JP2011152691A - Water repellent release film for manufacturing flexible flat cable (ffc) - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water repellent release film for manufacturing flexible flat cable (FFC), which has a water repellent continuous vapor deposition film of an organic silicon oxide containing an organic component. <P>SOLUTION: Disclosed is the water repellent release film for manufacturing the flexible flat cable (FFC), obtained by forming a carbon-containing silicon compound on a plastic base material by a plasma chemical vapor growth method (PE-CVD method), wherein as a release layer, the organic silicon compound containing Si-O bond in a molecular is used as the vapor deposition material and the continuous vapor deposition film of the organic silicon oxide is formed so as to contain an organic component on the plastic base material, and the water repellency based on the organic component in the organic silicon compound is developed to give the releasing property. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a release film to be used when thermocompression bonding a flexible flat cable (hereinafter abbreviated as FFC), and a vapor deposition film of carbon-containing organosilicon oxide on a plastic substrate by plasma chemical vapor deposition. The FFC having excellent releasability with excellent adhesion to the substrate, excellent surface smoothness, poor wettability (water repellency) and excellent film thickness uniformity. The present invention relates to a release film for manufacturing FFC that is extremely useful for manufacturing.
Specifically, plasma chemical vapor deposition is performed using an organic silicon compound as a deposition raw material and a plastic substrate is cooled and held in a low oxygen gas atmosphere at the time of vapor deposition. The present invention relates to a water-repellent release film for FFC production, which is formed on a substrate.

Conventionally, in electronic devices and electrical appliances, wiring materials such as electric wires have been used to supply signals and electricity for moving the devices, and electrical wiring has been performed. In recent years, various devices have been required to be small in size, high performance, high integration, light weight, etc., and have been required to perform electrical wiring in a narrow space of devices, and the same has been required for electrical wiring materials. .
However, conventional wires cannot handle the electrical connections of complicated and high-density electrical circuits and electronic circuits in a narrow space of miniaturized equipment, and do not take up new mounting space for electrical wiring. FFC has been introduced as an excellent wiring means that can be electrically connected in a lump.

FFC is a flame retardant adhesive insulating resin layer on the surface of a polyethylene terephthalate (PET) film, and uniformly disperses powders of flame retardant materials, concealment materials, filling materials, etc. in a polyester resin dissolved in a solvent. A film coated in a desired thickness is manufactured in advance, and a plurality of metal conductors arranged and supported at a predetermined pitch are supplied between the flame retardant adhesive insulating films for FFC. It is continuously manufactured as a laminate of insulating films with metal conductors sandwiched by passing and thermocompression bonding.
During production, when a flame-retardant adhesive insulating film is sandwiched between heat rolls, it is partially softened and melted by pressure and heat, and from both ends of the film or from a cut portion formed on a PET film at a predetermined interval Overflow, directly contact with the roll part which is an FFC manufacturing apparatus, adhere to the roll, and since the protruding molten resin is heated and pressed by the roll and sandwiched, it further adheres onto the roll. In order to prevent this, a release film for manufacturing FFC is required, because the surface of the FFC may be continuously roughened and the contamination may spread as the resin on the roll moves to the insulating film. ing.
Particularly in recent years, cleanness, heat resistance, dimensional stability, and the like of mold release process materials have become indispensable in the manufacturing process of electronic devices that are becoming multifunctional and miniaturized. 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.

  By the way, as a release film used for FFC production, conventionally, a polyolefin resin film such as OPP is laminated on one surface of a base material such as a polyester resin film by a dry laminating method with an adhesive. In general, those having a release property obtained by coating a curable silicone resin composition on one surface of a substrate such as a polyester resin film or the like are generally widely used. It has been broken.

In such a release film, when the release property is imparted by a silicone material having a main skeleton due to a siloxane bond, for example, a silicone laminate in which silicone is laminated as a release layer on PET and a method for producing the same (Patent Document 1) However, in the case of silicone laminates, excellent releasability, low surface energy, and coating processing are possible, but on the other hand, heavy peeling (deterioration of surface properties) is promoted by long-term exposure to the atmosphere, and the surface There is a problem that the characteristics change, and there is a problem that the silicone of the release layer is transferred at the time of peeling and becomes a defect.

  When fluorine-based materials are used, there are those that form a fluorine compound as a release layer on a base material, or those that use a fluororesin itself as a release layer (Patent Documents 2 and 3). Although it has excellent physical properties and performance in chemical resistance, flexibility, repeated durability, antifouling property, weather resistance, etc., in addition to the high material price of the fluorine compound itself, harmful fluorinated gas is generated during incineration. It is difficult to laminate with other base materials, it is difficult to create a composite material, and there are problems in terms of cost, disposal processing, difficulty of composite processing, and the like.

  In addition, when a sheet or film made of a polyolefin resin is used, there is a sheet (Patent Documents 4 and 5) that is used by laminating with the polyolefin itself or a base film and exhibits releasability. It has the advantages of low price, flexibility and excellent workability, and has a good balance between releasability and cost, but is inferior in terms of industrial usability in terms of high haze and heat resistance. There was a problem such as.

