JPH0790152A - Matted film of vinylidene fluoride resin - Google Patents

Abstract

PURPOSE:To provide the title film improved in colorability. CONSTITUTION:The title film is made of a composition comprising 100 pts.wt. vinylidene fluoride resin and 1-15 pts.wt. inorganic filler having an average particle diameter of 0.1-10mum, a ferric oxide content of 0.05wt.% or lower, and a titanium oxide content of 0.03wt.% or lower. This film is used as a covering material for various bases for the purposes of surface protection, decoration, etc., in particular for imparting a high-grade texture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a matt vinylidene fluoride resin film. More specifically, the present invention relates to a matt vinylidene fluoride resin film having an improved coloring degree, which is composed of a composition obtained by blending a vinylidene fluoride resin with a specific inorganic filler. The matt vinylidene fluoride resin film provided by the present invention is used for coating the surface of various base materials for the purpose of surface protection, decoration, etc., particularly for the purpose of imparting a high-grade feeling to the base material.

[0002]

2. Description of the Related Art Vinylidene fluoride resin films are excellent in weather resistance, chemical resistance, and stain resistance.
It is widely used as a protective film laminated on the surface of various base materials such as plastic, glass, slate, rubber, metal plate, and wood plate. These base materials whose surfaces are protected are used for interior and exterior materials of buildings, furniture and many other applications.

However, in recent years, there has been a demand for higher quality images for substrates such as wallpaper and leather furniture used indoors, and therefore, a matte film for laminating on the surface thereof is provided. ing. As a method for producing such a matte film, (1) a method of imparting fine irregularities to the film surface by a metal or rubber roll (mat roll) having a roughened surface and thermoforming,
(2) A method of spraying fine particles such as sand or metal onto the surface of the film to be treated to give fine irregularities (sand blasting method), (3) A method of coating the film to be treated with a matting agent, and further (4) Fine There is known a method of adding an organic or inorganic filler (matting agent) to the resin constituting the film.

However, the matte film matting method (1) using a matte roll has the problem that the matte roll is easily clogged with an ultraviolet absorber added to a vinylidene fluoride resin, and in the case of a thin film, uneven thickness occurs. There is a problem that it becomes glossy as it is and it is difficult to obtain a uniform matte film. In the sandblasting method (2), a thin and soft film has a problem that the film to be treated may be broken or stretched during sandblasting. Further, in the method (3) of coating with a matting agent, in the case of vinylidene fluoride-based resin, coating cannot be easily performed due to its non-adhesiveness (non-adhesiveness). Further, in the method (4) using a matting agent, the above-mentioned problems do not occur, but selection of the matting agent is generally not easy. That is, with a filler having poor compatibility with the vinylidene fluoride resin, voids are likely to occur in the obtained film, and the mechanical strength is reduced. Further, the addition of the filler causes a decrease in the transparency of the film. Further, there is a problem that the vinylidene fluoride resin film containing the filler is colored. This means that the film is colored especially when the composition made of the inorganic filler and the vinylidene fluoride resin is formed. That is, the problem of coloring due to high temperature heating in the melt extrusion pelletization step of mixing the inorganic filler with the vinylidene fluoride resin or the vinylidene fluoride resin crystal melting point to a certain temperature or higher, and the melt extrusion film formation step Is. In addition, the setting of the particle size and the addition amount of the filler is also important in relation to the matting effect and the thermal stability.

The method (4) using the above-mentioned matting agent is simpler than other methods for producing a matting film, and many proposals relating to this method have been made. However, no proposal has been made regarding the matte vinylidene fluoride resin film having a small degree of coloring, and when an inorganic filler is used, a matt vinylidene fluoride resin film having a small degree of coloring has also been obtained. There wasn't.

