JP4680045B2 - Release film for forming photocuring substrate and method for producing photocuring substrate - Google Patents

Description

  The present invention relates to a release film for forming a photocurable substrate, and more specifically, a release film for forming a photocurable substrate for continuously and efficiently producing a photocurable substrate, and a photocurable group. The present invention relates to a method for manufacturing a material.

  In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated. “CVD” is an abbreviation, functional expression, common name, or industry term for “chemical vapor deposition”, “PVD” for “physical vapor deposition”, and “PET” for “polyethylene terephthalate”. In addition, when a photocurable resin is cured (reacted), it becomes a photocurable resin.

(Background Art) Conventionally, a glass substrate is often used as a substrate such as a lens, a display substrate, an optical waveguide, a solar cell substrate, and an optical disk substrate in terms of transparency, strength, durability, and the like. However, the glass substrate has drawbacks such as being easily broken and heavy in structure, and the use of a resin substrate that can replace glass instead of the glass substrate in these applications has been studied.
Among the glass substitute resins, the photo-curing resin is excellent in moldability and productivity. However, general molding of a photo-curing resin is known by a so-called casting method in which a liquid photo-curing resin is injected into a mold having a certain volume and cured. Specifically, a photocurable resin is injected into a space formed by placing two plates facing each other with a certain distance between them, and the photocurable resin is cured by irradiation with energy rays, so that light is emitted. It was a so-called batch-type production method in which a method of using a curable resin (which can be used as a photo-curing substrate) was taken and the operation had to be repeated every time.
There is also a winding method in which a photocurable resin is flowed down and applied to the roll surface, covered with a cover film, cured through energy irradiation through the cover film, and then peeled off from the roll surface. However, when peeling from the roll surface, the surface is rough and the smoothness is lowered, the surrounding dust is attached, and there are disadvantages that require special and expensive production equipment.
As described above, the method for producing the photo-curing resin (photo-curing substrate) is not dependent on the casting method, and the surface is smooth, clean, preferably wound, and continuous and efficient. There was virtually no means to manufacture without a significant increase in.
Therefore, the method for producing a photo-curing substrate and the release film for forming the photo-curing substrate to be used in this method have a smooth surface, such as dust, without using a photo-curing resin instead of a glass substrate. There is a need for a clean, non-sticking, wound, continuous, efficient, manufacturable process that does not significantly increase costs.

(Prior Art) Conventionally, a method of manufacturing a substrate for an optical disk is known (for example, see Patent Documents 1 and 2). However, as a disadvantage of this method, there is a problem that the resin sticks to the mold and is not easily peeled off or cracked.
Moreover, in order to eliminate the above, what was devised such as forming a release layer or using a laminate of a metal or a metal compound that is easy to peel off on the inner surface of the mold is known (for example, (See Patent Documents 3 to 4.) However, in spite of these improvements, the casting method is prone to cracking the molded product during sheet recovery, and moreover, in these casting methods, it takes time to inject a viscous photocurable resin into the mold. Is disadvantageous in that the productivity is low and it is difficult to increase the area.

JP-A-60-202557 Japanese Patent Laid-Open No. 05-198018 JP 09-277277 A JP 09-278809 A

  Accordingly, the present invention has been made to solve such problems. Its purpose is to use a photo-curing resin instead of a glass substrate, without using a casting method, with a smooth surface, clean adhesion, dust, etc., rolled up, continuous, efficient, and a significant increase in cost. It is providing the release film for photocuring base material formation which can be manufactured, and the manufacturing method of a photocuring base material.

In order to solve the above-described problems, a release film for forming a photocurable substrate according to the present invention includes a strip-shaped film substrate, and a water repellent layer and a hydrophilic layer on at least one surface of the film substrate. The water-repellent layer is provided at both end portions of the base film, and the hydrophilic layer is provided at a portion excluding the water-repellent layer.
The release film for forming a photocurable substrate according to the present invention is such that the water-repellent layer is silicon oxycarbide or silicon oxycarbonitride formed using a plasma CVD apparatus.
The release film for forming a photocurable substrate according to the present invention is such that the water-repellent layer has a thickness of 1 to 100 nm and a contact angle with water of 80 to 150 °.
In the release film for forming a photocurable substrate according to the present invention, the hydrophilic layer contains one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, indium oxide, and magnesium oxide. As it is.
In the release film for forming a photocurable substrate according to the present invention, the hydrophilic layer has a thickness of 10 to 100 nm, a center line average roughness (Ra) of 30 nm or less, and a contact angle with water of 10. It is done so that it is ˜60 °.
In the method for producing a photocurable substrate according to the present invention, a photocurable resin composition is applied to the surface provided with the water-repellent layer and the hydrophilic layer of the release film for forming the photocurable substrate described above , Separately peel off the surface of the release film for forming the photo-curing substrate on which the water-repellent layer and hydrophilic layer are provided, and irradiate with active energy rays to cure the photo-curable resin composition. Then, at least one of the release films for forming the photocurable substrate is peeled off.

