JP4436174B2 - Spacer sheet and transport method using the same - Google Patents

Description

  The present invention relates to a spacer sheet used for the purpose of protecting the surface from scratches, dust adhesion and organic contamination when transporting and storing precision device substrates and precision device members, and a member using the spacer sheet and Relates to the device.

Occurs during transportation and storage of silicon, glass, plastic and other substrates used in manufacturing, ceramics and metal materials used in equipment components, etc., as the performance of electronic devices such as semiconductors and liquid crystal displays increases. A bug has become a problem.
It is known that defects that occur during transportation and storage include physical damage, dust adhesion, organic matter contamination, static electricity, and the like, which greatly affect the yield in manufacturing.
For example, silicon wafers used for semiconductor devices and glass substrates used for liquid crystal substrates are greatly deteriorated in the performance of devices such as MOSFETs and TFTs produced on the substrate due to contamination during transportation and storage. Thoroughly cleaned and used after acceptance.

However, with higher performance and miniaturization of devices, more precise cleaning is required, which increases cleaning costs and raises production costs.
Under these circumstances, various simple cleaning techniques have been invented in order to reduce the cleaning cost. However, if the amount of adsorbed organic matter or dust is large, the cleaning time may be prolonged or insufficient cleaning may occur. A problem has occurred.
Although the transport container is sealed, it has been devised to prevent contamination during transport and storage, but because of the problem of damage due to substrate contact, it is transported and stored by non-contact transport using cassettes and teeth. Most of the air is air, which increases the volume of the container and increases the transportation and storage costs.

In particular, in the case of a glass substrate for liquid crystal, the area of the substrate is steadily expanding, and accordingly, the size of a transport container for transporting the glass substrate for liquid crystal tends to increase.
In order to solve such a problem, as described in Patent Document 1 and Patent Document 2, a method of superposing and transporting using a spacer sheet has been devised.
By carrying the stacking and transporting, the volume can be greatly saved, so the transport and storage efficiency is dramatically improved and the cost is greatly reduced.

Patent Document 1 discloses a spacer sheet in which a concavo-convex shape with a height of 0.5 to 2.5 mm is formed on one side in order to ensure good air permeability between structures, and a region having a large projection density and a small size. A spacer sheet characterized in that the regions are mixed is disclosed.
Patent Document 2 discloses a glass slip sheet containing 0.1% by weight or more of sodium tripolyphosphate.
JP 2002-121835 A JP-A-6-316432

  By using the spacer sheet or glass slip sheet described in Patent Documents 1 and 2, it is presumed that the packing volume can be reduced and the transportation cost can be reduced. However, in the case of Patent Document 1, the adhesion of the organic component to the structure is not considered, and in particular, there is a problem that it cannot be used for applications where the adhesion of the organic substance affects the performance of the structure. In particular, it is difficult to apply the spacer sheet disclosed in Patent Document 1 to semiconductor applications, display device applications, optical-related product applications, semiconductor / display device manufacturing apparatus applications, and the like.

In the case of Patent Document 2, paper is used as a main raw material, and there is a problem that dust such as organic matter adhering from the paper or generated paper dust adheres to the substrate, and the object to be transported is carefully cleaned. It has become indispensable.
Furthermore, since alkali metal components such as tripolyphosphoric acid are contained in the interleaving paper, such as alkali-free glass and semiconductor substrates where the alkali metal component adsorbed on the surface is a problem, the performance is significantly deteriorated by the alkali metal component. Causes problems that cannot be used.

Furthermore, when the above-mentioned paper spacer sheet is used, the spacer sheet is used in close contact with the surface of the object, which causes a problem that a large amount of static electricity is generated when the spacer sheet is peeled off during use. Further, when static electricity is generated in this way, there is a problem that it becomes difficult to clean by attracting and adsorbing dust or dust in the surrounding atmosphere to the surface of the object.
In particular, the problem of static electricity is particularly noticeable in the case of an object that must be handled in a dry atmosphere in order to maintain device performance, such as a semiconductor substrate, a glass substrate, or a product using these.

The present invention has been made in view of the above-mentioned problems, and in order to suppress organic substances and dust that cause contamination, generation of static electricity, and the like, attention is paid to the contact area between the spacer sheet and the substrate, and the shape is devised. It aims at providing the member and apparatus using the spacer sheet | seat of this invention which can suppress contamination by doing.
Another object of the present invention is to provide a plurality of substrates capable of greatly reducing the space during transportation and storage by bringing the substrates into close contact with each other using a spacer sheet with very little organic matter adhering to contamination and transporting and storing them. It is to provide a transportation or storage method.

