JP2011012285A - Method for depositing water-repellent mold release thin film and water-repellent mold release laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent mold release laminated film which has a deposited film of an organosilicon compound with water repellency and usable for various applications, and to provide a method for producing the water-repellent mold release laminated film.SOLUTION: In the method for producing a water-repellent mold release laminated film obtained by depositing a carbon-containing organosilicon compound film on a plastic base material by a plasma-enhanced chemical vapor deposition process (PE-CVD process), an organosilicon compound containing an Si-O bond in the molecule is used as a vapor deposition raw material, and plasma-enhanced chemical vapor deposition is performed in a gas atmosphere containing no oxygen atoms upon the vapor deposition of the organosilicon compound gas (in a non-oxygen-state atmosphere) in a state where the plastic base material is cooled and held to Tg or below, and the vapor deposited film of a carbon-containing silicon compound with water repellency is deposited on the plastic base material.

Description

  The present invention relates to a water-repellent release film forming method and a water-repellent release laminated film, in which a carbon-containing silicon compound film is formed on a plastic substrate by a plasma chemical vapor deposition method (PE-CVD method). Uses an organic silicon compound as a raw material for vapor deposition, and plasma chemical vapor deposition is performed in a gas atmosphere that does not contain oxygen atoms at the time of vapor deposition and the plastic substrate is cooled to Tg or less, and a thin film of carbon-containing organic silicon compound is plasticized. The present invention relates to a method for forming a water-repellent release carbon-containing organosilicon compound thin film and a water-repellent release laminated film characterized by forming a film on a substrate.

  So-called release laminate film or sheet using a material that has releasability on paper or film, or a material whose base material itself has releasability, can be vacuum formed from adhesive tape, separator film of photosensitive agent, etc. It is also widely used in the manufacturing process as process paper for release films, electronic component carriers, ceramic sheets, carbon fiber prepregs, etc. used in in-mold molding such as in the production of multilayer printed circuit boards.

  And as a performance calculated | required from the specific utilization surface of a mold release laminated | multilayer film or a sheet | seat, for example in the process of FPC, a flat cable, etc., in the separate film used in the case of heat press processing, heat resistance and moderate Release properties, cushioning properties, and non-transferability to the base material are required. As cost merit, repeated resistance, low cost, and easy disposal are also important.

  For these required performances, it is mainly used as a release laminate film or sheet, and when it is given release properties by a silicone material having a main skeleton with siloxane bonds, it has excellent release properties and low surface energy. Fluorine-based materials that can be coated, but have problems in that, for example, heavy peeling (deterioration of surface properties) is promoted by prolonged exposure to the atmosphere, and transfer of silicone may occur. When used, it has excellent physical properties and performance in heat resistance, chemical resistance, flexibility, repeated durability, antifouling properties, weather resistance, etc., but it is expensive and generates toxic gases during disposal, combined processing There are problems in terms of difficulty, etc. Also, when using sheets and films made of polyolefin resin, there are advantages such as heat resistance, low cost, and flexibility, and a balance between releasability and cost. It is taken, but high haze and is known to be inferior in terms of industrial utility in terms of poor heat resistance.

  Particularly in recent years, cleanness, heat resistance, dimensional stability, etc. of mold release process materials have become indispensable in the manufacturing process of multifunctional and miniaturized electronic devices. Furthermore, from the viewpoint of environmental friendliness, reduction of the environmental load by processing the release material after use has been counted as one of important functions.

As such a release material, specifically, there is a silicone laminate (Patent Document 1) in which silicone is laminated as a release layer on polyethylene terephthalate, which has excellent release properties, but is exposed to the atmosphere for a long time. Further, the heavy release was promoted and the surface characteristics were changed, and the silicone of the release layer was transferred at the time of peeling.
There are those that form a fluorine compound as a release layer on a substrate, or those that use a fluororesin itself as a release layer (Patent Documents 2 and 3). In addition to the high material price of the fluorine compound itself, incineration Problems such as the generation of harmful fluorinated gas sometimes, and it is difficult to laminate with an external base material, making it difficult to produce a composite material.
In addition, there is a material that exhibits releasability using polyolefin (Patent Documents 4 and 5), and the olefin-based material is low in price and excellent in workability, but is inferior in heat resistance. It cannot be used for molding. In this way, there were various problems.

As a lamination method, a method using a vapor deposition method as a dry coating method has been proposed as a method other than wet coating.
In the case of the vapor deposition method, since an extremely thin film can be obtained, there is an advantage that mold release properties can be added while maintaining the physical properties of the combined base materials such as the surface shape, Young's modulus, and thickness. In addition, because of the thin film, even if a fluorine material is used for the release layer, the amount of fluoride generated during incineration is extremely small.
For example, there is one that imparts releasability by a method of surface treatment by adding fluorine gas into atmospheric pressure plasma by atmospheric pressure glow discharge plasma (Patent Document 6). Therefore, when using expensive gas such as helium or fluorine compound gas, it is industrially disadvantageous. Further, when the area is increased, it is difficult to maintain discharge control and uniformity.

Also, a method (Patent Document 7) in which a carbon compound is once laminated on a substrate and then reacted by contacting with a fluorine plasma gas is proposed (Patent Document 7). I have to say. Further, in the case of using a plastic material, when the temperature exceeds Tg, the base material may be deformed or impurities may be eluted, resulting in a defect in the deposited film.
Some have proposed a method (Patent Document 8) of laminating a fluorine-containing diamond-like carbon thin film using a cyclic fluorinated aromatic compound on a substrate. In addition to releasability, there is an advantage that a thin film having excellent hardness can be obtained. However, since the main film forming material is an expensive fluorinated aromatic compound, it is industrially disadvantageous when the area is increased. In addition, when vapor deposition is performed on a plastic material having a relatively low melting point at a high temperature, a defect may occur in the deposited film due to deformation of the base material or bleeding of a low molecular weight substance.

The release layer formed on the substrate is composed of a continuous vapor deposition film layer of silicon oxide, and the continuous vapor deposition film layer of silicon oxide includes one kind of carbon, hydrogen, silicon, and oxygen, or A process for producing a release laminate film or sheet (Patent Document 9) containing at least one compound composed of two or more compounds and having a carbon atom content of 5 atom% or more is proposed. This production method requires an oxygen gas or the like for the vapor deposition monomer gas such as an organosilicon compound, and the monomer gas and the oxygen gas chemically react to form a silicon oxide compound, and the reaction product is one of the base materials. The oxide thin film is densely bonded to the surface and dense and has a high flexibility.
However, the reaction between oxygen gas and the organosilicon compound reacts with the CH ₃ group and / or C ₂ H ₅ group in the organosilicon compound, and the methyl group or ethyl group disappears, or intermediate reaction products (for example, , CH ₃ OH, HCHO, etc.), the material itself or oxygen is exhausted, etc., and it did not follow the chemical formula, and did not form a film with the desired performance.

