JPS60255978A - Metallized film - Google Patents

Abstract

PURPOSE:To obtain a metallized film with superior slittability when a thin metal lic film is formed on the film of a poly-p-phenylene sulfide base resin composition to manufacture a metallized film, by specifying the density of projections on the surface of the resin composition film. CONSTITUTION:A biaxially oriented polyphenylene sulfide film is used as a base film. The film is made of a resin composition contg. poly-p-phenylen sulfide as the principal component and gas 20-300 pieces/mm. density Sd of small projections on the surface and <=5 pieces/mm. density Ld of large projections. A metallic layer is formed on at least one side of the base film by vapor deposition, sputtering or other method to obtain the metallized film which causes hardly troubles such as irregular winding, creasing and breaking when it is slit. The densities Sd, Ld are the linear densities of projections of >=0.02mum height and projections of >=0.2mum height, respectively.

Description

[Detailed description of the invention] [Technical field of invention] FIELD OF THE INVENTION This invention relates to metallized films.

[Conventional technology]

Conventionally, a metallized film with a biaxially oriented polyphenylene sulfide film as a base film and a metal thin film layer formed thereon has been used for various purposes such as stamping foil, gold and silver thread, etc., as disclosed in JP-A-57-187327. It has been proposed in et al.

In these applications, it is customary to shred (slit) the raw metalized film into appropriate widths depending on the purpose, but the conventional metallized film is
It rolls around. There are wrinkles.

There are many problems such as film breakage, and this tendency becomes stronger as the slit width becomes narrower, so its applications are extremely limited.

[Purpose of the invention]

An object of the present invention is to eliminate the above-mentioned drawbacks of conventional metallized films based on biaxially oriented polyphenylene sulfide films, and to provide a laminated film with excellent slitting properties.

[Structure of the invention]

The present invention has a primary configuration to achieve the above object.

That is, the resin composition is made of a resin composition containing poly-P-phenylene sulfide as a main component, and the surface fine protrusion density Sd is in the range of 20 to 3 [ID pieces/difficult], and the coarse protrusion density Ld is in the range of 5 pieces/plate or less. This metallized film is characterized in that a metal thin film layer is provided on one side of an axially oriented polyphenylene sulfide film where fx<to.

In the present invention, poly P-phenylene sulfide is
It refers to a polymer in which 70 moles or more (preferably 85 moles or more) of repeating units are structural units represented by the general formula -4-S+. If the content of such components is less than 70 molt, the crystallinity, heat transfer temperature, etc. of the polymer will be low, resulting in low heat resistance and 1-dimensional stability, which are the characteristics of films and laminates made of resin compositions containing P-phenylene sulfite as a main component.

Damages mechanical properties, etc.

<There is no problem even if a unit containing a copolymerizable sulfide bond is included as long as it is less than 30 molar units (preferably less than 15 molar units).

In the present invention, a resin composition containing poly-P-phenylene sulfide as a main component (hereinafter abbreviated as pps) refers to a composition containing 90% by weight or more of the above-mentioned poly-P-phenylene sulfide.

Poly P-phenylene sulfide content is 90% by weight
If it is less than this, the crystallinity, thermal transition temperature, etc. of the composition will be low, and the characteristics of the film and laminate thereof made of the composition, such as heat resistance, dimensional stability, and mechanical properties, will be impaired.

Less than 10 parts by weight of the balance in the composition may consist of polymers other than polyparaphenylene sulfide, inorganic or organic fillers, and the like. Further, additives such as inorganic or organic lubricant-free colorants, ultraviolet absorbers, and the like may be included.

The melt viscosity of the resin composition was determined at a temperature of 300°0. A range of 500 to 12,000 poise (more preferably 700 to 7,000 poise) at a shear rate of 200 sec is preferred from the viewpoint of film formability.

In the present invention, the biaxially oriented polyphenylene sulfide film (hereinafter abbreviated as PP S-B O) is formed by melt-molding the above pps to form a sheet.

The film is biaxially stretched and heat treated, and the degree of orientation is not particularly limited, but it is determined by the X-ray polar pattern method that 2θ=2
The degree of plane orientation from the crystal peaks existing in the range 0 to 216 is 0
75 or more is preferred.

In addition, its thickness is 0.3 to 10 μm (more preferably Vi
, 0.3 to 7 μm).

