JP4480834B2 - Vinylidene fluoride resin film - Google Patents

Description

【００３９】
【表２】

【００４０】
【発明の効果】
以上の説明からも明らかな様に、本発明によって得られる艶消し調の表面を有するフッ化ビニリデン系樹脂フィルムは、フッ化ビニリデン系樹脂の有する優れた長期耐候性、耐汚染性をそなえ、フッ素系フィルムの欠点である他の基材との接着性を保持した上、特に表面が優れた艶消し調の低光沢表面を有しかつ機械的強度および熱加工性に優れることを特徴とする。特に、フィルム成形時にエンボスロールを用い表面に凹凸を形成し艶消し表面を得るフッ素系樹脂フィルムでは、ＰＶＣ、ＡＢＳ等の基材と熱ラミネート法により接着する場合、ロールやプレスで熱がかけられる際少なくとも接着面は融点若しくは軟化点以上の環境にさらされるため、表面の凹凸形状も接着される前よりも緩やかになり、艶戻りが起こり艶消し表面が維持できなかったり艶斑が発生すると言った問題を生じるが本発明のフッ化ビニリデン系樹脂フィルムは表面層に球状形状の架橋アクリル樹脂が添加されたものであり、かつ本フィルム製膜時の押出直後にその表面側がエンボスロールに接触しながら該エンボスロールと金属ロールもしくはゴムロールにより圧着され成形されたフィルムで有るが故に優れた熱加工性を付与される。したがって建築物の内外装、自動車部材等の多岐にわたる用途、特に高い耐候性能の必要とされる用途の装飾や意匠性向上として好適に使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vinylidene fluoride resin film and a laminate obtained by laminating the film on a substrate. The film is excellent in fastness such as weather resistance, stain resistance, chemical resistance, etc. and adhesiveness to various substrates, especially has a matte-like low gloss on the surface, and has mechanical strength and heat processability. Because it is excellent, it is suitable for surface protection films to be bonded to the surface of other base materials such as plastic, rubber, metal plate, glass, wood board, slate, and can improve the protection, decoration and design of the base material. .
[0002]
[Prior art]
For the purpose of improving durability and decoration, plastic plates, metal plates, and other various base materials used for interior and exterior parts of buildings have their surfaces painted, and surface protection films of durable films, especially fluororesins It is used by laminating. Applications include, for example, wallpaper and vehicles, interior and exterior materials such as elevators, roofing materials, wall materials, gutters, garages, arcades, solariums, agricultural materials, tent sites, signs, signs, labels, marking films , Furniture, home appliances, trays, roof tiles, window glass, etc.
[0003]
In such applications, fluorine-based films and vinylidene fluoride-based resin films may be used alone, but mainly for the purpose of adhering to the surface of various materials, protecting the base material, and improving design. Used a lot. As target substrates for these laminations, in addition to plastic substrates such as polyvinyl chloride, polycarbonate, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, FRP, fluorine paint steel plate, CR, EPDM, There are a wide variety of materials such as CSM and other rubber materials, metals such as aluminum foil, stainless steel, galvanized steel, and plywood, wood board, glass, printing paper, slate and the like.
[0004]
As such a surface protective film, a film having a matte-like low gloss surface is used in order to enhance the sense of quality and design. To make the surface matt, (1) A method of subjecting the film surface to physical treatment such as sandblasting or polishing after molding the fluorine resin film, (2) A matting agent on the film surface after molding the fluorine resin film (3) A method of forming an unevenness on the surface by passing an embossing roll immediately after extrusion when extruding a fluororesin film (see JP-A-2-28239), (4) Matting agent There is a method of adding an inorganic substance or an organic substance to the fluororesin itself.
[0005]
Among them, the method (3) using an embossing roll and the method (4) adding a matting agent are simpler and less expensive than other methods. However, the conventional methods including those methods have a problem that the surface is glossy when thermally laminated, a problem of poor appearance due to deterioration of dispersibility due to the addition of a matting agent, and a problem of reduced mechanical strength.
