JP2008018679A - Release film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a release film which is suitable for an industrial adhesive tape and an optical pressure sensitive adhesive sheet and has high water repellency to prevent the adhesion of water droplets and contamination. <P>SOLUTION: The release film is formed on a polymer substrate which has a surface roughness of 5-200 nm and fine unevenness with an S/N ratio of 5-50 and has a water repellent layer with a contact angle with water of 100-160° and a contact angle with soapy water of 50-100° and which is made of a self-organizing monomolecular film on a non-release surface. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a release film. More specifically, the present invention relates to a release film suitable for, for example, an industrial adhesive tape or an optical pressure-sensitive adhesive sheet.

  For example, in industrial pressure-sensitive adhesive sheets, optical pressure-sensitive adhesive sheets, and other various fields, it is required to make the surface water-repellent in order to prevent adhesion of water droplets and contamination. Thus, as a method for imparting water repellency to the surface of a polymer substrate, a method of forming a hydrophobic material such as a fluorine-based or silicone-based water-repellent film on the surface of the substrate has been known. Since the contact angle is about 120 °, it is difficult to achieve high water repellency, problems such as poor abrasion resistance, chemical resistance, and heat resistance of the coating film, and changes over time There was a problem such as large.

Furthermore, as a method of imparting water repellency to the surface, a method of introducing an air layer and improving water repellency by producing a fine uneven shape on the surface by laser or wet etching or the like is known. However, this method has a problem that the base material is limited and the cost is high because the apparatus is large and expensive.
JP 2004-017591 A

  Therefore, it is desired to provide a highly water-repellent substance that can be manufactured by a simple process and has high water repellency.

  The release film according to the present invention is characterized by having a water-repellent layer formed on a polymer substrate having fine irregularities on the surface on a non-release surface. Here, the release film is a part composed of three elements of “substrate”, “adhesive”, and “release film”, and the release film is required to have performance such as ease of peeling and ease of processing. Such release films include, for example, films that are peeled off from the bonding surface of a bonding film such as an adhesive film or an adhesive film, and the release film itself does not exhibit adhesiveness or tackiness, such as a release film. Is done.

  Such a release film according to the present invention preferably includes the surface of the polymer substrate having a surface roughness of 5 to 200 nm and an S / N ratio in the range of 5 to 50. To do.

  In such a release film according to the present invention, preferably, the surface of the water-repellent layer has a contact angle with water of 100 to 160 ° and a contact angle with soapy water of 50 to 100 °. Including those formed of a certain material.

  Such a release film body according to the present invention preferably includes an organic film in which the water-repellent layer is composed of a metal skeleton and has an alkyl group, and an organic film composed of carbon and hydrogen.

  Such a release film according to the present invention preferably includes one in which the water repellent layer is a self-assembled monolayer.

  In addition, the bonding film according to the present invention is characterized in that the release film is detachably provided on the bonding surface of the bonding film.

  The release film according to the present invention is characterized by having a water-repellent layer formed on a polymer substrate having fine irregularities on the surface, on the non-release surface. In addition, the water repellent layer has high water repellency due to the effects of both water repellency and can be manufactured by a simple process.

  The present invention relates to a release film that can be produced by a simple process and has high water repellency. Hereinafter, these will be described separately.

1. Release Film The release film according to the present invention is characterized in that it has a water-repellent layer formed on a polymer substrate having fine irregularities on its surface on a non-release surface. In the present invention, by forming a water repellent layer on a polymer substrate having fine irregularities on the surface, the surface of the release film can also be shaped to have irregularities. The effect of both the water repellency and the water repellency of the water repellent layer makes it possible to obtain a release film having high water repellency.
Hereinafter, the configuration of the release film will be described.

<Polymer substrate>
The polymer substrate used in the present invention is a polymer substrate having fine irregularities on the surface, and if the fine irregularities can exhibit water repellency, the type of resin, etc. Is not limited, and may be transparent or opaque depending on the application, may be in the form of a film or plate, and may be a glass or silicon wafer. A substrate having a solid surface coated with a polymer may be used.

