JP2013091278A - Mold release film, method for producing the same, and mold release coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mold release film, the surface of which to be released can be restrained from being contaminated since a mold release layer is formed by using the silica, as a main component, which is obtained by subjecting a hydrolysate of polyalkoxysiloxane, that has the volatility much lower than that of alkoxy siloxanes being organosilanes, to a condensation reaction.SOLUTION: The mold release layer 3, which is based on the silica obtained by subjecting the hydrolysate of polyalkoxysiloxane having much lower volatility to the condensation reaction, is layered on at least one main surface of a film-shaped base material 2 by means of a hydrogen bond and/or a covalent bond, which is created by the condensation reaction of the hydrogen bond, by using a catalyst for accelerating the condensation reaction, in which catalyst chlorine, sulfur, phosphorus and aluminum are not contained. As a result, the surface of the mold release film to be released can be restrained from being contaminated since there is no risk of transferring alkyl silane being low-molecular-weight organosilane or low-molecular-weight cyclic siloxane in the same manner as the risk of the conventional mold release film.

Description

  The present invention relates to a release film in which a release layer is laminated on at least one principal surface of a film-like substrate, a method for producing the release film, and a laminate on at least one principal surface of a film-like substrate. It is related with the mold release coating agent which forms the mold release layer of a mold release film.

  In recent years, printed circuit boards, interposer boards, ceramic wiring boards, ceramic laminated parts, rubber sheets, polarizing films and anisotropic conductive films, etc., used in the manufacturing process of molded products, adhesive films and adhesive films The importance of a release film used as a protective film for protecting the adhesive surface is increasing. A release film is known in which a release layer is laminated on at least one main surface of a film-like substrate formed of a resin film such as polyester or paper, and the release layer is made of silicone or It is made of a highly releasable material such as fluororesin or polyolefin.

  The material for forming the release layer is selected in accordance with the purpose of use of the release film, but it has excellent release properties and heat resistance and is inexpensive. Silicone produced from alkylsilane, which is organosilane, is often used to form, and is formed by laminating a release coating agent based on silicone on at least one main surface of a film-like substrate. Various release films having a released release layer have been proposed (see, for example, Patent Documents 1 to 5).

JP-A-63-251465 JP 2009-12317 A JP 2010-17931 A JP 2010-143037 A JP 2007-237497 A

  By the way, although silicone has an excellent releasability, there is a problem that when a release film is peeled from a molded body, a surface to be released is contaminated by low molecular weight silicone or the like. In other words, the release surface of the molded body in which the release film is used is transferred by transfer of alkyl silane, which is a low molecular weight organosilane that forms a release layer, or low molecular weight cyclic siloxane, to the release surface. There is a possibility that the mold release property may occur, and there may be a problem in the adhesion property when another member is further laminated on the surface to be released.

  In addition, the catalyst and additives contained in the release coating agent used when laminating the release layer on the film-like substrate, or other impurities contained in the solvent of the release coating agent are removed from the molded product. By being transferred to the mold surface, there is a possibility that problems such as contamination of the surface to be released with impurities and reduction in reactivity of the surface to be released. In addition, low molecular weight organosilanes and low molecular weight cyclic siloxanes that remain after being transferred to the mold release surface of the molded body are high boiling point substances but are highly volatile. Diffusion causes vapor to be decomposed by heat from the current on the surface of electrical circuits and relay contacts, etc., in the manufacturing process of wiring boards and the like where release films are used, and insulative silica is deposited, resulting in poor contact. There was a fear and it was a problem.

  The present invention has been made in view of the above-described problems, and the main component is silica obtained by hydrolysis and condensation reaction of polyalkoxysiloxane having very low volatility among alkoxysiloxanes which are organosilanes. In addition to providing a release film and a release film manufacturing method capable of suppressing contamination of the release surface by forming a release layer to be laminated, the release layer is laminated on a film-like substrate It aims at providing the mold release coating agent which forms the said mold release layer by this.

  In order to achieve the above-described object, a release film of the present invention includes at least one of a film-like substrate having a plurality of hydroxyl groups over the entire surface of at least one main surface, and the substrate having a plurality of hydroxyl groups. A release layer laminated on one main surface, and the release layer is subjected to a condensation reaction by hydrolysis of polyalkoxysiloxane using a condensation reaction promoting catalyst not containing chlorine, sulfur, phosphorus and aluminum. Silica obtained as a main component is formed by stacking hydrogen bonds and / or covalent bonds formed by condensation reaction of the hydrogen bonds on at least one main surface of the substrate having the plurality of hydroxyl groups. (Claim 1).

