JPH0564233B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a vapor-deposited film, and more specifically, the surface of oriented polyester having a surface roughness (Ra) of 0.005 μm or more is subjected to spot corona treatment and then metal vapor-deposited. The present invention relates to a vapor-deposited film suitable for decorative purposes, which is provided with layers. BACKGROUND ART Conventionally, vapor-deposited films in which a light reflecting layer is integrated with the film have been used for applications such as gold and silver threads, namers, and reflective mirrors. In order for this vapor-deposited film to be used for this purpose and to exhibit an excellent appearance, it goes without saying that it has excellent reflectivity and gloss, and above all, it is most important that no vapor deposition spots occur. Therefore, technical means for producing vapor deposited films that do not cause vapor deposition spots have been investigated, and many related techniques have been proposed so far. However, in response to the diversification of lifestyles and hobbies, vapor-deposited films have come to be used in various forms in a wide range of fields other than those mentioned above. In order to meet this demand, there is a need for a vapor deposited film that has a glossy decorative pattern that does not give an artificial, geometric or regular appearance. Purpose of the Invention As a result of extensive studies on vapor deposited films with glossy artificial, geometric, or irregular decorative patterns, the inventors discovered that the surface of oriented polyester having a specific surface roughness was By applying corona treatment in a non-uniform and irregular manner, we succeeded in obtaining a deposited film with gloss with an extremely wide range of decorative patterns. The object of the present invention is to provide artificial,
To provide a vapor deposited film having a glossy decorative pattern that does not give a geometric or regular feel. According to the present invention, an object of the present invention is to provide a vapor deposited film comprising an oriented polyester film and a metal vapor deposited layer laminated on the surface thereof, the surface of which is
The surface roughness (Ra) is 0.005 μm or more, and the surface to be treated is circular, oval, or a modified shape with a diameter or major axis of 2 to 50 mm, and has a surface area of 10 mm.
This is achieved by a vapor-deposited film characterized by a surface that is corona-treated to account for ~50%. In the present invention, the base film is an oriented polyester film, and the surface thereof has a surface roughness of 0.005 μm or more. This polyester is a polyester having biaxial orientation ability, and aromatic polyesters (e.g., polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, etc.) are particularly preferred from the viewpoint of thermal properties, moisture absorption properties, etc. . The polyester can contain stabilizers, colorants, antioxidants, matting agents, and other additives, if necessary. An oriented polyester film has many fine protrusions on its surface. The large number of fine protrusions are derived from a large number of substantially inert solid particles that are normally dispersed and contained in the polyester. A polyester containing a large number of inert solid particles is usually produced at any time during the reaction to form a polyester, such as during a transesterification reaction or polycondensation reaction when using a transesterification method, or at any time when using a direct polymerization method. It can be produced by adding inert solid microparticles (preferably as a slurry in glycol) to the reaction system at the time of . Preferably, inert solid particles are added to the reaction system at the beginning of the polycondensation reaction, for example, until the intrinsic viscosity reaches about 0.3. In the present invention, the inert solid particles are preferably silicon dioxide (including hydrates, diatomaceous earth, silica sand, quartz, etc.); alumina;
Silicates containing 30% by weight or more of SiO ₂ (e.g. amorphous or crystalline clay minerals, aluminosilicates (including calcined products and hydrates), warm asbestos, zircon, fly ash, etc.); Mg, Zn, Zr, and
Ti oxide; Ca, and Ba sulfate; Li,
Phosphates of Na and Ca (including monohydrogen salts and dihydrogen salts); Benzoates of Li, Na, and K; Ca,
Terephthalates of Ba, Zn, and Mn; Mg,
Titanates of Ca, Ba, Zn, Cd, Pb, Sr, Mn, Fe, Co, and Ni; Chromates of Ba and Pb; Carbon (e.g. carbon black, graphite, etc.); Glass (e.g. glass powder) , glass beads, etc.); carbonates of Ca and Mg; fluorspar and ZnS. More preferably, anhydrous silicic acid, hydrated silicic acid, aluminum oxide, aluminum silicate (including fired products, hydrates, etc.), monolithium phosphate, trilithium phosphate, sodium phosphate,
Calcium phosphate, barium sulfate, titanium oxide, lithium benzoate, double salts of these compounds (including hydrates), glass powder, clay (including kaolin, bentonite, clay, etc.), talc, diatomaceous earth, calcium carbonate etc. are exemplified. These inert solid fine particles have an average particle size of 0.05 to 10 μm, and even 0.08 to 10 μm.
2.5 μm is preferable, and the amount added is 0.003 to 1.5
It is preferably 0.005 to 0.6% by weight (based on polyester), and more preferably 0.005 to 0.6% by weight (based on polyester). These inert solid fine particles may be used alone, or depending on the particle type,
Two or more types having different average particle sizes may be used in combination by changing the amount of each. The oriented polyester film of the present invention needs to have a surface roughness (Ra) of 0.005 μm or more as a film surface characteristic. The surface roughness (Ra) of a film is important from the standpoint of quality characteristics as a vapor-deposited film, but it is also important from the standpoint of handling in the film forming process or processing process. Regarding ease of handling in the film forming process or processing process, the balance between surface roughness (Ra) and film thickness comes into play. For example, the thickness of the film
When the thickness exceeds about 50μm, the strength of the film itself becomes effective, and for example, the surface roughness (Ra) becomes 0.01μm.