Preferable specific examples of the polymer substrate that can be used in the present invention include, for example,
-Polyolefin (PO) resin, for example, homopolymers or copolymers of ethylene, polypropylene, butene, etc.
-Amorphous polyolefin resin (APO) such as cyclic polyolefin,
-Polyester resins such as polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), etc.
-Polyamide (PA) resin, such as nylon 6, nylon 12, copolymer nylon, etc.
-Polyvinyl alcohol resin, for example, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH), etc.
・ Polyimide (PI) resin,
・ Polyetherimide (PEI) resin,
・ Polysulfone (PS) resin,
・ Polyethersulfone (PES) resin,
-Polyetheretherketone (PEEK) resin,
・ Polycarbonate (PC) resin,
-Polyvinyl butyrate (PVB) resin,
-Polyarylate (PAR) resin,
Fluorine-based resins such as ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF) ), Vinyl fluoride (PVF), perfluoroethylene 1-perfluoropropylene-perfluorovinyl ether copolymer (EPA), and the like can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use as a base material what laminated | stacked 1 type, or 2 or more types of these resin by means, such as a lamination and a coating. Furthermore, a base material obtained by coating these resins on a solid surface such as glass or a silicon wafer may be used.

  Among the above-mentioned polymer base materials, it is particularly preferable that the surface of the polymer base material is formed with fine irregularities by plasma irradiation on the surface of the polymer base material. Since the polymer base material is a material in which fine irregularities are formed on the surface by plasma irradiation, it becomes possible to obtain fine irregularities on the surface of the polymer substrate by plasma irradiation. This is because it is preferable in terms of cost.

  The polymer substrate in the present invention may be unstretched, but is preferably stretched. By stretching the polymer base material, regular orientation becomes possible, and irregularities are easily formed regularly on the entire surface, and the irregularities enable higher water repellency. is there. In addition, even when unstretched, random irregularities are formed, so that water repellency can be increased.

  As a specific stretching method, an unstretched substrate is flown by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. A stretched substrate can be produced by stretching in the (vertical axis) direction or in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Furthermore, the polymer base material of the present invention is preferably a polyester resin or a polycarbonate, among the polymer base materials described above. Among polyester resins, polyethylene terephthalate and polyethylene naphthalate are particularly preferable. Since the polymer base material is such a substance, it can be used for various applications because of its properties such as easy formation of fine surface irregularities and further ease of processing. This is because the water-repellent laminate can be used for various purposes.

  Here, the formation method of the unevenness of the polymer base material and the shape of the unevenness are not particularly limited, but as the unevenness formed on the surface of the polymer base material, the surface roughness is 5 to 200 nm, It is preferable to be in the range of 5 to 100 nm, particularly 5 to 50 nm. When the surface roughness is less than 5 nm, the surface flatness is high and super water repellency is lacking, which is not preferred. On the other hand, when the surface roughness exceeds 200 nm, the abrasion resistance is lowered, which is not preferred. This is because, when the surface roughness of the surface of the polymer substrate is within the above range, high water repellency and abrasion resistance can be expressed.

  Here, the surface roughness is based on JIS-B-0601 and is a reference length at the time of measurement in a contact mode using a desktop small probe microscope (trade name Nanopics 1000, manufactured by Seiko Instruments Inc.) capable of measuring in nm units. The thickness was measured as 100 μm.

  And as for the polymeric base material in this invention, it is preferable that S / N ratio exists in the range of 5-50, and it is especially preferable that it exists in the range of 10-40. Here, the S / N ratio is based on the JIS standard, and specifically, the surface unevenness is obtained by using a measurement method defined by JISB0601. When the S / N ratio is less than 5, the water repellency is small, whereas when it exceeds 50, the abrasion resistance is insufficient, which is not preferable. This is because when the surface roughness of the surface of the polymer substrate is within the above range, high water repellency can be expressed.