According to the present invention, the surface is smooth, clean with no adhesion of dust and the like, rolled up, continuous, efficient, and capable of being manufactured without significant increase in cost. A release film is provided.
According to the invention, the photocurable resin composition is applied by forming a water-repellent layer at the end of the film base and a hydrophilic layer at the center, and another release film is formed. Even if laminated, (1) liquid dripping and film thickness unevenness can be suppressed, and (2) smooth surface properties of the release film are transferred by curing by irradiation with active energy rays, so that the surface is smooth. (3) Since it is covered with two release films during production, a clean surface quality can be obtained without adsorbing or adhering dust around it, and (4) When the release film is peeled off, a release film for forming a photo-curing base material is provided that can be easily peeled off, so that a photo-curing base material can be obtained while maintaining a smooth surface property without roughening the surface. The
In addition, according to the present invention, the photocuring can be produced continuously and efficiently in a rolled form, with a smooth surface, no adhesion of dust, etc., and without using special equipment and without significantly increasing costs. A method of manufacturing a substrate is provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a perspective view showing one embodiment of a release film for molding a photocurable substrate of the present invention.
FIG. 2 is a cross-sectional view of a main part of a low temperature CVD apparatus for forming a water repellent layer and a hydrophilic layer.
FIG. 3 is a cross-sectional view in the flow direction for explaining the film formation zones of the water repellent layer and the hydrophilic layer.

  (Release Film) As shown in FIG. 1, a release film 10 for forming a photocurable substrate of the present invention has a strip-shaped film substrate 1 and a water repellent layer on at least one surface of the film substrate 1. 2 and the hydrophilic layer 3 are provided, the water-repellent layer 2 is provided at both end portions of the base film, and the hydrophilic layer 3 is provided at a portion excluding the water-repellent layer 2. Although the width of the water-repellent layer 2 provided on both side ends of the base film looks wide in FIG. 1 for the convenience of illustration, it is not particularly limited and may be uninterrupted. Further, the water-repellent layer 2 and the hydrophilic layer 3 may be slightly overlapped, and the water-repellent layer 2 is not interrupted. In addition, even if the base film is exposed at the outer end portion of the water repellent layer 2, the effect is not affected, and is within the scope of the present invention.

  (Method for Producing Photocuring Substrate) The method for producing a photocurable substrate of the present invention is as follows: (1) The water-repellent layer 2 and the hydrophilic layer 3 of the release film 10 for forming the photocured substrate of the present invention are provided. (2) The surface provided with the water-repellent layer and the hydrophilic layer of another release film 10 for forming the photo-curing substrate can be peeled off on the coated surface. (3) After irradiating active energy rays to cure the photocurable resin composition, (4) at least one of the release films 10 for forming the photocurable substrate may be peeled off. If necessary, the release films 10 for forming both photocuring substrates may be peeled off, and may be used as a protective film until processing to an intermediate product or assembly to a final product.

(Film Substrate) Next, in the present invention, the materials used for the release film 10 for forming the photocurable substrate according to the present invention, its production method, etc. will be described.
As the film substrate 1, this becomes a basic material constituting the release film 10 for forming the photocuring substrate, and further, a continuous thin film layer of the water repellent layer 2 and the hydrophilic layer 3 is provided on this, It is possible to use a resin film or sheet having excellent properties in mechanical, physical, chemical, etc., particularly having strength and toughness, and having heat resistance.
Examples of the film substrate 1 include polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer. (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins Resin, Polyamideimide resin, Polyarylphthalate resin, Silicone resin, Polysulfone resin, Polyphenylene sulfide resin, Polyethersulfone resin, Polyurethane resin, Acetal resin, Cellulose Fat, film or sheet of various resins other like - can be used and. In the present invention, it is particularly preferable to use a polypropylene resin, polyester resin, or polyamide resin film or sheet. The film thickness of various resin films or sheets is preferably about 50 to 200 μm, more preferably about 50 to 100 μm.

  Moreover, in order to improve the adhesiveness etc. with the continuous thin film layer which comprises the water-repellent layer 2 and the hydrophilic layer 3 on the surface of the above-mentioned various resin films or sheets, A desired surface treatment layer can be provided. In the present invention, examples of the surface treatment layer include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided. In addition, as a method for improving the tight adhesion and the like, in addition, for example, a primer coat layer, an undercoat layer, an anchor coat layer, an adhesive on the surface of various resin films or sheets in advance. A surface treatment layer can also be formed by arbitrarily forming a layer or a deposition anchor coating agent layer. Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. It is also possible to use a resin composition comprising a main component of a vehicle such as a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like.