Spacer sheet of the present invention, have a phase of fluorine atom content is more material than the spacer sheet inner layer portion in the surface layer of the spacer sheet, the spacer sheet is a single plate-like structure surface or a plurality of plate-like The pattern is disposed between structures, and has a direction in which the spacer sheet is peeled off from the plate-like structure, a pattern shape is formed on the surface of the spacer sheet, and the pattern viewed from a direction perpendicular to the surface of the spacer sheet The shape is a periodic pattern having a rhombus as a basic pattern, and each side of the rhombus formed on the surface of the spacer sheet has an angle smaller than 90 ° with respect to the peeling direction, and the side of the rhombus is The convex portion is formed, and the surface portion surrounded by the side forms a concave portion, and the long side direction of the spacer sheet and the rhombus The long diagonal direction, characterized in that it is parallel.

  A spacer sheet according to a preferred embodiment of the present invention is a spacer sheet disposed on the surface of a single plate-like structure or between a plurality of plate-like structures, and has a contact area between the plate-like structure and the spacer sheet. When S1 and the spacer sheet area is S2, S1 <S2.

The projection component onto the spacer sheet in the peeling direction is preferably in the long side direction of the spacer sheet.
Furthermore, in the spacer sheet of the present invention, the side of the basic pattern forms a convex part, the surface surrounded by the side of the basic pattern forms a concave part, and the convex part contacts the plate-like structure. It is characterized by that.

The spacer sheet of the present invention may be net-like, and in this case, a structure part constituting the net can be defined as a convex part and an opening part of the net can be defined as a concave part.
Furthermore, in the spacer sheet disposed between the plurality of plate-like structures, the constituent material of the spacer sheet is characterized in that the organic matter adheres less to the plate-like structure.
Furthermore, since the spacer sheet of the present invention can easily form a surface pattern, the constituent material contains at least an organic substance, and is preferably a resin.

The spacer sheet of the present invention is characterized in that the amount of organic matter attached to the plate-like structure is 100 ng / cm ² or less from the viewpoint of facilitating cleaning of the plate-like structure to be packed, The molecular weight of the organic substance adhering to the plate-like structure is 10,000 or less.
The plate-like structure may be any material as long as it is conveyed using the spacer sheet of the present invention, and includes a glass substrate, a semiconductor substrate, a resin substrate, a printed wiring board, a ceramic plate and a ceramic application product, a metal substrate, and a liquid crystal display device. , Organic EL display device, plasma address display device, semiconductor device, light guide plate, reflector plate, lens sheet, prism sheet, polarizing plate, circuit board, magnetic recording substrate, optical recording substrate, magneto-optical recording substrate, molded ceramic plate, etc. Examples include phase difference films, brightness enhancement sheets, field expansion sheets, electromagnetic wave shielding sheets, diffusion plates, diffusion sheets, lenticular lens sheets, reflection sheets and other optical sheets, lenses, prisms and other optical molded parts. Use spacer sheets to improve reliability and reduce post-processing washing It can be.

The contact surface of the spacer sheet and the plate-like structure in the present invention varies depending on the configuration of the spacer sheet, but can be roughly classified into two types: a simple sheet shape without an opening penetrating the front and back surfaces, and a net-like sheet shape.
In the former, the contact surface is defined by:
First, when the length in the short side direction of the spacer sheet is W, the reference length of the measurement curve is W, and an amplitude distribution curve defined by JIS B0601-1994 on one side surface of the spacer sheet is taken.
N = D / Ra, where n is the number of divisions and D is the distance between the highest peak of the measurement curve and the lowest valley. Ra is the arithmetic average roughness defined in JIS B0601-1994.

As shown in the lower part of FIG. 1 (a), in the case of the spacer sheet 10 having protrusions, the amplitude distribution curve on the one side surface of the spacer sheet is shown in FIG. 1 (a). Two peaks are taken at the top and bottom of the plate, the plate-like structure side of this peak is taken as the first peak 11, and the spacer sheet side is taken as the second peak 12.
At this time, a spacer sheet surface existing on the first peak 11 side is defined as a contact surface.

  On the other hand, as shown in FIG.1 (b), in the case of the net-like sheet | seat 15 formed by weaving a wire in length and breadth, a contact surface is defined by the following. The Ra of the spacer sheet structure part and the spacer sheet structure part thickness T are measured.