  The method for forming irregularities on the surface of the polymer substrate is arbitrary, and both dry etching and wet etching can be employed in the present invention. In the present invention, dry etching such as etching by plasma irradiation, reactive ion etching, sputter etching, photoetching, and the like are preferable. Among them, a method using plasma etching is preferable, and a plasma etching method using a gas containing oxygen atoms is particularly preferable, and oxygen plasma etching is particularly preferable.

  This is because the formation of projections and depressions on the surface of the polymer base material using plasma etching can be performed by a simple process and is preferable from the viewpoint of manufacturing efficiency and cost. In particular, it is possible to introduce a hydrophilic group onto the surface of the polymer substrate by using etching with plasma using a gas containing oxygen atoms, which will be described later on the polymer substrate into which the hydrophilic group has been introduced. By providing the water-repellent layer, the adhesion between the water-repellent layer and the polymer substrate is improved, and a release film having good mechanical properties can be produced.

<Water repellent layer>
The water repellent layer in the present invention is not particularly limited as long as it is a layer having water repellency formed by a vapor phase method on the above-described polymer substrate on which the surface irregularities are formed. The water repellent layer is preferably a material having a contact angle with water of 70 to 120 °, particularly 100 to 120 ° when formed on a flat surface. When the water-repellent layer is formed on a polymer substrate having irregularities on the surface because it is formed of a material whose contact angle with pure water is within the above range when formed on a flat surface. This is because higher water repellency can be imparted.

  The contact angle with water in the present invention is based on JIS R3257, and is specifically determined by the sessile drop method defined in 6 of JIS R3257. In the above, the contact angle with water is measured by using a contact angle measuring device (model number CA-Z) manufactured by Kyowa Interface Chemical Co., Ltd., specifically, one drop of pure water (constant constant) on the surface of the object to be measured. Amount) was dropped, and after a predetermined time (10 seconds), the shape of the water droplet was observed using a microscope or a CCD camera, and the contact angle was physically obtained.

  And it is preferable that the water repellent layer in this invention is formed with the material whose contact angle with soap water is 50-100 degrees, and is especially within the range of 60-100 degrees. As the soapy water used for contact angle measurement, the preparation method defined in 8.4.1 of JISK3362 is used.

  Further, the water repellent layer of the present invention is preferably a water repellent film formed by a vapor phase method or a self-assembled monomolecular film. Hereinafter, these will be described separately.

(1) Water-repellent film formed by vapor phase method First, the water-repellent film formed by the vapor phase method will be described.
The water repellent film formed by the vapor phase method in the present invention is an organic film having a metal skeleton and having an alkyl group, and an organic film composed only of carbon and hydrogen (C and H). The production method is not particularly limited as long as it is an aqueous layer, but it may be a water repellent layer formed by a CVD method because it can be formed without causing thermal damage to the substrate. This is particularly preferable.

  Hereinafter, an organic film made of a metal skeleton and having an alkyl group, and an organic film composed only of carbon and hydrogen (C and H) will be described. The alkyl group herein is preferably one having 1 to 30 carbon atoms, and most preferably a methyl group having 1 to 6 carbon atoms, especially 1 carbon atom or an ethyl group having 2 carbon atoms.

(A) Organic film comprising a metal skeleton and having an alkyl group Examples of the metal skeleton of such an organic film include Si, Ti and Al. Specific examples of the material include an organic silicon-based material represented by SixOyCzHα, or a polymer film using plasma CVD or plasma polymerization. Here, x means 1.0 to 2.0, y means 0.5 to 1.5, z means 0.5 to 2.0, and α means 1.0 to 7.5.

(B) Organic film composed only of carbon and hydrogen (C and H) Specifically, a hydrocarbon-based material or a polymerized film thereof can be mentioned. As a method for producing such a film, a plasma CVD method (plasma polymerization method) may be used, or a polyolefin material such as polyethylene may be deposited by a PVD method.