[0006]
[Problems to be solved by the invention]
The present invention solves such problems and maintains the weather resistance, contamination resistance, and solvent resistance, which are the characteristics of fluorine resin films, and other groups that are disadvantages of fluorine resin films. Maintains adhesiveness to the material, has excellent mass production, has a low-gloss surface with a matte finish without secondary processing, and suppresses matte and glossy spots during thermal lamination, as well as mechanical It is an object of the present invention to provide a vinylidene fluoride resin film having a matte surface, which is characterized in that the strength is not easily lowered.
[0007]
[Means for Solving the Problems]
That is, the present invention is a laminate in which the surface layer is a vinylidene fluoride resin film containing a crosslinked acrylic resin and a vinylidene fluoride resin, and the vinylidene fluoride resin film is laminated on a substrate. Among these, a vinylidene fluoride resin film having a matte surface with a surface glossiness of 60 or less is suitably used for improving the decoration and design of the surface protective film and giving a high-class feeling.
DETAILED DESCRIPTION OF THE INVENTION
[0008]
Hereinafter, the present invention will be described in more detail.
The vinylidene fluoride resin film of the present invention has a surface layer containing a crosslinked acrylic resin and a vinylidene fluoride resin, and the surface is matte. The film can be a single layer consisting of only the surface layer, or a two-layered film having a surface layer and a back layer laminated on the base material. In addition to the structure, the intermediate layer is increased, the front layer, the intermediate layer and the back layer are three layers, the front layer and the intermediate layer are two layers and the back layer is four layers, and the five intermediate layers are three layers. It can also be a structure. In the case of a multilayer structure of three or more layers, the composition of the intermediate layer is preferably an intermediate composition of the surface layer composition and the back surface layer composition of the two-layer structure.
[0009]
The surface layer must contain a crosslinked acrylic resin and a vinylidene fluoride resin (hereinafter referred to as PVDF). A methacrylic ester resin (hereinafter referred to as PMMA) can be further added to the surface layer. The back layer is made of PMMA or PMMA and PVDF.
[0010]
The PVDF used in the present invention refers to a homopolymer of vinylidene fluoride or a copolymer of monomers copolymerizable with vinylidene fluoride. Examples of the copolymerizable monomer include vinyl fluoride, tetrafluoroethylene, trifluorochloroethylene, and hexafluoropropylene, and one or more of these can be used.
[0011]
PMMA refers to a homopolymer of methyl methacrylate or a copolymer of a monomer copolymerizable with methyl methacrylate, and a mixture of a homopolymer or copolymer of polymethyl methacrylate and an acrylic rubber. Examples of the copolymerizable monomer include methacrylic acid esters having 2 to 4 carbon atoms, acrylate esters having 1 to 8 carbon atoms including butyl acrylate, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and others. Of ethylenically unsaturated monomers.
[0012]
The crosslinked acrylic resin blended as an essential component for constituting the present invention is obtained by polymerizing a monomer containing a carboxyl group and a polyfunctional monomer. For example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate are used as monomers containing a carboxyl group, and ethylene glycol dimethacrylate, ethylene glycol bismethacrylate, propylene glycol diacrylate, There are copolymers with methylolpropane trimethacrylate, pentaerythritol tetramethacrylate and the like. The above-mentioned monomer containing a carboxyl group and a polyfunctional monomer can be used as a copolymer of one kind, but one or both can also be used as a copolymer by mixing two or more kinds.
[0013]
The shape of the crosslinked acrylic resin is preferably spherical. Here, the spherical shape includes substantially spherical shapes including true spheres and mixtures thereof. If it is not spherical, a problem arises in dispersibility, and it causes a mechanical strength reduction such as the film being easily torn by the sharp corners of the crosslinked acrylic resin. The average particle size is preferably 1 to 20 μm, more preferably 3 to 15 μm, and most preferably 5 to 10 μm. If the average particle size is small, the glossiness of the surface increases and a matte surface cannot be obtained. Conversely, if the particle size is too large, the dispersibility deteriorates and a uniform matte surface cannot be obtained, and the mechanical strength is significantly reduced. To do. It is desirable that the crosslinked acrylic resin is dispersed without being compatible even when mixed with PVDF and PMMA.
