JP2003011284A - Laminated film or sheet and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film or sheet suitable for use application such as a rigid barrier film or sheet having a high surface hardness and an excellent gas barrier properties, a rigid low dielectric film or sheet having a high surface hardness and keeping a low permittivity as it is, a rigid antistatic film or sheet having a high surface hardness and an excellent antistatic performance, a UV and/or IR cut rigid film or sheet having a high surface hardness and an excellent UV and/or IR cut-off performance or the like, and its manufacturing method. SOLUTION: The laminated film or sheet and its manufacturing method includes a laminated structure consisting of a polymer material film or sheet having a thickness of 0.001 to 50 mm and a coating, which has a thickness of 1 to 1×10<5> nm, is made of a methylsilanes reaction product made from stock gas including 1 to 100 wt.% of tetramethylsilane gas, preferably of trimethylsilane gas, and laminated on one side or both the sides of the polymer material film or sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film or sheet and a method for producing the same, and more particularly, to use in the fields of information electronics, semiconductors, foods, medicals, industrial machinery or construction civil engineering. The present invention relates to a laminated film or sheet that can be manufactured, and a manufacturing method thereof.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in the fields of information and electronics, semiconductors, foods, medicals, industrial machinery, construction and civil engineering, etc., for the purpose of preventing oxygen and moisture from entering the inside of products, and A wide variety of gas barrier films are used for the purpose of preventing deterioration and deterioration of packaged foods and medical products.

For example, in the field of information and electronics, it is necessary to extend the life of solar cell panels, and solar cell panels have ethylene / vinyl alcohol copolymer resins (for the purpose of blocking transmission of ultraviolet rays and oxygen) on their surfaces. EVOH) films are used by being stuck together, and polyvinyl fluoride resin (PVF) films are used by being stuck together for the purpose of preventing moisture permeation. In the field of displays, a gas barrier film is attached to the surface of an indium tin oxide (ITO) transparent conductive film, which is widely used in touch panels and EL electrodes, for the purpose of preventing deterioration of internal elements. A hard coat is formed by post-treatment for the purpose of maintaining hardness. In this case, to satisfy transparency and gas barrier property,
Studies on SiN films and SiON films have been made. SiN
It has been experimentally confirmed that the (silicon nitride film) has a weak adhesion to a resin and has a problem in flexibility. Further, when hydrogen is added to the nitride film, ammonia may be generated during use, which is a problem.

On the other hand, also in the food field, various gas barrier films and gas control films are used for the purpose of preventing deterioration and deterioration of the food to be packaged, stabilizing the quality during long-term storage and improving convenience during food distribution. Widely used in vinyl chloride film (PVC), polyvinylidene chloride (PVDC) film, ethylene-vinyl alcohol copolymer (EVOH) film, biaxially oriented polyvinyl alcohol (PVA) film, polyacrylonitrile (PAN) film , Nylon resin film,
Silica vapor-deposited films, alumina vapor-deposited films, aluminum vapor-deposited films, aluminum thin films, and further multilayer films, coextrusion films, laminating films, coated films, coating films and the like have been put into practical use. In these gas barrier films for food packaging as well, there has been a strong demand for environmental consideration, which has become a hot topic in recent years, and the polyvinylidene chloride (PVDC) film, which has been widely and conventionally used, is now more environmentally friendly. In order to improve the gas barrier performance by switching to polyolefin (PO) films, silica vapor-deposited polyolefin films, and polyolefin resin multilayer films, which are less affected by R & D, new research and development of coating agents is being conducted. There is.

However, even with these gas barrier films, organic EL displays which are expected to be used as protective films for next-generation thin-film solar cells, which have been attracting attention in recent years, and which are expected as next-generation displays,
It is insufficient to prevent the deterioration of the internal elements of the paper display, and when applied to these information electronic devices,
The hardness of the gas barrier layer was also insufficient.
For that purpose, it is necessary to separately introduce a hard coat layer by laminating and to attach a protective film to the surface of the gas barrier film. Further, even if such a hard coat treatment is applied to the surface of the gas barrier film, a product such as a flexible solar cell or a flexible paper, which is freely deformable, is free from cracks or peeling in the hard coat layer or the gas barrier layer. It was a problem. Therefore, in order to improve the film hardness and the gas barrier performance, it is necessary to make the hard coat layer thick, but in order to prevent the occurrence of cracks and peeling, it is necessary to make the hard coat layer thin and strong. Therefore, such conflicting requirements often limit the product design.

[0006] Further, in response to the demand for lowering the dielectric constant of the film, the SiN film has a dielectric constant ε _r of 7, whereas Si
The C film has an ε _r of less than 5, and a film of a-SiOC: H having an ε _r of 2.9 is obtained, which can meet the demand. Under such circumstances, development of new high-performance gas barrier film is expected, and in particular, a hard gas barrier film or sheet having both surface hardness and gas barrier performance is required. In addition, in recent years, not only the physical and chemical performance of the product, but also the product that is compatible with the environment in which it is used is required. There has been a demand for a laminated film or sheet in consideration of environmental protection so as not to adversely affect the above.

