JPH09291352A - Member for paper processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem that a member for processing paper or a paper, on the surface of which an organic film is formed, is conventionally vigorously worm out and the organic film is coagulated and stuck to the member for paper processing. SOLUTION: The surface of the member for processing paper or the paper, on the surface of which is covered with the organic film, is constituted of a hard carbonaceous film having the perks at 1,340±40cm<-1> and 1,160±40cm<-1> in Raman spectroscopic spectrum and particularly having the peak intensity ratio of 0.05-2 expressed by H1 /H2 when the highest peak intensity in the peaks existing in 1,160±40cm<-1> is expressed by H1 in the Raman spectroscopic chart and the highest peak intensity in the peaks in 1,340±40cm<-1> is expressed by H2 .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paper or surface, for example, polyethylene terephthalate (PET),
The present invention relates to a paper processing member used as a cutting tool for cutting paper on which an organic film such as polyethylene, polypropylene, polyvinyl alcohol, or nylon is formed, a mold material for bending, and the like.

[0002]

2. Description of the Related Art Conventionally, as a member for punching or bending a paper or a paper having an organic film formed on the surface, a member mainly made of a metal has been widely used. There is a problem that the member wears due to contact with, and recently, it has been proposed to use ceramics such as alumina having excellent wear resistance.

Further, as one means for improving wear resistance, forming a diamond film of high hardness on the surface of a member has been conventionally performed.

[0004]

However, in the processing of paper, as the processing speed increases with the mass production thereof and the processing conditions become severe, the wear of the processing member becomes severe, and even in the conventional ceramic member. The wear tends to be extremely advanced. Further, when processing paper having an organic film formed on its surface, there is a problem that the paper or the organic film adheres to the processing member.

Further, when a conventionally known diamond film is formed on the surface of a member, although the wear resistance is improved to some extent, the diamond film is formed by large diamond crystal grains and minute voids are formed in the film. Due to the existence of the film, a crack is suddenly generated in the film, or a desired tip R shape cannot be obtained at the cutting edge used for cutting the paper.
There are problems that the sharpness becomes poor and that the organic film is adhered in the paper processing having the organic film.

[0006]

[Means for Solving the Problems] In order to solve the above-mentioned problems, as a result of repeated studies on a processing member suitable for processing paper or paper whose surface is coated with an organic film,
On the surface of the member in contact with the paper of the member or the organic film formed on the surface of the member, 1340 ± 4 in Raman spectrum
By coating a special hard carbon film having peaks at 0 cm ^-1 and 1160 ± 40 cm ^-1 , it is possible to significantly reduce wear during processing and also to reduce adhesion of the organic film. The present invention has been completed by finding that the life can be greatly improved.

Further, according to the present invention, an intermediate layer containing diamond and metal carbide is interposed between the member and the hard carbon film to provide a member for working having an extremely long life without film peeling. It was

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The paper processing member according to the present invention is
The surface of the member has a Raman spectrum of 1160.
A major feature is that the hard carbon film having peaks at ± 40 cm ⁻¹ and 1340 ± 40 cm ⁻¹ is coated. This hard carbon film is mainly composed of diamond,
A generally known diamond film is made of high-purity diamond, has a structure in which carbon atoms are bonded by SP ³ hybrid, and has a Raman spectrum of 1340 ± 40.
It has a peak at cm ^-1 , and is 1 when it contains graphite with a graphite structure bonded by SP ² hybridization in some cases.
It has a broad peak around 500 to 1600 cm ^-1 .

On the other hand, in the hard carbon film of the present invention, in addition to 1340 ± 40 cm ⁻¹ , 1160 ± 40 cm
^It has a peak at ^-1 . This 1160 ± 40c
The m ^-1 peak is considered to mean that the crystal period is short because it has a diamond structure but is composed of fine crystal diamond particles. Therefore,
In the hard carbon film of the present invention, the diamond crystal is composed of extremely fine particles, and is excellent in flatness without the unevenness caused by the conventional diamond crystal. Also, it has high hardness and abrasion resistance even if it contains a trace amount of a substance having a graphite structure.

Therefore, even if the surface of a member of any shape is coated, a smooth and dense covering surface can be formed that matches the surface shape of the member. For example, in a cutting edge used for cutting paper, a member having a sharp cutting edge can be used. Even with the hard carbon film described above, the surface after coating can also form a sharp coated surface that matches the shape of the cutting edge member.

