JPH1158491A - Mold for extruding resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the non-pressure-sensitive adhesive properties, durability and antiscorching properties of a surface coat layer by applying a composite plating coat containing a florocompound whose volume fraction is specified to the surface of a mold. SOLUTION: A composite plating coat formed on the surface of the mold 1a for extruding a resin sheet comprises a non-metallic fluorocompound and a matrix metal. The volume fraction of a fluorocompound particle contained in the composite plating coat is 15% or more. The fluorocompound to be used is polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer or the like. The composite plating coat is formed by an electrolytic plating method, and an electrolytic plating fluid to be used is, for example, nickel, copper, zinc, tin, iron, lead, cadmium, chromium, precious metals and their alloys in the form of salt. The diameter of the particle of the fluorocompound to be added to the plating fluid is preferably equivalent to that of a fine particle which is smaller than the thickness of the plating coat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin sheet extrusion die, and more particularly, to a resin sheet extrusion die provided with a composite plating film containing fine particles of a fluorine compound.

[0002]

2. Description of the Related Art In recent years, resin sheets have been frequently used in industrial equipment and the like. The method of manufacturing the resin sheet is to heat and melt the resin to make it flow, and then use a screw. In general, the sheet is pushed into a resin sheet extrusion die, further cut through a finishing roll, a conveyor, and a take-up roll, and then cut by a cutting machine. At this time, if a conventional mold is used as the resin sheet extrusion processing mold, the resin that has accumulated in the mold is scorched by heat and fixed, thereby blocking the resin flow path, or the scorched resin is a product. There is a problem that the product becomes a defective product by being mixed into the product.

[0003] Therefore, when the above-mentioned inconvenience occurs, the operation of the resin sheet extrusion processing apparatus is temporarily stopped, the mold for resin sheet extrusion processing is removed, and the adhered resin or the scorched resin is removed with a metal spatula or a metal spatula. A method of removing by removing with a brush has been adopted. However, it is troublesome to perform the above operation every time the resin adheres or burns, and the resin sheet extrusion processing device cannot be operated during such operation, so that there is a problem that productivity is reduced.

Therefore, a method of coating the mold surface with a highly water-repellent material such as a fluororesin (for example, polytetrafluoroethylene) is also conceivable. According to this method, the above-mentioned problem can be solved because the non-adhesive effect of the fluororesin or the like is exhibited in the early stage of the production. However, since the fluororesin coating layer is inferior in strength, when used for a long period of time, the coating layer gradually peels off, and the above-mentioned problem still arises. In addition, when the resin coating layer comes off, there is a problem that the resin coating layer is mixed into the resin sheet being manufactured and becomes a defective product.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in a resin sheet extrusion die, and has excellent non-adhesiveness, durability and scoring resistance. It is an object of the present invention to provide a resin sheet extrusion processing mold that includes a surface coating layer and can improve productivity and dramatically reduce the defective rate over a long period of time.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and found that fine particles of a fluorine compound having a volume fraction of 15% or more were formed on the surface of a resin sheet extrusion die. When a composite plating film is formed in which is dispersed and contained, the metal for resin sheet extrusion processing is excellent in adhesion between the plating film and the base material, and is excellent in non-adhesiveness and sticking resistance, and can maintain this for a long period of time. We found that a mold was obtained. Furthermore, it has been found that when such a composite plating film is subjected to a heat treatment at a predetermined temperature, a film having more non-adhesiveness, durability, and scorching resistance can be obtained. The present invention has been completed based on these findings, and has the following configuration.

That is, the first aspect of the present invention is characterized in that a composite plating film containing a fluorine compound in a volume fraction of 15% or more is applied to the surface.

According to a second aspect of the present invention, in the resin sheet extrusion die of the first aspect, the composite plating film is
At least one fluorine compound selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, fluorinated graphite, and fluorinated pitch It is characterized by comprising fine particles.

According to a third aspect of the present invention, in the resin sheet extrusion die according to the first or second aspect, the composite plating film is one in which a fluorine compound is codeposited in a metal plating base material. It is characterized by.

According to a fourth aspect of the present invention, there is provided the resin sheet extrusion die according to the third aspect, wherein the average particle diameter of the fluorine compound fine particles is 2 μm or less.