Japanese Patent No. 2846155 JP 2007-119640 A JP-A-8-186141 Japanese Patent No. 2619034 JP 2006-257399 A

  In a water-repellent release film for FFC production in which a carbon-containing silicon compound film is formed on a plastic substrate by plasma chemical vapor deposition (sometimes referred to as PE-CVD or plasma CVD), An organic silicon compound containing a Si-O bond is used as an evaporation source, and a gas obtained by vaporizing the organic silicon compound in a state where the plastic substrate is cooled and held in a gas atmosphere containing oxygen is subjected to plasma chemical vapor deposition to produce water repellency. The present invention relates to a water-repellent release film for FFC production, characterized in that a carbon-containing organic silicon oxide vapor-deposited film having the above is formed on a plastic substrate.

As described above, the performance required from the specific application surface of the release film for FFC production is, for example, a heat release and an appropriate release property and cushioning property in the release film used in the heat and pressure processing. Therefore, non-transferability to the base material is required. As cost merit, repeated resistance, low cost, and easy disposal are also important.
In addition, when a conventional release layer is used, the release film is maintained for a long period of time due to the transfer of the release layer and the change in surface characteristics due to heavy release, and it has controlled water repellency. It is difficult to prepare a releasable layer, and it is still difficult to form a water repellent release film that can produce FFC stably and reliably as a homogeneous and uniform water repellent release layer at a low cost. Not reached.

The present invention has been made in view of the state of the prior art as described above, and even if the heat and pressure treatment by a heat roll in FFC production and the contact partner is a molten resin having heat sealability, it is ensured. A uniform and uniform water repellency and releasability that can be easily peeled off by forming a smooth surface at the same time, providing a heat-resistant water repellent release layer stably and reliably at low cost. The present invention provides a water-repellent release film that eliminates technical problems.
Therefore, the present invention can provide a release layer with excellent film thickness uniformity on one surface of a substrate, and the release layer is formed of an inorganic vapor deposition film and is heat resistant. Excellent adhesion to the material, no transfer, excellent smoothness of the surface, poor wettability, uniform releasability, extremely useful for producing FFCs produced by thermal lamination It is providing the water-repellent release film for FFC manufacture.

As a result of various studies to solve the above-mentioned problems in the release film for FFC production, the vapor of the organosilicon compound is grown by chemical vapor deposition on the plastic substrate by PE-CVD using a plasma generator. The focus is on a continuously deposited film of carbon-containing organosilicon oxide.
The present invention provides a gas composition comprising at least a monomer gas comprising an organic silicon compound vapor as a deposition material, an inert gas comprising argon gas or helium gas as a carrier gas, and a low concentration oxygen gas as an oxygen supply gas. Continuous vapor deposition of organosilicon oxide prepared and formed by chemical vapor deposition of the gas composition on one surface of a plastics substrate film with PE-CVD method while the plastic substrate is cooled and held The film layer is a release layer, and the organic silicon oxide continuous vapor deposition film layer includes at least a compound composed of one or more of carbon, hydrogen, silicon, and oxygen in the layer. It is formed so as to contain one or more types. By forming the release layer directly on the plastics base film, a release film for FFC production is obtained. When the FFC was manufactured by a normal method using the release film, the manufactured FFC could be easily peeled from the release film, and there was no adhesion of a release layer, and a flexible flat cable having a smooth surface was obtained. I was able to manufacture it.
The above-mentioned water-repellent release film for manufacturing FFC has a thin and constant thickness and excellent uniformity, and also has an extremely strong and tight adhesion to the base material, does not transfer, has excellent adhesion, and has a smooth surface. It has excellent water resistance and water repellency having a high water contact angle and is poor in wettability. As a result, it has a uniform water repellant release vapor deposition film without unevenness in releasability.

Further, the FFC can be manufactured continuously and stably extremely well without being affected by the vicinity of the laminator roll of the FFC manufacturing apparatus being contaminated by the flame retardant heat seal material or the like.
Furthermore, by using the PE-CVD method, it is possible to form a deposited film that is firmly adhered to a plastic substrate, in particular, a material having low heat resistance and a low surface energy material that is difficult to be deposited by general physical vapor deposition. It is possible to select a plastic material and form a transparent water-repellent vapor-deposited film, which makes it possible to select various substrates according to the required mechanical properties and cost, and the design flexibility is extremely high. The present invention has been completed by finding that there is a merit that can be used as a high production method.

  In the present invention, as a reaction condition of the PE-CVD method, the reaction raw material is only an organosilicon compound, and the gas atmosphere is a gas composition containing only a rare gas and oxygen. When controlling, it is a simple system that controls only oxygen during plasma CVD deposition, and can reliably form a deposited film having a desired surface state (water repellency, releasability, contact angle, peel strength, etc.). . In addition, since the thickness, application width, and the like of the deposited film can be changed as desired by controlling the conveyance speed of the substrate, the deposited film can be formed uniformly and stably. As a result, it has excellent releasability as a release film for FFC production, and the frequency with which it can be repeatedly used as compared with the prior art is improved due to the close adhesiveness with the base material, so that a product with a good yield can be obtained.