  The release layer may further include a plurality of inorganic particles, and the surface may have irregularities formed by the plurality of inorganic particles (Claim 2).

  The film-like substrate may be a polymer of a vinyl monomer having at least one hydroxyl group or a polymer film made of celluloses (Claim 3).

  The film-like substrate may be a polymer film in which a hydroxyl group is formed on at least one main surface by a corona discharge treatment, a plasma treatment, or a hydrophilic treatment by treatment with a sodium / naphthalene complex solution. ).

  Further, in the method for producing a release film of the present invention, a film-like substrate having a plurality of hydroxyl groups over the entire surface of at least one main surface is used as a solvent on at least one main surface having the plurality of hydroxyl groups. A mold release coating agent formed by dissolving a solute containing a condensation reaction accelerating catalyst that contains polyalkoxysiloxane as a main component and does not contain chlorine, sulfur, phosphorus, and aluminum is applied, heated and dried to release the mold. The layer is laminated on the film-like substrate by hydrogen bonds and / or covalent bonds resulting from condensation reaction of the hydrogen bonds (Claim 5).

  The condensation reaction promoting catalyst may contain at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate, and a titanium-based organometallic compound. Item 6).

  In addition, a plurality of inorganic particles may be further added to the solvent.

  The release coating agent of the present invention is a release coating agent that forms a release layer of a release film by being laminated on at least one main surface of a film-like substrate, and a polyalkoxy as a solvent. A solute containing a condensation reaction promoting catalyst containing siloxane as a main component and not containing chlorine, sulfur, phosphorus, or aluminum is dissolved and formed (claim 8).

  The condensation reaction promoting catalyst may contain at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate, and a titanium-based organometallic compound. Item 9).

  In addition, a plurality of inorganic particles may be further added to the solvent (claim 10).

  The solvent may be any of alcohol, ether and ketone.

  Further, it is preferable that 1 to 100 parts by weight of polyalkylsilane is further dissolved in 100 parts by weight of polyalkoxysiloxane in the solvent.

  According to the first aspect of the present invention, at least one main surface of the film-like base material having a plurality of hydroxyl groups over the entire surface of at least one main surface does not contain chlorine, sulfur, phosphorus, or aluminum. A release layer mainly composed of silica obtained by hydrolyzing and condensing a polyalkoxysiloxane using a catalyst is laminated with a hydrogen bond and / or a covalent bond due to a hydrogen bond condensation reaction. Yes. Therefore, a release layer mainly composed of silica obtained by hydrolyzing and condensing a polyalkoxysiloxane having a very low volatility among alkoxysiloxanes, which are organosilanes, is formed on a film-like substrate. Therefore, unlike the conventional release film, there is no possibility that the release surface of the molded body will be contaminated by transferring the alkylsilane, which is a low molecular weight organosilane, or the low molecular weight cyclic siloxane. It is possible to provide a release film that can suppress the mold from being contaminated.

  The release layer mainly composed of silica having an OH group is laminated by being directly bonded to the film-like base material by a hydrogen bond and / or a covalent bond caused by a hydrogen bond condensation reaction. Therefore, there is no need for an adhesive layer (anchor coat layer) for adhering the release layer to the film-like substrate, and the substance forming the adhesive layer can be transferred to the release surface of the molded body as in the past. Thus, it is possible to provide a release film in which the release surface is not likely to be contaminated.

  The release layer is formed mainly of silica obtained by using a condensation reaction promoting catalyst that does not contain chlorine, sulfur, phosphorus, and aluminum and hydrolyzing the polyalkoxysiloxane to undergo a condensation reaction. Therefore, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as sulfonic acid and organic phosphoric acid are not used as condensation reaction promoting catalysts, so low molecular weight substances and ionic compounds can be molded. It is possible to provide a release film in which the release surface is not likely to be contaminated by transferring to the release surface. These ionic impurities such as chlorine, sulfuric acid, nitric acid, phosphoric acid, and aluminum cause corrosion of aluminum (Al) and copper (Cu) wiring provided on various wiring boards and semiconductors, and defects such as electromigration. It is known that a release film on which a release layer that does not contain these is laminated is most suitable for manufacturing various wiring boards and ceramic substrates. Moreover, since an aluminum-based organometallic compound is not used as the condensation reaction promoting catalyst, there is no possibility that the releasability of the release layer is lowered, and a release film having excellent releasability can be provided. it can.