In view of the situation in the industrial world, the inventors of the present invention have made earnest studies to develop a high-performance gas barrier film that can be applied to the next-generation information and electronic devices and the like that the industry particularly desires. The present invention has been completed. In advancing the development, the inventors of the present invention have developed the technology not only in the information electronic field but also in the semiconductor field, food field, medical field, industrial machine field, and construction civil field in which gas barrier films or sheets have already been used. For the same reason, development of a high-performance gas barrier film is expected, and it is also an object to obtain a film or sheet that can be applied as a common technique in these fields and can be widely used. As a result, the present invention was completed and the present invention was completed.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is preferably a transparent laminated film or sheet having a hard surface hardness and a high gas barrier property. Gas barrier film or sheet, hard film or sheet) and a method for producing the same. Further, the present invention provides a preferably transparent laminated film or sheet (hard low dielectric film or sheet) having a hard surface and a high gas barrier performance and maintaining a low dielectric constant, and a method for producing the same. The purpose is to do.

Further, the present invention is preferably a transparent laminated film or sheet (hard antistatic film or sheet) having a hard surface, high gas barrier performance and high antistatic performance, and a method for producing the same. Is intended to provide. Still another object of the present invention is to provide an ultraviolet and / or infrared cut hard film or sheet and a method for producing the same.

[0010]

SUMMARY OF THE INVENTION A laminated film or sheet according to the present invention comprises a polymer material film or sheet (A) having a thickness of 0.001 to 50 mm and the film or sheet (A).
1 to 100% by weight of a gas of methylsilane represented by the general formula Si (CH ₃ ) _n H _4-n (where n is an integer of 1 to ₄ ) on one or both sides of And a coating film (B) of a reaction product of methylsilanes having a thickness of 1 nm to 1 × 10 ⁵ nm.

That is, in this laminated film or sheet, one or more layers may be further formed on the surface of the coating (B) and / or the polymer material film or sheet (A). The film (B) of the reaction product of methylsilanes is formed on one side or both sides of the film or sheet (A) by further reaction of the reaction gas generated by the discharge decomposition of the raw material gas.

The hard gas barrier film or sheet, the hard film or sheet, and the hard low dielectric film or sheet according to the present invention are characterized by comprising the above-mentioned laminated film or sheet according to the present invention. The hard antistatic film or sheet according to the present invention comprises a laminated film or sheet according to the present invention, which has a coating (B) of a reaction product of methylsilanes formed by using a raw material gas containing a dopant gas such as diborane or phosphine. It is characterized by becoming.

The ultraviolet and / or infrared ray cutting hard film or sheet according to the present invention is characterized by comprising the above-mentioned laminated film or sheet according to the present invention. The method for producing a laminated film or sheet according to the present invention comprises the general formula Si (CH ₃ ) _n H _4-n (where n is 1 to
It is an integer of 4. ) The discharge gas decomposes a raw material gas containing 1 to 100% by weight of a methylsilane gas to further react the generated reaction gas to one or both sides of the polymer material film or sheet (A),
Thickness of reaction product of methylsilanes 1 nm to 1 × 1
It is characterized by forming a 0 ⁵ nm methylsilane such reaction product coating (B).

A laminated film or sheet according to the present invention,
In addition, in the method for producing the same, one or both surfaces of the polymer material film or sheet (A) may be surface-treated. The polymer film or sheet (A) is a thermoplastic material which is optically transparent or semi-transparent and contains 50 to 100% by weight of an organic polymer compound containing at least carbon atoms, oxygen atoms and hydrogen atoms. Is desirable.

Trimethylsilane is preferred as the methylsilanes. The raw material gas may be only trimethylsilane gas, may contain trimethylsilane gas in an amount of 1% by weight or more and less than 100% by weight, and further contains 99% by weight of silane gas other than methylsilane gas and / or diluent gas. A mixed gas containing not more than 0% and more than 0% by weight may be used.

The raw material gas may further contain a dopant gas. Conductivity can be imparted to the coating film (B) by including the dopant gas in the raw material gas. The average composition formula of the film (B) of the reaction product of methylsilanes is usually a-Si _x : C _y : H _z (where x is 0.999 or less and is a numerical value larger than 0, y Is a numerical value of 0.9 or less and greater than 0.001, z is a numerical value of 0 or more and 0.6 or less, and x + y + z
= 1. ).

[0017]

DETAILED DESCRIPTION OF THE INVENTION The laminated film or sheet according to the present invention and the method for producing the same will be specifically described below. In the laminated film or sheet according to the present invention, a film (B) of a reaction product of methylsilanes is formed on one or both sides of a polymer material film or sheet (A) by using a raw material gas containing methylsilanes. There is.

Polymer Material Film or Sheet (A) The polymer material film or sheet (A) used in the present invention has a thickness of 0.001 to 50 mm. The preferable range of the thickness varies depending on the use of the laminated film or sheet. For example, in the case of food packaging use, it is necessary to reduce the volume and reduce the amount of waste, so the thickness is 0.01 mm. ~ 0.3m
It is preferably about m and can be appropriately selected depending on the contents to be packed. In addition, organic E that needs to be lighter and smaller
In the case of information electronic equipment applications such as an L display and a paper display, the thickness is preferably about 0.05 to 2 mm because it is light, thin, short and small, but structural strength is required to some extent. In addition, it can be applied to industrial equipment, semiconductor devices, vacuum devices, transportation equipment, special containers or building materials. In these applications,
Since strength is generally required, it is not particularly limited, but a thin one needs a thickness of about 1 mm to a thick one of about 50 mm.