In the present invention, when forming the water-repellent film as described above, particularly preferable materials include hexamethyldisiloxane (HMDSO; (CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ ), tetramethyldisiloxane (TMDSO; CH ₃ ) ₂ HSiOSiH (CH ₃ ) ₂ ), tetramethylsilane (TMS; Si (CH ₃ ) ₄ ), C ₂ H ₂ , C ₂ H ₄ , CH ₄ , C ₂ H ₆ , polyethylene resin, cyclic polyolefin resin Etc.

  Here, when the water-repellent film is a silicon oxide film containing oxygen atoms, the concentration of oxygen atoms in the water-repellent film ranges from 0 to 100, particularly from 0 to 50 with respect to 100 Si atoms. It is preferable to be within. Since oxygen atoms easily form hydrogen bonds with water molecules, having oxygen atoms in the water-repellent film attracts water molecules and causes water repellency to decrease. In the water-repellent film, since the concentration of oxygen atoms is within the above-described range, it is possible to suppress a decrease in water repellency due to oxygen atoms and to make the laminate highly water-repellent. It is.

  Here, the component ratio in each part of the water-repellent film of the present invention is a value measured by XPS (X-ray Photoelectron Spectroscopy). The analysis method by XPS will be described below. When a solid surface is irradiated with X-rays in a vacuum, electrons are scattered from the surface atoms energized by the X-rays. This electron is called a photoelectron because it is generated by irradiation with light such as X-rays. Since this photoelectron has energy inherent to the element, qualitative analysis and quantitative analysis of the element can be performed by measuring the energy distribution. . In addition, photoelectrons generated deep from the surface lose their energy before coming out to the surface and are difficult to measure. The escape depth of electrons having a kinetic energy of 1000 eV is several nm (tens of atomic layers). Therefore, it is possible to obtain information on the outermost surface. Furthermore, in order to measure the deep part, the surface needs to be sputtered with ions such as argon, and selective sputtering occurs depending on the type of element, so correction is required for quantification.

  The preferred film thickness of the water-repellent film formed by the above-described vapor phase method is preferably in the range of 1 nm to 150 nm, more preferably in the range of 1 nm to 100 nm, and particularly preferably in the range of 1 nm to 50 nm.

  When the film thickness of the water repellent film is thinner than the above range, it is not preferable because the function as the water repellent layer may not be exhibited, for example, a portion where the water repellent film is not formed may occur. Even if the thickness is increased, the water repellency is not improved, which may cause a problem in terms of cost.

(2) Self-assembled monolayer Next, the water-repellent layer in the present invention may be a self-assembled monolayer, and the self-assembled monolayer will be described below.

  The self-assembled monomolecular film is an organic thin film that spontaneously forms organic monolayers while forming an aggregate by spontaneously gathering organic molecules at a solid / liquid or solid / gas interface. For example, when a substrate made of a specific material is exposed to a solution or vapor of an organic molecule having a high chemical affinity with the substrate material, the organic molecule chemically reacts and adsorbs on the substrate surface. If the organic molecule consists of two parts, a functional group with high chemical affinity and an alkyl group that does not cause any chemical reaction with the substrate, the molecule reacts when the functional group with high affinity is at its end. The sex terminal is adsorbed with the substrate side facing and the alkyl group facing the outside. When alkyl groups gather together, the whole becomes stable, so organic molecules gather spontaneously during the process of chemisorption. Since molecular adsorption requires a chemical reaction between the substrate and the terminal functional group, once the substrate surface is covered with organic molecules to form a monomolecular film, molecular adsorption does not occur thereafter. Absent. As a result, an organic monomolecular film in which molecules are densely gathered and aligned is formed. In the present invention, such a film is a self-assembled monolayer. Here, the reactive terminal group bonded to the substrate is an adsorbing group, and the group oriented to the outside is an aligning group.

  Since the water-repellent layer is a self-assembled monomolecular film as described above, it is possible to form a film with a single molecule along the unevenness of the polymer substrate described above. This makes it possible to obtain a release film due to the unevenness and water repellency of the orientation group of the self-assembled monolayer.