  (Manufacture of Release Film) As a method of manufacturing the release film 10 for forming the photocurable substrate of the present invention, a vacuum film forming apparatus, for example, at least one of the organosilicon compounds on one surface of the film substrate 1 is used. When a gas composition containing vapor and oxygen gas is used and this is subjected to chemical vapor deposition by a plasma chemical vapor deposition method using a plasma generator, three film forming mechanisms are installed in the width direction, respectively. By forming a room and blocking the structure, a different film is formed on both ends and the center, thereby forming the water-repellent layer 2 on both ends of one surface of the base material, and sandwiched between the both ends. By forming the hydrophilic layer 3 on the part of the film substrate 1, the release film 10 for forming the photocured substrate of the present invention can be produced. As the water repellent layer 2, a gas composition containing at least an organic silicon compound vapor and oxygen gas is preferably used to form silicon oxide carbide or silicon oxycarbonitride, and as the hydrophilic layer 3, gas The composition includes at least a monomer gas composed of a vapor of an organosilicon compound as a raw material, an inert gas composed of argon gas or helium gas as a carrier gas, and oxygen gas as an oxygen supply gas. What is necessary is just to form the metal oxide thin film using the gas composition which consists of a composition containing.

  As a (plasma CVD) vacuum film-forming apparatus, specifically, an example of the method for forming a continuous thin film layer by the low-temperature plasma chemical vapor deposition method will be described. It goes without saying that the present invention is not limited by this. As shown in FIG. 2, a plasma chemical vapor deposition apparatus (plasma CVD) apparatus 11 preferably used in the present invention unwinds the film substrate 1 from an unwinding roll 13 disposed in a vacuum chamber 12, and further, The film substrate 1 is transported and run on the circumferential surface of the electrode drum 15 cooled at a predetermined speed via an auxiliary roll. Oxygen gas, inert gas, vapor deposition monomer gas such as organosilicon compound, etc. are supplied from gas supply devices 16, 17 and raw material volatilization supply device 18, etc., and a mixed gas composition for vapor deposition composed of these is prepared. The mixed gas composition for vapor deposition was introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and the film was transferred onto the film substrate 1 conveyed on the peripheral surface of the cooling / electrode drum 15. Plasma is generated by the discharge plasma 20 or the like and irradiated to form a continuous thin film layer. At that time, a predetermined power is applied to the cooling / electrode drum 15 from a power source 21 disposed outside the vacuum chamber 12, and a magnet 22 is disposed in the vicinity of the cooling / electrode drum 15. Thus, the generation of plasma is promoted. Subsequently, the film base material 1 in which the continuous thin film layer is formed can be continuously wound around the take-up roll 24 via an auxiliary roll, whereby the release film 10 for forming a photo-curing base material can be continuously produced. In the figure, 25 represents a vacuum pump.

  As the above-described plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, or microwave plasma can be used. Further, in the above, as a Puma chemical vapor deposition method (referred to as CVD), for example, a winding type plasma chemical vapor deposition method or the like is used, and the release film 10 for photocuring substrate formation is continuously formed. It can also be manufactured.

  (Film formation zone) As shown in FIG. 3 which is a cross-sectional view from the right angle direction, the cooling / electrode drum 15 portion is formed in the width direction of the film substrate 1 when the continuous thin film layer is formed by irradiation with plasma. In contrast, this mechanism has a plurality of film formation zones. A plasma CVD mechanism for forming the water-repellent layer 2 is disposed at both ends to form a water-repellent layer forming zone 26, and a portion sandwiched between the water-repellent layer forming zones 26 serves as a hydrophilic layer forming zone 27, respectively. When the vapor deposition mixed gas composition is introduced through the raw material supply nozzle 19, different substances can be formed in the water-repellent layer forming zone 26 and the hydrophilic layer forming zone 27. Note that the film formation zone also has a film formation mechanism such as a PVD method, a sputtering method, a CVD method, or an ion plating method, and also has a structure obtained by the film formation mechanism.

  (Water-repellent layer) As the water-repellent layer 2, as a vapor deposition monomer gas such as an organosilicon compound forming a continuous thin film layer of silicon oxide carbide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material. Further, tetramethyldisilazane or the like is preferably used when forming silicon oxynitride carbide. In the above, as the inert gas, for example, argon gas, helium gas or the like can be used. The formation method is preferably a plasma CVD method.

  (Formation of water-repellent layer) Next, a continuous thin film layer of silicon oxycarbide or silicon oxycarbonitride that forms the water-repellent layer 2 will be described. Can be manufactured by using a chemical vapor deposition method or the like to form a single layer film consisting of one continuous thin film layer of silicon oxide carbide or silicon oxycarbonitride or a multilayer film consisting of two or more layers It is.