A mixed gas containing a monomer material containing Si atoms and CH ₃ groups and / or C ₂ H ₅ groups and oxygen gas is vacuumed at a ratio of 10 parts by weight to 1000 parts by weight of oxygen gas with respect to 100 parts by weight of the monomer material. Proposed a method of forming a thin film of SiO ₂ film on a substrate, which is introduced into a vapor deposition tank and having a CH ₃ group and / or C ₂ H ₅ group remaining by CVD, and a display member such as a computer display. There is known a method for forming a vapor-deposited film that can be used as an antifouling coating on a conspicuous surface (Patent Document 10).

Japanese Patent No. 2846155 JP 2007-119640 A JP-A-8-186141 Japanese Patent No. 2619034 JP 2006-257399 A Japanese Patent No. 2957068 Japanese Patent Publication No. 2-29749 JP 2007-213715 A JP 2002-210860 A JP 11-256339 A

  In the method for producing a water-repellent release laminated film in which a carbon-containing silicon compound film is formed on a plastic substrate by a plasma chemical vapor deposition method (sometimes referred to as a PE-CVD method or a CVD method or a plasma CVD method) The organosilicon compound gas containing the Si—O bond in the molecule is used as a deposition raw material, and the organosilicon compound gas is grown by chemical vapor deposition in a state where the plastic substrate is cooled and held below Tg in a gas atmosphere not containing oxygen. Further, the present invention relates to a water repellent release thin film forming method and a water repellent release laminated film, characterized in that a water-repellent carbon-containing organosilicon compound film is formed on a plastic substrate.

  When forming a release layer by conventional coating, it is difficult to prepare a release layer having controlled water repellency while maintaining the release properties of the release laminate film or sheet. Even if it is a vapor deposition method, the SiOx film produced by CVD method does not have high water repellency, and it has not yet been possible to form a thin film stably and reliably at a low cost as a homogeneous and uniform water repellent release layer.

  The present invention has been made in view of the above-described state of the art, and stably and surely reduces the cost under the control of a water-repellent release film capable of simultaneously expressing uniform and uniform water repellency and release properties. The present invention provides a water-repellent release film forming method and a water-repellent release laminated film that can be easily provided with the above-mentioned methods and also eliminate the problems of the prior art.

The present invention is based on the knowledge that water repellency decreases when oxygen is added, and the cause is that the organosilicon compound material loses as CO ₂ due to the presence of oxygen in the Si-C bond C in the molecule. In order to form a deposited film by the CVD method using an organic silicon compound as a deposition material, it is necessary to use oxygen in addition to the monomer material. As a result of diligent research based on the knowledge that it is necessary to introduce a gas, surprisingly, an organic silicon compound is plasma-phase-grown by plasma CVD in a gas atmosphere in which oxygen gas and oxygen atoms are not present. The present invention has been achieved based on the knowledge that a vapor-deposited film exhibiting aqueous and releasability can be formed.

  As a result of earnestly examining a method for forming a vapor-deposited film of a carbon-containing organosilicon compound by PE-CVD, the present inventors have included carbon on a plastic substrate by plasma chemical vapor deposition (PE-CVD). In a method for forming a water-repellent release thin film for forming a vapor-deposited film of an organic silicon compound, an organic silicon compound containing a Si-O bond in the molecule is used as a vapor deposition raw material, and oxygen is used as a gas other than the monomer during vapor deposition of the organic silicon compound gas In an atmosphere containing no atoms, more specifically, without using a mixed gas or a rare gas of a rare gas and the vapor deposition monomer material, a raw material for the vapor deposition monomer alone, or an inert gas and a vapor deposition monomer material excluding the rare gas. A vapor deposition film of a carbon-containing organosilicon compound is obtained by plasma chemical vapor deposition of a raw material of a mixed gas with a plastic substrate cooled to Tg or less. The film was formed on a plastic substrate, and it was found that a vapor-deposited film having high water repellency at a high speed and having a water contact angle of 90 ° or more and excellent in releasability was obtained, and the present invention was completed. It came to do.

In the present invention, deposition is performed by a plasma CVD method in a pressurized state, usually in the absence of oxygen of 3 Pa, so that side reactions do not occur and the Si—C bond in the deposited organosilicon compound is reliably high. The concentration can be maintained, and the concentration of Si—C bonds can be controlled, so that the surface state can be reliably controlled. In addition, since a vapor deposition film of a high carbon-containing organosilicon compound containing an organic component that causes water repellency at a high concentration is formed by chemically bonding to a plastic substrate, water repellency resulting from Si-C bonding and Water-repellent release laminate film that has both water repellency and releasability with controlled release of the release layer by the vapor-deposited film of water-repellent carbon-containing organosilicon compound in which the vapor-deposited film and plastic substrate are firmly bonded It can be manufactured with good yield.
Furthermore, PE-CVD can form a film that adheres firmly to a plastic substrate, particularly a low heat resistance material or a low surface energy material that is difficult to deposit by general physical vapor deposition. It is possible to select and form a transparent water-repellent film. Thereby, various base materials can be selected in accordance with required mechanical properties and costs, and there is an advantage that it can be used as a manufacturing method with extremely high design freedom.

In the conventional method, the carbon content can be controlled by the organosilicon compound / oxygen ratio, but the chemical reaction between oxygen and the organosilicon compound does not simply proceed, and many side reactions occur and are stable under control. In the present invention, an organic silicon compound deposition film having a desired performance could not be formed, and the present invention uses only an inert gas not containing oxygen atoms and a gas composition of an organic silicon compound as a deposition material. The reaction system is simple, and it has become possible to form a continuously deposited film of an organosilicon compound under conditions where no side reaction occurs.
Furthermore, in the method of the present invention, as a reaction condition of the CVD method, the reaction raw material is only an organosilicon compound, and the gas atmosphere is an inert gas containing no oxygen atoms such as a rare gas or an inert gas other than a rare gas and a rare gas. For example, since it is only a gas composition that only adds nitrogen, it is a simple system that controls only the CVD deposition conditions, and the desired surface conditions (water repellency, releasability, contact angle, peel strength, etc.) The deposited film can be reliably formed simply by controlling the controllable deposition conditions. Further, the thickness, application width, etc. of the deposited film can be changed as desired by controlling the conveyance speed of the substrate.