  The reference flat plate surface when set on the reference flat plate is 0, and the height of Ra from the spacer sheet surface inside the interleaf sheet, that is, the position of T-Ra is taken as the measurement line. A region formed by intersecting is defined as a contact surface. At this time, a non-intersecting portion exceeding 10 times the average interval between the local peaks defined in JIS B0601-1994 is not regarded as a contact surface.

In both, the spacer sheet area is the area of the entire sheet including the recesses or openings.
The pattern shape may be irregular or regular, but is preferably a regular periodic pattern from the viewpoint of manufacturing cost, and the shape viewed from the direction perpendicular to the spacer sheet surface is a parallelogram. The periodic pattern is preferably a basic pattern, and the parallelogram is more preferably a rhombus.
By doing in this way, the amount of static electricity generated at the time of peeling can be minimized while maintaining the mechanical strength.

  The resin used for the spacer sheet of the present invention is preferably a resin with a small amount of attached organic matter regardless of thermosetting or thermoplastic, and the molecular weight of the attached organic matter is preferably 10,000 or less, and 1000 or less. Is more preferable, and it is still more preferable that it is 100 or less. Furthermore, considering cost and productivity, thermoplasticity is preferable.

Specific examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyurethane, polyester, polycarbonate, polyamide, polycycloolefin, and the like.
Among the above thermoplastic resins, polyethylene, polyurethane, polyester, polycarbonate, and polyolefin are particularly preferable because they have a small amount of organic matter adhesion and excellent film performance.
Furthermore, among the above, polyolefin, polyethylene terephthalate which is polyester, and polycarbonate are preferable, and polyolefin and polycycloolefin are more preferable.

The plate-like structure of the present invention is basically a plate-like structure, but may be a structure having a protection target plane that requires a spacer sheet.
Examples of such plate-like structures include glass substrates for flat panel production such as liquid crystal displays, organic EL displays and plasma displays, silicon substrates for semiconductor production, device device stages such as semiconductors and flat panel displays, ceramics such as plates, and the like. Circuit boards such as metal boards and printed boards, CDs, DVDs, glass for recording media such as MO and hard disks, metals, plastic boards, prism sheets, lens sheets, retardation films, brightness enhancement sheets, field-of-view sheets, electromagnetic wave shields Examples thereof include optical sheets such as a sheet, a light guide plate, a diffusion plate, a diffusion sheet, a lenticular lens sheet, and a reflection sheet, and optical molded parts such as a lens and a prism.

  The spacer sheet of the present invention is tightly packed with a plate-like structure such as a substrate sandwiched, and the carrier sheet is transported and the spacer sheet is removed when the package is opened after transporting. This is referred to as peeling in this application. As for the direction of peeling, it is not practical to pull the spacer sheet completely perpendicular to the spacer sheet surface, that is, to lift the entire sheet up so that it can be lifted by pulling the spacer sheet in one direction from the edge. Is efficient. Since the direction is not parallel to the spacer sheet surface, it is preferable that the projection component onto the spacer sheet in the peeling direction is the long side direction of the spacer sheet. For example, when the operator peels off with one point, it is preferable to peel off from the corner of the sheet in the diagonal direction. When the worker peels off mechanically using a robot or the like, the corner 2 is peeled off. It is preferable to hold the point and peel it off in the direction of the side of the sheet. From the point of view of static electricity removal, if there is a long contact surface perpendicular to the peeling direction, a large amount of static electricity is generated instantaneously at the moment when the line is peeled off, so the peeling direction and the line direction are not parallel. Is preferred.

According to the spacer sheet of the present invention, since the amount of static electricity generated at the time of peeling can be greatly reduced, the surface is protected while stacking or packing the plate-like structure at a high density, and the volume of dust is reduced while reducing the packing volume. Since adhesion and the like can be reduced, transportation costs and the like can be reduced without reducing reliability.
Furthermore, it is arrange | positioned at the surface of a single plate-shaped structure, or between several plate-shaped structures, and the contact area which this plate-shaped structure and this spacer sheet contact can be made small compared with a spacer sheet area.