[0011] The invention according to claim 5 is the invention according to claims 1, 2, and 3.
Alternatively, in the resin sheet extrusion die according to 4, the composite plating film is obtained by heat-treating at a temperature of 150 to 350 ° C.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The components of the present invention will be sequentially described, and the embodiments of the present invention will be clarified through this description.

In the present invention, since the composite plating film formed on the surface of the resin sheet extrusion die comprises a non-metallic fluorine compound and a matrix metal, the composite plating film has both of the inherent properties of both. Become. In particular,
Derived from fluorine compounds, has high lubricity, abrasion resistance, antifouling properties, non-adhesive properties, etc., and also has particularly excellent durability, heat resistance, chemical resistance, water repellency, oil repellency Demonstrate the properties such as. In addition, high hardness,
With properties such as high strength, high thermal conductivity, high conductivity,
Demonstrates excellent adhesion to substrate materials.

Further, since the resin sheet extrusion die is used in a severe environment where the resin is fixed or scorched, it is required to have a high degree of non-adhesion, durability, scoring resistance and the like. However, as described above, in the present invention, a metal is used as a matrix, so that this requirement is satisfied.

However, if the addition amount of the fluorine compound is small,
Non-adhesiveness, which is a characteristic of fluorine compounds, is not sufficiently exhibited. Thus, the present inventors have conducted an experiment and found that the above-mentioned inconvenience can be sufficiently solved if the volume fraction of the fluorine compound fine particles is 15% or more. Therefore, as the volume fraction of the fluorine compound particles in the composite plating film,
It needs to be 15% or more.

However, in a composite plating film comprising a metal and an eutectoid, as the volume fraction of the eutectoid increases,
Adhesion and adhesion between the plating layer and the substrate are reduced. Therefore, when considering the adhesiveness between the composite plating film and the resin sheet extrusion die as a substrate material, the volume fraction of the eutectoid in the composite plating film is preferably set to 15 to 60%, More preferably, it is good to be 25-45%.

Here, fluorine compounds include polytetrafluoroethylene (hereinafter, referred to as PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter, referred to as FEP), and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer. Coalescence (hereinafter P
FA), fluorinated graphite and fluorinated pitch can be suitably used.

The features of the present invention are that a fluorine compound is used as a water repellent material for a composite plating film, and that a composite plating film is formed from this fluorine compound (dispersed phase) and a plating material (matrix phase). . For this reason, the plating material (base material) only needs to have a suitable covering property and be capable of incorporating a fluorine compound into the matrix. Therefore,
In the present invention, it is possible to use a base material other than the metal plating material, but in order to sufficiently exhibit the effects of the present invention, it is preferable to use a metal plating material, in this case, as a coating means, An electrolytic plating method or an electroless plating method is suitable.

As an electrolytic plating method which can be suitably used in the present invention, for example, a method described in JP-A-4-329897 can be mentioned. Examples of the electroless plating method include a method described in JP-A-49-27443. According to these plating methods, fine particles of a fluorine compound can be dispersed in a metal matrix phase and co-deposited. Therefore, it is possible to obtain a suitable composite plating film having both the properties of the non-metallic fluorine compound and the properties of the matrix metal.

The method for forming the composite plating film will be specifically described with reference to an electrolytic plating method as an example. When using the electrolytic plating method, as the metal plating solution, for example, nickel, copper,
Zinc, tin, iron, lead, cadmium, chromium, precious metals and their alloys are used in the form of salts. These plating solutions are known to have various compositions, and in the present invention,
Any of the known plating solutions can be used.

The particle size of the fluorine compound added to the plating solution is not particularly limited. However, it is preferable to use fine particles smaller than the thickness of the plating film. This is because, when particles having a diameter significantly larger than the film thickness of the entire film are used, the particles are likely to fall off the plating surface due to external force such as friction. Here, the thickness of the composite plating film is
It can be set appropriately according to the material, shape, type of matrix metal, etc. of the resin sheet extrusion die,
Usually, if it is about 1 to 50 μm, it can sufficiently serve as a protective film. From this, the particle diameter of the fluorine compound fine particles may be about 2 μm or less on average, preferably 1 μm or less on average, and more preferably, the uniformity of dispersion of the fluorine compound in the plating solution and the composite plating film. In order to ensure this, do not include coarse particles exceeding 30 μm.