Advantages of the present invention as a method for forming an organosilicon compound film using an organosilicon compound as a deposition monomer material by PE-CVD in the absence of oxygen (in the absence of oxygen) and as a deposited film of the obtained organosilicon compound As long as the property is a base film that can be deposited, such as PET and polyolefin, any material can be used, and any method can be used, and a water-repellent release film or sheet can be reliably controlled and manufactured. The design freedom is extremely high, and the desired physical properties and performance can be manufactured at low cost.
In addition, according to the method of the present invention, for example, if a substrate having a surface irregularity is used, a water-repellent release laminated film or sheet having an uneven surface on the same surface as that of the substrate can be produced. Can produce.
When a silicon vapor deposition film is formed from an organosilicon compound in an oxygen-free atmosphere by PE-CVD, a film having a large carbon content in the organosilicon compound can be formed, and an ethyl group (—CH ₂ —CH ₃ ), When the methyl group (—CH ₃ ) remains at the end and the Si—OH group decreases, an extremely low surface free energy is taken, and a hydrophobic film can be obtained.

In the method of depositing an organosilicon compound vapor-deposited film from the organosilicon compound of the present invention, the amount used for the deposition of the organosilicon compound is extremely different because of the dry process, unlike the release coat product in which the silicone release agent is applied. Less, because it forms a chemical bond with the substrate film, it has excellent adhesion, and when used as a release laminate film or sheet, the transferability of the organosilicon compound that is the release layer due to peeling of the deposited organic silicon compound film is extremely low Almost never seen.
The organic silicon compound vapor-deposited film according to the method of the present invention is an organic silicon compound vapor-deposited film containing an organic component, and can be said to be an organic-inorganic thin film (hybrid). A film having a stable state can be formed and can be wound up, and can be produced at a large area and at a low cost. Furthermore, there is an advantage that there is no toxicity of the organic silicon compound vapor deposition film itself of the present invention, it is recyclable, and no harmful gas is generated even if it is discarded by combustion.

Schematic sectional view showing a water-repellent release film according to the present invention Schematic cross section of plasma enhanced chemical vapor deposition system

In the present invention, a continuous vapor deposition film of an organic silicon compound contains an organic component, and the continuous vapor deposition film of an organic silicon compound formed by controlling the content of the organic component, that is, the carbon content has releasability. And a water-repellent release thin film forming method and a water-repellent release laminated film which can be formed in a state in which the water repellency is controlled.
According to the method for forming a water-repellent release film of the present invention, the thickness of the continuously deposited film of the water-repellent carbon-containing organosilicon compound is accurately controlled at any film thickness level from the nanometer level to the micrometer level. Thus, it is possible to form a stable continuous vapor deposition film that can maintain releasability, has little transferability, and can control water repellency.

The present invention uses a CVD method as a technique for forming a continuous vapor deposition film of a carbon-containing organosilicon compound formed by vapor deposition of an organosilicon compound, thereby reducing the amount of material involved in the supplied reaction system and controlling it. Thus, it is possible to provide a method capable of forming a release layer in which high water repellency is arbitrarily controlled while maintaining the release property on the surface of the release layer in a state that is easy to do.
In addition, in the release laminate film or sheet of the present invention, in addition to the releasability and water repellency required for the release layer, in consideration of resource saving, energy saving or disposal treatment, the base film and the release layer Since a chemical bond is formed between them and excellent adhesion is exhibited, a continuous vapor deposition film of an organosilicon compound is formed by a CVD method. The peeling force with the release layer is small, the base film and the release layer are excellent in adhesiveness, are difficult to peel off, and the release property of the release layer can be maintained for a long time.

The above-described present invention will be described in more detail below with reference to the drawings.
An example of the layer structure of a water-repellent release laminated film having a water-repellent carbon-containing organosilicon compound vapor deposition film and a method for forming a water-repellent thin film according to the present invention will be described with reference to the drawings. It is a schematic sectional drawing which shows an example of the layer structure about the water-repellent release laminated film which has a vapor deposition film | membrane of the water-repellent carbon containing organosilicon compound concerning.

As a water-repellent release laminated film having a continuous vapor deposition film of a carbon-containing organosilicon compound according to the present invention, as shown in FIG. 1, a substrate 1 and an organosilicon compound provided on one surface of the substrate 1 The continuous film deposition film (2a).
In the plasma chemical vapor deposition method for forming the water-repellent release layer as the vapor deposition film 2a, for example, a plasma chemical vapor deposition apparatus as shown in FIG. A water-repellent release thin film can be continuously formed by sequentially feeding into a phase-growing atmosphere and applying a take-up plasma chemical vapor deposition method.

The method for forming a water-repellent release film according to the present invention can produce a water-repellent release film or sheet that can be used in a wide range of applications.
The base film or sheet used in the present invention is selected from plastic materials suitable for the physical properties and performance required for the base film or sheet according to the application, and the surface roughness, the thickness of the base material, and the uneven surface shape. It is determined by setting and selecting the substrate properties according to the application.

  In the water repellent release thin film forming method according to the present invention and the water repellent release laminated film produced by the thin film forming method, materials, methods and the like used will be described.

  In the present invention, a plastic substrate, paper and treated paper thereof are generally used as the substrate for the water-repellent release film or sheet. Specific examples of materials that can be used as a plastic substrate include polyolefin resins such as polyethylene resins, polypropylene resins, and cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile. -Butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, (poly (meth) acrylic resin), (polycarbonate resin), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Examples include various resin films or sheets such as polyester resins, polyamide resins, polyaryl phthalate resins, polyurethane resins, and cellulose resins. Among them, in terms of heat resistance, mechanical properties, dimensional stability, adhesion, price, etc., in the present invention, in particular, a polypropylene resin, a polyester resin, or a polyamide resin film or sheet or paper or Functionally treated paper is preferred. Moreover, as a base material, the laminated film or sheet | seat of 2 or more layers using said 2 or more types of resin may be sufficient.

The method for producing the film or sheet of the present invention is not particularly limited, and a conventionally known method for producing a film or sheet such as an extrusion method, a cast molding method, a T-die method, or an inflation method is appropriately employed. Can be manufactured. In addition, a method of forming a multilayer film using two or more kinds of resins, and a method of using two or more kinds of resins to mix and form a film before forming a film, etc. Also good.
Further, for example, a uniaxial or biaxial stretching process may be performed using a tenter method or a tubular method.

  In the substrate of the present invention, the thickness of the film or sheet is not particularly limited, but is preferably 10 to 100 μm, more preferably about 20 to 50 μm. When the ratio of the thickness of the base material to the thickness of the release layer becomes thin, when forming the release layer, the dimensional stability of the base material decreases, the temperature during production such as CVD treatment or coating, airflow, support It is easily affected by manufacturing conditions such as the situation, and there is a risk of hindering the maintenance of the flatness and smoothness of the base film or sheet. When the thickness exceeds 100 μm, the material is wasted and the cost of resources and the environment is increased.

