.

The content of the plasticizer is preferably 10 to 23 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the content is less than 10 parts by weight, the thermoplastic resin layer 3 becomes too hard, resulting in a decrease in formability and the possibility of tearing of the film during forming. On the other hand, if it exceeds 23 parts by weight, the thermoplastic resin layer 3 becomes too soft, and the scratch resistance, scratch resistance, and abrasion resistance of the surface of the topcoat layer 1 of the decorative film 10 may decrease. A more preferable lower limit for the content of the plasticizer is 18 parts by weight, and a further preferable lower limit is 15 parts by weight.

The thermoplastic resin layer 3 contains additives such as stabilizers, ultraviolet absorbers, colorants, foaming agents, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents, if necessary. may As these additives, those generally blended with thermoplastic resins or vinyl chloride resins can be used.

Examples of the stabilizer include metal soaps such as fatty acid calcium, fatty acid zinc and fatty acid barium; hydrotalcite and the like. Examples of the fatty acid component of the metal soap include calcium laurate, calcium stearate, calcium ricinoleate, zinc laurate, zinc ricinoleate, zinc stearate, barium laurate, barium stearate, and barium ricinoleate. In addition, as the above stabilizers, epoxy stabilizers; barium stabilizers; calcium stabilizers; tin stabilizers; zinc stabilizers; -Zn system) can also be used.

When the stabilizer is contained, the content thereof is preferably 0.3 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. In addition, when the ultraviolet absorbing material is contained, the content thereof is preferably 0.3 to 2.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

The thickness of the thermoplastic resin layer 3 is 40-200 μm. If the thickness is less than 40 μm, the decorative film 10 becomes soft, and there is a possibility that scratch resistance, abrasion resistance, and abrasion resistance may not be obtained, and there is a possibility that the design will deteriorate. On the other hand, if the thickness exceeds 200 μm, the total amount of heat generated by the decorative film 10 may increase. Moreover, the film properties of the decorative film 10 may deteriorate. A more preferable lower limit of the thickness of the thermoplastic resin layer 3 is 50 μm, and a more preferable upper limit thereof is 150 μm.

The thermoplastic resin layer 3 preferably has high transparency in order to further enhance the design of the design layer 4. Specifically, the total light transmittance is preferably 80% or more, and 90% or more. It is more preferable to have

[Design layer]
The design layer 4 is a decoration layer containing dyes or pigments. By arranging the design layer 4, the designability of the decorative film 10 can be enhanced. The design layer 4 may be a colored film obtained by adding a dye or pigment to a resin composition, or a film made of a resin composition having characters, patterns, etc. printed on at least part of its surface. good. The dye or pigment is not particularly limited, and those commonly used in the field of decorative films can be used.

Examples of the resin composition used for the design layer 4 include vinyl esters such as vinyl chloride, vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; and methyl acrylate, ethyl acrylate and methyl methacrylate. (Meth) acrylic acid esters; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinylidene chloride and vinyl bromide and vinyl halides such as vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more. Moreover, these may be homopolymers or copolymers of two or more kinds.

Moreover, the design layer 4 may cover the entire surface of the base film 5 or may cover a portion thereof. For example, when the design layer 4 has a planar shape corresponding to an arbitrary design or information, the design layer 4 partially covers the surface of the base film 5 .

A printing method for forming the design layer 4 is not particularly limited, and examples thereof include inkjet printing and gravure printing. A specific example of inkjet printing is a method of discharging vinyl chloride-vinyl acetate copolymer/acrylic ink onto the base film 5 with an inkjet printer. A specific example of gravure printing is a method using a one-liquid curable ink or a two-liquid curable ink. In addition, the surface of the base film 5 may be surface-treated in order to improve the fixability of printing.

[Base film]
The base film 5 has a role as a support for the decorative film 10 and also has a role as a base material for the design layer 4 .