In the present invention, the fine protrusion density Sd refers to the protrusion height 0.
Linear density of protrusions of 0.02μm or more (number of false or false pieces of unit length)
means.

In particular, the protrusion height was measured by a stylus surface roughness meter (cutoff value 0.08 mm, stylus radius 2 μm), and was measured over the length of the film at a longitudinal magnification of N. When the level of the first peak on the roughness curve chart is Ml, and the level of the valley bottom to the left of the first peak is vl, Pl-(M'1-Vl)/N is the level of the first protrusion. Defined as protrusion height.

Sd of PPSBO used in the present invention is 20 to 6
00 (more preferably 60 to 200) pieces/m. If Sd is too large or too small, the object of the present invention cannot be achieved.

In the present invention, the coarse protrusion density Ld refers to the protrusion height 02
It refers to the linear density of protrusions larger than μm.

The Ld of PP5-BO used in the present invention needs to be 5 (more preferably 6) pieces/Im1 or less. Ld
If is too large, the object of the present invention cannot be achieved.

The value of Sd or Ld in the present invention and JISR-0
Average surface roughness R measured by the method specified in 601
Although the value of a does not uniquely correspond to the value of a, one P used in the present invention
The Ra of P5-BO is preferably in the range of approximately 002 to 008 μm. Reverse K.

It goes without saying that even if Ra is within this range, the object of the present invention cannot be achieved if the Sd and LdO values do not satisfy the above conditions.

The density of PP5-BO used in the present invention is 1.3568/
(2) It is preferable that it is 1 or more in terms of heat resistance.

In addition, the heat shrinkage rate of PP5-BOO used in the present invention is 25
From the viewpoint of heat resistance, it is preferable that it is 0 to 8% in the vertical and horizontal directions at 0°C for 130 minutes.

Furthermore, the moisture absorption rate of PP5-BO used in the present invention is 25'
a, 100% RI (rO, 1% or less, preferably Rucoto.

What is the dielectric breakdown voltage of PP5-BO used in the present invention?

It is preferable that the direct current is 240 kV/rnrn or more.

In the present invention, the metal thin film layer is formed on the surface of PP5-, BO as a support by a method such as vapor deposition, sputtering, plating, etc., and has a thickness of 0.5 μm or less (preferably 0.0 μm or less).
1 to 0.6 μm), and the material is not particularly limited, but may include aluminum and chromium.

Nickel, zinc, tin and alloys thereof are preferred.

In the present invention, the metallized film refers to a film-like laminate in which the metal thin film layer is formed on at least one surface of pps-BO.

In the metallized film of the present invention, a metal thin film layer may be provided directly on the surface of pps=BO as a support, or
5 = One layer of primer (depending on the purpose) between the BO and the metal layer.
An intermediate layer such as an adhesion improving layer) or a release layer may be included. Particularly for stamping foil applications, it is preferable to provide a release layer of silicone or the like as an intermediate layer.

Moreover, on the surface of the metal thin film layer side of the metallized film of the present invention,
) A lump coat layer, an adhesive layer, an adhesive layer, etc. may be provided.

Next, a method for producing a metallized film according to the present invention will be explained.

First, the method of reacting poly-P-phenylene used in the present invention is used. In particular, it is preferable to react sodium sulfide and P-dichlorobenzene in an amide high-boiling polar solvent such as N-methyl-pyrrolidone. In this case 1 to adjust the degree of polymerization.

Most preferably, a so-called polymerization aid such as a caustic alkali or an alkali metal carboxylic acid salt is added and the reaction is carried out at 260°C to 2800°C. The pressure within the polymerization system and the polymerization time are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like.

Poly P-phenylene sulfide obtained by oxidation,
Blend and add other polymers, additives, etc. as necessary.

The resin composition (pps) thus obtained is supplied to a well-known melt extrusion device, typically an extruder, and is melted.

In order to keep Sd and Ld on the film surface within the range of the present invention, if necessary, at any stage before the above melt extrusion step, the resin composition may be added with an average particle size of 0.1 to 1.
．． Fine particles of 5 μm are uniformly dispersed. The amount of mosquito fine particles added varies depending on the type and amount of particle components included in the resin composition and the average particle diameter of the added fine particles, but it is approximately 0.05wt5wt chill 0.05wt. It is within the range of

Next, the molten resin is cut 95% with a hole diameter of 3 to 20 mm.
After filtering with a high-precision filter of μm (preferably 3 to 15 μm), it is continuously extruded from a so-called T-die, cast onto a cooled metal drum, and rapidly solidified to form an unoriented amorphous sheet. . The surface of the metal drum is 1
．． It is preferable that the surface be finished to a mirror surface with a roughness of 0.4S or less.