The amount of the fluorine compound to be added to the plating solution is not particularly limited, and is appropriately set in consideration of the required degree of coloring, water repellency, oil repellency and the like. Usually, about 200 g / L (liter) or less, preferably 1 g / L
If the amount is added to about 100 g / L, the object can be sufficiently achieved.

Other additives that can be included in the composite plating film are not particularly limited. For example, a surfactant or a primary brightener, a secondary brightener, or a known dye or pigment can be added as an auxiliary colorant to the composite plating solution,
Of these, the addition of a surfactant is particularly recommended. This is because the fluorine compound has a very high water repellency and is hard to wet, so it is necessary to improve the wettability of the fluorine compound and the like to the electrolytic plating solution with a surfactant and to uniformly disperse the fluorine compound and the like in the plating solution. It is.

The surfactant to be added to the electrolytic plating solution is as follows:
The surfactant must exhibit cationicity in the pH range of the electrolytic plating solution. Examples of such a surfactant include a water-soluble cationic type, a nonionic type, and an amphoteric interface exhibiting cationicity at the pH value of the plating solution. There are activators. Specifically, quaternary ammonium salts, secondary amines and tertiary amines can be used as the cationic surfactant, and polyethylene imine-based, ester-based surfactants and the like as the nonionic surfactant. And carboxylic acid-based and sulfonic acid-based surfactants can be used as the amphoteric surfactant. Among these surfactants, fluorine surfactants having a CF bond in the molecule can be particularly preferably used.

The amount of the surfactant added to the electrolytic plating solution is usually about 1 to 500 mg, more preferably about 1 to 100 mg, per 1 g of the fluorine compound. The plating conditions may be appropriately determined according to the material of the resin sheet extrusion die as the substrate material, the type of the composite plating solution to be used, and the like. Generally, the solution temperature generally used in the composite plating method, What is necessary is just to employ | adopt pH value, electric current density, etc.

As described above, since the fluorine compound and the like are rich in water repellency, the plating solution is constantly stirred while the plating process is in progress.
Plating is preferably performed in a state where a fluorine compound or the like is uniformly dispersed in the plating solution. There is no particular limitation on the stirring method, and any ordinary mechanical stirring means such as a screw stirring method or a magnetic stirring method may be used.

The resin sheet extrusion die exemplified above is usually made of copper, stainless steel, general steel, aluminum,
Although composed of metals such as aluminum alloys, the composite plating film according to the present invention may be formed directly on a resin sheet extrusion die, or may be a substrate material (before assembly) such as copper. It is also possible to adopt a method of forming a known base plating layer (for example, nickel plating, copper plating, etc.) on a substrate material made of a metal such as aluminum, a resin, or a carbon material, and then applying a composite plating film. .

As the mold for resin sheet extrusion processing, there are a round die and a flat die, but the present invention can be applied to any of them. As a method for producing a resin sheet using the above-mentioned round die, a resin is extruded from a large-diameter round die as a thin-walled pipe, and this is immediately cut open by a cutter attached to the round die, and further spread flat. There is a way to cool. On the other hand, as a method for producing a resin sheet using the flat die, there is a method of extruding a resin as it is from a wide flat die as a flat sheet. In addition, as for the type of flat die, depending on its shape, T
There are a die (manifold die) and a fishtail die.

The resin sheet extrusion die according to the present invention can be manufactured by the method described above. A more preferred embodiment of the present invention is that the resin sheet extrusion die is subjected to composite plating. The heat treatment is preferably performed at a predetermined temperature. By the heat treatment, a composite plating film having more excellent durability and water repellency can be formed, and the adhesiveness / adhesion to a substrate material or the like can be enhanced.

In the above heat treatment, after the composite plating film is applied to the resin sheet extrusion die, the composite plating film is
The heating is performed at a temperature of 0 to 400 ° C, more preferably 200 to 350 ° C. If the temperature is lower than 150 ° C., a sufficient heat treatment effect cannot be obtained, and if the temperature is higher than 400 ° C., the fluorine compound is decomposed, which may cause deterioration, discoloration or fading of the film. For this reason, in order to safely and surely bring out the heat treatment effect, it is preferable to set the heat treatment temperature to 200 to 350 ° C.

As the heating means, for example, a method in which hot air is applied to the composite plating film, a resin sheet extrusion die itself provided with the composite plating film, or a substrate material provided with the composite plating film is put into a heater. Heating method. Further, the heat treatment time is not particularly limited and can be appropriately set in relation to the heat treatment temperature, but usually about 10 to 30 minutes is sufficient.