The surface of the polymer material film or sheet (A) is preferably a smooth flat surface for ordinary use, but if light confinement is required, 1 nm to 10 μm (=
1 × 10 ⁴ nm) tetrahedral structure, triangular prism, square prism, hexagonal prism, cylinder, elliptical cylinder, triangular pyramid, quadrangular pyramid, semi-conical pyramid,
A concavo-convex shape such as a random shape may be provided, and embossing of 1 nm to 10 μm may be performed in order to improve the adhesiveness with other materials.

The polymer material film or sheet used in the present invention is an organic polymer compound, and among them, it is optically transparent or semitransparent, preferably transparent, and composed of at least carbon atom, oxygen atom and hydrogen atom. A thermoplastic material containing 50 to 100% by weight of the organic polymer compound is desirable. Examples of the organic polymer compound forming the polymer material film or sheet (A) include low density polyethylene (LDPE) and linear low density polyethylene (LLDP).
E), high density polyethylene (HDPE), ultra high molecular weight polyethylene (HMWPE), polyethylene homopolymer, polyethylene copolymer, polypropylene-polyethylene block copolymer, polypropylene homopolymer, polypropylene copolymer, polymethylpentene,
Polyolefin resins such as cyclic olefin copolymers;
Polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PE
N) and other polyester resins; polyvinyl chloride (PV
C), polyvinylidene chloride (PVCD), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PFA) and other vinyl resins; polychlorinated polycarbonate (PC), polymethylmethacrylate (PMMA),
Transparent resins such as polystyrene (PS); polyacetal (POM), polyamide (PA), polyaramid, polyarylate (PAR), modified polyphenylene ether (modified PPE), polyphenylene sulfide (PP)
S), liquid crystal polymer (LCP), polysulfone (PS)
F), polyether sulfone (PES), polyetherimide (PEI), polyether nitrile (PE
N), polyetheretherketone (PEEK), engineering plastics resins such as polyimide (PI); microbial polyester, microbial polysaccharide, microbial cellulose, polylactic acid (PLA), polycaprolactone (PCL), aliphatic Polyester, polysaccharide derived from chitinous chitosan, N-acetylglucosamine polymer, polyvinyl alcohol (PVA), polyhydroxybutyrate, modified PVA, and organic natural polymer materials (for example, starch, wood flour, soybean or corn) Resins derived from the above) and resins such as biodegradable resins.

These resins may be used alone or in combination of two or more and used as a polymer material obtained by resin mixing or resin alloying. In the present invention, the organic polymer compound, if necessary, an additive such as a filler (composite material), a reinforcing material, an ultraviolet absorber, an infrared absorber, a flame retardant, and a stabilizer for the purpose of the present invention. It can be blended within a range that does not impair it.

Specific examples of the filler (composite material) include metal powders such as iron, copper, silver, gold, nickel, stainless steel, aluminum and lead; carbon powders such as carbon black, Ketjen black and graphite; Graphite, hollow carbon,
Carbon nanotubes, fullerenes, fired phenols, glass powder, glass flakes, glass beads, hollow glass, talc, mica, kaolin, wollastonite, montmorillonite; fumed silica, colloidal silica, alumina, ceria, iron oxide, oxidation Oxides of titanium, magnesia, etc .; hydroxides of aluminum hydroxide, magnesium hydroxide, antimony hydroxide, etc .; sulfides of molybdenum disulfide, tungsten disulfide, zinc sulfide, etc .; aluminum nitride, silicon nitride, boron nitride, etc. Nitride; Carbides such as silicon carbide and titanium carbide; Carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate; titanates such as potassium titanate, barium titanate and lead zirconate titanate;
Phosphates such as calcium phosphate and iron phosphate; barium ferrite, strontium ferrite, nickel ferrite,
Inorganic materials such as ferrite compounds such as samarium cobalt are included.

Further, as the reinforcing material, specifically,
Glass fiber, carbon fiber, aramid fiber, silicon carbide fiber,
Examples thereof include fiber materials such as alumina fiber, boron fiber, silicon carbide whiskers, silicon nitride whiskers, potassium titanate whiskers, zonotolite, gypsum, dawsonite, and zepiolite. As the above-mentioned ultraviolet absorber, infrared absorber, flame retardant and stabilizer, known additives which have been conventionally added to the above organic polymer compounds can be used.

The polymer material film or sheet (A) used in the present invention is, for example, mixed with one or more kinds of the above-mentioned organic polymer compounds and, if necessary, the above additives such as fillers and reinforcing agents. , Blended or composite (including nanocomposite) polymeric materials
Film forming or molding by die method, inflation method, casting method, casting method, injection molding method, injection compression molding method, transfer molding method, compression molding method, or other general film molding or sheet molding processing method. It can be obtained by

The polymeric material films or sheets obtained by these methods include unstretched films, unstretched sheets, uniaxially stretched films, uniaxially stretched sheets, biaxially stretched films, biaxially stretched sheets, inflation films, multilayer films, A coextrusion film, a cast film, a laminate film, a coating film, an extrusion molding sheet, an injection molding plate, a press molding plate, a laminating film, a coating film, a coating sheet and the like can be mentioned.

On the surface of the polymer material film or sheet obtained as described above, if necessary, an anchoring agent or an undercoating agent such as urethane resin, epoxy resin, polyvinyl alcohol resin, acrylic resin, urea resin is used. It can be treated, and can be treated with silica, alumina, titania, ceria, DLC coating (diamond-like carbon coating), K coating (polyvinylidene chloride coating), titanium, TiC, TiN, TiCN, W ₂ C,
Surface coatings such as fluorine, phosphorus and various polymer coatings can also be applied. In addition, aluminum (Al),
Tungsten (W), Chromium (Cr), Nickel (N
i), copper (Cu), silver (Ag), gold (Au), tin (S
n), tantalum (Ta), molybdenum (Mo), or other metal vapor-deposited thin film can be formed, but in consideration of environmental protection, it is preferable not to have a metal vapor-deposited thin film.