  Specific examples of the self-assembled monolayer forming material shown above include octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecylmethyldiethoxysilane, octadecyldimethylmethoxysilane, octadecylmethyldimethoxysilane, octadecyldimethyl (dimethylamino). ) Silane, octenyltrimethoxysilane, octylmethyldiethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, pentyltriethoxysilane, phenethyltrimethoxysilane, phenyldiethoxysilane, phenylmethyldimethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, isooctyltrimethoxysilane, isobutylto Ethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, decyl Triethoxysilane, decyltrimethoxysilane, and butyltrimethoxysilane are preferable.

  In the present invention, among them, octadecyltrimethoxysilane, octadecyltriethoxysilane, octenyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, pentyltriethoxysilane, phenethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, propyltriethoxysilane, isooctyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, Decyltriethoxysilane, decyltrimethoxysilane, and butyltrimethoxysilane are preferred, especially octadecyltrimethyl Kishishiran, octadecyl triethoxysilane, octyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane are preferred.

<Peeling film>
The release film of the present invention may be transparent or opaque as long as the water-repellent layer described above is formed on the polymer substrate described above.

  In the present invention, the surface roughness of the water repellent layer is preferably 5 to 200 nm, more preferably 5 to 100 nm, and particularly preferably 5 to 50 nm. This is because when the surface roughness of the water repellent layer is within the above range, high water repellency can be achieved by the effects of both surface irregularities and the water repellency of the water repellent layer. The surface roughness referred to here is measured by the method described above.

  In the present invention, the surface of the water-repellent layer of the release film preferably has a contact angle with water of 130 ° or more, particularly 140 ° or more. This is because, when the contact angle of the highly water-repellent laminate with water is within the above range, it can be used for various applications requiring high water repellency. In addition, the measuring method of the contact angle with water here is measured by the method mentioned above.

2. Manufacturing method of release film The release film of the present invention comprises an unevenness forming step in which unevenness is formed by dry etching on the surface of a polymer substrate, and a water repellent layer is formed on the polymer substrate on which the unevenness has been formed by a vapor phase method. It can manufacture by performing the water-repellent layer forming process to form. According to this manufacturing method, it is possible to form unevenness on the surface of the highly water-repellent laminate by having an unevenness forming step for forming unevenness by dry etching of the polymer substrate surface. It is possible to grant. In addition, by forming a water-repellent layer by a vapor phase method on the polymer substrate on which the unevenness is formed by the unevenness forming step, the water-repellent layer is formed without flattening the unevenness formed by the unevenness forming step. Since it can be formed, a highly water-repellent laminate having high water repellency can be formed due to the effects of the surface irregularities and the water-repellent layer.

  Hereinafter, the manufacturing method of said peeling film is demonstrated in detail.

<Roughness formation process>
The unevenness forming step in the present invention is a step of forming unevenness in the surface roughness of 5 to 200 nm, particularly 5 to 100 nm, particularly 5 to 50 nm on the polymer substrate surface by dry etching. The surface roughness referred to here is measured by the method described above.

  When the surface roughness of the polymer substrate in the present invention is within the above range, high water repellency can be expressed, and further, the water repellency is formed on the polymer substrate by the water repellent layer forming step described later. This is because even when the layer is formed, there is little possibility of being flattened by the water repellent layer.

  In addition, the polymer base material used in the present invention is not particularly limited as long as it is a resin base material capable of forming irregularities, and above all, from the aspect that uniform irregularities can be formed. It is preferable that the molecular substrate is stretched. Since the kind of the polymer substrate and the specific method of stretching in the present invention are the same as those described in the section of the polymer substrate of the release film, description thereof is omitted here.

The dry etching used in the unevenness forming step of the present invention can include plasma etching and sputter etching, and is not particularly limited as long as it is a method capable of forming a surface roughness within the above range. In particular, it is preferable to use a plasma etching method using a gas containing oxygen atoms. In the present invention, the gas containing oxygen atoms is, for example, a gas such as NO ₂ , CO ₂ , ozone, or O ₂ or a mixed gas such as NO ₂ (1 ppm) -He, NO (3%)-He. is there. By using a plasma etching method using a gas containing oxygen atoms in the unevenness forming step, the surface of the polymer substrate reacts with oxygen in the plasma simultaneously with the formation of unevenness on the surface of the polymer substrate. And —OH groups are introduced onto the surface of the polymer substrate. As a result, the adhesion between the surface of the polymer substrate and the water-repellent layer formed by the water-repellent layer forming step described later can be improved, and a laminate having high water repellency can be produced. It is.