[0014]
The addition amount of the cross-linked acrylic resin is preferably 0.5 to 30, more preferably 1 to 20 parts by weight, and most preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of PVDF and PMMA. If the addition amount is small, a matte surface cannot be obtained. Conversely, if the amount is too large, dispersibility deteriorates and a uniform matte surface cannot be obtained, and the mechanical strength is remarkably lowered.
[0015]
The surface layer is preferably PVDF alone, or PVDF less than 100 parts by weight and 50 parts by weight or more and PMMA more than 0 parts by weight and 50 parts by weight or less, more preferably 95 to 60 parts by weight PVDF and 5 to 40 parts by weight PMMA. When the content of PVDF is large, the adhesion between the surface layer and the back layer is lowered, and when it is low, the excellent weather resistance of PVDF is lowered, and the effect as a protective film layer is reduced.
[0016]
The back layer can be made of PMMA alone or PVDF and PMMA in combination. When laminating to a substrate other than the fluorine-based substrate, PMMA is preferably 100 to 35 parts by weight and PVDF is preferably 0 to 65 parts by weight, more preferably PMMA 95 to 60 in the back layer which is the lowermost layer with respect to the substrate. Parts by weight and 5 to 40 parts by weight of PVDF. When the content of PMMA is small, adhesive strength with the substrate cannot be obtained. Moreover, when adding a ultraviolet absorber to a lower layer, if there is little content of PMMA, volatilization of a ultraviolet absorber will occur and it is unpreferable. Moreover, when PMMA increases, the weather resistance tends to decrease.
[0017]
When laminating to the fluorine-based substrate, 0 to 50 parts by weight of PMMA and 100 to 50 parts by weight of PVDF are preferable in the back layer which is the lowermost layer with respect to the substrate, more preferably 5 to 40 parts by weight of PMMA and PVDF95. ~ 40 parts by weight. When the content of PVDF is small, adhesive strength with the surface layer or the fluorine-based substrate cannot be obtained. However, when an ultraviolet absorber is added to the lower layer, if the PMMA content is small, the ultraviolet absorber volatilizes and is not preferable. Therefore, it is desirable that the PMMA content be large.
[0018]
Antioxidants, dispersants, coupling agents, thermal stabilizers, surfactants, antistatic agents, antifogging agents, UV absorbers, and coloring are applied to the surface layer and the back surface layer as long as the respective performances are not impaired. As the agent, composite oxide inorganic pigments, inorganic pigments, carbon black, and pearl pigments can be used.
[0019]
The ultraviolet absorber is compatible with the resin used in each layer and preferably has a high molecular weight in order to prevent volatilization. For example, benzotriazole, oxalic acid, benzophenone, hindered amine, and many other types can be used. More specifically, 2- [3,5-di- (allopha-dimethylbenzyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H- Benzotriazol-2-yl) phenol]], 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazine- 2-I ) -5- (hexyl) oxyphenol, 2-ethoxy-2'-ethyl oxac acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl oxac acid bisanilide, 2-hydroxy-4- n-octoxybenzophenone, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (1- Octyloxy-2,2,6,6, -tetramethyl-4-piperidinyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyl) ethanol, 1- [ 2-3- (3,5-di-t-butyl-4-hydroxyphenyl) poropionyloxy] -2,2,6,6-T-tetramethylpiperidine and the like.
[0020]
A cross-linked acrylic resin is added to the surface layer of the vinylidene fluoride-based resin film of the present invention, but in order to make the surface have a good matte tone, the surface may be matted with an embossing roll during extrusion molding. In this case, it is preferable to use an embossing roll that satisfies the following formula (A) between the average particle diameter of the crosslinked acrylic resin and the surface roughness Rz of the embossing roll.