The material of the base film 5 is not particularly limited as long as it satisfies the above-described specific hardness, but thermoplastic resins such as polyethylene terephthalate and vinyl chloride resin can be used as in the thermoplastic resin layer 3 described above. . Polyethylene terephthalate and vinyl chloride resin have high flame retardancy, and therefore, by using them as the support of the decorative film 10, an increase in the total calorific value can be suppressed. When the base film 5 contains a vinyl chloride resin, the vinyl chloride resin may be the same as or different from the vinyl chloride resin used in the thermoplastic resin layer 3 in terms of composition, average molecular weight, etc. may be

The base film 5 may contain a plasticizer. The plasticizer used in the base film 5 may be the same as or different from the plasticizer used in the thermoplastic resin layer 3 in terms of composition, number average molecular weight, and the like.

The content of the plasticizer contained in the base film 5 is preferably 10 to 23 parts by weight with respect to 100 parts by weight of the resin solid content constituting the base film. If the content is less than 10 parts by weight, the base film 5 may become too hard and may tear during molding. On the other hand, if it exceeds 23 parts by weight, the base film 5 becomes too soft, and the scratch resistance, abrasion resistance, and abrasion resistance of the topcoat layer 1 of the decorative film 10 may be lowered. A more preferable upper limit of the content of the plasticizer is 18 parts by weight, and a more preferable upper limit is 15 parts by weight. Since the thermoplastic resin layer 3 and the base film 5 are laminated, it is preferable that they basically have the same hardness. Therefore, if the thermoplastic resin layer 3 and the base film layer 5 are both made of the same resin such as vinyl chloride resin and have the same thickness, it is preferable that the plasticizer content is the same.

The base film 5 may optionally contain additives such as stabilizers, ultraviolet absorbers, colorants, foaming agents, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents. good. As these additives, vinyl chloride resins and those generally blended with polyethylene terephthalate can be used, and the additives used in the thermoplastic resin layer 3 may be the same or different. may Since the base film 5 is arranged in a lower layer than the design layer 4, even if an additive is added to the base film layer 5, the change in color tone of the decorative film 10 due to the additive is hardly visible. For this reason, the base film layer 5 is suitable for adding additives for adjusting the properties of the decorative film 10 as a whole, and may contain, for example, a flame retardant.

Although the thickness of the base film 5 is not particularly limited, it is preferably 40 to 200 μm. If the thickness is less than 40 μm, the decorative film 10 may become too flexible, resulting in deterioration in workability and deterioration in weather resistance. On the other hand, if the thickness exceeds 200 μm, the total amount of heat generated by the decorative film 10 may increase. Moreover, the film properties of the decorative film 10 may deteriorate. A more preferable lower limit of the thickness of the base film 5 is 60 μm, and a more preferable upper limit thereof is 150 μm.

The surface of the base film 5 may be surface-treated in order to improve adhesion with the design layer 4 . Types of surface treatment include, for example, corona discharge treatment, plasma treatment, and ozone treatment.

[Adhesive layer]
The adhesive layer 6 contains an adhesive. Examples of the adhesive include acrylic adhesives, rubber adhesives, silicone adhesives, and the like. Among them, acrylic pressure-sensitive adhesives are preferably used because they are excellent in adhesiveness, workability, heat aging resistance, moisture aging resistance, and weather resistance, and are relatively inexpensive.

The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer. Examples of the acrylic polymer include homopolymers of (meth)acrylic acid alkyl esters and copolymers thereof.

The adhesive layer 6 is formed by, for example, coating an adhesive composition containing an adhesive, a cross-linking agent (curing agent), etc. on a support to form a coating film, and then curing the coating film by heating and drying it. can be formed by the method of The cross-linking agent (curing agent) is a compound that chemically reacts or interacts with the functional groups in the pressure-sensitive adhesive to form cross-links. As the cross-linking agent, known cross-linking agents such as isocyanate-based curing agents and epoxy-based curing agents can be used.

Various additives such as stabilizers, plasticizers, softeners, fillers, tackifiers, dyes, pigments, and inorganic fillers may be added to the pressure-sensitive adhesive composition as necessary.