The advantage of the continuous deposited film of organosilicon oxide formed by using PE-CVD method in the presence of low oxygen as a deposition monomer material in the present invention is that it is a base film that can be deposited such as PET and polyolefin. In particular, it is possible to produce a water-repellent release film that can be reliably controlled and manufactured regardless of the material, and it is difficult to peel off due to tight adhesion and excellent in releasability from heat seal resin. The degree of freedom is extremely high, and the desired physical properties and performance can be manufactured at low cost.
Further, an organic silicon compound is formed by a PE-CVD method in a low oxygen atmosphere to form a silicon oxide deposited film, and a film having a large carbon content in the organic silicon oxide is formed. _2- CH ₃ ), methyl group (—CH ₃ ) remains as a terminal, and Si—OH group is reduced, so that water repellency (value of water contact angle is large) becomes releasable and hydrophobic film Can be obtained.

  In the case of depositing an organic silicon oxide vapor-deposited film from the organosilicon compound of the present invention, the amount used for the deposition of the organosilicon compound for the dry process, unlike the release coat product to which the silicone release agent is applied. The deposited film formed is excellent in adhesion because it forms a chemical bond with the base film, and when used as a release film for FFC production, the deposited film of the organosilicon oxide that is the release layer The transferability due to peeling is extremely low and is hardly seen.

  The organic silicon oxide vapor-deposited film according to the method of the present invention is an organic silicon oxide vapor-deposited film containing an organic component and can be said to be an organic-inorganic vapor-deposited film. 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 a merit that there is no toxicity of the vapor-deposited film of the organic silicon oxide of the present invention, it can be recycled, and hardly any 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 Schematic diagram of flexible flat cable manufacturing equipment

In the present invention, the organic silicon oxide continuous vapor-deposited film contains an organic component, and the organic silicon oxide continuous vapor-deposited film formed by controlling the content of the organic component, that is, the carbon content has a releasability. It has a water repellent release film that can be formed in a state where the water repellency is controlled.
According to the water-repellent release film of the present invention, the thickness of the continuous vapor-deposited film of the water-repellent carbon-containing organosilicon oxide can be accurately controlled at any film thickness level from the nanometer level to the micrometer level. It is possible to form a stable continuous vapor deposition film that can be maintained, has releasability, has little transferability, and can also control water repellency.

The present invention uses the CVD method as a technique for forming a continuous vapor-deposited film of carbon-containing organic silicon oxide formed by vapor deposition of organic silicon oxide, thereby reducing the materials involved in the supplied reaction system. It is possible to provide a water-repellent release film for FFC production that maintains the water repellency and release property of the surface of the release layer in an easily controlled state and forms a controlled release layer.
Further, in the release film for FFC production of the present invention, under the severe use environment when performing heat lamination with a hot roll, in addition to the required heat resistance, releasability and water repellency, resource saving It is also excellent for energy saving or disposal. That is, a continuous vapor deposition film of carbon-containing organic silicon oxide is formed by a CVD method, does not contain a halogen element, a chemical bond is formed between the base film and the release layer, and excellent adhesion The base film and the release layer have excellent adhesion, are difficult to peel off, and there is a hydrophobic group on the surface of the release layer, and the release force between the release material and the release layer is small, The release property of the release layer can be maintained for a long time.

The water-repellent release film for FFC production having a continuous vapor deposition film of carbon-containing organosilicon oxide according to the present invention and the production method thereof will be described with reference to the drawings, illustrating an example of the layer configuration. It is a schematic sectional drawing which shows an example of the layer structure about the water-repellent release film which has the water-repellent continuous vapor deposition film of the carbon containing organic silicon oxide concerning this invention.
In addition, in this invention, a film means all the cases of a sheet | seat, a film, a film-form thing, or a sheet-form thing, and does not give a special meaning.

As shown in FIG. 1, the water-repellent release film for FFC production having a continuous vapor deposition film of carbon-containing organosilicon oxide according to the present invention is provided on a base 1 and one surface of the base 1. It consists of an organic silicon oxide continuous film deposition film (2a).
The plasma chemical vapor deposition method for forming the water-repellent release layer that is the vapor deposition film (2a) uses, for example, a plasma chemical vapor deposition apparatus as shown in FIG. It is possible to successively form a water-repellent release vapor deposition film by sequentially feeding into an atmosphere in which plasma chemical vapor deposition is performed and applying a winding-type plasma chemical vapor deposition method.
The water-repellent release film for FFC production according to the present invention can be used for a wide range of applications, and is particularly a water-repellent release film suitable for FFC production.

For the base film used in the present invention, a plastic material suitable for the physical properties and performance required for the base film of the release film is selected according to the use conditions, and the surface roughness, the thickness of the base material, and the surface uneven shape It is possible to set and select the substrate properties according to the application.
In the water-repellent release film for FFC production according to the present invention, 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. 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, polyester resin such as polyethylene naphthalate, polyamide Examples thereof include various resin films such as a resin, a polyaryl phthalate resin, a polyurethane resin, and a cellulose resin. Among these, from the viewpoints of heat resistance, mechanical properties, dimensional stability, adhesion, price, etc., a polypropylene resin, polyester resin, or polyamide resin film is particularly preferable in the present invention. Further, the base material may be a laminated film of two or more layers using the above two or more kinds of resins.