Furthermore, according to the spacer sheet of the present invention, since the pattern shape is formed on the surface, the contact cross-sectional area can be reduced while maintaining the mechanical strength.
Furthermore, in the spacer sheet arranged between a plurality of plate-like structures, the constituent material of the spacer sheet has little organic matter adhering to the plate-like structure, so that the plate-like structure is not contaminated with organic substances. It is possible to contribute to the improvement of the reliability of the structure and the reduction of the cleaning cost in the post-process. Furthermore, since the spacer sheet of the present invention is made of an organic material such as a resin, a surface pattern can be formed at a low cost.

  According to the spacer sheet of the present invention, a glass substrate, a semiconductor substrate, a resin substrate, a printed wiring board, a ceramic plate and a ceramic application product, a metal substrate, a liquid crystal display device, an organic EL display device, a plasma address display device, a semiconductor device, a conductive device. Optical plate, reflector, lens sheet, prism sheet, polarizing plate, circuit board, magnetic recording substrate, optical recording substrate, magneto-optical recording substrate, molded ceramic plate, retardation film, brightness enhancement sheet, field expansion sheet, electromagnetic wave shielding sheet, Optical sheets such as diffuser plates, diffuser sheets, lenticular lens sheets, and reflective sheets, optical molded parts such as lenses and prisms can be integrated at low cost, and contamination due to adhesion of organic substances and dust is unlikely to occur, so reliability It is possible to improve the quality and reduce the post-cleaning.

  In any case, according to the present invention, it is possible to suppress contamination by devising the shape by focusing on the contact area between the spacer sheet and the substrate in order to suppress static electricity that causes contamination and organic matter adhesion. A member using the spacer sheet and the spacer sheet of the present invention can be provided.

  In the process of studying the shape and material of various spacer sheets in order to suppress the static electricity that causes contamination and the adhesion of organic substances, the present inventors have a fluorine atom content in the surface layer portion of the spacer sheet rather than the inner layer portion of the spacer sheet. By forming a phase with a large amount of material, it has been found that static electricity generation and organic matter adhesion are reduced, and furthermore, it has been found that the contact area between the spacer sheet and the substrate should be reduced, and the optimum shape has been devised. As a result, the inventors have found that the surface of various structures to be protected is less likely to be contaminated, and have arrived at the present invention.

First, the present invention will be specifically described.
In the spacer sheet of the present invention, a phase of a material having a higher fluorine atom content than the inner layer portion of the spacer sheet is formed on the surface layer portion of the spacer sheet. The surface layer portion of the spacer sheet is a portion from the outermost surface of the sheet to a depth of about several nm to several μm. The inner layer portion and the surface layer portion are both made of the same material, have no laminated interface, and the surface layer portion has a higher fluorine atom content than the inner layer portion. The fluorine atom content can be confirmed by an analyzer such as X-ray electron spectroscopy (ESCA). The fluorine atom content may be distributed so as to gradually decrease from the surface layer portion toward the inner layer portion, or may be distributed stepwise from the surface layer portion toward the inner layer portion. Good.

  A method of forming a phase of a material having a fluorine atom content higher than that of the inner layer portion on the surface portion of the spacer sheet includes bringing the spacer sheet obtained by the following shape forming method into contact with an atmosphere containing fluorine gas.

  The spacer sheet is formed into various shapes by the following method. 2 to 4 are partial schematic sectional views showing examples of the spacer sheet shape of the present invention. As shown in FIGS. 2 to 4, minute convex portions and concave portions are formed on the surface. The height of the irregularities is usually 1 mm or less, preferably 0.5 mm or less, and more preferably 0.1 mm or less.

The heights of the convex portions and the concave portions need not be the same, but are preferably as uniform as possible. The contact area S1 and the spacer sheet area S2 only have to satisfy S1 <S2, but S2 is preferably 2 times or more, more preferably 5 times or more than S1, and further more preferably 10 times or more. preferable.
The contact surface is preferably at least partially periodic, but it may be continuous or non-continuous.
The contact surface is preferably dispersed as uniformly as possible throughout the spacer sheet, and the peripheral portion of the spacer sheet preferably forms a convex portion.

The method for forming the shape of the spacer sheet is not particularly defined, but usually, a transfer method using a transfer roll, a press method using a mold, a compressed air or a vacuum press method, or the like is used.
An etching method using a solvent or photolysis, or a bank forming method for forming a convex portion is also possible.
The bank of convex portions may be formed using a printing method using a printing technique such as inkjet.
The spacer sheet thus formed is fluorinated through the following steps. The method for obtaining the spacer sheet of the present invention will be described more specifically with reference to the drawings.
FIG. 4 shows an example of a reaction apparatus used for obtaining the present invention. This reaction apparatus includes a chamber 1 and a heating device 5 for controlling the temperature of the chamber, and a fluorine gas supply line 2 and an inert gas supply line 3 for introducing fluorine gas and inert gas into the chamber. Are connected. An exhaust line 4 for extracting unnecessary gas is connected to another position of the chamber. The chamber has a space where the spacer sheet can be placed, and the spacer sheet can be placed there. The gas extracted from the exhaust line 4 can be recycled as it is or can be separated and purified and returned to each gas supply line.