The main proposals regarding the technique of adding a filler to a vinylidene fluoride resin are as follows, but these do not suggest the degree of coloring of the matte film. That is, Japanese Patent Publication No. 46-16430 discloses that
Polyvinylidene fluoride resin with terephthalic acid or kaolin,
Although a composition for a coating film containing talc or diatomaceous earth is disclosed, the problem to be solved is to make resin spherulites fine (fine spherulites diameter). In addition, Japanese Patent Publication Sho-48-34
In Japanese Patent No. 823, calcium chloride or aluminum silicate is added in the range of 0.0001 to 0.02% by weight as a heat stabilizer to polyvinylidene fluoride resin, or methylcellulose is added in the range of 0.0001 to 1% by weight. Compositions are disclosed. However, it is not intended for a matte film even if judged from the contents described or judged from the compounding amount. In addition, Japanese Patent Publication Sho 51-29
Japanese Patent No. 890 discloses a coating composition in which polyvinylidene fluoride resin is mixed with silica sand (silica), graphite, molybdenum disulfide, chromium oxide and the like as an inorganic substance. The problem to be solved is to improve the adhesiveness to a metal surface and to provide durability that does not cause troubles such as peeling of the coating even when used in a high temperature and long-term corrosive environment. Further, JP-A-61-111376 discloses that a fluorine-containing polymer has an average particle diameter of 0.01 to 10 μm,
A primer composition comprising an aluminosilicate powder having an aluminum oxide content of 10 to 60% by weight and a liquid medium is disclosed. The problem to be solved is to improve the adhesion to the substrate to be coated. In that case, it is necessary not to affect the appearance, roughening of the surface is considered to deteriorate the appearance, and matte is not intended at all. In addition, JP-A-60-262845
The publication discloses a radiation-irradiable crosslinkable fluororesin composition comprising a hydrogen atom-containing fluororesin such as vinylidene fluoride resin and the like containing a crosslinking accelerator and silica. It is said that the problem to be solved is to provide a composition capable of obtaining a molded article having a good appearance by improving the crosslinking efficiency while avoiding the reaction between the fluororesin and the crosslinking accelerator. Specifically, hydrophobic silica (trade name Aerosil 200, R97
2) is used and the outer circumference of the conductor is extrusion coated. Further, JP-A-62-285939 discloses a composition having an improved charging property, which comprises a fluorocarbon polymer and a positively chargeable inorganic filler such as magnesium oxide, zinc oxide, cobalt oxide, and asbestos having an average particle size of 5 μm or less. It is disclosed, but not the film. Further, in Japanese Patent Application Laid-Open No. 4-62132 and Japanese Patent Publication No. 4-58497, a method of matting by adding an inorganic substance such as titanium oxide or silica to a vinylidene fluoride resin film is added to the description of the conventional art. It is briefly introduced. However, there is no specific description about the degree of coloring.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have been keenly aware of the factors affecting the coloring degree of a matt vinylidene fluoride resin film obtained from a composition obtained by blending a vinylidene fluoride resin with an inorganic filler. As a result of examination, even in a composition containing a specific amount of an inorganic filler, it is extremely effective to use an inorganic filler in which the content of a specific component contained as an impurity in the inorganic filler is a specific value or less. It was found that the present invention has been completed.

That is, in the present invention, the average particle size of the inorganic filler is in the range of 0.1 to 10 μm and the ferric oxide content is 0.10 with respect to 100 parts by weight of the vinylidene fluoride resin.
0.05% by weight or less and a titanium oxide content of 0.03
The present invention relates to a matt vinylidene fluoride resin film comprising a composition containing 1 to 15 parts by weight of an inorganic filler in an amount of 1% by weight or less.

In this case, a matt vinylidene fluoride resin film having a yellowness of 3.0 or less and a glossiness of 60 or less defined by JIS K7105 is preferable, and the inorganic filler has a refractive index of 1. It is preferably 55 or less, and the average particle diameter of the inorganic filler is preferably in the range of 0.5 to 6 μm, more preferably 1 to 5
It is in the range of μm. Further, the inorganic filler is preferably one or more selected from aluminosilicate, silica and crystalline quartz. Further, a laminated matt vinylidene fluoride resin film having such a matt vinylidene fluoride resin film as a surface layer is preferable.
Hereinafter, the present invention will be described in detail.

The vinylidene fluoride resin constituting the film of the present invention is not limited to a vinylidene fluoride homopolymer, but includes a copolymer containing vinylidene fluoride units in an amount of 70 mol% or more as a constituent unit of the resin. Further, it may be a mixture of two or more kinds of the homopolymer and the copolymer. Monomers that can be copolymerized with vinylidene fluoride include tetrafluoroethylene (tetrafluoroethylene), trifluoroethylene (trifluoroethylene), trifluorochloroethylene (trifluorochloroethylene), hexafluoropropylene (hexafluoroethylene). In addition to fluoroolefin monomers such as propylene oxide and vinyl fluoride, acrylic acid esters such as methyl acrylate and ethyl acrylate, and methacrylic acid esters such as methyl methacrylate and ethyl methacrylate.