The remarkable improvement in water repellency and adhesion to the substrate due to the heat treatment is due to thermal reforming of the composite plating film itself and removal of the surfactant (by thermal decomposition, evaporation, sublimation, etc.). It is presumed to be due to a decrease in wettability. It is also presumed that the film itself is due to thermal reforming,
It has been empirically confirmed that the heat treatment significantly improves the adhesion and adhesion of the film to the substrate.

[0033]

EXAMPLES The contents of the present invention will be specifically described below based on examples of the present invention and comparative examples.

[Invention Example 1-1] Plating Object The following was prepared as a plating object. (A) SUS430 test piece (b) Mold for resin sheet extrusion processing (material is SACM64
5) As shown in FIG. 1, the resin sheet extrusion die 1a is
It is formed at a resin outlet of the double-screw resin extruder 1, and more specifically, has a resin flow path 7 having a manifold 6 as shown in FIG. 2. A die lip 2 for discharging the resin in a sheet shape is provided downstream of the resin flow path 7, and a thickness adjusting bolt 3 for adjusting the thickness of the resin is provided above the die lip 2. . Further, a restriction bar 5 for adjusting the flow rate of the resin is provided at an intermediate position of the resin flow path 7, and the restriction bar 5 is structured to be moved up and down by bolts 4. The mold 1a has a structure that can be divided into upper and lower parts (shown by the line AA in FIG. 2). When performing electrolytic plating, separate the top and bottom of the mold,
Plating was performed with the surface in contact with the resin fixed so as to be parallel to the anode. At this time, the bolt 4 and the restriction bar 5 were removed, and the surface of the restriction bar in contact with the resin was plated. Also in the case of performing electroless plating, the upper and lower portions of the mold and the restriction bar were divided and put in a plating tank, and the entire surface was plated. However, no plating was applied to the bolts. Although it is possible to mask portions not in contact with the resin and not form a plating film, the masking process is time-consuming and rather expensive, and was not performed this time.

For the SUS430 test piece, the eutectoid amount of the fluorine compound was measured, and the contact angle with water was measured by a droplet method using a FACE contact angle meter. Force) used as a sample for the test and the impact deformation test. In addition, regarding the mold for resin sheet extrusion processing, when the resin extruder was actually operated, the presence or absence of scorching of the resin and clogging of the inside of the mold were examined. Details of these results and the test method will be described later.

Preparation of composite electrolytic plating bath A nickel sulfamate bath having the composition shown in Table 1 was prepared.
To this solution, PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) are added at 5% by weight based on the weight of the solution, and a tertiary perfluoroammonium salt (Dai Nippon Ink Chemical ( Co., Ltd., trade name "MegaFac F150") was added at 30.0 g / g of PTFE fine particles.
mg of the composite electrolytic plating bath.

[0037]

[Table 1]

Formation of Base Plating Film The above-mentioned plating object was used as a cathode and immersed in a wood bath containing a composition solution shown in Table 2 at a solution temperature of 25 ° C. and a current density of 10 A /
Under the conditions of dm ² and plating time of 2 minutes, the object to be plated was preliminarily plated with nickel.

[0039]

[Table 2]

Formation of Composite Plating Film The plating object (undercoated nickel plating) was
The PTFE fine particles were immersed in the composite electrolytic plating bath in which 5.0% by weight of the PTFE particles were dispersed, and the plating bath was constantly screw-stirred, and at a liquid temperature of 50 ° C., a ph of 4.2 and a current density of 2 A / dm ² , a film thickness of 10 μm. Composite plating was performed until

Heat Treatment The composite plate was subjected to a heat treatment at 350 ° C. for 30 minutes and then left at room temperature for 1 hour. The heat treatment was performed by placing the SUS430 test piece subjected to the composite plating and the resin sheet extrusion processing mold in a hot air circulating drying oven at 350 ° C. for 30 minutes. Thus, a surface-treated test piece and a resin sheet extrusion die were obtained.

[Inventive Example 1-2] In the preparation of the composite electrolytic plating bath, the addition amount of the PTFE fine particles was set at 2.
A test piece and a resin sheet extrusion die were surface-treated in the same manner as in Inventive Example 1-1 except that the content was changed to 5% by weight. Such a processed product is referred to as Invention Example 1-2.