  According to the invention of claim 2, the release layer further includes a plurality of inorganic particles, and the surface has irregularities formed by the plurality of inorganic particles. For example, a thermosetting resin that forms a laminated plate or the like is used. When molding, unevenness is formed on the release surface of the thermosetting resin that is the molded body, so the adhesion strength of the adhesive surface when the thermosetting resin is further laminated on the release surface due to the anchor effect Can be improved. Also, for example, when a release film is used as a protective film for an adhesive or pressure-sensitive adhesive, since the unevenness is formed in the release layer, the area of the contact portion between the adhesive or pressure-sensitive adhesive and the release layer Therefore, it is possible to provide a release film that is easier to peel off.

  According to the third and fourth aspects of the present invention, since a hydroxyl group is formed on at least one main surface of the film-like substrate, silica obtained by hydrolysis and condensation reaction of polyalkoxysiloxane is the main component. A release film in which the release layer is securely bonded to a film-like substrate by covalent bonding due to condensation reaction of hydrogen bonds and / or hydrogen bonds can be provided.

  According to the inventions of claims 5 and 8, at least one main surface having a plurality of hydroxyl groups of the film-like substrate having a plurality of hydroxyl groups over the entire surface of at least one main surface is coated with a polyalkoxy as a solvent. Application is performed with a release coating agent in which a solute containing a condensation reaction promoting catalyst containing siloxane as a main component and not containing chlorine, sulfur, phosphorus, or aluminum is dissolved. Then, the coated release coating agent is heated and dried to hydrolyze a silica obtained by a hydrolysis reaction of polyalkoxysiloxane having a very low volatility among alkoxysiloxanes which are organosilanes. A release layer as a main component is laminated on a film-like substrate by hydrogen bonds and / or covalent bonds formed by condensation reaction of the hydrogen bonds. Therefore, unlike the conventional release film, there is no possibility that the release surface of the molded body will be contaminated by transferring the alkylsilane, which is a low molecular weight organosilane, or the low molecular weight cyclic siloxane. A release film that can prevent the surface from being contaminated can be produced.

  According to the inventions of claims 6 and 9, a condensation reaction comprising at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate and a titanium-based organometallic compound. By using a promotion catalyst, the release property is not impaired and the release surface is prevented from being contaminated by the transfer of the substance that forms the condensation reaction promotion catalyst to the release surface of the molded body. It is possible to form a release layer that can be formed on a film-like substrate.

  As mentioned above, ionic impurities such as chlorine, sulfuric acid, nitric acid, phosphoric acid, and aluminum are known to cause defects such as corrosion and electromigration of aluminum and copper wiring provided on various wiring boards and semiconductors. Various amines, titanium-based organometallic compounds, and the like are known as condensation reaction promoting catalysts that do not contain these. However, since various amines are very active catalysts, release coating agents containing various amines are poor in storage stability of release coating agents because the reaction proceeds even at room temperature.

  When various amines are carboxylic acids and carbonates, the carboxylic acid and carbonic acid cannot be removed unless the temperature is applied, so that an amine catalyst having low reaction activity at room temperature can be obtained. Furthermore, compounds containing isocyanate groups or isocyanurate groups can generate amines by reacting with moisture in the air, so if the release coating agent does not contain moisture, it promotes condensation reactions that are storage stable. A catalyst can be provided.

  According to the seventh and tenth aspects of the present invention, since a plurality of inorganic particles are further added to the solvent forming the release coating agent, the solvent contains a plurality of inorganic particles, and the surface has irregularities due to the plurality of inorganic particles. The formed release layer can be easily formed on a film-like substrate.

  According to the eleventh aspect of the present invention, a release coating agent having a practical configuration can be provided by forming the release coating agent using any one of alcohol-based, ether-based, and ketone-based solvents. .

  According to the invention of claim 12, since the polyalkylsilane is further dissolved in 1 to 100 parts by weight with respect to 100 parts by weight of the polyalkoxysiloxane in the solvent of the release coating agent, the release coating agent is a film. The mold release property of the mold release layer formed by laminating | stacking on a shaped base material can be improved.