(1) A step of leaving the spacer sheet in an inert gas atmosphere or under reduced pressure.
This step (1) is not necessarily a step that must be performed, but through this step, a phase of a material having a high fluorine atom content can be present in the spacer sheet surface layer portion without in-plane distribution. Therefore, it is preferable to go through the step (1).
In step (1), first, a spacer sheet is placed in the chamber, the chamber is closed, and the valve of the inert gas supply line 3 is opened to allow the inert gas to flow into the chamber. Examples of the inert gas include argon, nitrogen, helium, neon, krypton, and xenon. In the present invention, argon is preferably used. The chamber used is preferably made of stainless steel or aluminum.
It is preferable to heat the spacer sheet in the chamber with a heating device in an inert gas atmosphere. By this heating, moisture, oxygen, and volatile components contained in the spacer sheet can be efficiently removed. The heating temperature is the surface temperature of the spacer sheet and is usually 60 to 180 ° C, preferably 80 to 130 ° C. The heating time is 1 to 360 minutes, preferably 2 to 200 minutes.

Instead of leaving in an inert gas atmosphere, the spacer sheet may be left under reduced pressure. When left under reduced pressure, the pressure is usually 500 mmHg or less, preferably 100 mmHg or less. The lower limit of the pressure is 1 mmHg. If the pressure is extremely reduced, contaminants such as oil and moisture may reversely diffuse from the exhaust system. Heating is also preferred when left under reduced pressure. The heating temperature is usually 15 to 100 ° C. In addition, it is preferable to inject a high-purity inert gas simultaneously with decompression because the amount of oxygen and water can be efficiently removed. The decompression time is 1 to 360 minutes, preferably 1 to 200 minutes.
If oxygen or moisture is present in the spacer sheet in the next step (2), the surface is easily hydrophilized, so it is preferable to reduce the amount of oxygen or moisture in step (1). A preferable amount of oxygen and water in the spacer sheet is usually 1% by weight or less, preferably 100 ppm by weight or less, more preferably 10 ppm by weight or less.

(2) A step of bringing the spacer sheet into contact with an atmosphere containing fluorine gas.
After step (1), the valve of the inert gas supply line is closed, the chamber is cooled if necessary, and then the valve of the fluorine gas supply line 2 and the valve of the inert gas supply line 3 are opened if necessary, Fluorine gas is allowed to flow into the chamber, and the chamber is brought into an atmosphere containing fluorine gas.
The atmosphere containing fluorine gas may be an atmosphere composed only of fluorine gas, but is preferably composed of fluorine gas diluted with an inert gas in order to moderate the reaction. The atmosphere containing fluorine gas is preferably free of oxygen and water. Specifically, the amount of oxygen and water is preferably 100 ppm by weight or less, more preferably 10 ppm by weight or less, and particularly preferably 1 ppm by weight or less.
By bringing the spacer sheet surface into contact with an atmosphere containing fluorine gas, fluorine gas gradually introduces fluorine atoms into the molecule from the surface of the spacer sheet to the surface layer part and further to the inner layer part, thereby constituting the spacer sheet. The fluorine atom content in the material will increase. The penetration depth of fluorine atoms from the spacer sheet surface and the content of fluorine atoms vary depending on the concentration, temperature, and time of the fluorine gas.

  The concentration of the fluorine gas diluted with an inert gas is usually 0.1 to 50% by volume, preferably 0.1 to 30% by volume, more preferably 0.1 to 20% by volume. The surface temperature of the spacer sheet when contacting the fluorine gas is not particularly limited, but is usually −50 to 150 ° C., preferably −20 to 80 ° C., and particularly preferably 0 to 50 ° C. The contact time is usually 0.1 second to 600 minutes, preferably 0.5 seconds to 300 minutes, more preferably 1 second to 60 minutes. When the fluorine gas concentration is high, the temperature is high, or the time is long, the penetration depth of fluorine atoms becomes deep and the fluorine atom content increases. As the fluorine atom content increases, the chargeability of the portion where the fluorine atoms are introduced (surface layer portion) decreases, so that the desired chargeability is controlled by appropriately selecting the fluorine gas concentration, temperature, and time. be able to. When the fluorine gas concentration is extremely high, or when the temperature is extremely high for a long time, the material constituting the spacer sheet is deteriorated. Therefore, it is preferable to contact the fluorine gas within the above range.