In the present invention, when forming a base film or sheet, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy In order to improve and improve antifungal properties, electrical properties, strength, etc., various plastic compounding agents and additives can be added. It can be selected and added within a range that does not affect the formation.
As a general additive in the present invention, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a filler are used to maintain a function necessary as a base material for a release laminate film or sheet. Further, colorants such as antistatic agents, lubricants, antiblocking agents, dyes and pigments can be used.

  In the present invention, the surface of the base film or sheet is subjected to a desired surface treatment in advance as necessary in order to improve the close adhesion with the continuous deposition film of the organosilicon compound constituting the release layer. Can do. Examples of the surface treatment include pretreatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, and the like. it can.

  As a method for improving the tight adhesion between the base film or sheet and the organic silicon compound continuous vapor deposition film layer constituting the release layer, the organic silicon compound continuous vapor deposition film formed by the plasma CVD method and the base material are used. For example, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, an adhesive layer, a vapor deposition anchor coating agent layer, or the like can be formed. Examples of the pretreatment coating material include polyester resins, polyamide resins, polyurethane resins, polyvinyl acetate resins, polyolefin resins such as polyethylene and polypropylene, and copolymers or modified resins thereof. Can be used.

The thin film forming method of the present invention uses a gas composition containing a vapor deposition raw material monomer gas of an organosilicon compound having an oxygen atom in the molecule, and is subjected to plasma chemical vapor deposition under the conditions of a predetermined CVD method. A continuous vapor deposition film of a compound is formed by chemical vapor deposition on one surface of a plastic substrate fed at a predetermined conveying speed.
In the method of the present invention, an organic component having a carbon atom derived from the organosilicon compound is contained in the continuous vapor deposition film of the organosilicon compound formed by simply changing the supply amount of the gas composition, and Si— A release layer having uniform water repellency formed by adjusting the C bond content can be formed, and the water-repellent release laminated film or sheet according to the present invention can be produced easily and reliably.

  Table 1 below shows the results obtained for the contact angle for water and diiodomethane of the deposited carbon-containing organosilicon compound obtained in relation to the mixing ratio of vapor deposition monomer and oxygen gas. . Since diiodomethane has a small change in contact angle and is not suitable for measurement, water contact angle was measured in the present invention. As the amount of oxygen increased, the contact angle with water decreased, and in an oxygen-free state, a value of 90 ° or more, which is generally recognized as water repellency, was obtained.

In the present invention, what is important is that the release layer of the continuously deposited film of the organosilicon compound includes a compound having a C—H bond or a Si—C bond, an organosilicon compound that is a monomer of the deposition material, and derivatives thereof. It is to form a vapor-deposited film by chemical bonding or the like while leaving an organic component, and in particular, to form by a CVD method so as to leave a CH ₃ group and / or a C ₂ H ₅ group. Although the water contact angle, that is, the surface free energy changes depending on the density contained in the organic component, a continuous vapor deposition film of a carbon-containing organosilicon compound exhibiting uniform water repellency and releasability can be formed. .
As the compound contained in the organic silicon compound continuous vapor deposition film layer, a compound containing a large amount of a hydrocarbon having a CH ₃ site as a basic structure is particularly preferable as the water-repellent release layer.
In the method of the present invention, the carbon-containing organic component resulting from the organosilicon compound is surely contained in the continuous deposited film of the organosilicon compound to be formed, by simply changing the supply amount of the gas composition, and A release layer having a uniform and sufficient water repellency that allows the content of Si-C bonds to take a predetermined value can be formed, and an excellent water-repellent release film or sheet according to the present invention is produced. can do.

  In the present invention, the water repellent mold release is derived from a methyl group or an ethyl group bonded to Si, and therefore, an organic silicon compound containing a Si—C bond needs to be used as a material. The degree of water repellency is determined by how much Si-C bonds can be left or formed in the deposited film. Therefore, in the case of physical vapor deposition as a vapor deposition method, silicon monoxide is evaporated and oxygen is supplied to form a silicon oxide film. Therefore, even if carbon dioxide, methane gas, or the like is added, a Si-C bond is formed. Since this is not possible, a water-repellent vapor-deposited film cannot be formed. Therefore, it is necessary to form a film by the CVD method as in the present invention and introduce a methyl group or an ethyl group into the film.

  Accordingly, the organosilicon compound used for forming the organosilicon compound thin film containing the organic component that forms the release layer of the present invention includes a methyl group or an ethyl group, and Si is the main chain. Monomer materials such as 1,1,3,3-tetramethyldisiloxane (TMDSO), hexamethyldisiloxane (HMDSO), vinyltrimethylsilane, methyltrimethylsilane (MTMOS), hexamethyldisilane, methylsilane, dimethyl Silane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxysilane, octamethyl Siku It can be used tetrasiloxane like. Moreover, these 1 type or 2 types or more may be included.

Regardless of the above example, the monomer material for forming a vapor-deposited film of an organic silicon compound having water repellency is an organic silicon compound containing Si atoms and CH ₃ groups and / or C ₂ H ₅ groups, which is suitable at room temperature. Any material having a vapor pressure and capable of performing the CVD method may be used.
In the present invention, as the organosilicon compound, in particular, 1,1,3,3-tetramethyldisiloxane (TMDSO), tetraethoxysilane (TEOS) or hexamethyldisiloxane (HMDSO) is used as a raw material. It is particularly preferable from the viewpoint of its handleability and water repellency of the formed organic silicon compound vapor deposition film.

To form a deposited film of an organic silicon compound which water repellency is imparted by a CVD method, Si atoms and CH ₃ groups and / or C ₂ CH ₃ group in the organic silicon compound containing H ₅ group and / or C ₂ As described above, it is necessary that the H ₅ group generates COx, H ₂ O and the like and does not lose them.
Therefore, it is necessary for the gas composition to stop supplying oxygen gas as in the ordinary vapor deposition method as another gas component of the above-mentioned monomer material and to be in an oxygen-free state. In addition, it is necessary to stop the use of an oxidizing gas, such as ozone gas or laughing gas (N ₂ O), which is usually used in vapor deposition. The water repellency can be controlled by the abundance of CH ₃ groups and / or C ₂ H ₅ groups, and the oxygen supply source can be controlled only by the intramolecular oxygen atom content in the organosilicon compound as a gas component.

In addition to the monomer gas, the gas (carrier gas) for efficiently introducing the monomer vapor into the vacuum chamber, plasma generation, and the purpose gas for enhancing the plasma may be introduced as needed. Used.
As the carrier gas, an inert gas such as a rare gas such as argon gas or helium gas, a nitrogen gas, or a mixed gas thereof can be contained.