It is sectional drawing which shows 1st Embodiment of the release film of this invention. It is sectional drawing which shows 2nd Embodiment of the release film of this invention. It is a figure which shows an example of the release film of this invention. It is a figure which shows an example of the release film of this invention.

<First Embodiment>
1st Embodiment of the release film of this invention is described with reference to FIG. FIG. 1 is a view showing a first embodiment of a release film of the present invention.

  As shown in FIG. 1, the release film 1 of the present invention includes a film-like substrate 2 and a release layer 3 laminated on the film-like substrate 2, and a) a laminate, an interposer, or the like Wiring board, b) used when forming a green sheet for a ceramic capacitor, c) used as a release film such as a film-like anisotropic conductive film or die bond film used when manufacturing a semiconductor, d) Used as a release film for CFRP (carbon fiber reinforced plastic).

  The release film 1 has a release coating agent applied to at least one main surface having a plurality of hydroxyl groups of the film-like substrate 2 having a plurality of hydroxyl groups over the entire surface of at least one main surface, The applied release coating agent is heated by an oven furnace or the like and dried, whereby a release layer 3 is formed on the base material 2 by a covalent bond resulting from a hydrogen bond and / or a hydrogen bond condensation reaction. The

  The base material 2 has a plurality of hydroxyl groups over the front surface of at least one main surface. Specifically, the film-like substrate 2 is a polymer film made of a polymer of a vinyl monomer having at least one hydroxyl group, and is a polyvinyl alcohol, a partially saponified polyvinyl acetate (vinyl alcohol vinyl acetate copolymer). , Ethylene vinyl alcohol, vinyl alcohol copolymers, for example, polyvinyl alcohol resins containing 1,2-diol structural units disclosed in JP 2006-124682 A in the side chain, polyvinyl butyral, etc., or It is formed by cellulose (cellophane paper), partially modified cellulose, cellulose such as paper, or a film coated on one or both sides with a polymer having a hydroxyl group.

  The substrate 2 may be a polymer film in which a hydroxyl group is formed on at least one main surface by corona discharge treatment, plasma treatment, or hydrophilic treatment with a sodium / naphthalene complex solution on the surface of the polymer film.

  The release layer 3 is composed mainly of silica obtained by hydrolysis reaction of polyalkoxysiloxane using a condensation reaction promoting catalyst that does not contain chlorine, sulfur, phosphorus, and aluminum, and has a plurality of hydroxyl groups. It is laminated on one main surface of the substrate 2 by a hydrogen bond and / or a covalent bond caused by a condensation reaction of the hydrogen bond.

  The release coating agent for forming the release layer 3 of the release film 1 by being laminated on at least one main surface of the film-like base material 2 is mainly composed of polyalkoxysiloxane as a solvent, chlorine, sulfur, A solute containing a condensation reaction promoting catalyst not containing phosphorus or aluminum is dissolved and formed.

  As the solvent, an alcohol type such as ethanol or 2-propanol can be used. In consideration of safety when storing the release coating agent, a polar solvent such as an ether or ketone that does not have a flash point of less than 20 ° C. may be used.

  Specifically, examples of the alcohol solvent include 1-propanol, butanol, 2-methyl-1-propanol, n-butoxyethanol, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol-n-propyl ether, di- Examples include propylene glycol-n-propyl ether and propylene glycol-n-butyl ether. In consideration of safety when storing the release coating agent, a low flammable alcohol such as methanol, ethanol or isopropyl alcohol may be blended if the flash point of the mixed solvent does not fall below 20 ° C. Also good.

  Examples of the ketone solvent include methyl-n-butyl ketone, methyl pentyl ketone, and diisobutyl ketone. Examples of the ether solvent include dibutyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, and propylene glycol diacetate.

  The condensation reaction promoting catalyst includes at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate, and a titanium-based organometallic compound.

  Examples of the compound containing an isocyanate group include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and the like.

  In addition, an isocyanate block obtained by blocking an isocyanate is deblocked by heating to regenerate the isocyanate, and is particularly effective in the present invention in which the release layer is cured by heating. Examples of the isocyanate block body include 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate having a pyrazole-blocked isocyanate group as a blocking agent and methacrylic acid having a methylethylketoxime group as a blocking agent 2- (0- [ 1'-methylpropylideneamino] carboxyamino) ethyl and the like, and examples of other blocking agents include diethyl malonate and caprolactam.