Next, the sheet thus obtained is biaxially stretched to a degree of plane orientation of 0.75 or more. As a stretching method, well-known methods such as a sequential biaxial stretching method and a simultaneous biaxial stretching method can be used, and after the sheet is stretched in the longitudinal direction by a group of rolls, it is stretched in the width direction by a tenter. It is preferable to use the so-called longitudinal and transverse sequential biaxial stretching method. The stretching temperature is in the range of 95 to 110°C in both length and width. On the other hand, the stretching ratio varies depending on resin viscosity, stretching temperature, etc., and is in the range of about 3.5 to 48 times, although it cannot be said generally.

Next, the stretched film thus obtained is subjected to fixed length heat treatment. Fixed length heat treatment here means that the change in width and length during heat treatment is 10 inches or less. The heat treatment conditions are 2005~290℃ for 2 seconds, but 250~285℃
It is preferable to do this for 5 to 60 seconds.

After the constant length heat treatment, it is also preferable to perform relaxation of several inches or less in the longitudinal direction and/or width direction at a temperature of 290° C. or less.

In the manner described above, a biaxially oriented polyphenylene sulfide film (PPS-BO) is obtained.

If necessary, an intermediate layer is formed on the surface of the film by a method such as coating, or a surface treatment such as corona treatment or plasma treatment is performed.

Next, a metal thin film layer is formed on one or both sides of the support thus obtained. As a method for forming the metal thin film layer, well-known methods such as vacuum evaporation, sputtering, and plating can be used.

Furthermore, if necessary, a top coat layer and an adhesive layer are formed on the surface of the metal thin film layer by a method such as a coating method.

A metallized film of the present invention is obtained by providing an adhesive layer and the like.

〔Effect of the invention〕

As a result of the metallized film of the present invention having the above-described structure, it is a metallized film with excellent slitting properties that eliminates problems such as uneven winding, wrinkles, and film breakage during slitting. It is widely applicable to a variety of applications where metallized films can be utilized.

When the metallized film of the present invention is applied to stamping film applications, it is difficult to heat shrink (200'a and 260'a
The heat shrinkage rate at °0 is less than 2% and less than 5%, respectively), so it has excellent heat resistance, making it possible to stamp with higher precision than the conventionally widely used polyester film base film. Become.

Furthermore, when the metallized film of the present invention is used as gold and silver thread, when piece-dyed a white fabric in which the gold and silver thread is woven into a normal thread cloth, the gold and silver thread based on the polyester film that has been widely used in the past has no color. However, the laminated film of the present invention has the property of being extremely difficult to be dyed by dyes (particularly disperse dyes), so it does not have the above drawbacks. This is resolved and piece dyeing becomes possible.

The following one was used in the description of the invention. The measurement and evaluation method of the characteristic values of the base film and metallized film will be explained.

(1) A metallized film (width: 520, length: 1.000 m) is cut into a width of 10 mm using a micro slitter using a slitting laser cutting method.
When micro-slit into mm, one turn is disordered, wrinkles,
The state of film breakage was evaluated based on the following criteria.

Among the 50 reels of A1 rolled and slit metalized film, excluding the 2 reels at both ends, the percentage of reels that were well slit (disturbance at the reel end of 0.3 mm or less) is expressed in terms of percentage. Needless to say, the slitting property of #1, which has a large proportion, is good.

B. Wrinkle-slit metallized film, 5 reels out of 50, excluding 2 reels at both ends, were randomly taken out and rewound once, and the state of wrinkles was visually observed and ranked according to the following criteria.

○: No wrinkles are observed on any of the reels.

△: Wrinkles are observed in a small portion.

×: Wrinkles are frequently observed over 2 rills or more.

C. Film breakage The above slit was turned over 100 times and the film was evaluated based on the number of times the film broke. Needless to say.

The smaller the number of times, the better the slitting performance is.

〔Example〕

Next, the present invention will be explained in more detail by giving examples.