The production method of the film of the present invention is not particularly limited, and it is appropriately produced by employing a conventionally known film production method such as extrusion method, cast molding method, T-die method, inflation method and the like. Can do. In addition, a multilayer film is formed by a method of forming a multilayer film using two or more kinds of resins, and further, a method of using two or more kinds of resins and mixing and forming a film before forming a film. 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 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 flatness and smoothness of the base film. 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, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties Various plastic compounding agents and additives can be added for the purpose of improving and modifying electrical characteristics, strength, etc., and the amount added affects the formation of the release layer, such as surface roughness. It can be selected and added within a range that does not reach.
As a general additive in the present invention, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, an antistatic agent are used to maintain the functions necessary as a base material for a release film. Agents, lubricants, antiblocking agents, colorants such as dyes and pigments can be used.

  In the present invention, on the surface of the base film, a desired surface treatment may be performed in advance, if necessary, in order to improve the tight adhesion with the organic silicon oxide continuous vapor deposition film constituting the release layer. it can. 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 close adhesion between the base film and the organic silicon oxide continuous vapor deposition film layer constituting the release layer, the organic silicon oxide continuous vapor deposition film formed by plasma CVD and the base material are used. For example, a primer coat layer, an undercoat layer, an anchor coat layer, an adhesive layer, a vapor deposition anchor coat layer, or the like can be formed within a range in which the tight adhesion with the coating layer does not deteriorate. As the pre-treatment coating material, for example, a polyester resin, a polyamide resin, a polyurethane resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof is used. be able to.

[Release layer of organic silicon oxide containing organic components]
The method for forming a vapor deposition film according to the present invention uses a gas composition containing a vapor deposition raw material monomer gas of an organic silicon compound, and forms a predetermined vapor deposition film of an organic silicon oxide by a PE-CVD method under a predetermined vapor deposition condition. It is formed by chemical vapor deposition on one surface of a plastic substrate that is fed at a transport speed of 5 mm.
In the method of the present invention, the organic component resulting from the organosilicon compound is contained in the continuously deposited film of the organosilicon oxide formed by simply changing the supply amount of the gas composition at a low oxygen concentration, and A release layer having a uniform and sufficient water repellency can be formed by adjusting the Si-C bond content to a high concentration, and the water-repellent release film for FFC production according to the present invention can be easily and easily obtained. Can be manufactured.

In the present invention, the important thing is that the release layer of the organic silicon oxide continuous vapor deposition film includes a compound having a C—H bond or a Si—C bond, an organic silicon compound which is a monomer of a vapor deposition raw material, or a derivative thereof. organosilicon oxide containing organic component (hereinafter, may be simply referred to as a carbon-containing organic silicon oxide) is to form a deposited film on a plastic substrate by a chemical bond or the like, in particular, CH ₃ groups and It is formed by PE-CVD so as to leave a C ₂ H ₅ group. As a result, the organic component is arranged on the film surface, and the water contact angle, that is, the surface free energy changes depending on the density contained in the organic component, but the carbon-containing organosilicon oxide that exhibits uniform water repellency and releasability is continuously deposited. A film can be formed.
As the compound contained in the organic silicon oxide continuous vapor-deposited 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.

  Therefore, as an organosilicon compound used for forming a continuous vapor deposition film of an organosilicon oxide containing an organic component that forms the release layer of the present invention, the organosilicon compound contains a methyl group or an ethyl group, and Si is a main chain. The following monomer materials, for example, 1,1,3,3-tetramethyldisiloxane (TMDSO), hexamethyldisiloxane (HMDSO), vinyltrimethylsilane, methyltrimethylsilane (TMS), hexamethyldisilane , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Silane, octamethi It can be used cyclotetrasiloxane and the like. Moreover, these 1 type or 2 types or more may be included.

Regardless of the above example, the monomer material for forming a water-repellent organic silicon oxide vapor-deposited film is an organic silicon compound containing Si atoms and CH ₃ groups and / or C ₂ H ₅ groups, and is suitable at room temperature. Any material may be used as long as it has a suitable vapor pressure and can perform the plasma CVD method.
Specific examples include hydrocarbons having a CH ₃ 2 site.
In the present invention, as the organic silicon 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 properties such as the water repellency of the formed deposited organic silicon oxide film.

To form a deposited film of an organic silicon oxide water repellency imparted by the plasma CVD method, a CH ₃ group in the organic silicon compound containing Si atoms and CH ₃ groups and / or C ₂ H ₅ group and / or It is necessary to leave the C ₂ H ₅ group and not oxidize and decompose all to COx, H ₂ O and the like.
Therefore, it is necessary for the gas composition to stop supplying oxygen gas at a high concentration as in the normal vapor deposition method as a gas component other than the monomer material, and to make it into a low oxygen state. The water repellency can be controlled by the abundance of CH ₃ groups and / or C ₂ H ₅ groups, by controlling the oxygen supply source, or by controlling the density of the water repellent film (water repellent group), The water repellency, that is, the release property can be controlled.
In addition to the above, by changing the conditions of the vapor deposition process, the surface shape of the substrate, etc., the type, amount, etc. of the organic component contained in the organic silicon oxide continuous vapor deposition film layer can be changed.

In addition to the monomer gas, a gas (carrier gas) for efficiently introducing the monomer vapor into the vacuum chamber, a plasma for generating plasma, and a gas for the purpose of enhancing the plasma are also introduced as necessary. The
As the carrier gas, an inert gas such as a rare gas such as argon gas or helium gas, 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. As a result, plasma chemical vapor deposition can be performed on the plastic substrate to form a water-repellent release vapor deposition film of organic silicon oxide.