Further, the polymer material film or sheet (A) may be subjected to surface treatment, for example, conventionally known surface treatment such as corona discharge treatment, flame treatment and chromic acid treatment. By performing such a surface treatment, it is possible to improve the interfacial adhesion between the polymer material film or sheet (B) and the coating film (C) made of the reaction product of methylsilanes. It is preferably treated.

Film (B) of reaction product of methylsilanes The laminated film or sheet according to the present invention has a film (B) of reaction product of methylsilane formed on one side or both sides of the above-mentioned polymer material film or sheet. ing.
First, the raw material gas containing methylsilanes used for forming the coating film (B) will be described.

[Raw Material Gas] The raw material gas used in the present invention contains a methylsilane gas represented by the following general formula as a main raw material gas in an amount of 1 to 100 wt% of the total raw material gas. Si (CH ₃ ) _n H _4-n ( _{n in the} formula is an integer of 1 to 4.) Specific examples of the methylsilanes represented by the above formula include monomethylsilane, dimethylsilane, trimethylsilane and tetra. Methylsilane may be mentioned. Of these, trimethylsilane, which is a gas at room temperature and has many methyl groups, is preferable.

These methylsilanes are used alone,
Alternatively, two or more kinds can be used in combination. That is, for example, only trimethylsilane gas can be used as the source gas. Also, monomethylsilane,
When dimethylsilane or tetramethylsilane gas is used as a source gas, trimethylsilane is particularly preferably used together. When trimethylsilane gas is used, it has excellent gas barrier properties and high surface hardness.
Since an uncolored laminated film or sheet can be obtained, it is industrially useful.

The raw material gas used in the present invention contains trimethylsilane gas in an amount of 1% by weight or more and less than 100% by weight, and further contains silane gas other than methylsilane gas and / or diluent gas in an amount of 99% by weight or less and 0% by weight. It may be a mixed gas containing more than%. The silane gas other than the methylsilane gas is a silane gas represented by the following general formula.

Si _m H _{2m + 2} (m in the formula is an integer of 1 to 3) Specific examples of the silane represented by this formula include monosilane, disilane, and trisilane. Further, as the diluent gas, specifically, helium (He), neon (Ne), argon (Ar), krypton (Kr),
Inert gas such as xenon (Xe); hydrogen, oxygen, nitrogen,
Methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H
₈ ) Auxiliary gas such as; semiconductor gas used for adjusting surface hardness of chlorine (Cl ₂ ), germane, silicon tetrafluoride, etc., boron, diborane containing phosphorus (B ₂ H ₆ ), phosphine Dopant gases used for the purpose of imparting conductivity such as (PH ₃ ) may be mentioned.

The types of gas components other than these methylsilane gases and methylsilane gases other than trimethylsilane gas and their mixed gas composition are appropriately selected depending on the polymer material used as the raw material of the film or sheet and the intended use of the laminated film or sheet. However, gas components other than the methylsilane gas may or may not be used as the raw material gas.

In the present invention, by using a raw material gas containing at least the above-mentioned methylsilanes, preferably 1 to 100% by weight of trimethylsilane, a laminated film or sheet having excellent gas barrier properties and high surface hardness can be obtained. You can [Coating (B)] The coating (B) constituting the laminated film or sheet according to the present invention is a thin film of a reaction product of methylsilanes formed from the above raw material gas, and the thickness of the thin film is 1 nm to 1 ×. 10 is ⁵ nm, although it varies depending laminated film or sheet applications, in general, preferably 1nm~10 ³ nm, more preferably 5nm
It is desirable that the thickness is ˜500 nm. When the thickness of the thin film is within the above range, a laminated film or sheet having high surface hardness, excellent gas barrier property and excellent flexibility can be obtained.

The average compositional formula of the coating film (B) composed of this reaction product of methylsilanes is usually represented by the following formula. a-Si _x : C _y : H _{z In} this composition formula, x is a value of 0.999 or less and greater than 0, y is 0.9 or less and greater than 0.001 and z is It is a numerical value of 0 or more and 0.6 or less, and x + y + z = 1. Further, a-means that it is amorphous. Needless to say, microcrystals may sometimes be mixed depending on the production conditions.

Laminated Film or Sheet The laminated film or sheet according to the present invention comprises the above-mentioned polymer material film or sheet (A) and a coating film (B) of the reaction product of methylsilanes formed on one side or both sides thereof. It may be a laminated film or sheet having 3 or more layers or 4 or more layers, including a laminated structure of 2 layers or 3 layers. That is, another coating may be formed on the surface of the coating (B), or another coating may be formed on the surface of the polymer material film or sheet (A). These other coatings are appropriately determined depending on the application of the laminated film or sheet, the purpose of use, the required physical properties, and the like.