  The continuous thin film layer of silicon oxycarbide by the chemical vapor deposition method will be further described. As the continuous thin film layer of silicon oxycarbide by the chemical vapor deposition method, for example, a chemical vapor phase such as a plasma chemical vapor deposition method can be used. It can be formed using a growth method (Chemical Vapor Deposition method, CVD method) or the like. In the present invention, specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a substrate, and an inert gas such as argon gas or helium gas is used as a carrier gas. Further, a gas composition is prepared using oxygen gas or the like as an oxygen supply gas, and then this is continuously formed using a low-temperature plasma chemical vapor deposition method using a low-temperature plasma generator or the like. A thin film layer can be formed. In the above, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a high-frequency plasma generator.

  Although not shown in the drawings, in the present invention, the continuous thin film layer of silicon oxycarbide is not limited to one layer of the continuous thin film layer of silicon oxycarbide, but may be a multilayer film in which two or more layers thereof are laminated, The materials used may be used alone or in a mixture of two or more, and a continuous thin film layer of silicon oxide mixed with different materials may be formed.

In the above, the inside of the vacuum chamber-12 is decompressed by the vacuum pump 25, and it is desirable that the degree of vacuum is adjusted to about 10 to 1 × 10 −6 Pa, preferably about 1 × 10 −1 to 1 × 10 −5 Pa. Is. In the raw material volatilization supply device 18, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply devices 16, 17, and this mixed gas is supplied to the raw material supply nozzle 19. And introduced into the vacuum chamber-12. In this case, the contents of the organosilicon compound, oxygen gas, inert gas, and the like in the mixed gas can be changed with any composition. On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power source 21, the glow discharge plasma 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. 20 is generated, and the glow discharge plasma 20 is derived from one or more gas components in the mixed gas, and this process is simultaneously performed by two film forming mechanisms. In this state, the film substrate 1 is conveyed at a constant speed, and a continuous thin film layer of silicon oxycarbide is formed on the edge of the film substrate 1 on the circumferential surface of the cooling / electrode drum 15 by the glow discharge probe 20. It is something that can be done. In addition, it is desirable to adjust the degree of vacuum in the vacuum chamber at this time to about 10 to 1 × 10 ⁻² Pa, preferably about 10 to 1 Pa, and the conveyance speed of the substrate 1 is It is desirable to prepare at 10 to 500 m / min, preferably 10 to 350 m / min.

  In the plasma chemical vapor deposition apparatus 11 described above, the continuous thin film layer of silicon oxycarbide is formed on the film base 1 in the form of the formula SiOxCz while oxidizing the plasma source gas with oxygen gas. Therefore, the formed silicon oxide carbide vapor-deposited film is a continuous layer that is dense, has few gaps, and is highly flexible. Therefore, the continuous thin film layer of silicon oxide is Excellent close adhesion to the base material, high uniformity of film thickness, and since it is formed into a film in a vacuum, there is no adhesion of dust etc. to the surface, and it has a uniform releasability. A film having excellent characteristics can be formed.

In the present invention, the surface of the film substrate 1 is cleaned by plasma, and polar groups, free radicals, and the like are generated on the surface of the film substrate 1, so that a continuous thin film layer of silicon oxide carbide is formed. And the film substrate 1 have an advantage of high close adhesion. Furthermore, the degree of vacuum during the formation of the continuous thin film layer of silicon oxide carbide as described above is adjusted to about 10 to 1 × 10 ⁻² Pa, preferably about 10 to 1 Pa. Since the degree of vacuum when forming a silicon oxide carbide vapor deposition film is lower than that of 1 × 10 ⁻² to 1 × 10 ⁻³ Pa, the substrate 1 is in a vacuum state when the raw material is replaced. The set time can be shortened, the degree of vacuum is easily stabilized, and the film forming process is stabilized.

In the present invention, a continuous thin film layer of silicon oxycarbide formed by using a vapor-deposited monomer gas such as an organosilicon compound causes a chemical reaction between the vapor-deposited monomer gas such as an organosilicon compound and oxygen gas. The product is intimately bonded to one surface of the substrate to form a dense thin film having high flexibility and the like. Usually, the general formula SiOxCz (where x is 1 to 2, z is 0) Is a continuous thin film mainly composed of silicon oxide carbide represented by Thus, the above-mentioned continuous thin film layer of silicon oxycarbide is an oxide represented by the general formula SiOxCz (where x represents a number of 1 to 2) in terms of transparency, releasability and the like. A thin film mainly composed of a continuous thin film layer of silicon carbide is preferable.

Further, the continuous thin film layer of oxide of silicon carbide above, the oxidation of silicon carbide as a main component, to which further comprises at least carbon, hydrogen, one of silicon or oxygen, or a compound consisting of two or more elements 1 It consists of a continuous thin film layer containing a kind by a chemical bond or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, a compound having a Si—C bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc., An organosilicon compound or a derivative thereof may be contained by a chemical bond or the like. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type and amount of the compound contained in the continuous thin film layer of silicon oxide carbide can be changed by changing the conditions of the vapor deposition process.