As a matter of course, a composition in which a homopolymer or a copolymer of the above-mentioned monomers is mixed with another type of resin having compatibility with them can be used as long as the effects of the present invention are not impaired. Examples of the compatible resin include acrylic ester resin, methacrylic ester resin,
Examples thereof include cyanoethylated ethylene vinyl alcohol copolymer. Among them, methyl methacrylate resin can be mentioned as a preferable example. When the methyl methacrylate resin is used, the composition ratio is preferably 40% by weight or less based on the total weight of the vinylidene fluoride resin.

The above ethylene-based resin and vinylidene fluoride-based resin may optionally contain an oxidation stabilizer, a heat stabilizer,
One or more stabilizers such as ultraviolet absorbers and weathering stabilizers,
One or more processing aids such as a lubricant, a release agent and a plasticizer may be added.

The inorganic filler constituting the matt vinylidene fluoride resin film of the present invention has a ferric oxide content of 0.05% by weight or less, preferably 0.03% by weight or less, and a titanium oxide content of Is 0.03% by weight or less, preferably 0.02% by weight or less. In both cases, the lower limit of the content is of course not limited, but it is preferable that it is usually the detection limit value or less. By using an inorganic filler having a ferric oxide content and a titanium oxide content within the above-mentioned limits, a matt vinylidene fluoride resin film having a low degree of coloring can be obtained.

In the present invention, the lower limit of the blending amount of the inorganic filler is set mainly in terms of the matting effect, and the matting effect increases as the blending amount increases. On the other hand, the upper limit is set in consideration of the mechanical strength of the film, other optical properties such as glossiness, and the upper limits of the ferric oxide content and the titanium oxide content, and 100 parts by weight of vinylidene fluoride resin. On the other hand, it is 1 to 15 parts by weight, preferably 5 to 12 parts by weight.

The average particle size of the inorganic filler used in the present invention is in the range of 0.1 to 10 μm, preferably 0.5.
To 6 μm, and more preferably 1 to 5 μm. The average particle size of the inorganic filler is preferably 1.5 times or less the film thickness in view of the mechanical strength of the resulting matt vinylidene fluoride resin film, and more preferably 0.8. It is less than twice.

In selecting the inorganic filler used in the present invention, it is preferable to consider the affinity with the vinylidene fluoride resin and the refractive index of the inorganic filler. The refractive index of the inorganic filler is mainly related to the transparency of the obtained matt vinylidene fluoride resin film and is 1.55 or less, which is close to the refractive index (about 1.42) of the vinylidene fluoride resin, It is particularly preferably 1.50 or less. From these viewpoints, the inorganic filler is preferably selected from aluminosilicate, silica and crystalline quartz, and particularly preferably silica or crystalline quartz.

The factors affecting the degree of coloring of the matt vinylidene fluoride resin film provided by the present invention are mainly the ferric oxide and titanium oxide contents in the inorganic filler as described above. JIS K7 is used as an index of the coloring degree of the matt vinylidene fluoride resin film obtained in the present invention.
It is represented by the yellowness index specified in 105.

The matte vinylidene fluoride resin film provided by the present invention is not only a single-layer film made of the above composition but also a laminated matt vinylidene fluoride resin film laminated with another film layer. Can also be used as In this case, a multilayer film such as a two-layer film or a three-layer film, which is arranged so as to be the outermost layer when the matte vinylidene fluoride resin film made of the composition is coated on the surface of the substrate, can be mentioned. Examples of the thermoplastic resin forming the other film layer include a methacrylic acid ester-based resin, a composition of a methacrylic acid ester-based resin and a vinylidene fluoride-based resin, a vinyl chloride resin, a styrene resin, an ABS resin, a polyester resin, a polycarbonate. Resin, polyamide resin, etc. can be mentioned. Preferred examples of the multilayer film include a two-layer film including the matte vinylidene fluoride resin film layer and the methacrylate ester resin film layer, the matte vinylidene fluoride resin film layer and the methacrylate ester resin film layer. Other thermoplastic resin film layers, for example, a three-layer film in which vinyl chloride resin film layers are laminated in this order can be cited. In the case of the two-layer film, the methacrylic acid ester resin film layer adheres to the substrate to be matted, and in the case of the three-layer film, the vinyl chloride resin film layer adheres to the matte target substrate.