(3) A step of leaving the spacer sheet subjected to the fluorine gas contact treatment again in an inert gas atmosphere or under reduced pressure after contacting the fluorine gas.
After contacting a fluorine gas and a predetermined time has elapsed, the inert gas supply line 3 is opened, the valve of the fluorine gas supply line 2 is closed, and the chamber is brought to an inert gas atmosphere. Examples of the inert gas are the same as those described in the step (1). And it is preferable to heat a spacer sheet with a heating apparatus. Excessive fluorine gas that could not be introduced into the spacer sheet can be removed by this heating. The heating temperature is the surface temperature of the spacer sheet and is usually 60 to 180 ° C, preferably 80 to 130 ° C. The heating time is 1 to 120 minutes, preferably 2 to 90 minutes.

Instead of leaving in an inert gas atmosphere, a spacer sheet subjected to a fluorine gas contact treatment under reduced pressure may be left. When left under reduced pressure, the pressure is usually 500 mmHg or less, preferably 100 mmHg or less. The lower limit of the pressure is 1 mmHg. If the pressure is extremely reduced, contaminants such as oil and moisture may reversely diffuse from the exhaust system. Heating is also preferred when left under reduced pressure. The heating temperature is usually 15 to 100 ° C. In addition, it is preferable to inject a high-purity inert gas simultaneously with the decompression because the fluorine gas can be efficiently removed. The decompression time is 1 to 120 minutes, preferably 1 to 60 minutes.
This step (3) is not necessarily a step, but by passing through this step, the phase of the material having a high fluorine atom content can be present in the spacer sheet surface layer portion without in-plane distribution. Therefore, it is preferable to go through step (3).
After completion of the step (3), the spacer sheet can be taken out from the chamber and used according to each application.

When using a plate-like structure such as a glass substrate or a silicon substrate alone, the spacer sheet of the present invention is used by being sandwiched between a packing container or a packing bag and the structure.
When a plurality of structures are used, they are sandwiched between the structures.
Although the packaging container and the packaging bag are not particularly defined, a metal, ceramic, or plastic container or bag that has good sealing properties and is free from contamination from the container or the bag itself is preferable.
Further, it is more preferable that the container or bag is made of polycycloolefin or a purified resin.

  Examples are shown below.

The structure of the spacer sheet in Example 1 of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram showing the structure of the spacer sheet of Example 1, and is formed by forming table-like convex portions 21 and 22 on the sheet surface by embossing on both surfaces of the sheet.
In this example, polycycloolefin (Zeonor: manufactured by Nippon Zeon Co., Ltd.) was used as the sheet material.

The thickness of the spacer sheet can be appropriately selected according to the shape and size of the plate-like structure. In this example, from the viewpoint of workability, the sheet base material portion thickness is 75 μm, and the height of the convex portion 21 is 50 μm. did. The upper surfaces of the convex portions 21 and 22 were formed in a square shape with a side of 10 μm. At this time, the contact area where one of the convex portions 21 and 22 was in contact with the plate-like structure was measured by the above-described method and found to be 100 μm ² .

The spacer sheet formed as described above was placed in a chamber made of SUS316L and heated at 120 ° C. for 3 hours in a high purity argon stream having an oxygen and moisture content of 1 weight ppb or less to remove oxygen and water. The amount of oxygen and water was less than 10 ppm by weight. Cool to room temperature, switch the valve while taking care not to mix oxygen and moisture from the outside air, and 30% 1% by volume fluorine gas diluted with argon gas (content of oxygen and water is less than 1 ppm by weight) Introduced at ° C. After 15 minutes, the valve was switched to introduce high-purity argon having an oxygen and water content of 1 weight ppb or less, and the mixture was heated at 90 ° C. for 1 hour to remove excess fluorine gas.
It was confirmed by ESCA measurement that many fluorine atoms exist in the surface layer portion of the transfer surface. Furthermore, when this spacer sheet was immersed in ultrapure water for 24 hours and ESCA was measured, many fluorine atoms were present in the surface layer portion as before the immersion. Further, when the film surface was measured by the FTIR-ATR method, a broad peak was observed at 1400 to 1000 cm ⁻¹ derived from CF stretching vibration.