Thus, the content of the above compound in the continuous thin film layer of silicon oxide carbide is preferably about 0.1 to 80%, preferably about 5 to 60%. In the above, if the content is less than 0.1%, the releasability of the continuous thin film layer of silicon oxide carbide decreases, or the impact resistance, spreadability, flexibility, etc. become insufficient, Bending, etc. is likely to cause scratches, cracks, etc., making it difficult to maintain the stability, and if it exceeds 80%, the releasability and the like are lowered, and the adhesion of the film is also lowered. This is undesirable.

  Furthermore, in the present invention, in the continuous thin film layer of silicon oxycarbide, the content of the above compound is preferably decreased from the surface of the continuous thin film layer of silicon oxycarbide in the depth direction. On the surface of the continuous thin film layer of silicon carbide, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, at the interface with the resin film, the content of the above compound is small, so This has the advantage that the tight adhesion with the continuous thin film layer of silicon carbide becomes strong. Moreover, in this invention, when said compound contains in the continuous thin film layer of silicon oxycarbide which comprises a mold release layer, carbon atom content is 5 in said continuous thin film layer of silicon oxycarbide. It is desirable that it is contained in an atomic% or more, specifically in the range of 5 atomic% to 70 atomic%, preferably in the range of 10 atomic% to 50 atomic%. In the above, if the carbon atom content is less than 5 atomic%, and more preferably less than 10 atomic%, the presence of methyl groups (CH3), which are water repellent groups, decreases, and the peelability and the like deteriorate. It is not preferable, and if the carbon atom content exceeds 50 atomic%, and further exceeds 70 atomic%, it is not preferable because the hardness, strength, etc. of the film are reduced and peeling off occurs. is there.

  Thus, in the present invention, the silicon oxide carbide continuous thin film layer constituting the water-repellent layer 2 is, for example, an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary Ion Mass Spectrometer). The above physical properties are obtained by conducting elemental analysis of a continuous thin film layer of silicon oxide carbide using a method of analyzing by ion etching in the depth direction using a surface analyzer such as Spectroscopy (SIMS). Can be confirmed. In the present invention, the film thickness of the above-mentioned continuous thin film layer of silicon oxycarbide is preferably about 20 to 4000 mm, and specifically about 50 to 1000 mm. Thus, in the above, if it is thicker than 1000 mm, and more than 4000 mm, it is not preferable because cracks and the like are likely to occur in the film, and a gap with a non-film-formed surface is generated during winding, and wrinkles are generated. Therefore, it is not preferable. On the other hand, if it is less than 50 mm, or less than 20 mm, it is not preferable because it is difficult to obtain the effect of releasability.

  In the above, the film thickness can be measured using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as means for changing the film thickness of the continuous thin film layer of silicon oxycarbide described above, the volume velocity of the continuous thin film layer is increased, that is, a method of increasing the amount of monomer gas and oxygen gas or vapor deposition It can be performed by a method of slowing down the speed of performing.

  (Hydrophilic layer) The hydrophilic layer 3 contains one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, indium oxide, and magnesium oxide. Any of the ion plating method and the sputtering method can be used, but the plasma CVD method is preferable.

  (Characteristics of water-repellent layer) The water-repellent layer 2 has a thickness of 1 to 100 nm and a contact angle with water of 80 to 150 °. If the film thickness is less than 1 nm, a uniform water-repellent surface cannot be obtained, and if it exceeds 100 nm, the film formation time increases, which is not preferable for production. Further, if the contact angle is less than 80 °, a uniform contact angle cannot be obtained in the plane, and a larger contact angle is preferable because a sufficient difference in contact angle with the hydrophilic surface can be obtained. The photocurable resin cannot be uniformly applied, which is not preferable.

  (Properties of hydrophilic layer) The hydrophilic layer 3 has a film thickness of 10 to 100 nm, a center line average roughness (Ra) of 30 nm or less, and a contact angle with water of 10 to 60 °. If the film thickness is less than 10 nm, a uniform hydrophilic surface cannot be obtained, and if it exceeds 100 nm, the film formation time increases, which is not preferable for production. Further, if the contact angle is less than 10 °, a uniform contact angle cannot be obtained in the plane, and a difference in contact angle with the water repellent surface can be sufficiently obtained. The difference in contact angle is not preferable.

  In addition, since the photocurable resin is applied and cured through the hydrophilic layer 3 on the surface of the film substrate 1, the smoothness of the surface is also transferred to the surface of the photocurable substrate. Smoothness is desirable, and the center line average roughness (Ra) is 30 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less.