On the other hand, when high smoothness is required for the surface coated with a hard carbon film such as a sliding surface when bending paper, the desired surface can be easily obtained by finishing the member surface to a desired surface roughness. Obtainable. Moreover, since the film surface immediately after the film formation is excellent in smoothness as compared with the conventional diamond film, the polishing process can be easily performed.

Further, the hard carbon film of the present invention is a dense film and has no defects such as voids as in the conventional diamond film, and the surface of the member of the organic film even when sliding with paper or the like on which the organic film is formed. Can be prevented from sticking to.

The peak intensity at 1160 ± 40 cm ⁻¹ in the Raman spectrum of the hard carbon film of the present invention will be specifically described. In the Raman spectrum curve obtained as shown in FIG. 1, 1100 cm ⁻¹ and 17
Pull the hatched between positions 00cm ^-1, this as a baseline, H ₁ the highest intensity peak intensities of the peaks present in 1160 ± 40cm ^-1, 1340 ± 40cm
High peak intensity of most intense among the peaks present to ^-1 and H _2. At this time, it is desirable that the composition has a peak intensity ratio represented by H ₁ / H ₂ of 0.05 to 2.
If this peak intensity ratio is too small, the diamond crystal particles will grow too large and voids will be generated in the film, the surface roughness of the film will be large, and the abrasion resistance will be reduced and the adhesion of the organic film will easily occur. Become. On the other hand, if the peak intensity ratio is too large, the presence of amorphous diamond may increase, and the hardness of the hard carbon film itself may decrease, resulting in a decrease in wear resistance.
More preferably, the peak intensity ratio is 0.1 to 1.0.

The processing member in the present invention is formed by coating the above-mentioned hard carbon film, but the coating of the film on the surface of the member may cause a new problem of peeling of the film. However, according to the processing member of the present invention, by interposing a layer containing at least diamond and silicon carbide between the member and the hard carbon film, it is possible to form a hard carbon film having excellent adhesion. it can.

The reason why the adhesion strength between the hard carbon film and the base material is improved by such a film structure is considered as follows.
Atoms are bonded by intervening electrons, but in general, electrons are shared by both atoms rather than ionic bonds, in which electrons between atoms are present on one side and bonded by electrical connection. An existing covalent bond has a stronger binding force. Diamond has a strong bonding force because it is constituted by a covalent bond of carbon. Therefore, in order to improve the adhesion strength between diamond and a different compound, it is considered that a covalent compound having a similar bonding mode is desirable. Also, it seems that a compound containing carbon which is a component of diamond has better consistency. Although there are many carbon-containing compounds, most of them are mainly composed of ionic bonds, and examples of the covalent metal carbide include silicon carbide.

By forming a layer in which these metal carbides and diamond are mixed between the hard carbon film and the base material, the adhesion strength between the hard carbon film and the base material is improved. Further, this diamond and the metal carbide have a structure that surrounds the diamond, and since the diamond has a structure in which it is distributed in an island shape, a so-called anchor effect can be expected and the adhesion strength between the hard carbon film and the base material can be expected. improves.

The method of producing such a film structure is based on the vapor phase growth method, and hydrogen, carbon-containing gas, and silicon-containing gas are introduced as raw material gases into the reaction chamber in which the processing member is installed. A layer in which diamond and silicon carbide are mixed can be formed by excitation, and a hard carbon film can be formed by stopping the supply of the silicon-containing gas.

The carbon-containing gas used at this time is
For example, alkanes such as methane, ethane, propane,
Examples thereof include alkenes such as ethylene and propylene, alkynes such as acetylene, aromatic hydrocarbons such as benzene, cycloparaffins such as cyclopropane, and cycloolefins such as cyclopentene. In addition, carbon monoxide, carbon dioxide, oxygen-containing carbon compounds such as methyl alcohol, ethyl alcohol and acetone, mono (di,
Nitrogen-containing carbon compounds such as tri) methylamine and mono (di, tri) ethylamine can also be used as the carbon source gas.

These may be used alone or in combination of two or more.

Examples of the silicon-containing gas include halides such as silicon tetrafluoride, silicon tetrachloride and silicon tetrabromide, oxides such as silicon dioxide, mono (di, tri, tetra, penta) silane, Examples thereof include silane compounds such as mono (di, tri, tetra) methylsilane and silanol compounds such as trimethylsilanol. These can be used alone or in combination of two or more.

Further, as the base material type of the paper processing member,
Examples thereof include ceramics such as silicon nitride, silicon carbide, alumina and zirconia, titanium alloys, cemented carbides, cermets, metals such as stainless steel. Among these, silicon nitride, silicon carbide, cemented carbide and cermet are preferable. These base materials may be used as they are, or may be formed as a thin film on the surface of an appropriate member by a thin film forming technique such as a vapor phase growth method.