In the present invention, an organic silicon oxide continuous vapor deposition film formed using a vapor deposition monomer gas such as an organosilicon compound is usually a carbon represented by the general formula SiOxCy (where 0 <x ≦ 2.5). As a releasable layer of a continuous vapor-deposited film of an organic silicon oxide containing x-containing silicon oxide as a main component, x is in the range of 0.3 to 1.5, and y is 1 Preferably it is in the range of .2 to 2.4, and x is preferably in the range of 1.0 to 1.4 and y is preferably in the range of 1.5 to 2.1.

The content of the organic component can be considered to vary depending on the organosilicon compound of the vapor deposition monomer as the raw material, and the water repellency and releasability are determined by the density of carbon contained in the vapor deposition film of the carbon-containing organosilicon oxide and It can be expected that the density distribution of the planar spread is predicted from the molecular structure of the organosilicon compound and controlled.
Generally, it is desirable that the content of the organic component is about 20 to 80%, preferably about 30 to 60%. If the content is less than 20%, the releasability of the organic silicon oxide continuous vapor deposition film layer decreases, or the impact resistance, spreadability, flexibility, etc. become insufficient, and due to bending, 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 also unfavorable.

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.
Further, in order for the vapor deposition film to exhibit water repellency and releasability, the thickness of the water repellent vapor deposition film is required to be at least 10 mm. If the thickness of the water-repellent vapor deposition film is less than 10 mm, it does not exist as a continuous vapor deposition film.

  In the present invention, in the organic silicon oxide continuous vapor deposition film, the content of the organic component is preferably decreased in the depth direction from the surface of the organic silicon oxide continuous vapor deposition film. On the surface of the continuous vapor-deposited film, water repellency, releasability, impact resistance and the like are enhanced by the organic component. On the other hand, at the interface with the resin film, the content of the organic component is small, and -SiO Since the chemical bond due to-is formed between the base film and the base film, the adhesiveness between the base film and the silicon oxide continuous vapor deposition film becomes strong.

When the content of the organic component contained in the organic silicon oxide continuous vapor deposition film constituting the release layer is reduced, it means that the presence of methyl groups (CH ₃ ), which are water repellent groups, is reduced. This is not preferable because the moldability is lowered. Further, when the carbon atom content is increased, the hardness, strength and the like of the film are lowered, and this is not preferable because the phenomenon of peeling off occurs.

In the present invention, the film thickness of the organic silicon oxide continuous vapor-deposited film is such that the vapor-deposited film is a carbon-containing organic silicon oxide and has a composite property of organic and inorganic, Since there is no rigidity and the film is flexible, there is no particular problem as long as the film thickness is in the range of 2 nm to 400 nm.
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 oxide continuous vapor deposition film layer, the volume velocity of the continuous vapor deposition film layer is increased as a condition during vapor deposition, that is, the vapor deposition monomer gas of the organic silicon compound is changed. The film thickness can be increased by increasing the number and the conveying speed of the substrate, and the film thickness can be decreased by decreasing the deposition rate.
In the present invention, the organic silicon oxide continuous vapor deposition film layer may be not only one layer of the organic silicon oxide continuous vapor deposition film layer, but also a multilayer film in which two or more layers are laminated, The organic silicon compound to be used may be used alone or as a mixture of two or more thereof, and a continuous vapor deposition film layer of an organic silicon oxide mixed with different materials may be formed.

  A method of forming a continuously deposited film layer of organosilicon oxide 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 the above-mentioned organic silicon oxide continuous vapor deposition film layer is formed by plasma chemical vapor deposition.
In the present invention, the base film 1 is unwound from the unwinding roll 13 disposed in the vacuum chamber 12 of the plasma chemical vapor deposition apparatus 11, and is transported onto the circumferential surface of the cooling / electrode drum 15 at a predetermined speed. Mixing with oxygen gas, inert gas, etc. from the gas supply device and raw material volatilization supply device 16, etc., and volatilizing and supplying the vapor deposition monomer gas etc. of the organic silicon compound as the raw material, and preparing the vapor mixture composition for vapor deposition While introducing the mixed gas composition for vapor deposition into the vacuum chamber through the raw material supply nozzle, the plasma generated by glow discharge plasma on the substrate film conveyed on the peripheral surface of the cooling / electrode drum To form a continuous vapor deposition film layer of an organic silicon oxide.
In addition, content, such as the organosilicon compound in a mixed gas, a noble gas, and an inert gas, can be changed by arbitrary compositions according to the property calculated | required by the continuous vapor deposition film layer of an organosilicon oxide.
Then, the base film on which the organic silicon oxide continuous vapor-deposited film is formed is wound around the take-up roll 14 at a predetermined winding speed, and the organic silicon oxide continuous vapor-deposited film according to the present invention is converted into a plasma chemical vapor phase. The substrate film is formed by a growth method.
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.