  Among the above etching methods using plasma using a gas containing oxygen atoms, it is particularly preferable to use etching using oxygen plasma in the present invention. The etching method using oxygen plasma that is preferably used in the present invention is specifically a chemical effect caused by active molecules decomposed and generated by oxygen plasma, here, active oxygen species (a broad radical including atoms and molecules). This is an etching technique based on a physical effect and a synergistic effect of ions accelerated by an ion sheath formed on a substrate surface.

<Water repellent layer forming step>
In the water-repellent layer forming step in the present invention, a thickness of 1 to 150 nm, preferably 1 to 100 nm, particularly 1 to 50 nm is formed by a vapor phase method on the polymer substrate on which the unevenness is formed by the above-described unevenness forming step. Is a step of forming a water-repellent layer within the range.

  The water repellent layer of the present invention is preferably a water repellent film formed by a vapor phase method or a self-assembled monomolecular film, and a method for forming these water repellent layers will be described below.

(1) Water-repellent film formed by vapor phase method First, a water-repellent film in which the water-repellent layer is formed by a vapor phase method will be described.

  The vapor phase method in the present invention may be a PVD method or a CVD method, and is not particularly limited as long as it is a film forming method performed via the gas phase, but in particular, plasma CVD. It is preferable to carry out by the method.

  The plasma CVD method can form a desired material at a low temperature (a range of about −10 to 200 ° C.) that does not cause thermal damage to the polymer base material. Since there is an advantage that the type and physical properties of the film to be obtained can be controlled by the input power, there is little possibility of causing thermal damage to the above-mentioned base material, etc. Since there is little possibility of flattening the unevenness of the surface of the polymer substrate, it is possible to use, for example, a polymer substrate having low thermal resistance as a substrate, and can be used for various applications. This is because a film can be formed.

  As a specific film formation method in the present invention, first, the temperature of the substrate during film formation is set within the range of -20 to 100 ° C, preferably within the range of -10 to 50 ° C. Next, using any of the following materials as the source gas, the input power per unit area in the plasma generating means of the plasma CVD apparatus is set to a size that allows the organic thin film to be formed, and the film forming pressure is free from particles. The pressure is set within a range of high pressure (50 to 300 mTorr). Further, by forming a plasma confinement space such as a magnet and increasing its reactivity, the effect can be enhanced.

Here, as the water repellent film of the present invention,
(A) Thin film rich in alkyl group (b) Any one of hydrocarbon films composed only of C 1 and H 2 can be formed by the above method. Hereinafter, the source gas used for these will be described.

(A) In the case of alkyl-rich silicon-based thin film formation As the organosilicon compound gas, hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane (TMDSO), tetramethylsilane (TMS), vinyl Trimethoxysilane, vinyltrimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetraethoxysilane (TEOS), dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexa Methyldisilazane can be preferably used, and conventionally known ones such as tetramethyldisiloxane and normal methyltrimethoxysilane can be used singly or in combination.

However, in this case, an organosilicon compound having many carbon-silicon bonds in the molecule is preferably used for the purpose of forming an alkyl-rich film. Specifically, hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane (TMDSO), tetramethylsilane (TMS), vinyltrimethoxysilane, vinyltrimethylsilane, methyltrimethoxysilane, Examples include dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and hexamethyldisilazane. Among them, hexamethyldisiloxane (HMDSO) having many carbon-silicon bonds in the molecule. (CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ ), tetramethyldisiloxane (TMDSO; (CH ₃ ) ₂ HSiOSiH (CH ₃ ) ₂ ), tetramethylsilane (TMS; Si (CH ₃ ) ₄ ) I can say that.