The coating amount of the adhesive composition is preferably 5 to 90 g/m ² (converted to dry weight). In other words, the coating amount of the adhesive layer 5 obtained by drying the adhesive composition is preferably 5 to 90 g/m ² . A more preferable lower limit of the coating amount is 10 g/m ² . A more preferable upper limit of the coating amount is 60 g/m ² .

The thickness of the adhesive layer 6 is preferably 10-60 μm. If the thickness is less than 10 µm, sufficient adhesiveness may not be obtained. On the other hand, if the thickness exceeds 60 μm, the total amount of heat generated by the decorative film 10 may increase. A more preferable lower limit of the thickness of the adhesive layer 6 is 20 μm, and a more preferable upper limit thereof is 50 μm. The thickness of the adhesive layer 6 is the thickness after drying.

[separator]
The decorative film 10 may be provided with a separator on the side of the adhesive layer 6 opposite to the base film 5 . By providing the separator, the adhesive layer 6 is not exposed during manufacture, transportation, and storage of the decorative film 10, thereby preventing deterioration of the adhesive layer 6 and improving the handleability of the decorative film 10. The separator may be peeled off immediately before being attached to the substrate.

The separator is not particularly limited, and those commonly used in the field of decorative films can be used. The separator is preferably one that can be easily peeled off without damaging the adhesive layer 6, and examples thereof include a resin film (release film), paper (release paper), and a laminate film of paper and a coating layer. Examples of the release film include resin films such as polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene. It is preferable that the surface of the resin film that comes into contact with the adhesive layer 6 is coated with a silicone resin, a fluorine resin, or the like so as to be easily peeled off. Examples of the release paper include fine paper and glassine paper.

The surface of the decorative film 10 on the topcoat layer 1 side may be subjected to surface processing such as embossing, if necessary. By providing the surface of the decorative film 10 with an embossed shape (concavo-convex shape) by embossing, the decorativeness of the pattern imparted by the design layer 4 and the design imparted by the embossed shape can be greatly enhanced. The surface of the topcoat layer 1 may be embossed, or the surface of the thermoplastic resin layer 3 may be embossed before the topcoat layer 1 is formed. It is preferable to emboss the thermoplastic resin layer 3 of . This is because if the top coat layer 1 after curing is embossed, cracks or the like may occur, which may impair the design.

The decorative film 10 preferably has a total thickness of the organic resin layers of 100 to 500 μm. If the total thickness is less than 100 μm, there is a possibility that the workability may deteriorate and the weather resistance may deteriorate. On the other hand, if the total thickness exceeds 500 μm, it may be difficult to suppress the total amount of heat generated. The total thickness of the organic resin layer refers to the total thickness of the topcoat layer 1 , primer layer 2 , thermoplastic resin layer 3 , design layer 4 , base film 5 and adhesive layer 6 . The total thickness of the organic resin layer does not include the thickness of the separator. A more preferable lower limit of the total thickness of the organic resin layer is 120 μm, and a more preferable upper limit thereof is 300 μm.

The decorative film 10 preferably has a total calorific value of 7.2 MJ/m ² or less. The above total calorific value is the total calorific value in a heat generation test using a cone calorimeter tester according to the fire resistance test method and performance evaluation standards based on Article 2, Item 9 of the Building Standards Law and Article 108-2 of the Enforcement Order of the Building Standards Law. is. The measurement of the above total calorific value is carried out in accordance with the "Exothermic test method" of the "Fireproof performance test and evaluation work method manual" of the Japan Testing Center for Building Materials. Specifically, a gypsum board having a thickness of 12 mm or more is used as a base material, and a heat generating test device (cone calorimeter) for fireproof materials is used. The gypsum board is laminated in the order of base paper/gypsum/base paper, and has the highest calorific value among noncombustible materials. Therefore, if it passes the exothermic test using gypsum board, it can be considered that other noncombustible materials also pass the exothermic test. If the total calorific value for 20 minutes after the start of heating is 7.2 MJ/m ² or less, it sufficiently satisfies the standard of the total calorific value (8 MJ/m ² or less) as a fireproof material. In addition, the decorative film 10 of the present invention should be "free from cracks and holes penetrating to the back surface harmful to fire prevention for 20 minutes after the start of heating" and "heating 20 minutes after the start, the maximum heat generation rate shall not exceed 200 kW/ ^m2 continuously for 10 seconds or longer".