[Inventive Example 1-3] In the preparation of the composite electrolytic plating bath, the addition amount of the PTFE fine particles was 7.
A test piece and a resin sheet extrusion die were surface-treated in the same manner as in Inventive Example 1-1 except that the content was changed to 5% by weight. Such a processed product is referred to as Invention Example 1-3.

[Inventive Example 2] In preparing the composite electrolytic plating bath, 5% by weight of FEP fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) was used instead of PTFE fine particles, and a surfactant (trademark “ Mega Fuck F150 ")
Was added at a rate of 65.0 mg per 1 g of FEP fine particles, and the heat treatment was performed at 250 ° C. for 30 minutes.
A test piece and a resin sheet extrusion die were subjected to surface treatment in the same manner as in Inventive Example 1-1. Such a processed product is referred to as Inventive Example 2.

Invention Example 3 In the preparation of the composite electrolytic plating bath, 5% by weight of PFA fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) were used instead of PTFE fine particles, and a surfactant (trademark “ Mega Fuck F150 ")
Was added at a rate of 30.0 mg per 1 g of PFA fine particles, and the heat treatment conditions were changed to 250 ° C. for 30 minutes.
A test piece and a resin sheet extrusion die were subjected to surface treatment in the same manner as in Inventive Example 1-1. Such a processed product is referred to as Inventive Example 3.

Inventive Example 4 In the preparation of the composite electrolytic plating bath, 5% by weight of fluorinated graphite fine particles (particle size: 1 μm or less, manufactured by Asahi Glass Co., Ltd.) was used instead of PTFE fine particles, and a surfactant (trademark) was used. "Mega Fuck F150")
Was added at a ratio of 40.0 mg per 1 g of the fluorinated graphite fine particles to obtain a test piece and a resin sheet extrusion die, which had been subjected to a surface treatment in the same manner as in Invention Example 1-1. Such a processed product is referred to as Invention Example 4.

[Invention Example 5] In preparing a composite electrolytic plating bath, 5% by weight of pitch fluoride fine particles (particle size: 2 μm or less, manufactured by Osaka Gas Co., Ltd.) were used instead of PTFE fine particles, and a surfactant ( Trademark "MegaFac F150")
Was added at a ratio of 25.0 mg / g of fluorinated pitch fine particles, and the heat treatment was performed at 250 ° C. for 30 minutes, except that the test piece and the resin sheet were surface-treated in the same manner as in Invention Example 1-1. An extrusion die was obtained. Such a processed product is referred to as Inventive Example 5.

Inventive Example 6 In the preparation of the composite electrolytic plating bath, 2.5% by weight of PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) and FEP fine particles (particle size: 2 μm) were used instead of PTFE fine particles. Hereinafter, fine particles mixed with 2.5% by weight of Daikin Industries, Ltd.) were used, and the surfactant (trade name “MegaFac F150”) was changed to [PT
Invention Example 1-1 except that only the amount calculated by using the amount of FE fine particles (g) × 30.0 + the amount of FEP (g) × 65.0] mg was used, and the heat treatment was performed at 250 ° C. for 30 minutes. In the same manner as in the above, a test piece and a resin sheet extrusion die subjected to a surface treatment were obtained. Such a processed product is referred to as Invention Example 6.

Inventive Example 7 In the preparation of the composite electrolytic plating bath, 1.25% by weight of PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) and PFA fine particles (particle size: 2 μm) were used instead of PTFE fine particles. Hereinafter, 1.25% by weight of Daikin Industries, Ltd.) and 2.5% by weight of FEP fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.)
And a surfactant (trade name “MegaFac F150”) [PTFE used amount (g) × 30.
0 + PFA used amount (g) × 30.0 + FEP used amount (g) × 65.0] mg, except that the heat treatment conditions were 250 ° C. for 30 minutes.
In the same manner as in 1-1, a test piece and a resin sheet extrusion die subjected to surface treatment were obtained. Such a processed product is referred to as Invention Example 7.

Inventive Example 8 Preparation of Electroless Nickel Plating Bath An electroless nickel plating bath having the composition shown in Table 3 was prepared .