(B) In the case of a hydrocarbon-based material Preferred examples of the hydrocarbon-based material include CH ₄ , C ₂ H ₂ , C ₂ H ₄ , and C ₃ H ₈ , and particularly preferably C ₂ H. ₂ and C ₂ H ₄ .

  As described above, an organic compound having a large number of carbon-silicon bonds is used as the organic silicon compound gas in the raw material gas, and the temperature of the base material at the start, the flow rate ratio of the raw material gas as described above, and further in the plasma generating means By making the input power and the film forming pressure within the above-mentioned ranges, a more excellent water-repellent film can be obtained because the decomposability of the organosilicon compound gas is low and an alkyl group or fluorine is easily taken into the film. (In the case of (A)), or a film having a high water repellency effect as a result of the film being composed only of CH bonds (in the case of (B)). The alkyl referred to here preferably has 1 to 30 carbon atoms, and most preferably 1 to 6 carbon atoms, particularly 1 methyl group or 2 ethyl groups.

(2) Self-assembled monolayer Next, the case where the water-repellent layer in the present invention is a self-assembled monolayer (SAM) will be described. The method for forming the self-assembled monolayer in the present invention is not particularly limited, but it is particularly preferably formed by a thermal CVD method. Since the process of forming a self-assembled monolayer is a thermal CVD method, in the thermal CVD method, a material as a raw material is vaporized, and the material is sent uniformly on a substrate, and then oxidized, reduced, Since a reaction such as substitution is performed, it is possible to form a self-assembled monolayer evenly on the uneven surface of the polymer substrate, and the uneven surface formed on the surface of the polymer substrate is flat. The water repellent layer can be formed without becoming.

  As preferable film forming conditions of the thermal CVD method in the present invention, the higher the heat resistant temperature of the above-described polymer base material, the higher the better, but it is preferable to be within the range of 50 ° C to 200 ° C. In addition, it is preferable that moisture or oxygen is contained in the reaction system because the hydrolysis reaction of the alkoxy group of the self-assembled monolayer-forming substance is further promoted and the reactivity with the substrate is increased.

  The material of the self-assembled monolayer by the thermal CVD method in the present invention is the same as the description of the self-assembled monolayer of the water-repellent layer of the highly water-repellent laminate described above, and the description is omitted here To do.

<Bonding film>
The bonding film according to the present invention is characterized in that the release film is provided on the bonding surface of the bonding film so as to be peelable.

  The bonding film includes, for example, both an adhesive film and an adhesive film, and includes a wound product of such an adhesive film and an adhesive film, and a tape-like adhesive film and an adhesive film.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and any device that has substantially the same configuration as the technical idea of the present invention and has the same function and effect is included in the technical scope of the present invention. The

  The present invention will be described more specifically with reference to the following examples and comparative examples.

[Example 1]
(Surface unevenness formation)
The PET substrate was subjected to oxygen plasma etching by the following method using a capacitively coupled high-frequency plasma apparatus. First, after placing the PET base material in the chamber, the inside of the reaction chamber was evacuated to 1.0 × 10 ⁻³ Pa or less by a decompression means. 12 μm-PET (manufactured by Unitika Ltd., PTM) was used as the substrate. Next, oxygen gas was used as a gas containing oxygen atoms, and 5 Pa was introduced into the chamber. A high frequency of 13.56 MHz was used for plasma generation. Oxygen plasma etching was performed at a power of 100 W for 10 minutes. The mean square roughness of the PET surface after etching was about 10 nm. The surface roughness was measured in a contact mode using an atomic force microscope (manufactured by Seiko Instruments Inc .; SPI3800N).

(Water repellent layer formation by thermal CVD process; self-assembled monolayer film formation)
About 0.2 ml of the above-mentioned oxygen plasma-etched PET base material and octadecyltrimethoxysilane (ODS) (Tokyo Kasei Kogyo Co., Ltd. 00256) in a glass container were deposited on Teflon ODS-SAM. When the contact angle and the film thickness were measured, the contact angle with water was about 140 °, the S / N was 13, and the film thickness was 1.8 nm. Since the water droplet contact angle before SAM film formation was 10 ° or less, it was found that SAM was formed by thermal CVD.