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. Since the degree of vacuum is 1 x 10 ^-4 to 1 x 10 ^-5 Torr according to the conventional vacuum deposition method, the vacuum state setting time when replacing the base film can be shortened. The degree of vacuum is easy to stabilize, and the film forming process is stabilized.
Moreover, the conveyance speed of the base material 1 is related to the film thickness, density, productivity, etc. of the continuous vapor deposition film layer of the organic silicon oxide to be formed, and is usually 10 to 500 m / min, preferably 20 to 100 m / min. It is preferable to adjust to. The plasma generation voltage is related to the film thickness, density, productivity, etc. of the continuously deposited organic silicon oxide film layer to be formed, and is particularly mild so as not to react with the organic silicon compound or decompose the organic silicon compound. It is preferable to adjust to 5-20 kW normally under conditions.

  Formation of a layer of an organic silicon oxide continuous vapor deposition film using the above-described plasma chemical vapor deposition apparatus is performed by introducing a raw material gas of an organosilicon compound into plasma on a base film, Since the surface is cleaned and polar groups, free radicals, and the like are generated on the surface of the substrate 1, a bond between the formed organic silicon oxide continuous vapor deposition film layer and the substrate 1 is formed, and adhesion is improved. It has the advantage of being expensive. Therefore, the continuous vapor deposition film layer of organosilicon oxide 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.

[Manufacture of flexible flat cables]
Next, an example of the manufacturing method of FFC using the water-repellent release film for FFC manufacture of this invention is demonstrated.
Using an FFC continuous manufacturing apparatus 9 as shown in FIG. 3, a plurality of conductors 5 arranged and supported at predetermined intervals on a support roller, and polyethylene terephthalate (PET) resin so as to sandwich the conductors from both the upper and lower surfaces An insulating film 4 provided with an adhesive layer is continuously supplied to the base film 3 to be passed between a pair of rotary thermocompression-bonding rolls 8 and 8 and fixed integrally by thermocompression lamination, The flexible flat cable 6 is manufactured. At that time, the water-repellent release film A for FFC production of the present invention is supplied between the upper and lower insulating films and the rotary thermocompression-bonding roll so that the release layer 2 is on the insulating film side, and thermocompression-bonded. The wound FFC is wound on a roll. Here, the insulating film on the upper surface is not limited as an insulating layer, but is preferably a laminate of a 20 to 60 μm thermoplastic film on a 12 to 50 μm thick polyester film, and a conductor exposed window at a predetermined interval. What has the part 7 formed is used.

As an insulating film, the same handling as FFC is possible as a base film, and the conductor protruding from each FFC is reinforced (protected), and any material having such a function should be formed. Can do. The insulating material layer is formed of various resin materials having insulating properties, for example, polyethylene terephthalate, a heat-adhesive thermoplastic resin film is used, and has good adhesion to the conductor, for example, an unsaturated polyester type Adhesive thermoplastic resins such as thermoplastic resins, ethylene vinyl acetate, and ionomers are used.
Here, the conductor constituting the FFC is formed as a flat conductor, and any material can be used as long as it is a conductive material. For example, a tin-plated flat annealed copper wire or the like can be used. The size and number of conductors are also arbitrary. For example, the conductor has a thickness of 35 to 100 μm and a width of about 0.3 to 0.8 mm.

By using the water-repellent release film according to the present invention between rolls during thermal lamination for FFC production, the surface release layer of the water-repellent release film is a release agent that uses a silicone resin as a release agent. Compared to the mold film, the release layer can be formed with a thickness of angstrom units, and it consists of a continuous vapor-deposited film of inorganic silicon-based organic silicon oxide. Do not generate causative substances that worsen or destroy.
In addition, since a continuous vapor deposition film of organic silicon oxide is formed by a CVD method, a release film having excellent releasability at a nano-order film thickness with excellent adhesion to a base film can be obtained. There is no transfer of the release layer to the product, as seen in coating-type release films, it is excellent in terms of product post-processing, product quality control, etc., yield is improved, and water-repellent release film The use period 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.
The examples in the present invention were evaluated by performing various measurements or observations using the following measurement or evaluation methods. The measurement method and evaluation method of the physical property values of the examples will be described below.

(Measuring method)
(1) Measurement of water contact angle In order to evaluate the water repellency of the surface of the water-repellent release layer of the manufactured FFC-producing water-repellent release film, the contact angle of water with the surface of the prepared FFC-producing water-repellent release film Was measured five times at different locations using a contact angle tester (Kyowa Interface Science Co., Ltd .: DropMaster 700), and the measured value of the contact angle was determined using the average value of the five times.

(2) Releasability: Measurement of peel strength Sample preparation: The water-repellent release film for manufacturing FFC (38 μm) is overlapped with the release layer side of the flexible flat cable as a base material for bonding. Heat-sealing with a flat cable laminator and bonding, and ORIENTIC as a peel strength test
Using TENSILON RTC-1310A, a flat cable test piece with a release film cut out to a width of 15 mm as a test piece was subjected to T-peeling at a peeling rate of 50 mm / min, and the peel strength was measured.

(3) Appropriate evaluation of high-temperature hot roll Sample preparation: The manufactured FFC-manufactured water-repellent release film (38 μm) and two flexible flat cable insulating materials are overlapped, and a flat cable laminator hot roll is used. Thermal lamination and bonding were performed to form a flat cable test piece with a release film, and the appearance such as heat resistance, heat shrinkability, and no wrinkling was observed and evaluated.
In evaluating, ○: good, Δ: wrinkle generation, x: both wrinkle and heat shrinkage occurred.