(A) Average particle diameter of crosslinked acrylic resin ≦ surface roughness Rz of embossing roll
When the film is heat laminated by hot roll pressing or hot press pressing, it is important that the average particle size of the crosslinked acrylic resin is equal to or less than the surface roughness of the embossing roll. That is, as in the case of the present invention film, if the average particle diameter of the cross-linked acrylic resin is equal to or less than the surface roughness of the embossing roll, gloss reversal and luster are suppressed even by processing such as thermal lamination. The reason for this is that the convex portions of the surface irregularities formed by the embossing roll mainly contact with the surface of the hot roll or hot press preferentially. It is considered that the unevenness due to the cross-linked acrylic resin is present, so that the unevenness is maintained without being greatly influenced by the cushioning effect of the convex portion.
[0021]
The average particle diameter of the cross-linked acrylic resin with respect to the surface roughness Rz of the embossing roll of the vinylidene fluoride resin film having a matte surface of the present invention is preferably equal to or less than that, and more preferably, The average particle diameter of the crosslinked acrylic resin is 80% or less with respect to the surface roughness Rz, and most preferably the average particle diameter of the crosslinked acrylic resin is in the range of 70% to 20% with respect to the surface roughness Rz of the embossing roll. . If the average particle size is extremely small relative to the surface roughness Rz of the embossing roll, the matte effect by the crosslinked acrylic resin itself will be reduced, and a good matte surface will not be obtained, and the cause of matte return during heat processing There is a risk of becoming. In addition, when the average particle size is larger than the surface roughness Rz of the embossing roll, the uneven portions due to the cross-linked acrylic resin itself are preferentially affected by the pinch pressure bonding, etc., rather than the surface unevenness due to the embossing roll during thermal lamination. There is a high possibility of causing return and gloss spots.
[0022]
The vinylidene fluoride resin film of the present invention can be used for various applications by subjecting the surface layer, the intermediate layer, or the back layer to a printing treatment or the like.
[0023]
The film thickness of the vinylidene fluoride resin film is determined in accordance with various uses, but is 150 μm or less as a whole, and preferably in the range of 10 to 100 μm. Furthermore, it is desirable that the thickness ratio of each layer is 50% to 95% of the total thickness of the film made from the back layer, from the viewpoint of ensuring the mechanical strength of the film. If it exceeds 95%, it becomes difficult to obtain an excellent matte surface, and if it is less than 50%, the mechanical strength is impaired.
[0024]
The vinylidene fluoride resin film of the present invention can be laminated on various substrates to form a laminate. Examples of the substrate include plastic, rubber, paint surface, metal, glass, wood, slate and the like, but are not particularly limited thereto. In order to form a laminate, the film can be bonded to the base material using an adhesive, or depending on the type of the base material, it can be bonded only by heat processing utilizing the excellent heat workability. As the adhesive to be used, general adhesives such as epoxy resin, acrylic resin, urethane resin, etc. can be used, and pressure sensitive adhesives using natural rubber, acrylic resin, etc. are preliminarily used as vinylidene fluoride. It can be used after being applied to the adhesive surface of the resin film. Furthermore, a release paper can be attached to the pressure-sensitive adhesive, and the release paper can be peeled off during use and bonded to the substrate.
[0025]
The vinylidene fluoride resin film of the present invention can be produced by melt extrusion molding, and in the case of a plurality of layer structures, a coextrusion molding method can be used. A co-extrusion method using a T-die using a plurality of extruders to bond a resin in a molten state to form a multilayer is called a multi-manifold die, and after making a plurality of resin layers into a sheet state, There are a method of bringing them into contact and a method of bonding them, and a method of spreading a plurality of resins in a sheet form after joining and bonding using a joining device called a feed block. Moreover, a multilayer film can be shape | molded also by the method of using a round die | dye called the inflation molding method. The melt-extruded resin is pressed and molded between the embossing roll and the metal roll immediately after extrusion while the matte surface is in contact with the embossing roll side.