Example 1 +11 Preparation of biaxially oriented polyphenylene sulfide film (PPS-BO) used in the present invention In an autoclave, 32.6 kg of sodium sulfide (250 mol, containing 4 [1 wt% of crystallized water)] and sodium hydroxide were added. 100 g, 36.1 kg (250 mol) of sodium benzoate, and N
-Methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) 792 ml was prepared and dehydrated at 205°C,
1,4 dichlorobenzene (abbreviated as p-D CB)
37.5 kg (255 mol), and NMP20.0
kg was added and reacted at 265"C for 4 hours. The reaction product was washed with water and dried to obtain poly-p-phenylene sulfide having a melt viscosity of 3100 poise and 100 mol of potassium. 21.1 kg (yield 78
%) was obtained.

To this composition, 0.00% of fine silica powder with an average particle size of 07 μm was added.
1 wt%, calcium stearate 0. C] Added 5 wt% and heated at 310° using a 40 mm diameter extruder.
95% cut hole diameter 10μ using metal fiber melted at 0
After filtering with a filter of length 4DOmm, gap 1
．． Extrusion 1 from T-die with 5mm linear lip
It was cast on a metal drum whose surface was kept at 25°O and solidified by cooling to obtain an unstretched film with a thickness of 52 μm.

This film is stretched by a longitudinal stretching device consisting of a group of rolls.
Film temperature 98°0. 4 at a drawing speed of 30,000 inches/min
．． Stretched 6 times lengthwise and then using a tenter.

It was laterally stretched 68 times at a temperature of 100°C and a stretching speed of 1000%/min.
Heat treated at ℃ for 10 seconds to form a PP5-B with a thickness of 4 μm.
O was obtained (referred to as film A).゛This film's Sd
is 67 pieces/mm, Ld is 1 piece/mm, density is 1.3
60 and satisfies the conditions for PP5-BO used in the present invention.

(2) Creation of metallized films The above films A and B were each placed in a vacuum evaporation device, and aluminum was deposited on one side to a thickness of 60 nm to obtain metallized films (metalized films A and B, respectively) were deposited on one side to a thickness of 60 nm. do).

(3) Evaluation Table 1 shows the evaluation results of the metallized film obtained.

It is shown together with the characteristic values of the base film used. Table 1 shows that the metallized film of the present invention (metalized film A) has excellent slitting properties.

Table 1 Example 2 Preparation of fil P P S -B O Five types of PP5 were prepared in the same manner as film A in Example 1, except that only the average particle diameter and amount of fine silica powder added before melt extrusion were changed. -BO (thickness 6 μm) was prepared (referred to as film C, a).

(2) Preparation and evaluation of metallized films In the same manner as in Example 1, aluminum was vacuum-deposited on one side of films C to G to a thickness of 50 nm to produce five types of metallized films (metalized film C). , a) were obtained.

P using the evaluation results of the metallized film obtained in Table-2
It is shown together with the characteristic values of P5-BO. From this table, it can be seen that the metallized film of the present invention, in which the fine protrusion density Sd and the coarse protrusion density Ld are within a specific range, has excellent slitting properties.

Example 5 In the same manner as in Example 1, 05' of calcium carbonate fine powder with an average particle size of 2 μm was added before melt extrusion.

The melt was cut by 95% using metal fibers with a hole diameter of 10 μm.
PP5-BO with a thickness of 25 μm was obtained (referred to as film H).

On the other hand, for comparison, 95% of the melt was cut with a hole diameter of 40
A biaxially stretched film with a thickness of 25 μm was prepared in the same manner as above except that it was filtered with a μm filter (
film).

Next, in the same manner as in Example 1, aluminum was vacuum-deposited on one side of each of films H and (2) to a thickness of 5 Qnm to obtain two types of metallized films (metalized film H
and engineering).

Table 6 shows the evaluation results of the metallized film obtained.

It is shown together with the characteristic values of PP5-BO used. From this table, it can be seen that the object of the present invention cannot be achieved if the coarse protrusion density is too large.

Table-3 Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] The resin composition is made of a resin composition containing p-phenylene sulfide as a main component, and the surface microprotrusion density Sd is 2.
A metallized film characterized in that a metal thin film layer is provided on at least one side of a biaxially oriented polyphenylene sulfide film having a coarse protrusion density Ld of 0 to 300 protrusions/round and 5 protrusions/mm or less.