There are no particular problems with its handling even at the following levels. From the viewpoint of ease of handling, it is preferable that the surface roughness (Ra) increases as the thickness of the film decreases. It is best to use the surface roughness (Ra) and film thickness as appropriate depending on the application.
However, the surface roughness (Ra) is preferably kept at 0.065 μm or less, more preferably 0.045 μm or less, particularly 0.030 μm or less. The corona treatment in the present invention is carried out so that the corona discharge treatment surface is non-uniform and irregular on the film surface. When corona treatment is applied irregularly and locally, each treated surface often becomes circular or oval, but depending on the treatment conditions, it can further deform and the oval becomes curved, forming an arc, crescent, or oval shape. It can also be shaped like a horseshoe. Here, the shape of each surface to be treated can be determined by the image of the portion to be treated when powdered slaked lime is evenly sprinkled on the surface of the film after corona treatment. The size of this shape is determined by its diameter if it corresponds to a circle, or by its major axis if it corresponds to an oval shape, and if it is shaped like an arch, crescent, or horseshoe, it is formed by tying the two ends together. Each shape is expressed by the longest straight line distance.
This size needs to be 2 mm or more and 50 mm or less. If the size is smaller than 2 mm, it cannot function as a decorative pattern in practical terms, and if it is larger than 50 mm, it is not desirable in terms of overall decorative balance. The total proportion of the surface of the film occupied by the surface to be treated is 10 to 50% as an area ratio.
Even if this ratio is smaller than 10% or larger than 50%, it is difficult to obtain a decorative effect. To create a decorative effect on the film surface by applying corona treatment unevenly and randomly,
It is essential to have a morphological effect that does not give an artificial feel, which is created by the combination of the features (size, shape) of the surface to be treated, but the decorativeness of the vapor-deposited film depends on the corona-treated and untreated areas. The reason for this is that the difference in the vapor deposition properties of the metals in the parts plays a large role. In other words, the thickness of the metal vapor deposited layer can be made thicker or thinner in the corona-treated area compared to the untreated area by controlling the charging characteristics of the metal molecules being vapor-deposited. By making the thickness of this metal vapor deposited layer slightly different, it is possible to create a subtle gloss over the entire surface of the film, which, together with the above-mentioned morphological effect that does not give an artificial feel, is achieved. The decorative effect is extremely effective. In order to apply corona treatment unevenly and irregularly to the film surface, important factors include the shape of the corona discharge electrode, the distance between the electrode and the film, and the running speed of the film (corona treatment speed). As a result of detailed examination of each of these factors, the present inventor found that, first, the width of the electrode should be 5 mm to 30 mm in order to achieve the aim of the present invention, which causes uneven corona discharge and causes uneven spots on the film surface. It is recommended that electrodes of these widths be arranged horizontally irregularly in the film running direction to form the electrodes, and that the distance between the electrodes and the film should be adjusted.
If the width is more than 1.5 mm, the process will be non-uniform. Therefore, the above-mentioned electrodes are arranged irregularly in a series with the width of the electrode and the distance from the running film exceeding 1.5 mm to about 5 mm. We discovered that it is good to shape the electrodes. Corona treatment is preferably performed using this electrode. At this time, for films with a thickness of 25 μm or less, particularly less than 20 μm, it is possible to change the distance between the electrode and the film by providing unevenness on the processing roll. There are no major restrictions on the film processing speed (running speed), other than the need to be careful not to cause problems such as the film flapping and coming into contact with the electrodes and causing scratches. Considering the gender aspect
The speed is preferably 100 m/min or more, and in order to suitably implement the present invention, the speed can be changed continuously or discontinuously at 200 m/min or more, approximately 300 m/min without mechanically small periodicity. preferable. Furthermore, the voltage applied to the electrodes may be appropriately set in consideration of the film running speed. In the present invention, a metal vapor deposition layer is provided on the film surface after the above-mentioned corona treatment. Methods for forming a metal thin film on the film surface include physical vapor deposition, for example, vacuum evaporation, sputtering, etc. is usually used. In the case of vacuum evaporation, the evaporation source is preferably heated by electron beam heating, and the degree of vacuum is 3×
From the range of 10 ^-4 to 1 x 10 ^-6 Torr, the evaporation source temperature is
It can be adopted as appropriate from the range of 1400 to 1800°C. In the case of sputtering method, usually 5×10 ^-2 ~1×
An argon gas atmosphere of about 10 ^-3 Torr is used. The thus obtained vapor-deposited film exhibits the luster of a decorative pattern, but by further providing a colored layer on the metal vapor-deposited layer via an adhesive, it can be used in a wide variety of decorative applications. As the adhesive, epoxy resin type, urethane resin type, silicone resin type, nitrile rubber type, etc. can be used as appropriate. The colored resin layer is formed by applying a solvent solution of one or more thermosetting resins such as epoxy resins, amino resins, urethane resins, acrylic resins, silicone resins, alkyd resins, unsaturated polyesters, etc. and colorants and drying. It can be formed by The colored resin layer is usually provided with a thickness of about 1 to 3 μm. Dyes or transparent organic pigments can generally be used as colorants. A normal coating method can be used as the coating method. The vapor-deposited film thus obtained has an unprecedented non-uniform and irregular glossy pattern.