[0051]

[Table 3]

The electroless nickel-PTFE composite plating bath
An electroless nickel plating bath having the composition shown in Preparation Table 3 was prepared , and PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) were added to this solution in an amount of 5% by weight based on the weight of the solution. A tertiary perfluoroammonium salt (manufactured by Dainippon Ink and Chemicals, Inc., trade name “MegaFac F150”) as an activator is added at 30.0 g / g of PTFE fine particles.
mg electroless nickel-PTFE composite plating bath.

The above electroless nickel plating bath, electroless nickel-PTFE composite plating bath and Table 2 shown in Invention Example 1-1
, A base plating film and a composite plating film shown below were formed in order. The formation of the base plating film includes a base nickel strike plating process and a base electroless nickel plating process.

Formation of Base Plating Film The above-mentioned plating object was used as a cathode and immersed in a wood bath containing a composition solution shown in Table 2 at a solution temperature of 25 ° C. and a current density of 10 A /
Under the conditions of dm ² and plating time of 2 minutes, the object to be plated was preliminarily subjected to a nickel strike plating treatment.

Next, the object to be plated was immersed in an electroless nickel plating bath containing a composition solution shown in Table 3, and the solution temperature was adjusted to 90 ° C., pH 4.6 under screw stirring, and the film thickness was 3 μm.
Electroless plating was carried out until the following conditions were reached to form a base electroless nickel plating film.

Formation of Composite Plating Film The object to be plated (the one subjected to nickel base plating) was
Immerse in the electroless nickel-PTFE composite plating bath in which 5.0% by weight of PTFE fine particles are dispersed, and constantly stir the plating bath with a screw until the film thickness becomes 10 μm at a liquid temperature of 90 ° C. and a ph of 5.1. Composite plating was performed. In this way, a test piece and a resin sheet extrusion die were surface-treated in the same manner as in Invention Example 1-1 except that electroless plating was performed. Such a processed product is referred to as Invention Example 8.

Comparative Example 1 SUS4 similar to Invention Example 1-1
30 test pieces were subjected to base nickel strike plating using the same nickel wood bath as in Example 1-1, and the object to be plated was immersed in a nickel sulfamate plating bath containing the composition solution shown in Table 1 above. Then, under screw stirring, at a liquid temperature of 50 ° C. and a current density of 4 A / dm ² ,
Electrolytic nickel plating was performed until the film thickness became 10 μm. Such a processed product is referred to as Comparative Example 1.

[Comparative Example 2] The addition amount of the PTFE fine particles in the preparation of the composite electrolytic plating bath was 1.7 with respect to the weight of the solution.
A test piece and a resin sheet extrusion die were surface-treated in the same manner as in Invention Example 1-1 except that the content was changed to wt%. Such a processed product is referred to as Comparative Example 2. Here, the various tests were performed as follows.

(1) Measurement test of eutectoid content of fluorine compound A SUS430 test piece was immersed in an aqueous nitric acid solution having a weight ratio of 1: 1 to dissolve the plating film. .2 μm), dried and cooled in a desiccator at 80 ° C. for 1 hour, and measured by gravimetric analysis.

(2) Contact angle test FACE contact angle measuring device (CA-A, manufactured by Kyowa Interface Science Co., Ltd.)
), And the contact angle of water to the sample (film surface) was measured by a droplet method. The quality of the water repellency can be evaluated by the magnitude of the contact angle.

(3) Adhesion test The adhesion test was carried out according to the adhesion test method (cross-cut tape method) of JIS K5400. Specifically, three samples having 100 grids per cm ^{2 on} the film surface were prepared, and each of the samples was (1)
Leave at 250 ° C for 2 hours, (2) Leave at -10 ° C for 2 hours,
(3) An operation of repeating a cycle of standing at 200 ° C. for 1 hour and then standing at −10 ° C. for 1 hour 10 times was added. Thereafter, the sample was returned to room temperature, a cellophane adhesive tape was placed on a grid, and this was peeled off. Then, the number x of the grids peeled off on the tape was visually read, and the adhesive strength was evaluated based on the number x / 100 of the peelings.

(4) Impact deformation test An impact deformation test using a 20 ° C. DuPont method (JIS K5400)
Was performed to deform the sample, and the damage of the film at the deformed portion was examined. The conditions of the shock deformation test are as follows.
Dropping from a drop height of 00 mm.