The matt vinylidene fluoride resin film of the present invention can be produced from a vinylidene fluoride resin and an inorganic filler by a known method. That is, after a composition is obtained from a vinylidene fluoride resin and an inorganic filler by a roll, a Brabender, and a kneading extruder, it may be formed into a film by pressing, T-die or melt extrusion film formation by an inflation method. Further, in order to produce a laminated matt vinylidene fluoride resin film by laminating the matt vinylidene fluoride resin film of the present invention with another film, the composition and the other resin are coextruded and laminated. Known methods such as a method, a method of laminating the respective films by thermocompression bonding with a hot press, a method of laminating both films with an adhesive can be adopted. During these moldings, it is preferable to suppress excessive heating of the vinylidene fluoride resin, and the resin temperature of the vinylidene fluoride resin is preferably 230 ° C. or lower, particularly 210 ° C. or lower.

The matt vinylidene fluoride resin film or laminated matt vinylidene fluoride resin film of the present invention is a plastic, glass, slate, rubber, metal plate,
It is laminated on the surface of a base material such as a wooden board and can be used for interior and exterior materials of buildings, furniture and many other applications. The heating temperature of the film of the present invention at the time of lamination is preferably as low as possible, but is usually 120 to 200 ° C, preferably 150 to 170 ° C.

[0021]

EXAMPLES The present invention will be described below with reference to examples and useful comparative examples. However, the scope of the invention is not limited thereby.

Examples 1 to 5 and Comparative Examples 1 to 4 Vinylidene fluoride resin powder {trade name: KF1000 (manufactured by Kureha Chemical Industry Co., Ltd.)} 100 parts by weight of the various inorganic fine particles shown in Table 1 A composition for producing a matte film was prepared by uniformly blending the amounts shown in the table. These matte film manufacturing compositions and methyl methacrylate resin {trade name: HB
S001 (manufactured by Mitsubishi Rayon Co., Ltd.) and co-extrusion molding,
A two-layer matte film having a total thickness of 50 μm and comprising a matte layer having a thickness of 10 μm and a methyl methacrylate resin layer having a thickness of 40 μm was obtained. The measurement results of the glossiness, total light transmittance, parallel light transmittance, and yellowness of these various laminated matte films are also shown in Table 1 together with the properties of the inorganic filler. The yellowness per unit blending amount of the inorganic filler is also a rational index and is therefore shown for reference. Table 2 shows the types of inorganic fillers used and the main component compositions.

The measuring methods of glossiness, total light transmittance, parallel light transmittance and yellowness are in accordance with JISK7105,
The measurement was performed using “Σ80 type” manufactured by Nippon Denshoku Industries Co., Ltd.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

Industrial Applicability The matte vinylidene fluoride resin film or the laminated matte vinylidene fluoride resin film provided by the present invention has an excellent matte effect and a small coloring degree, and has a weather resistance of the vinylidene fluoride resin. It also has excellent resistance and stain resistance.

Claims (6)

[Claims] 1. An inorganic filler having an average particle size of 0.1 to 10 μm, a ferric oxide content of 0.05% by weight or less, and 100 parts by weight of a vinylidene fluoride resin. A matte vinylidene fluoride resin film, comprising a composition containing 1 to 15 parts by weight of an inorganic filler having a titanium oxide content of 0.03% by weight or less. 2. The matte vinylidene fluoride resin film according to claim 1, which has a yellowness of 3.0 or less and a glossiness of 60 or less according to JIS K7105. 3. The matt vinylidene fluoride resin film according to claim 1, wherein the inorganic filler has a refractive index of 1.55 or less. 4. The average particle size of the inorganic filler is 0.5 to 6 μm.
The matte vinylidene fluoride resin film according to claim 1, wherein 5. The matte vinylidene fluoride resin film according to claim 1, wherein the inorganic filler is one or more selected from aluminosilicate, silica and crystalline quartz. 6. A laminated matt vinylidene fluoride resin film having a matt vinylidene fluoride resin film according to claim 1 as a surface layer.