It can be suitably used for decorative purposes. Next, methods for measuring main physical properties in the present invention will be described. 1 Shape of corona-treated surface Sprinkle powdered slaked lime evenly on the film surface after corona treatment to create a phenomenon, and visually judge. 2 Surface roughness (Ra) Measure the radius of the stylus using a stylus surface roughness meter (SURFOOM 3B) made by Tokyo Seimitsu Co., Ltd., for example.
Obtain the film roughness curve under the conditions of 2 μm and 70 mg load, extract a part of measurement length L (reference length 2 mm), and examine the center line of this extracted part with X-rays.
With the vertical magnification direction as the Y axis, the roughness curve is Y=f
When expressed as (x), the value given by the following formula is μ
Expressed in units. Ra=1/L∫ ^L _O |f(x)|dx This measurement is performed on eight samples, the three with the largest values are excluded, and the average value of the five is expressed. Note that the measurement is performed in the vertical direction and the horizontal direction, and the average value of both is used. 3. Winding form After providing a vapor deposition layer and a release layer on a film having a width of 500 mm and a length of 2000 m, it was wound up onto a roll. The appearance of this roll is evaluated by measuring the number of wrinkles on the film surface and the number of protrusions caused by wrinkles with a major diameter exceeding 1 mm, and grading as follows. 0 pieces 1st grade 1-2 pieces 2nd grade 3-5 pieces 3rd grade 6-10 pieces 4th grade (fail) 11 or more pieces 5th grade (fail) 4 Particle size and composition ratio of inert substance Shimadzu automatic sedimentation balance Using the Stokes equation, T = 18ηh/G (P _p - P _p ) x d ² , where: T: Sedimentation time (hr) η: Viscosity of the medium (g/cm・sec=poise) h: Sedimentation distance ( cm) G: Gravitational acceleration (980cm/cm ³ ) P _p : Density of inert substance (g/cm ³ ) P _p : Density of medium (g/cm ³ ) d: Particle size of inert substance (diameter: cm ) to calculate the settling time corresponding to each particle size, find the settling time range corresponding to each particle size range, calculate the weight of the inert substance within that settling time range, and calculate the total inertness. The ratio to the polymerization of the substance is expressed in % and is referred to as the composition ratio. 5 Average particle size Determine the composition ratio using the method described in measurement method 4, and integrate from the larger particle size to the smaller particle size (at particle size 0 μm)
100%) is created, and the particle size shown at an integration rate of 50% is taken as the average particle size (μm). [Example] The present invention will be explained in detail below using specific examples. Examples 1 to 5 and Comparative Example 1 Polyethylene terephthalate was produced by a conventional method using dimethyl terephthalate and ethylene glycol as raw materials, manganese acetate as a transesterification catalyst, antimony trioxide as a polymerization catalyst, and phosphorous acid as a stabilizer. At that time, by dispersing kaolin, silica, or calcium carbonate as an inert substance in ethylene glycol, a predetermined amount was contained in the polymer (Table 1). The obtained polymer was melt-extruded by a conventional method to form a film, and the stretching temperature was 90 to 120°C, the horizontal magnification was 3.6 times, and the vertical magnification was
Biaxially stretched at 3.9 times and heat set at 220℃ to increase the film thickness.
A 25 μm biaxially oriented film was obtained. Next, one side of the biaxially oriented film was treated using a commercially available ordinary corona treatment machine while changing the shape of the electrode and the distance between the electrode and the film as shown in Table 1. The running speed of the film is 250m/
It was kept constant at minutes. Approximately 10 ^-5 on the treated side of the film
Approximately
A vapor deposited film was obtained by vapor deposition to a thickness of 0.1 μm. Table 1 shows the results of observing the vapor deposition state. Example 1
Items No. 5 to 5 were suitable for decorative purposes. Example 6 A colored film was obtained in the same manner as in Example 4 except that the film thickness was changed to 100 μm. Table the results.
Also listed in 1. 【table】

Claims (1)

[Scope of Claims] 1. A vapor deposited film consisting of an oriented polyester film and a metal vapor deposited layer laminated on its surface, the surface having a surface roughness (Ra) of 0.005 μm or more and a surface to be treated. 1. A vapor-deposited film having a circular, oval, or modified shape having a diameter or major axis of 2 to 50 mm, and having a surface treated with corona so as to occupy 10 to 50% of the surface area. 2. The vapor-deposited film according to claim 1, further comprising a colored layer provided on the metal vapor-deposited layer via an adhesive.