[0026]
As a method of mixing PVDF, PMMA, cross-linked acrylic resin, ultraviolet absorber, and other additives, there is a method in which the resin and additives are mixed in advance and melt kneaded using a commonly used single-screw extruder. Can be adopted. Even when a spherical cross-linked acrylic resin is added to PVDF and PMMA, the surface state is determined by a method of melt-kneading each with a single-screw extruder after pre-blending due to the excellent compatibility with the spherical shape and PVDF and PMMA. A raw material having excellent dispersibility can be provided. In addition, as a method for further improving the dispersibility of the additive such as a cross-linked acrylic resin in the resin component, a method using part or all of PVDF and / or PMMA as a powdery raw material, or a high kneading type biaxial extrusion Needless to say, it is possible to use a method using a machine or a method of premixing at a high temperature using a high-speed rotary mixer and then melt-kneading with a single-screw extruder.
[0027]
【Example】
Hereinafter , this description will be described in more detail with reference to Examples , Experimental Examples and Comparative Examples.
(Example 1) The resin for the surface layer and the resin for the back layer were blended with a tumbler at the blending ratio shown in Table 1, and kneaded with a φ45 mm twin screw extruder to obtain a compound. Next, a thin film having a film thickness ratio shown in Table 1 was formed by a feed block method using two φ50 mm single screw extruders. At this time, an embossing roll having a surface roughness shown in Table 1 was used. Next, the base material shown in Table 1 was used, and heating lamination was performed. The heating laminate used a roll laminator and was thermally bonded under the condition of a heating temperature of 140 ° C. to obtain a laminated sheet.
[0028]
(Example 2)
According to the blending ratio shown in Table 1, a compound for the surface layer resin and the back surface layer resin was obtained in the same manner as in Example 1. Next, a thin film having a film thickness ratio shown in Table 1 was obtained by a co-extrusion method using two φ50 mm single-screw extruders and a multi-manifold die. At this time, an embossing roll having a surface roughness shown in Table 1 was used.
Next, using the base material shown in Table 1, heat lamination was performed in the same manner as in Example 1 to obtain a laminated sheet.
[0029]
(Example 3)
A thin film was formed in the same manner as in Example 1 according to the blending ratio and film thickness ratio shown in Table 1. At this time, an embossing roll having a surface roughness shown in Table 1 was used.
Next, using the base material shown in Table 1, heat lamination was performed in the same manner as in Example 1 to obtain a laminated sheet.
[0030]
( Experimental example 2 ) The resin for the surface layer and the resin for the back layer were blended with a Henschel mixer at the blending ratio shown in Table 1, and kneaded with a φ45 mm twin screw extruder to obtain a compound. Thereafter, in the same manner as in Example 1, a thin film having a film thickness ratio shown in Table 1 was formed. At this time, an embossing roll having a surface roughness shown in Table 1 was used. Next, the base material shown in Table 1 was used, and heating lamination was performed. The heating laminate used a roll laminator and was thermally bonded under the condition of a heating temperature of 140 ° C. to obtain a laminated sheet.
[0031]
(Comparative Example 1)
A thin film was obtained in the same manner as in Example 1 except that the blending ratios shown in Table 2 were used. Next, using the base material shown in Table 2, heat lamination was performed in the same manner as in Example 1 to obtain a laminated sheet.
[0032]
( Experimental Example 1 ) A thin film was obtained in the same manner as in Example 2 except that the mixing ratio shown in Table 2 was used and an embossing roll having the surface roughness shown in Table 2 was used. Next, using the base material shown in Table 2, heat lamination was performed in the same manner as in Example 1 to obtain a laminated sheet.
[0033]
(Comparative Example 2)
A thin film was obtained in the same manner as in Example 3 except that the blending ratios shown in Table 2 were used.
[0034]
(Evaluation) The following items were evaluated for the thin film and the heat-bonded laminated sheet obtained in Examples, Experimental Examples and Comparative Examples. The results are shown in Tables 1 and 2.
1) Appearance The appearance of the obtained thin film was visually evaluated. The thin film films of Examples 1 to 3 , Experimental Examples 1 and 2 and Comparative Example 1 were films having a good low gloss surface without poor dispersion of the matting agent. The appearance of the thin film of Comparative Example 2 was significantly deteriorated due to poor dispersion.