  As is apparent from the above description, the present invention provides a continuous thin film of silicon oxycarbide or silicon oxynitride carbide obtained by chemical vapor deposition of a vapor of an organosilicon compound by a plasma chemical vapor deposition method using a plasma generator. It is possible to form a water-repellent layer with excellent film thickness uniformity, uniform water repellency, and film formation in a vacuum. There is no problem of dust adhering, the surface is smooth, no dust adhering, clean, rolled up, continuous and efficient, and can be manufactured without significant cost increase A release film 10 for forming a photocuring substrate having characteristics can be obtained.

(Method for Producing Photocuring Substrate) As described above, using the release film for forming a photocurable substrate of the present invention, first, (1) the release film 10 for forming the photocurable substrate. The photocurable resin composition is applied to the surface on which the water repellent layer 2 and the hydrophilic layer 3 are provided.
The photo-curing resin is not particularly limited. For example, the photo-curing resin is obtained by curing a curable resin composition (also referred to as a precursor) with ultraviolet rays (UV) or the like, and reacting with polymerization (also referred to as curing). , Containing a curable component having a functional group. As the curable component, a compound having a radical polymerizable unsaturated double bond can be applied, and examples thereof include a monofunctional monomer, a bifunctional or higher polyfunctional monomer, a functional oligomer, and a functional polymer. The functional group that is polymerized (also called cured) by ionizing radiation is an acryloyl group, a methacryloyl group, an allyl group, or an epoxy group. Further, the curable resin composition may contain at least one monomer, or may further contain a monomer called a reactive diluent. Furthermore, monomers and oligomers can increase the speed of the polymerization reaction, and oligomers and polymers can adjust the crosslinking density and cohesion after curing. Furthermore, you may add additives, such as a polymerization inhibitor and anti-aging agent, to a curable resin composition as needed. In the curable resin composition, if necessary, a plasticizer, a lubricant, a colorant such as a dye or a pigment, a filler such as an extender pigment or a resin for increasing weight or preventing blocking, a surfactant, an antifoaming agent, Additives such as leveling agents and thixotropic agents may be added as appropriate.

  A gravure coating method, a roll coating method, a comma coating method, a knife on the entire surface of the release film 10 for forming a photocurable base material on which the water repellent layer 2 and the hydrophilic layer 3 are provided. Coating is performed by a known coating method such as a coating method or a die coating method. Since the liquid photocurable resin composition applied to the entire surface is repelled by the water-repellent layer 2 and gathers to the hydrophilic layer 3 at the center, liquid leakage and There is no dripping, and the film thickness is less likely to be uneven, resulting in a uniform coating film.

  Next, (2) pressure bonding between two heated or non-heated rolls to the surface provided with the water-repellent layer and hydrophilic layer of another release film 10 for forming the photocuring substrate on the coated surface Then, they may be laminated to form a so-called sandwich. Even in the sandwich shape, since the film is repelled by the water-repellent layers at both ends of the film base and does not flow to the end even after the photocurable resin composition is sandwiched between the film bases, the film thickness is more uniform. A uniform coating film can be obtained.

  In this sandwich state, the photocurable resin composition is cured by irradiating (3) active energy rays from at least one side. As the active energy rays, ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays, X-rays, electron beams (EB) and the like can be applied, and UV is preferable from the viewpoint of handling and cost.

  Next, (4) the release film 10 for forming at least one of the photocuring substrates is peeled off. If the two release films 10 for forming a photocuring substrate on both sides of the sand are peeled off, a photocuring substrate can be obtained. According to the method for producing a photo-curing substrate of the present invention, the surface is smooth, clean with no adhesion of dust, etc., without using special equipment and without significant increase in cost, and in a wound form, continuous. It can be manufactured efficiently.

  In addition, the obtained photocured substrate is very uniform with no film thickness unevenness, and is covered with two release films 10 for forming a photocured substrate during manufacture. Clean surface quality that does not adsorb or adhere dust. Furthermore, since it can be easily peeled when peeling, the surface is not rough, and the smooth surface property of the release film 10 for forming the photocuring substrate is transferred, so that the centerline average roughness (Ra ) Is 30 nm or less, more preferably 10 nm or less, and still more preferably 5 nm or less.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

(Example 1) A biaxially stretched PET film having a width of 640 mm and a thickness of 50 µm was used as a film substrate, and this was mounted on a delivery roll of a vacuum film forming apparatus. A water repellent layer composed of a continuous thin film layer of silicon oxide carbide having a thickness of about 30 mm and a thickness of 500 mm is formed by plasma CVD at both ends of the untreated surface of the axially stretched PET film, and at the same time sandwiched between the water repellent layers A hydrophilic layer of indium oxide having a thickness of 500 mm was formed on the part by plasma treatment, and then formed by a pressure gradient ion plating method to obtain a release film for forming a photocuring substrate of Example 1.
・ <Water-repellent layer deposition conditions, plasma CVD method>
Vapor deposition surface; corona treatment carried out amount of introduced gas; hexamethyldisiloxane: oxygen: helium = 10: 1: 10 (slm)
Power: 0.5kW
Deposition rate: 10 m / min
Deposition pressure: 2Pa
・ <Hydrophilic layer deposition conditions, ion plating method>
Material: Indium oxide (tin-doped)
Amount of introduced gas; argon: oxygen = 20: 20 (sccm)
Power: 5.0kW
Deposition rate: 10 m / min
Deposition pressure: 0.1 Pa
Electrode drum temperature: 5 ° C