The laminated film or sheet according to the present invention has a very high surface hardness because the chemical bonds between Si atoms and between Si and C atoms in the coating (B) are extremely strong, and
Since the coating (B) layer is densely filled with hydrophobic methyl groups, the permeation of polarized molecules such as water molecules and molecules with high electronegativity is hindered and the gas barrier performance is enhanced. Further, the thickness of the coating film (B) formed on at least one surface of the polymer material film or sheet (A) is 1 nm to 1
Even if the laminated film or sheet according to the present invention has a thin film of × 10 ⁵ nm, even if the film is deformed, the stress is dispersed in the chemical bonding portion, and thus macroscopic cracking or peeling is unlikely to occur. Have an effect. That is, the laminated film or sheet according to the present invention can be suitably used as a hard barrier film or sheet having higher performance than conventional products.

Further, as will be described later, the laminated film or sheet according to the present invention is different from the conventionally known gas barrier films or sheets in that it generates a plasma at low temperature and low energy to form a thin film ( Since it enables the film formation of B), it is energy-saving in the process, and since this film (B) has high performance and high surface hardness, it is a polymer material film or sheet (A).
It is possible to reduce the thickness of itself, and as a result, it is possible to reduce the amount of industrial waste. Therefore,
The laminated film or sheet according to the present invention can be positioned as a laminated film or sheet having less adverse effect on the environment, which is another issue in industry.

Next, a method for manufacturing the above-mentioned laminated film or sheet according to the present invention will be described. Method for producing laminated film or sheet The laminated film or sheet according to the present invention is produced by subjecting a raw material gas containing 1 to 100% by weight of the above-mentioned gas of methylsilane to discharge decomposition to further react the generated reaction gas, A film (B) of a reaction product of methylsilane having a thickness of 1 nm to 1 × 10 ⁵ nm and composed of a reaction product of methylsilane is formed on one surface or both surfaces of the polymer material film or sheet (A).

As a method of causing the above-mentioned discharge decomposition,
Conventionally known plasma CVD (PCVD) method, plasma polymerization method, plasma sputtering method, DC discharge method and the like can be mentioned, and the plasma CVD method is preferable. Plasma CVD (P
CVD) is, for example, Proceedings of the 48th Joint Lecture on Applied Physics, Lecture No. 30a-ZT-6 (200
1.3. The atmospheric pressure plasma CVD method described on page 953 of Meiji University) can be used.

As described above, in the method for producing a laminated film or sheet according to the present invention, as compared with the conventional method for producing a laminated film or sheet, plasma is generated at low temperature and low energy to produce the composition formula a- Si _x : C _y : H _z
The film (B) represented by can be formed, and the manufacturing process is simple. In addition, the laminated film or sheet obtained by the above-mentioned production method should be obtained as a laminated film or sheet having excellent gas barrier properties, high surface hardness, and other excellent performance such as low dielectric property and antistatic property. You can

Uses of Laminated Film or Sheet The uses of the laminated film or sheet according to the present invention are as follows: 1) hard gas barrier film or sheet, 2) hard low dielectric film or sheet, 3) hard antistatic film or sheet, 4) Ultraviolet (UV) and / or infrared (IR) cut hard films or sheets may be mentioned.

The hard gas barrier film or sheet according to the present invention is specifically a packaging material, a substrate cover sheet for information electronic devices, an IC protective sheet, a touch panel sheet, an LCD sheet, a gas barrier film for organic EL, an electronic device. It can be used for applications such as a protective film for paper. The hard low-dielectric film or sheet according to the present invention is specifically a substrate for semiconductor circuit production,
It can be used as a flexible circuit substrate, a high-frequency circuit substrate, a protective film for semiconductor manufacturing equipment, and the like.

Such a hard low-dielectric film and sheet can be produced by the above-mentioned "method for producing a laminated film or sheet".
Specifically, trimethylsilane is used as a methylsilane gas, and low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and ultra high molecular material films and sheets are used. High molecular weight polyethylene (HMWP
E), polyethylene homopolymer, polyethylene copolymer, polypropylene-polyethylene block copolymer, polypropylene homopolymer, polypropylene copolymer, polymethylpentene, polyolefin resin such as cyclic olefin copolymer (COC), polyimide resin and the like. In this case, the heat resistance performance can be selected over a wide range by selecting the type of polymer material as the raw material of the film or sheet (A).

The hard antistatic film and sheet according to the present invention can be specifically used for a semiconductor film of a semiconductor circuit, a touch panel sheet and an LCD substrate sheet. Such a hard antistatic film or sheet is produced according to the above-mentioned "method for producing laminated film and sheet", and specifically, a thin film is doped with a dopant gas such as boron and phosphorus in an amount of 0.1 to 10000 ppm.
Conductivity can be imparted by mixing such an extremely small amount. In this case, a p-type semiconductor film can be obtained when the dopant is boron, and an n-type semiconductor film can be obtained when the dopant is phosphorus.
It is also possible to form a pn junction. Further, in this case, use as an optical sensor is also conceivable.

The ultraviolet (UV) cut hard film or sheet according to the present invention can be specifically used for LCD protective sheet, solar cell protective sheet, solar cell deterioration suppressing film and the like. The infrared (IR) cut hard film or sheet according to the present invention can be specifically used for applications such as IR cut emitted from an organic EL light emitting device.