The decorative film 10 can be manufactured using a conventionally known manufacturing method. The top coat layer 1 is formed, for example, on the thermoplastic resin layer 3 or via the primer layer 2 formed on the thermoplastic resin layer 3, by a bar coating method, a roll coating method, a blade coating method, or a reverse coating method. , gravure coating method, die coating method, etc., after forming a coating film by applying a composition for forming a topcoat layer, and then heat drying, UV irradiation, etc. to cure the coating film. method can be used.

For the primer layer 2, for example, the thermoplastic resin layer 3 is coated with a resin composition using a bar coating method, a roll coating method, a blade coating method, a reverse coating method, a gravure coating method, a die coating method, or the like, It can be formed using a conventionally known method such as a drying method.

The thermoplastic resin layer 3 and the base film 5 can be produced by conventionally known molding methods such as calendar molding, extrusion molding, and injection molding. Examples of the calender type used for the calender molding include an inverted L type, a Z type, an upright 2-line type, an L type, and an inclined 3-line type.

The design layer 4 can be formed by a conventionally known printing method such as inkjet printing or gravure printing.

The method of forming the adhesive layer 6 is not particularly limited, and for example, a conventionally known method such as a method of directly coating an adhesive composition on a separator using a bar coater or the like and drying it can be used. In this case, the decorative film 10 can be manufactured by bonding the adhesive layer 6 formed on the separator to the base film 5 . The decorative film 10 is further subjected to processing such as cutting and winding into a roll, if necessary.

When the decorative film 10 is embossed, for example, it may be carried out as follows.
A laminate in which the thermoplastic resin layer 3, the design layer 4, and the base film 5 are laminated in this order is heated with a preheating roll to soften the thermoplastic resin layer 3, and then peeled off from the preheating roll and transferred to the embossing roll. and rubber rolls to make unevenness. The pressure during sandwiching is, for example, 20 kg/cm ² . Next, the composition for forming a topcoat layer is applied onto the thermoplastic resin layer 3 after embossing, for example, ultraviolet irradiation is performed so that the cumulative amount of ultraviolet light is 600 mJ/cm ² , and the topcoat has a desired thickness. Layer 1 can be formed to obtain an embossed decorative film 10 . By the above method, a surface roughness of about Ra: 2 to 6 μm, Rz: 7 to 21 μm, and Ry: 14 to 28 μm (JIS 1994) is obtained. can be enhanced.

Applications of the decorative film of the present invention are not particularly limited, but examples thereof include decorative panels (wall covering materials) attached to walls, interior doors, doors of closets and kitchens, furniture, and interior materials such as flooring. Moreover, you may use for the wall decoration of water-related areas, such as a bathroom, a kitchen, a washroom, and a toilet. According to the decorative film of the present invention, a design equivalent to that of a painted product can be obtained by a simpler and safer method than painting.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited only to these Examples.

(Example 1)
18 parts by weight of diisononyl phthalate (DINP) as a plasticizer was added to 100 parts by weight of polyvinyl chloride (PVC) having an average degree of polymerization of 1000 to obtain a PVC compound. The resulting PVC compound was melt-kneaded in a Banbury mixer and then formed into a sheet having a thickness of 80 μm by an inverted L-shaped calender to prepare a PVC film. The resulting PVC film was used as a thermoplastic resin layer and a base film.

Next, a design layer was formed on one surface of the base film using an inkjet printer using a vinyl chloride-vinyl acetate copolymer/acrylic ink. Subsequently, the obtained thermoplastic resin layer was attached to the surface of the base film on which the design layer was formed by thermal lamination to prepare a laminated film. The obtained laminated film was heated with a preheated roll to soften the thermoplastic resin layer, then peeled off from the preheated roll and sandwiched between an embossing roll and a rubber roll to form unevenness. The pressure during pinching was 20 kg/cm ² .