(Example 2) A biaxially stretched PET film having a width of 640 mm and a thickness of 100 μm was used as a substrate, and this was mounted on a delivery roll of a vacuum film forming apparatus. A water-repellent layer composed of a continuous thin film layer of silicon oxide carbide having a thickness of about 500 mm was formed on both end surfaces of one surface of the terephthalate film using a plasma CVD method and was sandwiched between the water-repellent layers at the same time. Using a plasma CVD method, a silicon oxide hydrophilic layer having a thickness of 500 mm was formed in the center portion after plasma treatment to obtain a release film for forming a photocuring substrate of Example 2. .
・ <Water-repellent layer deposition conditions, plasma CVD method>
Vapor deposition surface; corona treatment introduced Gas amount introduced: hexamethyldisiloxane: oxygen: helium = 1: 1: 1 (slm)
Power: 0.5kW
Deposition rate: 10 m / min
Deposition pressure: 30 Pa
・ <Hydrophilic layer deposition conditions, plasma CVD method>
Introduction gas amount: tetraethoxysilane: oxygen: helium = 1: 20: 10 (slm)
Power: 3.0kW
Deposition rate: 10 m / min
Deposition pressure: 30 Pa

(Example 3) A biaxially stretched polypropylene film having a width of 640 mm and a thickness of 50 μm was used as a base material, and this was mounted on a delivery roll of a vacuum film forming apparatus. A water repellent layer composed of a continuous thin film layer of silicon oxynitride carbide having a thickness of about 30 mm and a thickness of 500 mm was formed on both end faces of the untreated surface of the film by plasma CVD, and was sandwiched between the water repellent layers at the same time. In the center portion, a hydrophilic layer of aluminum oxide having a thickness of 500 mm was formed by plasma treatment using the PVD method, and a release film for forming a photocuring substrate of Example 3 was obtained.
・ <Water-repellent layer deposition conditions, plasma CVD method>
Vapor deposition surface; corona treatment carried out Amount of introduced gas; hexamethyldisilazane: nitrogen: helium: argon = 1: 5: 1: 0.1 (slm)
Power: 3.0kW
Deposition rate: 10 m / min
Deposition pressure: 30 Pa
・ <Hydrophilic layer deposition conditions, PVD method>
Film-forming material: Al
Introduced gas amount; oxygen (introduced to be 0.05 Pa)
EB emission current: 1.0A
Deposition rate: 10 m / min

(Comparative Example 1) A biaxially stretched PET film having a width of 640 mm and a thickness of 25 μm was used as a base material, and this was mounted on a delivery roll of a vacuum film forming apparatus. Then, under the conditions shown below, On the untreated surface of the biaxially stretched PET film, a water-repellent layer composed of a continuous thin film layer of silicon oxide having a thickness of 500 mm is formed at both ends with a width of 30 mm, and in the central part sandwiched between the water-repellent layers A release film for forming a photocurable substrate of Comparative Example 1 was obtained without forming a hydrophilic layer.
・ <Water-repellent layer deposition conditions, plasma CVD)
Vapor deposition surface; corona treatment introduced Gas amount introduced; hexamethyldisiloxane: oxygen: helium = 1: 15: 10 (slm)
Power: 0.5kW
Deposition rate: 10 m / min
Deposition pressure: 2Pa

  (Comparative Example 2) A biaxially stretched PET film having a width of 640 mm and a thickness of 188 μm was used as a film base material, and the film was formed under the same conditions as in Comparative Example 1 except that the vapor deposition surface was untreated. A release film for forming a photocurable substrate 2 was obtained.

  (Comparative Example 3) A mold release material for forming a photocuring substrate of Comparative Example 3 using a biaxially stretched PET film having a width of 640 mm and a thickness of 100 μm as the film substrate, and having no water-repellent layer and hydrophilic layer. A film was obtained.

(Evaluation) The evaluation of the release film 10 for forming a photocurable substrate produced in Examples 1 to 3 and Comparative Examples 1 to 3 described above is based on the contact angle (water) on the surface of the water repellent layer (water) and hydrophilicity. The contact angle (water) of the surface of the layer, the surface roughness Ra of the surface of the hydrophilic layer, and the appearance of winding were visually observed.
In addition, the surface contact angle (water) of the surface was measured using a contact angle tester (Kyowa Interface Science Co., Ltd., model name, CA-DT type).
The center line surface roughness (Ra) is measured in a measuring range of 100 × 100 μm using a stylus microscope Nanopics1000 manufactured by Seiko Instruments Inc. according to JIS-B-0601. did. The results are shown in Table 1.