The ultraviolet (UV) and infrared (IR) cut hard film or sheet according to the present invention can be specifically used for applications such as LCD, organic EL, and thin film device. Such an ultraviolet (UV) cut hard film and sheet are produced according to the above-mentioned “method for producing laminated film and sheet”. Specifically, a gas containing trimethylsilane as methylsilanes is used, and The thin film produced is expected to have properties as a UV cut film. Moreover, by using a diluent gas suitable for the purpose, a thin film having an arbitrary optical gap can be obtained. Regarding the optical band gap of the thin film (measured by the TAUC'S plotting method), a comparatively transparent thin film with Eopt = 2 to 3 eV can be easily obtained. Also,
On the contrary, even with a relatively thin film thickness of 1 to 100 nm, the transmittance can be T <10% for UV light having a wavelength λ <400 nm. In this case, the weather resistance of the polymer material film and sheet is improved. Moreover, by adding an infrared absorber, an infrared (IR) cut hard film and sheet, and an ultraviolet (UV) and / or infrared (IR) cut hard film and sheet can be produced.

Further, as another application of the laminated film or sheet according to the present invention, the durability and the light transmittance are better than those of ordinary hard coat polycarbonate sheet or plastic sheet such as polymethylmethacrylate resin sheet. Therefore, it can be considered to be used for window film, lighting plate, exterior, transparent sound insulation plate, transparent partition, etc. in the field of construction.

The laminated film or sheet used for such an application is produced according to the above-mentioned "method for producing laminated film and sheet", and specifically, a gas containing trimethylsilane as methylsilane is used,
As the polymer material film or sheet, a transparent polymer material film or sheet such as polyethylene terephthalate (PET), cyclic polyolefin copolymer (COC), polycarbonate (PC) is used. Laminated films and sheets used in the above other applications,
Because of its good optical characteristics and weather resistance, it can be used as an optical film or sheet having good surface hardness. Further, phthalocyanine, copper phthalocyanine, naphthalocyanine metal complex dye, nitroso organic pigment, dithiol / nickel complex dye, indoaniline metal complex dye, intermolecular CT dye, indigo carmine lake, brilliant green lake, malachite green lake,
By adding a pigment such as phthalocyanine green, a dye, an infrared absorbing agent, etc., it can be used as an infrared absorbing film or sheet as a building material used outdoors.

[0050]

According to the present invention, a hard barrier film or sheet having a high surface hardness and an excellent gas barrier property,
Hard low-dielectric film or sheet with high surface hardness and low dielectric constant, hard antistatic film or sheet with high surface hardness and excellent antistatic performance, and high surface hardness for blocking UV and / or infrared rays It is possible to provide a laminated film or sheet suitable for applications such as an excellent ultraviolet (UV) and / or infrared (IR) cut hard film or sheet, and a method for producing the same.

The laminated film or sheet according to the present invention is used in the fields of information electronics, semiconductors, foods, medical fields,
It is suitable for applications in the industrial machinery field, construction civil engineering field, and the like.

[0052]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0053]

Reference Example 1 A glass substrate having a size of 5 × 5 cm and a film thickness of 0.5 mm [product number: 7059 (manufactured by Corning Incorporated)] was applied with a plasma polymerization device at an applied power of 5 W and a film forming temperature of 80.
At a temperature of ℃ and a film forming speed of 1 nm / sec, the gas was supplied so that the concentration of the supplied gas was almost 50% by weight of trimethylsilane gas, 5% by weight of monosilane gas and 45% by weight of hydrogen gas, and the thin film was formed. On one surface of the glass substrate,
An a-SiC: H thin film having a thickness of about 200 nm was obtained. When this optical band gap was measured by the TAUC'S plotting method, the refractive index n was 2.2 and the optical band gap Eopt was 2.8 eV. Dark conductivity σ
_d was as low as less than 10 ¹² S / cm and was below the measurement limit. In addition, the photoconductivity σ _p is the pseudo sunlight (AM−
15), under a light amount of 100 mW / cm ² , 2 × 10 ⁹ S
Was / cm.

[0054]

Reference Example 2 In addition to the raw material gas used in Reference Example 1, 1 ppm of diborane (B ₂ H ₆ ) gas was added in a total raw material gas ratio to have a thickness of about 200 nm on one surface of the glass substrate. A p-type a-SiC: H thin film was obtained. When this optical gap was measured, the refractive index n was 2.2 and the optical band gap Eopt was 2.8 eV. The dark conductivity σ _d increased to 3 × 10 ¹¹ S / cm. Also, the photoconductivity σ
_p is pseudo sunlight (AM-1.5), 100 mW / cm
It was 1 × 10 ⁹ S / cm under the light amount of ² .

[0055]

[Example 1] Cyclic olefin copolymer resin [Mitsui Chemicals, Inc., trade name: Apel, brand APL6011T]
By a known extrusion molding machine (extrusion molding machine manufactured by Thermoplastics: φ30 mm, molding temperature 230
~ 250 ℃, take-up roll temperature 80 ℃), width 20c
A sheet having a thickness of m and a thickness of 1 mm was obtained. Visual observation of this sheet revealed that there were no scratches on the surface of the sheet, no internal foaming was observed, and a transparent, defect-free sheet was obtained.
When the tensile strength (ASTM D638) was measured,
It was 900 kg / cm ² .

A plasma polymerization apparatus (plasma applied power: 500 W, film formation temperature: 80 ° C., film formation rate: 1 nm /
In a sheet feeding speed of 50 m / H), the gas is supplied so that the concentration of the supply gas is substantially maintained at 50 wt% of trimethylsilane gas, 5 wt% of monosilane gas and 45 wt% of hydrogen gas, and the thin film is formed. The surface of one side of the polymer material sheet was laminated and coated to obtain a hard gas barrier sheet having a thickness of 20 ± 5 nm. According to JIS Z0208, the moisture permeability (g / m ² · 24 hr) of this sheet is obtained under the conditions of a temperature of 40 ° C and a humidity of 90%, and divided by 1 / thickness (mm) to obtain a moisture permeability coefficient ( The value of g · mm / m ² · 24 hr) was 0.05. The surface hardness of this sheet was higher than that of the sheet of Comparative Example 1 described later.
When this sheet was folded by hand, cracks such as cracks did not occur on the surface, and it remained a colorless and transparent sheet.