As the plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, or microwave plasma can be used.
Furthermore, as a method of applying plasma chemical vapor deposition to a plastic substrate, generally, a plastic substrate passes through the plasma generator while winding a roll-shaped plastic substrate in the plasma generator. By performing plasma chemical vapor deposition on a plastic substrate, forming a continuous vapor deposition film of an organosilicon compound, and forming a water repellent release thin film and a water repellent release laminated film or sheet it can.

  As a substrate constituting the water-repellent release laminate film or sheet according to the present invention, it becomes a basic material constituting the release laminate film or sheet, and further, an organic component constituting the release layer on the substrate film. Since a continuous vapor deposition film layer of the organic silicon compound contained is provided, it has excellent properties in mechanical, physical and chemical properties, in particular, has strength, toughness, and heat resistance. Resin films or sheets can be used. Specifically, a plastic material as described above can be used.

In the present invention, a continuous vapor deposition film of an organosilicon compound formed using a vapor deposition monomer gas such as an organosilicon compound causes a chemical reaction between the vapor deposition monomer gas such as an organosilicon compound and a base material plastic in a plasma state. The product is closely bonded to one surface of the base material to form a dense continuous vapor deposition film rich in flexibility and the like. Usually, it is a continuous vapor deposition film mainly composed of a silicon oxide represented by the general formula SiO _x (where X represents a number from 0 to 2), and the organic silicon compound continuous vapor deposition film is transparent. In view of the above, it is mainly composed of a silicon oxide represented by the general formula SiO _x (where X represents the number of 1 to 2), and contains an organic component from the viewpoint of water repellency and releasability. is there.

A continuous vapor deposition film of an organosilicon compound is composed of a continuous vapor deposition film containing the silicon oxide as a main component and containing at least one organic component by chemical bonding or the like. Examples of the organic component include C—H. A compound having a bond, a compound having a Si—C bond, or an organic silicon compound as a raw material vapor deposition monomer gas or a derivative thereof is formed by chemical bonding or the like.
Specific examples include hydrocarbons having a CH ₃ 2 site. In addition to the above, it is possible to change the type, amount, etc. of the organic component contained in the continuous vapor deposition film layer of the organosilicon compound by changing the conditions of the vapor deposition process.

The content of the organic component contained in the continuously deposited film of the organosilicon compound is generally considered to be water-repellent if the water contact angle is 90 ° or more in the industry, and is 90 ° or more. The content of the organic component is controlled so that the deposited film has a water contact angle. By setting the content of the organic component exhibiting water repellency, a laminated film having water repellency and releasability and excellent adhesion to a plastic substrate can be obtained.
It can be considered that the content of the organic component varies depending on the organosilicon compound of the vapor deposition monomer as a raw material, and the water repellency and releasability can be easily controlled. It can be expected that the carbon-containing density and the planar spread density distribution in the vapor-deposited film of the carbon-containing organosilicon compound are predicted from the molecular structure of the organosilicon compound and controlled. Generally, it is desirable that the content of the organic component is about 0.1 to 80%, preferably about 5 to 60%. If the content is less than 0.1%, the releasability of the continuously deposited film layer of the organosilicon compound is lowered, or its impact resistance, spreadability, flexibility, etc. are insufficient, and due to bending, etc. Scratches, cracks and the like are likely to occur, and it is difficult to maintain the stability, and if it exceeds 80%, the releasability and the adhesion of the deposited film are deteriorated, which is not preferable.

The conditions for introducing the methyl group and / or ethyl group by the CVD method are not only the use of the aforementioned materials, but also a monomer material composed of an organosilicon compound containing Si atoms and CH ₃ groups and / or C ₂ H ₅ groups. The composition ratio with the rare gas is 30 to 100 parts by weight of the rare gas with respect to 100 parts by weight of the monomer material. If the rare gas is less than 10 parts by weight, the SiO ₂ film cannot be formed, and if the oxygen gas under low oxygen conditions exceeds 10 parts by weight, the SiO ₂ film contains methyl or ethyl groups. This is not preferable because water repellency is lost.
In order for the deposited film to exhibit water repellency, the thickness of the water-repellent coating film is required to be at least 10 mm. When the thickness of the water repellent coating film is less than 10 mm, it does not exist as a continuous vapor deposition film.

  In the present invention, in the continuous vapor deposition film of the organic silicon compound, it is preferable that the content of the organic component is decreased from the surface of the continuous vapor deposition film of the organic silicon compound in the depth direction. On the surface of the deposited film, the organic component can improve the releasability and impact resistance. On the other hand, at the interface with the resin film, the content of the organic component is small, and the chemical bond by -SiO- is based. Since it is formed between the material films, it has an advantage that the adhesion between the base film and the silicon oxide continuous vapor deposition film becomes strong.

  In the present invention, the organic component content ratio C / Si in the continuously deposited film layer of the organosilicon compound constituting the release layer is, for example, an X-ray photoelectron spectrometer (XPS), secondary ion mass spectrometry, or the like. It can be obtained by conducting an elemental analysis of a continuously deposited film layer of an organosilicon compound using a method of analysis using a surface analyzer such as an apparatus (Secondary Ion Mass Spectroscopy, SIMS). The properties (physical properties) of the release layer can be confirmed.

The C / Si ratio varies depending on the organic component content contained in the organic silicon compound continuous vapor deposition film constituting the release layer, and the carbon atom content in the organic silicon compound continuous vapor deposition film Since the C / Si ratio is reduced when the amount is reduced, this means that the presence of methyl groups (CH ₃ ), which are water-repellent groups, is reduced, resulting in a decrease in releasability. It is not preferable. Further, when the carbon atom content is increased, the C / Si ratio is increased, which is not preferable because of the phenomenon that the hardness and strength of the film are lowered and the film is peeled off.

  In the present invention, the film thickness of the organic silicon compound continuous vapor-deposited film is such that the vapor-deposited film is a carbon-containing organic silicon compound and has a composite property of organic and inorganic, and has a rigidity as high as that of the inorganic oxide film. There is no particular problem as long as the film thickness is in the range of 2 nm to 400 nm because the film is flexible. Specifically, the film thickness is preferably 5 to 200 nm, and if the film thickness is more than 200 nm, and more than 400 nm, it is not preferable because cracks and the like are likely to occur in the film due to increased rigidity. When the thickness is 5 nm or less, the planar density of the deposited film is reduced and the base film is exposed on the surface, the peelability is lowered, the release layer itself adheres to the release material, and the release layer is The possibility of peeling increases. Further, if it is less than 2 nm, it is not preferable because it becomes difficult to exert the effect of releasability as a release layer.