[0035]
2) Surface glossiness The surface glossiness of the obtained thin film was measured using a gloss meter (Nippon Denshoku Co., Ltd. gloss meter VGS-1D). Examples 1 to 3 , Experimental Examples 1 and 2 and Comparative Example 1 were confirmed to have a low gloss surface. About the comparative example 2, since the external appearance was bad, evaluation was stopped.
[0036]
3) Mechanical strength: Tensile elongation As an evaluation of the mechanical strength of the obtained thin film, the tensile elongation was measured according to JIS K6732, using a tensile tester (Tensile tester AGS-100A manufactured by Shimadzu Corporation). Examples 1 to 3 , Experimental Examples 1 and 2 and Comparative Example 1 showed good elongation, but Comparative Example 2 confirmed a decrease in elongation.
[0037]
4) Thermal workability The surface glossiness of the obtained laminated sheet was measured using a gloss meter (Nippon Denshoku Co., Ltd. gloss meter VGS-1D), and the glossiness before heating lamination was compared. For Examples 1 to 3 and Experimental Example 2 , it was confirmed that there was little change in gloss after heat lamination and excellent heat workability. In Comparative Example 1, gloss return occurred and the glossiness increased remarkably. Experimental example 1 had a greater change in gloss than Examples 1-3 and Experimental example 2 , but was better than Comparative example 1.
[0038]
[Table 1]

[0039]
[Table 2]

[0040]
【The invention's effect】
As is clear from the above description, the vinylidene fluoride resin film having a matte surface obtained by the present invention has excellent long-term weather resistance and stain resistance that the vinylidene fluoride resin has. In addition to maintaining the adhesiveness to other base materials, which is a drawback of the system film, it has a particularly low-glossy surface with an excellent matte tone and is excellent in mechanical strength and heat workability. In particular, in a fluororesin film that uses an embossing roll to form a matte surface by using an embossing roll during film formation, heat is applied by a roll or a press when bonded to a base material such as PVC or ABS by a heat laminating method. At the same time, at least the adhesive surface is exposed to an environment above the melting point or softening point, so that the uneven shape of the surface becomes gentler than before bonding, and matte return occurs and the matte surface cannot be maintained or glossy spots occur. The vinylidene fluoride resin film of the present invention has a surface layer added with a spherical cross-linked acrylic resin, and the surface side of the film comes into contact with the embossing roll immediately after extrusion during film formation. However, because it is a film formed by pressure bonding with the embossing roll and metal roll or rubber roll, it has excellent heat workability. That. Therefore, it can be suitably used as a decoration or design improvement for a wide variety of uses such as interior and exterior of buildings and automobile members, particularly where high weather resistance is required.

Claims (5)

A vinylidene fluoride resin film having a surface layer and a back surface layer and satisfying the following requirements (1) to (4) .
(1) The surface layer is less than 100 parts by weight of vinylidene fluoride resin and 50 parts by weight or more, methacrylate resin 50 parts by weight or less, and the total amount of vinylidene fluoride resin and methacrylate resin is 100 parts by weight. On the other hand, it contains 0.5 to 30 parts by weight of a crosslinked acrylic resin.
(2) The crosslinked acrylic resin is spherical and has an average particle diameter of 1 to 20 μm.
(3) The back surface layer contains 0.1 to 10 parts by weight of the ultraviolet absorber with respect to 100 parts by weight of the methacrylic ester resin or 100 parts by weight of the total of the methacrylic ester resin and the vinylidene fluoride resin.
(4) The surface of the surface layer is formed by pressure bonding to an embossing roll during film formation, and the average particle diameter of the crosslinked acrylic resin is not more than the surface roughness Rz of the embossing roll. The vinylidene fluoride resin film according to claim 1 , wherein the crosslinked acrylic resin is obtained by polymerizing a monomer containing a carboxyl group and a polyfunctional monomer. The vinylidene fluoride resin film according to claim 1 or 2, which is printed. The vinylidene fluoride resin film according to any one of claims 1 to 3 , wherein the surface layer has a surface glossiness of 60 or less. The laminated body formed by laminating | stacking the vinylidene fluoride resin film as described in any one of Claim 1 to 4 on a base material.