Add 9 parts by weight of alumina with an average particle size of 2 μm to 100 parts by weight of ultraviolet curable resin (manufactured by Kyoeisha Chemical, product name: HX-RPH), adjust the viscosity with methyl ethyl ketone for dilution, and use it for the top coat layer. A composition was obtained. The ultraviolet curable resin (HX-RPH) contains 30 to 40 parts by weight of silica particles with respect to 100 parts by weight of the resin (HX-RPH). The obtained composition for top coat layer was coated on the thermoplastic resin layer of the laminated film with a bar coater, dried at 85 ° C. for 2 minutes, and irradiated with a UV irradiation machine so that the cumulative amount of ultraviolet light was 600 mJ / cm ² . (manufactured by Eye Graphics) was used to irradiate with ultraviolet rays to form a top coat layer having a thickness of 5 μm. As a result, a laminate was obtained in which the topcoat layer, the thermoplastic resin layer, the design layer, and the base film were laminated in this order. White Morundum (manufactured by Showa Denko KK) was used as the alumina.

In addition, on one side of a 100 μm thick separator (biaxially stretched polyester (PET) film), an acrylic pressure-sensitive adhesive solution is applied with a bar coater so that the dry thickness is 40 μm to form a coating film. bottom. The acrylic adhesive solution was prepared by blending 100 parts by weight of an acrylic adhesive ("SK2094" manufactured by Soken Chemical Co., Ltd.) with 1.2 parts by weight of an epoxy curing agent ("E-AXM" manufactured by Soken Chemical Co., Ltd.). It was something. The coating film was dried by heating in a drying oven at 80° C. for 1 minute to remove the solvent in the coating film and prepare an adhesive layer.

Next, the separator and the laminate were bonded together via the adhesive layer, and the adhesive layer formed on the separator was transferred to the base film side of the laminate. Thus, a decorative film of Example 1 was obtained.

(Examples 2 to 11 and Comparative Examples 1 to 8)
Examples 2 to 11 and Decorative films of Comparative Examples 1 to 8 were produced. However, when the type of base film was PET, the above embossing was not performed. When the type of the base film was vinyl chloride, the embossing had a surface roughness of Ra: 2 to 4 μm, Rz: 8 to 13 μm, and Ry: 15 to 18 μm (JIS 1994). The hardness and thickness of each layer were measured by the following methods.

(hardness)
For the thermoplastic resin layers according to the examples and comparative examples, a thermoplastic resin layer formed by lamination so as to have a thickness of 2 mm or more and 2.5 mm or less was prepared as a hardness measurement sample, and the hardness was measured as follows. Using an Asker rubber hardness meter D type (manufactured by Kobunshi Keiki Co., Ltd., type D durometer), measurement was performed under the condition of a load of 200 g, and the value 1 second after the load was recorded.
The hardness of the top coat layer was determined by laminating the thermoplastic resin layers according to Examples and Comparative Examples so that the thickness was 2 mm or more and 2.5 mm or less. And a topcoat layer having the same thickness as the decorative film of the comparative example was laminated as a sample for measuring the hardness of the topcoat layer, and the hardness of the topcoat layer was measured in the same manner as the hardness measurement of the base film. The measurement results are shown in Table 1 below.

(Thickness of topcoat layer)
The decorative films according to Examples and Comparative Examples were measured using a microgauge. The thicknesses of the laminated films before forming the topcoat layer according to Examples and Comparative Examples were also measured in the same manner, and the difference between them was calculated as the thickness of the topcoat layer. The measurement results are shown in Table 1 below.

(Evaluation test)
The decorative films produced in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1 below.