[0057]

[Comparative Example 1] Cyclic olefin copolymer resin [Mitsui Chemicals, Inc., trade name: Apel, brand APL6011T]
By a known extrusion molding machine (extrusion molding machine manufactured by Thermoplastics: φ30 mm, molding temperature 230
~ 250 ℃, take-up roll temperature 80 ℃), width 20 cm,
A sheet having a thickness of 1 mm was obtained. Visual observation of this sheet revealed that there were no scratches on the surface of the sheet, no internal foaming was observed, and a transparent, defect-free sheet was obtained.

Tensile strength of this sheet (ASTM D6
38) was measured and found to be 900 kg / cm ² . Also, in accordance with JIS Z0208, a temperature of 40 ° C,
The moisture permeability (g / m ²
* 24 hr) was obtained and divided by 1 / thickness (mm) to obtain a moisture permeability coefficient (g · mm / m ² · 24 hr), which was 0.09.

[0059]

Example 2 Ultra-high molecular weight polyethylene [Intrinsic viscosity [η] measured in 135 ° C. decalin solvent: 16.5 dl /
g, MFR (ASTM D 1238, 190 ° C, load 2.16 kg): 0.
Less than 01 g / 10 minutes, melting point: 136 ° C., bulk density: 0.4
Powder resin of 5 g / cm ³ , manufactured by Mitsui Chemicals, Inc., trade name:
Hi-Zex Million 240M], inflation molding machine (screw outer diameter 30 mmφ, screw length (L / D) 34, flight pitch 20 mm constant, screw compression ratio 1.8, adapter length 200 mm, tube die length 550 mm, tube die Length (L / D) 2
5, die outlet outer die inner diameter 22mmφ, die outlet mandrel outer diameter 18mmφ, S1 / S2 = 1.4, S2 / S3
= 1.57 (S1: cross-sectional area of resin flow path at tube die inlet, S2: cross-sectional area of resin flow path at intermediate junction of tube die, S3: cross-sectional area of resin flow path at tube die exit), inside screw And 6mmφ gas flow passage extending inside the tube die mandrel, cooling ring inner diameter 66mm
φ, stabilizer, pinch roll and product winder), extruder, adapter (AD), die base (D1)
And the set temperature of the die end (D2) are 280 ° C. and 2
70 ° C., 180 ° C. and 150 ° C., the screw rotation speed is set to 15 rpm, and the film is pulled inside by a pinch roll at a speed of 1.2 m / min while extending inside the screw and inside the mandrel of the tube die. 6 mmφ
Compressed air was blown in from the gas flow passage to expand the tube to a size so as to come into contact with the cooling ring inner diameter 66 mmφ (expansion ratio = 3) to obtain an ultra high molecular polyethylene inflation film having a folding width of 104 mm and a thickness of 200 μm.

The oil and fat remaining on the surface of this film was washed with an isopropyl alcohol (IPA) / water-based cleaning material and the film was dried (60 ° C.), and this film was subjected to an atmospheric pressure plasma polymerization apparatus (plasma applied power: 500 W, film forming process). Temperature 80 ℃, film forming speed 1nm / sec, sheet feeding speed 50
m / H), the supply gas concentration is trimethylsilane gas concentration 50% by weight, monosilane gas concentration 5% by weight,
Gas was supplied so that the hydrogen gas concentration was maintained at 45% by weight, and the thin film was laminated and coated on one surface of the polymer material film to obtain a hard low dielectric film having a thickness of 20 ± 5 nm. The dielectric constant (ASTM D150) of this film was measured and found to be 2.3 in the region of 10 ⁶ Hz.

[0061]

[Comparative Example 2] Ultra high molecular weight polyethylene [135 ° C decal
Intrinsic viscosity [η] measured in a solvent: 16.5 dl / g,
MFR (ASTM D 1238, 190 ℃, load 2.16kg): 0.01
g / 10 minutes or less, melting point: 136 ° C., bulk density: 0.45 g
/cm³Powder resin, brand name: Hi-Zex Million 24
0M, manufactured by Mitsui Chemicals, Inc.]]
Machine (screw outer diameter 30 mmφ, screw length (L /
D) 34, flight pitch 20 mm constant, screw compression
Ratio 1.8, adapter length 200mm, tube die length
550 mm, tube die length (L / D) 25, die out
Outer outer die inner diameter 22mmφ, die exit mandrel outer diameter
18mmφ, S1 / S2 = 1.4, S2 / S3 = 1.5
7. Inside the screw and inside the tube die mandrel
6mmφ gas flow passage extending to the inside, cooling ring inner diameter 6
6mmφ, stabilizer, pinch roll and product winder
Equipment), extruder, adapter (AD), die base
(D1) and die end (D2) are set to 28
Set to 0 ℃, 270 ℃, 180 ℃ and 150 ℃, and
Set the rotation speed to 15 rpm and pinch roll to 1.
While pulling the film at a speed of 2 m / min, screw
Do not extend inside and inside the tube die mandrel.
Blow compressed air from the 6 mmφ gas flow passage
Inflate the blade to a size that contacts the cooling ring inner diameter 66 mmφ.
Set (expansion ratio = 3) Folding width 104 mm, thickness 200 μm
Ultra high molecular polyethylene blown film
Obtained. Oils and fats remaining on the surface of this film are treated with IPA / water system.
Wash with cleaning material and dry (60 ° C) for comparison
A film made of ultra high molecular weight polyethylene resin was obtained. this
Measure the dielectric constant of a film (ASTM D150)
And 10 ⁶It was 2.3 in the Hz region.