Further, in the present invention, the above-mentioned 1
To form a hard carbon film having peaks at 340 ± 40 cm ⁻¹ and 1160 ± 40 cm ⁻¹ , for example, the above-mentioned source gas is introduced into the reaction chamber and at the same time, a microwave of 2.45 GHz is introduced and further 875 An electron cyclotron resonance plasma is generated by applying a magnetic field of a Gauss level or higher. And 0.01 to 0.10 t in the reaction chamber
Maintaining a pressure of orr and keeping the temperature of the member from 400 ~
It can be formed by forming a film at a relatively low temperature of 650 ° C.

As described above, according to the present invention, the surface of the member contacting the paper is coated with the fine hard carbon film having the fine grain structure and having no surface defect to form the sharp cutting edge aligned with the surface of the paper processing member. In addition, by adapting to the sliding surface of the member when bending the paper, abrasion due to contact with the paper is suppressed and adhesion of the organic film also occurs when processing the paper on which the organic film is formed. Can be prevented,
The service life of the processing member can be extended. Further, by interposing a layer containing at least diamond and silicon carbide between the surface of the member and the hard carbon film, it is possible to provide a member without film peeling.

[0024]

【Example】

Example 1 (Sample Nos. 1 and 2) A raw material gas was introduced into the reaction furnace so that the pressure in the reaction chamber was 0.0.
It was set to 5 Torr. Table 1 shows the types and flow rates of the raw material gases. Electron Cyclotron Resonance (ECR) Plasma CV
A magnetic field having a maximum intensity of 2 kGauss was applied by the D method, and the tip made of cemented carbide or titanium alloy (Ti-6Al-4V) had a radius of 0.
A hard carbon film having a film thickness of 1 μm is formed on the surface of a blade member for paper cutting having a sharp edge of 5 μm.
An intermediate layer 0.5 μm) was formed.

Table 1 shows the changes in the raw material gas flow rate and the pressure during film formation, along with the elapsed film formation time.

[0026]

[Table 1]

As a result of X-ray diffraction analysis of the obtained films, the presence of diamond and silicon carbide was confirmed in all the films, and in sample No. 2 using a titanium alloy as a member, TiC was also formed in the intermediate layer. confirmed. Moreover, when the spectrum of this hard carbon film was measured by Raman spectroscopy, both films were 1337 cm ⁻¹ and 1154 cm ^−1.
A peak was confirmed at. (Sample Nos. 1 and 2). When the blade edge after film formation was polished, a good blade edge shape could be formed.

For these paper cutting blades, a thickness of 0.
The experiment of cutting 5 mm paper was repeated up to 1,000,000 times. Table 2 shows the number of times of cutting and the maximum wear amount of the cutting edge.

Example 2 (Samples No. 3, 4, 6, 7) Under the film forming conditions in Example 1, the source gas concentration and pressure during the formation of the hard carbon film were changed within the range of 0.01-0.10. that deposition be performed in exactly the same manner except for, H ₁ / H ₂
Hard carbon films having different peak ratios were coated and the surface was polished. Among them, Sample No. 3 was difficult to polish the cutting edge, and required 10 times as long as Sample Nos. 1 and 2. Then, a paper cutting test was conducted in the same manner as in Example 1. The results are shown in Table 2.

Example 3 (Sample No. 5) Under the film forming conditions of Example 1, an intermediate layer (0.5 μm thick) made of SiC alone was formed, and a hard carbon film (0.5 μm) was further formed. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 (Sample Nos. 8 and 9) A hard carbon film was formed by a microwave CVD method, which is a conventional general method, to form an intermediate layer of 0.5 μm and a hard carbon film of 0.5 μm. . Raman spectroscopic analysis was performed on the obtained hard carbon film, and a paper cutting test was performed in the same manner as in Example 1. When the surface of the cutting edge was polished, the desired tip R shape could not be obtained due to the large diamond crystal grains. The results are shown in Table 2.

Comparative Example 2 (Sample No. 10) A paper cutting test was similarly performed using a cutting blade made of stainless steel, which is one of conventional materials. The results are shown in Table 2.

[0033]

[Table 2]

In Table 2, Raman spectroscopic analysis charts of Sample No. 1 (invention product) and Sample No. 8 (comparative product) are shown in FIGS. 1 and 2, respectively.