  In addition, this contact angle measurement method uses a contact angle measuring device (model number CA-Z) manufactured by Kyowa Interface Chemical Co., Ltd., and drops pure water on the surface of the object to be measured (a certain amount). After a certain period of time, a method of observing the shape of a water droplet using a CCD camera and physically obtaining the contact angle was used.

  After the ODS-SAM film formation, the film characteristics were evaluated by XPS, and the presence of Si and C was confirmed from the film. The evaluation by XPS was carried out using XPS 220iXL (manufactured by ESCALAB) under the conditions of using MgKα, 15 kV, 20 mA (300 W).

[Example 2]
(Surface uneven shape formation)
Unevenness was formed on PET in the same manner as in Example 1.

(Water repellent layer formation by plasma CVD process; silica-based thin film formation)
Subsequent to the oxygen plasma etching step, a silicon-based thin film (SiCxHy-based thin film) was formed on the etched PET substrate by capacitively coupled high-frequency plasma CVD. After the plasma etching, the degree of vacuum in the chamber was again reduced to 1.0 × 10 ⁻³ Pa or less, and then a source gas was introduced into the reaction chamber. As a source gas, tetramethylsilane (T2050 manufactured by Chisso Corporation) was used as an organosilicon compound. The pressure was adjusted so that the total chamber pressure was 10 Pa. A high frequency of 13.56 MHz was used for plasma generation and raw material decomposition. A silicon-based thin film was formed at a power of 200 W for a film formation time of 15 seconds. During film formation, the substrate surface temperature was 50 ° C. or lower. After forming the silicon-based thin film, the water droplet contact angle and the film thickness were measured. The contact angle with water was about 140 °, the contact angle with soapy water was about 70 °, and the S / N was 25. The thickness was about 5 nm.

  After film formation of the silicon-based thin film, the film characteristics were evaluated by XPS. As a result, the presence of Si, C, and H was confirmed from the film.

[Comparative Example 1]
When ODS-SAM was formed on a PET substrate without performing oxygen plasma etching (ODS-SAM film formation was the same as in Example 1), the water droplet contact angle was about 85 °, and the S / N was 3 Met.

[Comparative Example 2]
A silicon-based thin film was formed on a PET substrate without performing oxygen plasma etching (silica-based thin film was prepared in the same manner as in Example 2). The water droplet contact angle was about 80 ° and the S / N was 4. there were.

<Evaluation results>
In Examples 1 and 2, the peelability of Nichiban using cellophane tape is good, and as a result of optical microscope observation, no water repellent layer remains, and the peelability of Nichiban using cellophane tape in Comparative Examples 1 and 2 is poor. As a result of observation with an optical microscope, the remaining water-repellent layer was observed.

  Further, when the optical adhesive was applied and transferred to the polarizing plate film for liquid crystal, no foreign matter and water repellent layer remained in the optical microscope.

  In any case, the magnification of the optical microscope was 500 times.

Claims (7)

  A release film having a water-repellent layer formed on a polymer substrate having fine irregularities on the surface on a non-release surface.   The release film according to claim 1, wherein the surface of the polymer substrate has a surface roughness of 5 to 200 nm and an S / N ratio of 5 to 50.   The surface of the water repellent layer is formed of a material having a contact angle with water of 100 to 160 ° and a contact angle with soap water of 50 to 100 °. A release film according to 1.   The release film according to any one of claims 1 to 3, wherein the water-repellent layer comprises an organic film comprising a metal skeleton and having an alkyl group, and an organic film comprising carbon and hydrogen.   The release film according to any one of claims 1 to 4, wherein the water repellent layer is a self-assembled monolayer.   A bonding film, wherein the release film according to any one of claims 1 to 5 is detachably provided on a bonding surface of the bonding film.   An optical pressure-sensitive adhesive film comprising the bonding film according to claim 6.