(4) Evaluation of silicone transferability Transferability of release layer For transferability of the release layer, the insulating material of the flexible flat cable is overlapped and insulated with the heat roll when heat-sealed using a heat roll. An FFC with a heating temperature of 20 ° C. and a thickness of 20 μm was formed by interposing a water repellent release film for FFC production between the raw material and the material. After forming the FFC with a water repellent release film for FFC production, the FFC and the release film were peeled off.
After peeling the FFC, before and after peeling using a fluorescent X-ray analyzer (RIX2000 manufactured by Rigaku) to confirm the transfer of the release layer from the water-repellent release film for FFC production to the surface of the FFC release film side The Si strength of the surface of the release film was measured, and the change in the Si strength before and after peeling was examined. By comparing with the Si strength on the release layer side before the FFC formation, the transition property of the release layer (the Si strength decreases if it has been transitioned, so the presence or absence of the transition is evaluated) is evaluated.

(5) Evaluation of Combustion Disposability Combustion discardability was evaluated based on the generation of harmful gases (halogen gas) in the atmosphere and the presence or absence of combustion residues. Fluorine resin generates harmful halogen gas, and the release layer is made of silicone resin. It is flame retardant and difficult to incinerate, and there are many residues.

The present invention will be described more specifically with reference to the following examples.
Example 1
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm ("PTH" manufactured by Unitika, PET # 12, having a surface roughness (Ra) of 50 nm and subjected to corona treatment on one side) is used as a base film. The film is placed on the feed-out side of the wind-up PE-CVD deposition apparatus so that the corona-treated surface becomes the deposition surface, then the substrate film is unwound and the winding tension is set to 1.4 N / m Then, the container of the wind-up PE-CVD vapor deposition apparatus was sealed, and the pressure was reduced using an exhaust pump, and the outlet side temperature of the vapor deposition drum cooling apparatus was cooled to 0 ° C.
When the pressure inside the device is measured with a capacitance manometer and reaches 0.3 Pa, hexamethyldisiloxane (HMDSO) is adopted as the vapor deposition monomer, the flow rate is measured in the liquid state, and the flow rate of the supply line is 1000 sccm (standard) This means slm standardized at a constant temperature such as 1 cm, 1 atm, 0 ° C. or 25 ° C.), and helium is used as the atmospheric gas in the apparatus, and the flow rate of the supply line is set to 1000 sccm, oxygen The gas was set to 100 sccm and supplied into the vacuum chamber of the PE-CVD deposition apparatus, and the vacuum pressure in the container of the PE-CVD deposition apparatus was adjusted to 3.0 Pa.
After the operation of the PE-CVD deposition apparatus set as described above is stabilized, the following PE-CVD deposition conditions are as follows: applied voltage: 40 kW AC power supply 8 kW, film transport speed: 30 m / min, deposition pressure : 3.0 Pa, substrate holding temperature: 0 ° C., plasma chemical vapor deposition using hexamethylenedisiloxane as a deposition material was performed on the corona discharge treated surface of a biaxially stretched polyethylene terephthalate film, and an organic silicon oxide having a thickness of 8 nm was formed. After manufacturing a water-repellent release film having a continuous vapor-deposited film of carbon-containing organosilicon oxide, the conveyance of the base film is stopped, and the water-repellent release film at the scraping portion is The collected physical properties were measured.
The composition of the deposited film was C: 29.53, O: 40.28, Si: 30.19, O / Si: 1.33.

(Deposition conditions)
Base material: Biaxially stretched polyethylene terephthalate ("PET # 25" manufactured by Unitika)
Deposition surface: Corona discharge treatment Deposition material: Hexamethylenedisiloxane (HMDSO)
Atmosphere gas: He gas Introduction gas ratio: HMDSO: O2: He = 1.0: 0.1: 1.0 [slm]
Winding type PE-CVD apparatus Applied voltage: 40 KHz AC power supply, 8 kW
Film transport speed: L / S = 30 m / min
Deposition pressure: 3.0 [Pa]
Substrate holding temperature: 0 ° C

(Manufacturing example of flexible flat cable)
Next, as shown in FIG. 3, a plurality of conductors (solder-plated annealed copper) are juxtaposed on the roller in the same plane along the longitudinal direction at a predetermined interval and run in an aligned state. A water repellent release agent produced in Example 1 of the present invention was supplied so as to supply an insulating film of a 12 μm polyester film and an unsaturated polyester flame retardant adhesive layer having a thickness of 40 μm and to be superposed on the insulating film. Supply the film so that the continuous vapor deposition layer of organosilicon oxide is on the insulating film side, sandwich the insulating film with the water-repellent release film for FFC production, and then heat-fuse and integrate with a thermocompression roll To produce a flexible flat cable. In FFC production, the water-repellent release film of the present invention is particularly suitable for producing a flexible flat cable. In addition, it was excellent in silicone transfer properties and combustion disposal properties, and generally exhibited excellent physical properties and performance.

(Example 2)
Example except that a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (Embret “PTH” manufactured by Unitika, surface roughness (Ra)> 300 nm) subjected to corona treatment on one side was used as a substrate. In the same manner as in No. 1, a water repellent release film for FFC production having a continuously deposited organic silicon oxide film was obtained by plasma chemical vapor deposition. An FFC was produced in the same manner as in Example 1 using the water repellent release film.