(1) Flexibility According to the mandrel test described in JIS-K5600-5-1 (a test in which a sample is wrapped around a metal cylinder of 2 mm to 32 mm), a SUS cylinder of 12 mmφ was used in Examples and Comparative Examples. The decorative film was wound in the length direction with the top coat layer facing outward, and the occurrence of cracks was visually observed and evaluated according to the following criteria.
〇: No noticeable cracks △: Minor cracks ×: Large cracks

(2) Bendability The decorative films according to Examples and Comparative Examples were bent 180 degrees, and the bent portions were visually observed and evaluated according to the following criteria.
○: No break in the film △: No break even though a strong trace remains due to the crack ×: The film breaks (breaks) due to a large crack

(3) Haze and Transmittance Haze and transmittance were measured using a turbidity meter "HazeMeter NDH5000" manufactured by Nippon Denshoku Industries Co., Ltd. Haze was measured by a method based on "JIS K 7136". Transmittance was measured by a method conforming to "JIS K 7361-1".

(4) The transparent decorative film was visually observed from the topcoat layer side and evaluated according to the following criteria.
〇: Although some cloudiness is observed, there is no effect on the appearance of the design layer. Decrease in the appearance of the layer design is observed

(5) Abrasion resistance The surface of the top coat layer of the decorative film according to the examples and comparative examples was rubbed back and forth 10 times with #000 steel wool at a friction load of 500 g/cm ² , and then the top coat was applied. Changes in glossiness of the layer were visually observed and evaluated according to the following criteria.
○: No change in gloss △: Slight change in gloss ×: Scratches

(6) Coin Scratchability A copper coin was scratched with a coin scratch tester under a load of 1 kg.
〇: No scratches
△: Minor scratches occurred
×: Scratches occur

In Table 1, the unit "phr" for the amount of alumina added represents the number of parts by weight per 100 parts by weight of the resin solid content in the topcoat layer.

From the results shown in Table 1 above, the top coat layer contains alumina, the thickness of the top coat layer is 5 μm or more, and the hardness of the thermoplastic resin layer is 62 (JIS K6253-3 Type D durometer) or better, coin scratch resistance (scratch resistance and abrasion resistance) and abrasion resistance are obtained. Further, when the content of alumina in the top coat layer is 5 to 15 parts by weight with respect to 100 parts by weight of the resin solid content of the top coat layer, transparency is obtained and excellent coin scratch resistance (scratch resistance and It was found that both scratch resistance and wear resistance and excellent design properties can be achieved. It was also found that film properties were obtained when the topcoat layer thickness was in the range of 5 to 15 µm, and excellent film properties were obtained in the range of 5 to 10 µm.

1 Topcoat layer 2 Primer layer 3 Thermoplastic resin layer 4 Design layer 5 Base film 6 Adhesive layer 10 Decorative film

Claims (7)

A decorative film having a base film, a polyvinyl chloride film , and a topcoat layer in that order,
The topcoat layer contains an ultraviolet curable resin, silica and alumina, and has a thickness of 5 μm or more and 10 μm or less ,
The polyvinyl chloride film has a thickness of 40 to 200 μm, and the hardness of the polyvinyl chloride film is 62 (JIS K6253-3 type D durometer) or more and 68 or less at a thickness of 2 mm or more and 2.5 mm or less,
A decorative film , wherein the alumina content is 5 to 11 parts by weight with respect to 100 parts by weight of the resin solid content of the top coat layer . The decorative film according to claim 1 , wherein the ultraviolet curable resin contains a urethane (meth)acrylate resin. 3. The decorative film according to claim 1, further comprising a design layer between the base film and the polyvinyl chloride film . The decorative film according to any one of claims 1 to 3 , wherein the polyvinyl chloride film is embossed. The polyvinyl chloride film contains a plasticizer,
The decorative film according to any one of claims 1 to 4, wherein the content of said plasticizer is 10 to 23 parts by weight with respect to 100 parts by weight of polyvinyl chloride. The base film contains polyvinyl chloride and a plasticizer,
The decorative film according to any one of claims 1 to 5, wherein the content of said plasticizer is 10 to 23 parts by weight with respect to 100 parts by weight of said polyvinyl chloride. Any one of claims 1 to 6, wherein the hardness of the top coat layer is 65.9 (JISK6253-3 type D durometer) or more and 69.7 or less at a thickness of 2 mm or more and 2.5 mm or less. Decorative film as described.

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