In Example 1, as compared with the cyclic olefin copolymer resin alone sheet of Comparative Example 1, a hard gas barrier sheet having improved gas barrier properties and high surface hardness was obtained. Further, in Example 2, a hard low-dielectric film having the same dielectric constant as the ultra-high molecular weight polyethylene resin simple substance film of Comparative Example 2 and having high surface hardness was obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Makoto Tsuzuka             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F term (reference) 4F100 AK01A AK03 AK52B AK52C                       AL01 AL05B AL05C BA02                       BA03 BA10B BA10C EJ082                       EJ552 EJ611 EJ641 GB08                       GB16 GB23 GB41 GB66 JB16A                       JD02 JD09 JD10 JG03 JG05                       JK12 JN01A JN02A YY00A                       YY00B YY00C

Claims (20)

[Claims] 1. A polymer material film or sheet (A) having a thickness of 0.001 to 50 mm and one or both surfaces of the film or sheet (A) having the general formula Si (CH ₃ ) _n H _4-n ( In the formula, n is an integer of 1 to 4).
1 nm thickness formed from a source gas containing 0% by weight
A laminated film or sheet comprising a laminated structure comprising a coating film (B) of a reaction product of 1 × 10 ⁵ nm of methylsilanes. 2. The laminated film or sheet according to claim 1, wherein one or both surfaces of the polymer material film or sheet (A) is surface-treated. 3. A polymer material film or sheet (A) which is optically transparent or translucent and contains 50 to 100% by weight of an organic polymer compound containing at least carbon atoms, oxygen atoms and hydrogen atoms. The laminated film or sheet according to claim 1 or 2, which is a plastic material. 4. The film or sheet (A), wherein the coating film (B) of the reaction product of methylsilanes is further reacted with the reaction gas generated by the discharge decomposition of the raw material gas.
The laminated film or sheet according to any one of claims 1 to 3, wherein the laminated film or sheet is formed on one side or both sides. 5. The laminated film or sheet according to claim 1, wherein the methylsilanes are trimethylsilane. 6. The laminated film or sheet according to claim 1, wherein the raw material gas is only trimethylsilane gas. 7. The raw material gas contains trimethylsilane gas in an amount of 1% by weight or more and less than 100% by weight, and further contains silane gas other than methylsilane gas and / or diluent gas in an amount of 99% by weight or less and 0% by weight. The laminated film or sheet according to claim 1, which is a mixed gas containing an excess amount. 8. The laminated film or sheet according to claim 1, wherein the source gas further contains a dopant gas. 9. The average composition formula of the film (B) of the reaction product of the methylsilanes is a-Si _x : C _y : H _z (where x is 0.999 or less and is a numerical value larger than 0). , Y is a numerical value of 0.9 or less and greater than 0.001, z is a numerical value of 0 or more and 0.6 or less, and x + y + z
= 1. ).
8. The laminated film or sheet according to any one of 8 to 8. 10. A hard gas barrier film or sheet comprising the laminated film or sheet according to any one of claims 1 to 9. 11. A hard film or sheet comprising the laminated film or sheet according to any one of claims 1 to 9. 12. A hard low dielectric film or sheet comprising the laminated film or sheet according to any one of claims 1 to 9. 13. A hard antistatic film or sheet comprising the laminated film or sheet according to claim 8. 14. An ultraviolet and / or infrared ray cut hard film or sheet comprising the laminated film or sheet according to any one of claims 1 to 9. 15. The general formula Si (CH ₃ ) _n H _4-n (wherein n
Is an integer of 1 to 4. ), A raw material gas containing 1 to 100 wt% of a methylsilane gas is discharged and decomposed to further react the generated reaction gas,
A film of a reaction product of methylsilanes having a thickness of 1 nm to 1 × 10 ⁵ nm formed from a reaction product of methylsilanes on one or both sides of the polymer material film or sheet (A) according to claim 1. A method for producing a laminated film or sheet, which comprises forming B). 16. The manufacturing method according to claim 15, wherein the methylsilanes are trimethylsilane. 17. The method according to claim 15, wherein the source gas is trimethylsilane gas only. 18. The raw material gas contains trimethylsilane gas in an amount of 1% by weight or more and less than 100% by weight, and further contains silane gas other than methylsilane gas and / or diluent gas in an amount of 99% by weight or less and 0% by weight. 16. The manufacturing method according to claim 15, wherein the mixed gas is an excess amount of the mixed gas. 19. The method according to claim 15, wherein the source gas further contains a dopant gas. 20. The average composition formula of the coating film (B) of the reaction product of methylsilanes is a-Si _x : C _y : H _z (where x is 0.999 or less and is a numerical value larger than 0). , Y is a numerical value of 0.9 or less and greater than 0.001, z is a numerical value of 0 or more and 0.6 or less, and x + y + z
= 1. ).
The manufacturing method according to any one of 5 to 19.