(Comparative Example 1)
An FFC was produced in the same manner as in Example 1 using a biaxially stretched PET film (use of unite emblet “PTH”, 12 μm, surface roughness (Ra) 50 nm) as a release film.

(Comparative Example 2)
An FFC was produced in the same manner as in Example 1 using a non-stretched CPP film (FHK2 25 μm) manufactured by Phutamura Chemical as the release film.

(Comparative Example 3)
An FFC was produced in the same manner as in Example 1 using a Toray biaxially stretched PET film (E7002 25 μm) as a release film.

(Comparative Example 4)
An FFC was produced in the same manner as in Example 1 using a fluororesin film (Aflex 25 μm) manufactured by Asahi Glass as a release film.

About FFC with a release film manufactured using the release film of each Example and Comparative Example of the present invention, water contact angle, release property, high temperature hot roll suitability, silicone transfer property, cost and combustion waste property The measurement was performed according to the measurement method or the evaluation method, and each evaluation was performed.
The results are as follows.

(Evaluation of results)
When Example and Comparative Example 1 are compared, in the present invention, due to the presence of organic components such as methyl groups in the organosilicon compound, the water contact angle is increased due to hydrophobic groups such as methyl groups. The releasability of the continuous vapor deposition film is increased, and a proper releasability as a release film is exhibited.
In addition, when comparing the water contact angles of Examples 1 and 2, the composition of the vapor deposition film is the same and the surface roughness is different, so the material with a larger surface roughness has a larger surface area. It turned out that the effect of a water-repellent vapor deposition film becomes strong.
And, as is clear from the results of the comparative examples in which the examples and conventional release films used in the FFC production were used, the oxygen atmosphere was maintained even under severe conditions of use in the FFC production. By using a release film for FFC production using a continuous vapor-deposited film of an organic silicon oxide containing an organic component exhibiting excellent water repellency and releasability under the above conditions, as in Comparative Example 2 At the time of heat laminating the FFC insulating film by a heat roll, it is excellent in high temperature heat roll without curling and heat shrinkage. In addition, there is no silicone component transfer as in Comparative Example 3 in which a conventional silicone resin having a large water contact angle is used as a release layer, and it is excellent in releasability with a heat-sealable resin. there were.
Moreover, at the time of FFC manufacture, a mold release film can be stably maintained over a long period of time,
The amount discarded as a release film can be reduced, which is advantageous in terms of running cost. Furthermore, the release layer is as thin as nm, and the material is a vapor-deposited film of organosilicon oxide. It becomes silicon dioxide at the time of combustion, and is excellent in environmental friendliness.
It has been found that the release film of the present invention exhibits extremely excellent performance that sufficiently satisfies the performance required for the release film in FFC production.

  According to the present invention, a water-repellent release film for FFC production which is efficient, low in cost and excellent in physical properties can be stably controlled with accurate control. The obtained water-repellent release layer is excellent in releasability, especially when manufacturing a flexible flat cable, preventing the transfer of the protruding resin when the heat seal is integrated with the insulating material, and there is no transfer of the release layer. As a result, it can be used repeatedly, does not generate wrinkles or heat shrinkage, is excellent in high-temperature hot roll suitability, silicone transfer property, combustion waste property, and the like, and is suitable for FFC production. Further, the water-repellent release film for FFC production of the present invention is a process for manufacturing various composite materials, FPC, multilayer printed circuit board, a separate film for adhesive, a release film for photosensitive agent, and a process for electronic materials / functional materials. It can be used for many release film applications such as paper.

A: Release film 1: Base film 2 (2a): Release layer, organic silicon oxide deposition film containing organic components 3: Reinforcing sheet 4: Insulating sheet 5: Multiple conductors 6: Flexible flat cable 7: Conductor exposure window 8: Thermocompression-bonding roll 9: FFC continuous production apparatus 11: Plasma chemical vapor deposition apparatus 12: Vacuum chamber 13: Unwinding roll 14: Winding roll 15: Cooling / electrode drum 16: Raw material volatilization supply apparatus

Claims (4)

  When producing a flexible flat cable in which a plurality of conductors are arranged at a constant interval between two insulating films and a fixed length conductor is exposed at both end portions, they are sandwiched by a thermocompression roll over the insulating film, A water-repellent release film for FFC production having a release layer for thermally fusing two insulating films, wherein the release layer contains Si—C or C—H bonds in the molecule It is characterized in that it is formed by plasma chemical vapor deposition of a continuous vapor-deposited film of organosilicon oxide so as to contain an organic component on a plastic substrate in a low oxygen gas atmosphere using a compound as a raw material for vapor deposition. Water repellent release film for FFC manufacturing.   The water-repellent release film for FFC production according to claim 1, wherein the low oxygen gas atmosphere is a gas atmosphere containing a rare gas or an inert gas other than the rare gas.   The organosilicon compound having a Si—O bond in the molecule is 1,1,3,3-tetramethyldisiloxane (TMOS), tetraethoxysilane (TEOS), or hexamethyldisiloxane (HMDSO). The water-repellent release film for FFC production according to claim 1 or 2.   The water-repellent release film for FFC production according to any one of claims 1 to 3, wherein the plastic substrate is a biaxially stretched polyester film or a biaxially stretched polyamide film.

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