When a glass substrate having a thickness of 0.7 mm, a width of 1100 mm, and a length of 1300 mm was used as the plate-like structure, the contact area was 794 cm ² . At this time, since the sheet area was 14300 cm ² , the contact area ratio was 5.6%, which was about 1/20 of the amount of static electricity generated compared to the case of full contact.

  In order to evaluate the chargeability of the spacer sheet of Example 1, the spacer sheet obtained in this example and subjected to the fluorine gas contact treatment and the spacer sheet not treated with the fluorine gas were prepared, and a glass plate was prepared. The spacer sheet (10 × 15 cm, thickness 100 μm) was brought into close contact with (10 × 15 cm thickness 7 mm) and left in a clean room (23 ° C., humidity 50%) for one day and night. The spacer sheet was slowly peeled from the glass plate, and the amount of charge on the surface of the spacer sheet was measured with a charge measuring device. In the measurement, the device was moved up, down, left and right at a distance of 1 to 3 cm from the spacer sheet, and a value indicating the maximum of the measured value was obtained. The charge amount measurement by this peeling was performed twice at five locations. The average charge amount of the spacer sheet of Example 1 was 0.5 keV. On the other hand, the average charge amount of the spacer sheet that was not subjected to the fluorine gas contact treatment was 10.9 keV.

  According to the spacer sheet of Example 1, it is possible to reduce the amount of static electricity generated at the time of peeling while suppressing contamination of the substrate surface due to adsorption of organic substances. In addition, although FIG. 2 demonstrated the case where the convex parts 21 and 22 were provided in both surfaces of a sheet | seat, you may provide a convex part only in a sheet | seat one side. In this case, instead of making the upper surface of the convex part a flat surface, the front end of the convex part may be cut so that the convex part surrounds the concave part. That is, you may employ | adopt the structure which forms a closed curve by the convex part surrounding a recessed part. This configuration has an effect that the contact area can be reduced and the mechanical strength can be maintained.

The spacer sheet in Example 2 of the present invention will be described with reference to FIG.
FIG. 3 is a schematic diagram showing the structure of the spacer sheet in Example 2, and a rhombus-shaped pattern is formed on the surface by a roll transfer method.
The side portions of the rhombus form the convex portions 31, and the surface portion surrounded by the sides forms the concave portions 32. The height of the convex portion was 50 μm, and the thickness of the sheet portion serving as the substrate was 100 μm.
Of the rhombus diagonals, the longer long diagonal is 8 mm, and the shorter short diagonal is 4.6 mm. The component projected onto the surface of the spacer sheet in the direction in which the spacer sheet is peeled off (the direction of the black arrow) is on the right side in the figure, and is set in the long side direction of the spacer sheet.
By doing in this way, the area peeled off within a unit time when peeling off at a constant speed can be minimized while maintaining the structural strength of the spacer sheet.
That is, the generation of static electricity within a unit time can be minimized.

The spacer sheet formed as described above was placed in a chamber made of SUS316L and heated at 120 ° C. for 3 hours in a high purity argon stream having an oxygen and moisture content of 1 weight ppb or less to remove oxygen and water. The amount of oxygen and water was less than 10 ppm by weight. Cool to room temperature, switch the valve while taking care not to mix oxygen and moisture from the outside air, and 30% 1% by volume fluorine gas diluted with argon gas (content of oxygen and water is less than 1 ppm by weight) Introduced at ° C. After 60 minutes, the valve was switched to introduce high-purity argon having an oxygen and moisture content of 1 weight ppb or less, and the mixture was heated at 90 ° C. for 1 hour to remove excess fluorine gas. It was confirmed by ESCA measurement that many fluorine atoms exist in the surface layer portion of the transfer surface. Furthermore, when this spacer sheet was immersed in ultrapure water for 24 hours and ESCA was measured, many fluorine atoms were present in the surface layer portion as before the immersion. Further, when the film surface was measured by the FTIR-ATR method, a broad peak was observed at 1400 to 1000 cm ⁻¹ derived from CF stretching vibration.