  The film thickness of the deposited film can be measured using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. In order to change the film thickness of the above-mentioned organic silicon compound continuous vapor deposition film layer, the volume velocity of the layer of the continuous vapor deposition film is increased as a condition during vapor deposition, that is, the vapor deposition monomer gas of the organic silicon compound is increased. It is possible to increase the film thickness by slowing down the conveying speed of the substrate and the substrate, and it is possible to reduce the film thickness by decreasing the deposition speed.

  A method for forming a continuously deposited film layer of an organosilicon compound by the low temperature plasma chemical vapor deposition method of the present invention will be described using an example of a plasma chemical vapor deposition apparatus.

FIG. 2 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus used when forming a continuous vapor deposition film layer of the organosilicon compound by a plasma chemical vapor deposition method.
In the present invention, the base material 1 is unwound from an unwinding roll 13 disposed in the vacuum chamber 12 of the plasma chemical vapor deposition apparatus 11, and the base material 1 is cooled and electroded at a predetermined speed via an auxiliary roll 14. The drum 15 is conveyed on the circumferential surface. Oxygen gas, inert gas, monomer gas for vapor deposition of organosilicon compounds, etc. are supplied from the gas supply devices 16, 17 and the raw material volatilization supply device 18 etc., and a vacuum is passed through the raw material supply nozzle 19 while preparing a mixed gas composition for vapor deposition. The vapor deposition mixed gas composition is introduced into the chamber 12, and plasma generated by the glow discharge plasma 20 is irradiated on the substrate 1 conveyed on the peripheral surface of the cooling / electrode drum 15 to form an organic material. A continuous vapor deposition film layer of a silicon compound is formed. The cooling / electrode drum 15 applies predetermined power from a power source 21 disposed outside the vacuum chamber 12. Further, a magnet 22 is disposed in the vicinity of the cooling / electrode drum 15 to promote the generation of plasma.
And the base material 1 which formed the layer of the continuous vapor deposition film | membrane of the organosilicon compound is wound up by the winding roll 24 through the auxiliary roll 23 with predetermined winding speed, and the continuous vapor deposition of the organosilicon compound concerning this invention is carried out. The film layer is used as a base material formed by plasma chemical vapor deposition. In the figure, 25 represents a vacuum pump.
The above illustration shows an example of the plasma chemical vapor deposition method, and it goes without saying that the present invention is not limited thereto.
Although not illustrated, in the present invention, the continuous vapor deposition film layer of the organic silicon compound is not limited to one layer of the continuous vapor deposition film layer of the organic silicon compound, but may be a multilayer film in which two or more layers are laminated. Moreover, the organosilicon compound to be used can also be used by 1 type, or 2 or more types of mixtures, and the continuous vapor deposition film layer of the organosilicon compound mixed by the dissimilar material can also be comprised.

The raw material volatilization supply device 18 for supplying the raw material volatilizes the organic silicon compound as the raw material and mixes it with a rare gas, inert gas or oxygen gas supplied from the gas supply devices 16, 17. Introduced into the vacuum chamber 12 via the supply nozzle 19, the content of the organosilicon compound, rare gas, inert gas, etc. in the mixed gas is a property required for the continuous vapor deposition film layer of the organosilicon compound. Depending on the composition, it can be changed. In the present invention, since oxygen gas is not used, He is supplied as a rare gas or N ₂ as an inert gas from a gas supply device.

  As for plasma generation, a predetermined voltage is applied to the cooling / electrode drum 15 from the power source 21, and glow discharge plasma 20 is generated in the vicinity of the opening of the raw material supply nozzle 19 in the vacuum chamber 12 and the cooling / electrode drum 15. To do. The glow discharge plasma 20 is derived from one or more gas components in the mixed gas. In this state, the glow discharge plasma 20 is cooled and cooled by conveying the substrate 1 at a constant speed. A continuous vapor deposition film layer of an organosilicon compound is formed on the substrate 1 on the circumferential surface of the electrode drum 15.

In the present invention, the degree of vacuum in the vacuum chamber is adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably, the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Moreover, the conveyance speed of the base material 1 relates to the film thickness, density, productivity, etc. of the continuous vapor deposition film layer of the organosilicon compound to be formed, and is usually 10 to 500 m / min, preferably 20 to 100 m / min. It is preferable to adjust. The plasma generation voltage is related to the thickness, density, productivity, etc. of the continuously deposited film layer of the organosilicon compound to be formed, and in particular, mild conditions that do not cause reaction with the organosilicon compound or decomposition of the organosilicon compound. It is preferable to adjust to 5-20 kW normally.

Formation of a layer of continuous deposited film of organosilicon compounds using the plasma chemical vapor deposition apparatus 11, the continuous deposition material gas of an organic silicon compound plasma onto the plastic substrate 1 in the form of a formula SiO _X Since it is formed in a film shape, the vapor-deposited film of the organosilicon compound is dense and has few gaps.
It becomes a continuous vapor deposition film layer rich in flexibility. Moreover, since the surface of the base material 1 is cleaned by the plasma and polar groups, free radicals, etc. are generated on the surface of the base material 1, the bonding between the continuously deposited film layer of the formed organosilicon compound and the base material 1 Is formed, and has an advantage of high adhesion. Therefore, the continuous vapor deposition film layer of the organosilicon compound has excellent adhesion to the base material, and also has high film thickness uniformity. Further, since the deposited film of the organic silicon oxide is formed in a vacuum, dust or the like does not adhere to the surface of the deposited film, and a deposited film is formed by linking Si—O bonds of the basic structure of the organosilicon compound. Therefore, a Si—C bond is uniformly arranged in the molecular chain, and a deposited film having excellent characteristics having uniform water repellency and releasability is formed.

In the present invention, the vacuum degree during formation of the continuous deposited film layer of an organic silicon ^{compound, 1 × 10 -1 ~1 × 10} -4 Torr, preferably, adjusted to ^{1 × 10 -1 ~1 × 10 -2} Torr Therefore, since the degree of vacuum is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr when the deposited film of silicon oxide is formed by the conventional vacuum deposition method, It is possible to shorten the vacuum state setting time at the time of replacing the original fabric, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

By using the water-repellent release laminate film or sheet of the present invention for process paper, the surface release layer of the laminate film or sheet is compared with the release laminate film or sheet using a silicone resin as a release agent, The release layer can be formed with a thickness of angstrom units, and it consists of a continuously deposited film of an inorganic material-based organosilicon compound, which deteriorates and destroys the environment when disposing of the release laminated film or sheet. Do not generate such causative substances.
Moreover, since a continuous vapor deposition film of an organosilicon compound is formed by a CVD method, a release laminated film or sheet having excellent releasability with a nano-order film thickness that is excellent in adhesion to a base film is obtained. , The transfer of the release layer to the product as seen in the coating-type release laminated film or sheet does not occur, it is excellent in terms of product post-processing, product quality control, etc., and the yield is also improved, and The use period of the water-repellent release laminated film or sheet becomes longer, and the manufacturing cost can be reduced.