According to the results shown in Table 2, in the conventional stainless steel, cutting defects frequently occur after cutting 100,000 times and the wear of the cutting edge is 5 times.
It is as large as μm, and even with a sample coated with a hard carbon film,
Although there is a peak at 1340 ± 40 cm ^-1 , it is 1160 ±
It is considered that in Samples Nos. 8 and 9 in which no peak was observed at 40 cm ^-1 , cutting failure occurred at the initial stage and a desired R shape could not be obtained.

On the other hand, in Raman spectroscopic analysis, Sample Nos. ¹ to 7 having peaks at 1340 ± 40 cm ⁻¹ and 1160 ± 40 cm ⁻¹ were capable of cutting well up to 1,000,000 times. However, in the sample No. 7 in which the H ₁ / H ₂ peak ratio deviates from the range of 0.05 to ₂ , the wear tended to increase. Further, in the sample No. 5 in which the intermediate layer was composed of only SiC, the occurrence of cracks was observed between the hard carbon film and the member. However, in the sample No. 1, 3 in which the intermediate layer was composed of diamond and silicon carbide, In Nos. 6 and 7, no cracks and no film peeling were observed even after the test.

Example 4 For paper molding using a silicon nitride chamber sintered body and a titanium alloy (Ti-6Al-4V) as a base material, in the same manner as in Examples 1 and 2 and Comparative Examples 1 and 2. The mold surface was coated with various hard carbon films. The film thickness was 5 μm (intermediate layer 1 μm). Further, a metal mold made of cemented carbide was prepared as a conventional material.

Experiments for molding paper having a PET (polyethylene terephthalate) resin formed on the surface of these molds were repeated up to 1,000,000 times. The molding was performed so that the resin-formed surface was in contact with the mold. During the test, the test was stopped when the adhesion of the PET resin was confirmed on the sliding surface. The results are shown in Table 3.

[0039]

[Table 3]

According to the results shown in Table 3, the conventional cemented carbide No.
In No. 20, adhesion was recognized about 500 times. Also in the sample coated with the hard carbon film, the adhesion of the resin was observed in Sample Nos. 18 and 19 in which the peak was observed at 1340 ± 40 cm ⁻¹ but the peak was not observed at 1160 ± 40 cm ⁻¹ .

On the other hand, in Raman spectroscopic analysis, Sample Nos. 11, 12, and 14 to 17 having peaks at 1340 ± 40 cm ⁻¹ and 1160 ± 40 cm ⁻¹ were all good at up to 1,000,000 times. Molding was possible,
In Sample No. 13 having a H ₁ / H ₂ peak ratio of less than 0.05, PET resin adhesion occurred after 500,000 moldings.

Further, the sample No.
In No. 17, local abrasion was observed on the carbon film after molding 1 million times. Further, the samples having the H ₁ / H ₂ peak ratio in the range of 0.05 to ₂ showed almost no wear even after molding 1,000,000 times, and no adhesion by the resin was observed. Further, in the sample No. 15 in which the intermediate layer was composed of only SiC, cracks were found between the hard carbon film and the member, but in the sample in which the intermediate layer was composed of diamond and silicon carbide, there was no problem even after the test. Neither cracking nor film peeling was observed.

[0043]

As described above in detail, in the paper processing member of the present invention, the surface thereof is coated with a specific hard carbon film to suppress abrasion due to contact with paper and to form an organic film. Even in the case of processing rolled paper, it is possible to prevent the adhesion of the organic film, and it is possible to prolong the life of the paper cutting member, the punching member, the molding member when folding the paper, and the like.

[Brief description of drawings]

FIG. 1 is a Raman spectroscopic analysis chart of a hard carbon film according to the present invention.

FIG. 2 is a Raman spectroscopic analysis chart of a conventional hard carbon film.

Claims (3)

[Claims] 1. A member for processing paper or paper having a surface coated with an organic film, the surface of which is 1340 ± 40 cm ⁻¹ and 1160 ± ¹ in Raman spectrum.
A member for paper processing, which is coated with a hard carbon film having a peak at 40 cm ^-1 . 2. In the Raman spectroscopic analysis chart of the hard carbon film, the highest peak intensity among the peaks existing at 1160 ± 40 cm ⁻¹ is H ₁ , 1340 ± 40 c.
When the high peak intensity of most intense among the peaks and with H ₂ present in m ^-1, for paper coating, wherein the peak intensity ratio represented by H ₁ / H ₂ is 0.05 to 2 Element. 3. Between the hard carbon film and the surface of the member,
The paper processing member according to claim 1, wherein an intermediate layer containing at least diamond and metal carbide is present.