When a glass substrate having a thickness of 0.7 mm, a width of 1100 mm, and a length of 1300 mm was used as the plate-like structure, the contact area was 715 cm ² . At this time, since the sheet area was 14300 cm ² , the contact area ratio was 5%, which was 1/20 of the amount of static electricity generated compared to the case of full contact. In addition, the average value of the charge amount of the spacer sheet of Example 2 was −2.5 kev.
That is, according to the spacer sheet of Example 2, it is possible to reduce the amount of static electricity generated at the time of peeling while suppressing contamination of the substrate surface due to adsorption of organic substances.

  In addition, it has a rhombus shape on the surface, and the long diagonal of the rhombus is parallel to the projection component direction to the spacer sheet in the peeling direction, so that a large area is peeled off locally while maintaining mechanical strength. Generation of static electricity can be suppressed.

  Organic EL display panel, plasma display panel, semiconductor substrate, ceramic substrate, metal substrate, circuit board, CD, DVD, MO, hard disk substrate, prism sheet, lens sheet, retardation film, brightness enhancement sheet, field of view expansion sheet , Electromagnetic wave shielding sheet, light guide plate, diffusion plate, diffusion sheet, lenticular lens sheet, reflection sheet, lens, prism, and as a result of testing, there was very little adhesion of dust to the surface and contamination by organic matter , Found that the reliability of the product is improved.

It is a figure explaining the definition of the contact surface which concerns on this invention using an amplitude distribution curve. It is a figure explaining the definition of the contact surface which concerns on this invention using an amplitude distribution curve. It is a schematic diagram which shows the surface of the spacer sheet which concerns on Example 1 of this invention. It is the schematic which shows the surface of the spacer sheet which concerns on Example 2 of this invention. It is the schematic which shows an example of the reaction apparatus used in order to obtain the spacer sheet | seat of this invention.

Explanation of symbols

1 .. Chamber 2. Fluorine gas supply line 3. Inert gas supply line 4. Exhaust line 5. Heating device 6. Spacer sheets 21, 22, 31.

Claims (11)

Have a phase of the material content of fluorine atoms is larger than said spacer sheet inner layer portion in the surface layer of the spacer sheet,
The spacer sheet is disposed on the surface of a single plate structure or between a plurality of plate structures,
The spacer sheet has a direction to be peeled off from the plate-like structure;
A pattern shape is formed on the spacer sheet surface, and the pattern shape viewed from a direction perpendicular to the spacer sheet surface is a periodic pattern having a rhombus as a basic pattern,
Each side of the rhombus formed on the surface of the spacer sheet has an angle smaller than 90 ° with respect to the peeling direction,
The side of the rhombus forms a convex portion, the surface portion surrounded by the side forms a concave portion, and the long side direction of the spacer sheet is parallel to the long diagonal direction of the rhombus Spacer sheet. When the contact area where the plate-like structure and the spacer sheet are in contact is S1, and the spacer sheet area is S2, the structure has an organic matter adhesion preventing structure to the plate-like structure satisfying the relationship of S1 <S2. The spacer sheet according to claim 1, wherein: 3. The spacer sheet according to claim 1, wherein a long diagonal of the basic pattern is substantially parallel to a spacer sheet peeling direction. Claim 3 sides of the basic pattern forms a convex portion, an area bounded by a side portion of the basic pattern is a recess, the protrusion is equal to or in contact with the plate-like structure the spacer sheet according to. Said spacer sheet is disposed between the plurality of plate-like structure, the spacer sheet according to claim 1, the material of the spacer sheet is characterized in that it comprises an organic substance adhesion prevention material into plate-like structure . The spacer sheet according to claim 5, wherein the constituent material includes at least an organic substance. The spacer sheet according to claim 5, wherein the constituent material is a resin. The spacer sheet according to claim 5, wherein an organic substance adhesion amount to the plate-like structure is 100 ng / cm ² or less.   6. The spacer sheet according to claim 5, wherein the molecular weight of the organic substance adhering to the plate-like structure is 10,000 or less. The plate-like structure is a glass substrate, a semiconductor substrate, a resin substrate, a printed wiring board, a ceramic substrate, a display device, a semiconductor device, a light guide plate, a reflection plate, a lens sheet, a prism sheet, a retardation plate, a polarizing plate, and a circuit board. , magnetic recording substrate, an optical recording substrate, a magneto-optical recording substrate, the spacer sheet according to any one of claims 1-9, characterized in that either a molded ceramic plate. The glass substrate is transported by sandwiching the spacer sheet according to any one of claims 1 to 10 between a plurality of glass substrates and transporting the glass substrate and the spacer sheet in close contact with each other. Method.