(5) Operation Test The resin sheet extrusion processing dies prepared by the methods of Invention Examples 1 to 8 and Comparative Examples 1 and 2 were attached to a double-screw resin extruder 1 as shown in FIG. 1 polyvinyl chloride containing 30 wt% of di-2-ethylhexyl phthalate as a plasticizer
Continuously feed from the hopper 1b at a speed of 30 kg per hour,
Extruding a sheet of polyvinyl chloride resin from a T-die,
Further, a finishing roll 8, a conveyor 9, and a take-up roll 10
Then, the sheet was conveyed to a cutting machine 11, and the sheet was cut by the cutting machine 11 to prepare a resin sheet (600 mm in width × 1000 mm in length). At this time, the heating temperature is 120 ° C., and the produced resin sheet is transported by the stacker 12. Then, the double-screw resin extruder is set to 24
It was operated continuously for a time, and in that case, the presence or absence of scorching of the resin and blockage of the inside of the mold were examined.

The production conditions are listed in Tables 4 and 5, and the results of various tests are listed in Tables 6 and 7.

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

[0068]

[Table 7]

Test Results As shown in Table 6, the results of the eutectoid amount test of the fluorine compound were as good as 15 to 45% in all of the examples of the present invention, and the contact angle test of the composite plating film was carried out. As a result, it was confirmed that all of the examples of the present invention had a larger contact angle than Comparative Examples 1 to 3 and had extremely good water repellency.

As shown in Table 6, with respect to the poor adhesion and the impact deformation resistance of the composite plating film to the substrate, the example of the present invention is excellent in the adhesion to the substrate and the impact deformation resistance. confirmed. The adhesion test in Table 6 shows the results of the tests performed under the conditions 1 to 3 above. However, since no poor adhesion was observed in both the present invention and the comparative examples, it was simply indicated as 0/100. ing.

Further, as shown in Table 7, in the operation test results, in Comparative Example 1, the resin was scorched one hour after the operation.
Comparative Example 2
In 3 hours after the operation, the resin was scorched and the inside of the mold was blocked, and the operation became impossible. On the other hand, in the examples of the present invention, even after the operation was performed for 24 hours, the resin was scorched and the mold was not operated. It was confirmed that there was no internal blockage and continuous operation was possible smoothly.

[0072]

According to the present invention, the composite plating film formed on the surface of the resin sheet extrusion die, which is a substrate material, comprises a non-metallic fluorine compound and a matrix metal. Demonstrates high lubricity, abrasion resistance, heat resistance, chemical resistance, water repellency, oil repellency, etc., and high hardness, high strength, and high thermal conductivity due to the properties of matrix metal Has properties such as heat resistance and high heat resistance. Furthermore, since the composite plating film has good adhesion and adhesion to the substrate, peeling of the film due to a difference in the coefficient of thermal expansion between the substrate and the film is unlikely to occur.

Further, the volume fraction of the fluorine compound fine particles is set to 1
Since the content is regulated to 5% or more, the non-adhesive property of the fluorine compound is sufficiently exhibited. Therefore, sticking and scorching to the resin sheet extrusion die can be prevented.

As described above, according to the present invention, it is possible to prevent sticking and scorching to the resin sheet extrusion die and maintain such excellent usability over a long period of time. It has excellent effects.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a production process when producing a resin sheet.

FIG. 2 is a cross-sectional view of a resin sheet extrusion die.

[Explanation of symbols]

 1a: Mold for resin sheet extrusion processing 2: Die lip 7: Resin channel

Claims (5)

[Claims] 1. A resin sheet extrusion die having a composite plating film containing at least 15% by volume of a fluorine compound on a surface thereof. 2. A fluorine compound comprising polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, fluorinated graphite, and fluorinated pitch. The resin sheet extrusion processing mold according to claim 1, wherein the mold comprises one or more kinds of fluorine compound fine particles selected from the group. 3. The resin sheet extrusion processing die according to claim 1, wherein the composite plating film has a fluorine compound co-deposited in a metal plating base material. 4. The resin sheet extrusion processing die according to claim 3, wherein the average particle diameter of the fluorine compound fine particles is 2 μm or less. 5. The composite plating film according to claim 1, wherein the composite plating film has a thickness of 150 to 350.
The resin sheet extrusion die according to claim 1, wherein the die is subjected to a heat treatment at a temperature of ° C.