The present invention will be described based on the following examples. However, the present invention is not limited to these examples.
Examples in the present invention were evaluated by performing various measurements using the following measurement methods. The measurement method and evaluation method of the physical property values of the examples will be described below.

(Measuring method)
(1) Measurement of carbon content Using an X-ray photoelectron analyzer (ESCA3400 manufactured by Shimadzu Corporation), 3.0 nm ion etching is performed in the depth direction from the outermost surface, and an organosilicon compound constituting the etched release layer is formed. The carbon content was calculated from the elemental analysis of the deposited film by the C / Si ratio.

(2) Measurement of water contact angle In order to evaluate the water repellency of the surface of the water-repellent release layer of the produced water-repellent release laminate film or sheet, the water contact angle with respect to the surface of the water-repellent release laminate film or sheet prepared. The contact angle of diiodomethane was measured 5 times at different locations using a contact angle tester (Kyowa Interface Science Co., Ltd .: CA-DT type), and each contact angle was measured with an average value of 5 times. The value was determined. As the wetting tension in JIS, it was also measured by a method using a wetting indicator defined in JIS K 6768. However, it was not accurate enough to evaluate the content of a trace amount of methyl groups and / or ethyl groups.

(3) Measurement of peel strength Sample preparation: Corona of 50 μm-thick unstretched polyethylene film (LS-722CN manufactured by Idemitsu Unitech) as the release layer side of the manufactured water-repellent release film (12 μm) and the base material for bonding With the discharge-treated surface as a urethane adhesive, the coating amount after drying ethyl acetate: Rock Paint Adlock RU-77: Aliphatic Isocyanate (Rock Paint: H-7) = 30: 10: 1 is 4. Coated (4 μm) to 0 g / m ² and bonded together, ORIENTIC TENSILON RTC-1310A was used as a peel strength test, and a T-shaped product was cut into a 15 mm width as a test piece at a peel rate of 50 mm / min. Peeling was performed and the peel strength was measured.

The present invention will be described more specifically with reference to the following examples.
Example 1
As a base material, a biaxially stretched polyethylene terephthalate film ("P60" manufactured by Toray Industries, Inc.) having a thickness of 12μ is subjected to corona treatment, and the biaxially stretched polyester film is rolled up by PE-CVD. Installed so that the corona-treated surface becomes the surface to be deposited on the delivery side of the process vapor deposition apparatus, then unwinds the base film, sets the winding tension to 1.4 N / m, and winds up PE-CVD The vessel of the vapor deposition apparatus was sealed, the exhaust pump was operated to reduce the pressure, and the outlet side temperature of the vapor deposition drum cooling device was cooled to 0 ° C.
When the pressure inside the device is measured with a capacitance manometer and reaches 0.5 Pa, hexamethyldisiloxane (HMDSO) is used as the vapor deposition monomer. Since HMDSO is in a liquid state at room temperature, the flow rate is measured in the liquid state. The flow rate of the supply line is 1600 sccm (meaning standard cc / min, 1 atm, 0 cm, or sccm standardized at a constant temperature such as 25 ° C.), and helium is used as the atmospheric gas in the apparatus. The flow rate of the supply line was set to 800 sccm and supplied into the vacuum chamber of the PE-CVD deposition apparatus, and the pressure in the container of the PE-CVD deposition apparatus was adjusted to 5.0 Pa.
After the PE-CVD method vapor deposition apparatus was set as described above and the operation of the vapor deposition apparatus was stabilized, the following PE-CVD method vapor deposition conditions were as follows: applied voltage: 40 kW AC power supply 8 kW, film transport speed: 30 m / min The film forming pressure is 5.0 Pa, the substrate holding temperature is 0 ° C., and plasma chemical vapor deposition using hexamethylenedisiloxane as a deposition raw material is performed on the corona discharge treated surface of the biaxially stretched polyethylene terephthalate film, and the thickness is 10 nm. After forming a vapor-deposited film of an organosilicon compound and producing a water-repellent release laminated film having a vapor-deposited film of a carbon-containing organosilicon compound, the conveyance of the base film is stopped, and the water-repellent mold release of the scraped portion The laminated film was collected, and predetermined physical properties were measured.
(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("P60" manufactured by Toray Industries, Inc.)
Deposition surface: Corona discharge treatment Deposition material: Hexamethylenedisiloxane (HMDSO)
Atmospheric gas: He gas introduction gas ratio: HMDSO: He = 1600: 800 [sccm]
Winding type PE-CVD apparatus applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 5.0 [Pa]
Substrate holding temperature: 0 ° C

(Example 2)
Plasma chemical vapor phase in the same manner as in Example 1 except that the vapor deposition material is a dimer of HMDSO, the atmosphere gas is nitrogen gas, and the introduced gas ratio is TEOS: N ₂ = 800: 800 [sccm]. The film-forming conditions of the vapor-deposited organic silicon compound film were set as follows to obtain a water-repellent release laminated film having a carbon-containing organic silicon compound vapor-deposited film.
(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("P60" manufactured by Toray Industries, Inc.)
Deposition surface: Corona discharge treatment Deposition material: Hexamethylenedisiloxane (HMDSO) dimer atmosphere gas: Nitrogen gas introduction gas ratio: HMDSO (dimer): He = 800: 800 [sccm]
Winding type PE-CVD apparatus applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 5.0 [Pa]
Substrate holding temperature: 0 ° C

Example 3
Deposition of an organic silicon compound vapor-deposited film by plasma chemical vapor deposition in the same manner as in Example 1, except that tetraethoxysilane was used as the vapor deposition material and the introduced gas ratio was TEOS: He = 1600: 1600 [sccm]. Conditions were set as follows to obtain a water-repellent release laminated film having a vapor-deposited film of a carbon-containing organosilicon compound.
(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("P60" manufactured by Toray Industries, Inc.)
Deposition surface: Corona discharge treatment Deposition material: Tetraethoxysilane (TEOS)
Atmospheric gas: He gas introduction gas ratio: TEOS: He = 1600: 1600 [sccm]
Winding type PE-CVD apparatus applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 5.0 [Pa]
Substrate holding temperature: 0 ° C