(Examples 4 to 6) Photocurable substrates were produced by the method for producing a photocurable substrate of the present invention. As the first release film to be fed, the release film for forming a photocurable substrate obtained in Examples 1 to 3 is used, and hydroxymethyltricyclodecane dimethacrylate is provided on the surface side of the water-repellent layer and the hydrophilic layer. 94 parts, 6 parts of hydroxymethyltricyclodecane monomethacrylate, 6 parts of β-thiopropionate, 0.1 part of photoinitiator ("Lucirin TPO" manufactured by BASF) and 0.1 part of benzophenone were uniformly mixed with stirring. Coating was carried out by adjusting a photocurable resin composition comprising an acrylic composition to a thickness of 100 μm by a knife coating method.
The same release film as the first release film was used as the second release film to be bonded so that the surface of the photocurable resin composition was touched, and the water repellent layer and the hydrophilic layer were bonded to each other. Then, after sending out to the temperature control drum section adjusted to 20 ° C. and irradiating with 5.0 J of ultraviolet rays using an electrodeless lamp and curing (the cured resin becomes a photo-curing substrate) and winding it, the first and The second release film was peeled off to obtain a photocured substrate.
In addition, what was manufactured with the manufacturing method of the photocuring base material using the release film for photocuring base material formation obtained in Example 1, 2, 3 as a 1st and 2nd release film was implemented, respectively. The photocured substrates of Examples 4, 5, and 6 were used.

  (Comparative Examples 4-6) Photocured substrates were prepared in the same manner as in Examples 4-6. As the first and second release films, those using the release films for forming the photocurable substrate obtained in Comparative Examples 1, 2, and 3 were used as the photocurable substrates of Comparative Examples 4, 5, and 6, respectively. Tried to get.

  (Evaluation) From the cured resins of Examples 4 to 6 and Comparative Examples 4 to 6 (being photocured substrates), each of Examples 1 to 3 and Comparative Examples 1 to 3 for forming a photocured substrate The release state when peeling the release film was visually confirmed. In Examples 4 to 6, the release film for forming the photocuring substrate is easily peelable from the cured resin (photocuring substrate), and is represented by “◯” in Table 1. However, in Comparative Examples 4 to 6, it cannot be peeled off, and only the cured resin (photocured substrate) cannot be taken out, and is indicated by “x”.

It is a perspective view which shows one Example of the release film for photocuring base material shaping | molding of this invention. It is sectional drawing of the principal part of the low temperature CVD apparatus which forms a water repellent layer and a hydrophilic layer. It is sectional drawing of the flow direction explaining the film-forming zone of a water repellent layer and a hydrophilic layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1: Base material 10: Release film for photocuring base material formation 11: Plasma chemical vapor deposition apparatus 12: Vacuum chamber 13: Unwinding roll 15: Electrode drum 16, 17: Gas supply apparatus 18: Raw material volatilization supply apparatus 19: Raw material supply nozzle 20: Glow discharge plasma 21: Power supply 22: Magnet 24: Winding roll 25: Vacuum pump 26: Water repellent layer deposition zone 27: Hydrophilic layer deposition zone

Claims (4)

A band-shaped film substrate and a water-repellent layer and a hydrophilic layer are provided on at least one surface of the film substrate, the water-repellent layer is provided on both side ends of the substrate film, and the hydrophilic layer is Ri Na provided in a portion except for the water-repellent layer,
The water repellent layer is silicon oxide carbide or silicon oxycarbonitride formed using a plasma CVD apparatus, and has a contact angle with water of 80 to 150 °,
The lyophilic layer contains one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, indium oxide, and magnesium oxide, and has a contact angle with water of 10 to 60 °. release film for photocurable base form, characterized in that it. Release film for photocurable base form of claim 1, the film thickness of the water repellent layer is equal to or Ru 1~100nm der. The thickness of the hydrophilic layer is 10 to 100 nm, the center line average roughness (Ra) for photocuring substrate formed of claim 1 or claim 2, wherein the Ru Der below 30nm Release film. A photocurable resin composition is applied to the surface provided with the water-repellent layer and the hydrophilic layer of the release film for forming a photocurable substrate according to any one of claims 1 to 3 , and the coating is applied. The surface provided with the water-repellent layer and the hydrophilic layer of another release film for forming the photo-curing substrate on the surface is peelably laminated, and the photo-curable resin composition is cured by irradiating active energy rays. And then peeling off at least one of the release films for forming the photocuring base material.

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