(Comparative Example 1)
Deposition of a vapor-deposited organic silicon compound film by plasma chemical vapor deposition in the same manner as in Example 1 except that the substrate holding temperature of the substrate film on which the plasma chemical vapor deposition film is formed is 100 ° C. Conditions were set as follows, and an organic silicon compound was vapor-deposited to obtain a laminated film having an organic silicon compound vapor-deposited film.
(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("P60" manufactured by Toray Industries, Inc.)
Deposition surface: Corona discharge treatment Deposition material: Hexamethylenedisiloxane (HMDSO)
Atmospheric gas: He gas introduction gas ratio: HMDSO: He = 1600: 800 [sccm]
Winding type PE-CVD apparatus applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 5.0 [Pa]
Substrate holding temperature: 100 ° C

(Comparative Example 2)
As the vapor deposition material, a mixed gas of hexamethylenedisiloxane and oxygen gas is supplied, and a mixed gas of helium gas and oxygen gas is supplied as an atmospheric gas, respectively, and the introduced gas ratio is HMDSO: O ₂ : He: O ₂ = 800: 800: 800: 100 [sccm] was set in the same manner as in Example 1 except that the oxygen-excess state was set, and the film formation conditions of the deposited organic silicon compound film by plasma chemical vapor deposition were set as follows. Then, an organic silicon compound was vapor-deposited to obtain a laminated film having an organic silicon compound vapor-deposited film.
(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("P60" manufactured by Toray Industries, Inc.)
Deposition surface: Corona discharge treatment Deposition material: Hexamethylenedisiloxane (HMDSO) + oxygen gas atmosphere gas: He gas + oxygen gas introduction gas ratio: (HMDSO: O ₂ ) :( He: O ₂ ) = 800: 800: 800 : 100 [sccm]
Winding type PE-CVD apparatus applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 5.0 [Pa]
Substrate holding temperature: 0 ° C

(Comparative Example 3)
As the vapor deposition material, a mixed gas of hexamethylenedisiloxane and oxygen gas is supplied as an atmosphere gas, and a mixed gas of helium gas and oxygen gas is supplied, respectively, and the introduced gas ratio is HMDSO: O 2: He: O 2 = 800: 2700. : 800: 100 [sccm], and the conditions for forming the deposited film of the organosilicon compound by plasma chemical vapor deposition are the same as in Example 1 except that the oxygen-excess state is set to be higher than that of Comparative Example 2. The organic silicon compound was vapor-deposited to obtain a laminated film having an organic silicon compound vapor-deposited film.
(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("P60" manufactured by Toray Industries, Inc.)
Deposition surface: Corona discharge treatment Deposition material: Hexamethylenedisiloxane (HMDSO) + oxygen gas atmosphere gas: He gas + oxygen gas introduction gas ratio: (HMDSO: O ₂ ) :( He: O ₂ ) = 800: 2700: 800 : 100 [sccm]
Winding type PE-CVD apparatus applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 5.0 [Pa]
Substrate holding temperature: 0 ° C

With respect to the laminated film having the vapor-deposited film of the carbon-containing organosilicon compound obtained by the method described in each of the above Examples and Comparative Examples, the water contact angle and the peel strength were measured by the measurement method, and each laminated film was measured. Was evaluated. The results are as follows.
Water contact angle and peel strength

(Evaluation of results)
Compared with the Examples and Comparative Examples, a vapor-deposited film exhibiting excellent water repellency and releasability is obtained under the condition of an oxygen-free atmosphere. It turns out that it falls. Also, the concentration of the organosilicon compound during vapor deposition seems not to be particularly relevant from Examples 1 and 3. In addition, the degree of water repellency can be improved by changing the methyl group, the type of ethyl group, the concentration in one molecule, the arrangement, etc. of the organosilicon compound seen in the comparison between Example 1 or 3 and Example 2 and Comparative Example. It seems to change. When the abundance of organic components such as methyl groups and ethyl groups in the organosilicon compound increases (the C / Si ratio increases), hydrophobic groups such as methyl groups and ethyl groups increase and surface free energy decreases. It is thought that this is because the water repellency can be easily controlled by the kind of the organosilicon compound. In addition, it becomes clear that there is a difference in peel strength depending on the type of organosilicon compound in an oxygen-free atmosphere, and since it has sufficient releasability, stable water repellency is combined with ease of water repellency control. It is expected that an aqueous releasable vapor deposition film can be formed. In addition, comparing Example 1 and Comparative Example 1 clearly shows a significant effect on the water repellency and releasability depending on the substrate holding temperature, and the dimension stable condition below the glass transition temperature of the substrate film. It can be seen that it is necessary to obtain a uniform and homogeneous water-repellent release layer by forming a vapor deposition film.

  According to the present invention, a water-repellent release film having excellent physical properties can be efficiently controlled and stably manufactured at low cost. The obtained water repellent release layer is excellent in water and oil repellency, antifouling properties, peelability, low friction, chemical resistance, etc. Used in the production of materials, FPC, multilayer printed circuit boards, separation films for adhesives, release laminated films or sheets for photosensitive agents, release laminated films or sheets such as process paper for electronic materials and functional materials it can.

A: Carrier sheet (release film or sheet)
1: substrate 2 (2a): release layer, organic component-containing organic silicon oxide vapor deposition film 11: plasma chemical vapor deposition apparatus 12: vacuum chamber 13: unwinding roll 14, 23: auxiliary roll 15: cooling / electrode Drums 16 and 17: Gas supply device 18: Raw material volatilization supply device 19: Raw material supply nozzle 20: Glow discharge plasma 21: Power source 22: Magnet 24: Winding roll 25: Vacuum pump

Claims (4)

  In a method for producing a water-repellent release laminate film in which a carbon-containing silicon compound film is formed on a plastic substrate by a plasma chemical vapor deposition method (PE-CVD method), an organic material containing Si-O bonds in the molecule A carbon-containing organosilicon compound film having water repellency by plasma chemical vapor deposition of the organosilicon compound gas using a silicon compound as a vapor deposition raw material in a gas atmosphere containing no oxygen and with the plastic substrate cooled and held at Tg or lower. A method for forming a water-repellent release film, characterized by forming a film on a plastic substrate.   The method for forming a water-repellent release thin film according to claim 1, wherein the gas atmosphere containing no oxygen is a gas atmosphere containing a rare gas or an inert gas other than the rare gas.   The method for forming a water-repellent release thin film according to claim 1 or 2, wherein a contact angle of water with respect to the surface of the carbon-containing silicon compound film is 90 ° or more.   A water repellent release laminated film having a water repellent carbon-containing silicon compound film formed by the method of forming a water repellent release thin film according to any one of claims 1 to 3.

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