  Examples of the compound containing an isocyanurate group include Asahi Kasei Chemicals' Duranate TSA-100, TSS-100, TSE-100 and the like, NK assist NY of Nikka Chemical, and the like. It is known that an isocyanurate group is a trimer of an isocyanate group and similarly reacts with water to produce an amine.

  The carboxylic acid and carbonate of the 1-4th class amine refers to a salt obtained by reacting a 1st to 3rd class amine containing a polymer type amine with carboxylic acid or carbonic acid. Examples of the carboxylic acid include ammonia, acetic acid, and the like. When acetic acid reacts with a tertiary amine, an acetate of the tertiary amine is obtained. Further, carboxylic acids and carbonates of quaternary amines can be obtained by anion exchange of quaternary ammonium salts. Primary amine is ethylenediamine, 2-aminoethanol, hexamethylenediamine, aniline, aminosilane, etc. Secondary amine is diethylamine, tertiary amine is N, N-dimethyl-2-propanamine, tetramethylethylenediamine, triethanol Examples of amines and polymer-type amines include polyethyleneimine, polyethylenediamine, and polyallylamine.

  In general, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid is used as a catalyst for condensing reaction of organosilane (alkylsilane and alkoxysilane). In addition, organic acids such as carboxylic acid, sulfonic acid, and organic phosphoric acid, various amines, and titanium and aluminum-based organometallic compounds can also be used. The condensation reaction accelerating catalyst is not particularly limited as long as it promotes the condensation of silanol and alkoxy groups, but as the condensation reaction accelerating catalyst, in particular, inorganic acids, amines, and titanium-based catalysts are used for curing speed and coating film. It is preferable in terms of strength.

  However, contamination of the release surface due to transfer or transfer of low molecular weight substances, ionic compounds, and the like from the substrate 2 and the release layer 3 of the release film 1 to the release surface of the molded body. Considering this, it is not appropriate to use inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as sulfonic acid and organic phosphoric acid, and aluminum-based organometallic compounds as condensation reaction accelerating catalysts. When this organometallic compound is used as the condensation reaction promoting catalyst, the release property of the release layer 3 is very small, and it is not appropriate to use an aluminum-based organometallic compound as the condensation reaction promoting catalyst.

  Accordingly, in consideration of the contamination of the molded product on the release surface due to the transfer or transfer of the substance from the release coating agent (release layer 3) to the release surface of the molded product, various amine-based catalysts are used as condensation reaction promoting catalysts. However, since amine-based catalysts have high reaction activity at room temperature, they are unsuitable due to lack of stability when storing a release coating agent.

  In order to solve this problem, the present inventor repeated various experiments to add various carbonic acid or carboxylic acid having a boiling point of 150 ° C. or lower to various amines so that the acidity is changed from slightly alkaline to slightly acidic. It was possible to obtain a release coating agent that suppresses the reaction activity of amine at room temperature and has excellent storage stability.

  Examples of the carboxylic acid include formic acid, acetic acid, and propionic acid, and acetic acid is particularly preferable. For various amines, a wide range of compounds can be used, from low molecular compounds having one or more amino groups to high molecular compounds, but from the release layer 3 (release coating agent) to the release surface of the molded product. In consideration of contamination of the surface to be separated due to migration or transfer of a substance, a polymer compound having one or more amino groups is optimal. Examples of the polymer compound having one or more amino groups include polyethyleneimine, polyvinylamine, polyallylamine and the like, or a copolymer of these monomers and vinyl alcohol.

  Further, as the compound having one or more amino groups, the substance can be transferred or transferred from the release layer 3 to the release surface of the molded body by reacting with the polyalkoxysiloxane. Also suitable are compounds containing one or more hydroxyl and amino groups. Examples of aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropylmethyldimethoxysilane. Is done. Examples of the compound containing one or more hydroxyl groups and amino groups include 2-aminoethanol, ethanolamine, diethanolamine, triethanolamine, and aminoglucooxides such as kanamycin.

  In addition, it is generally known that a compound containing an isocyanate group reacts with water and is converted into carbon dioxide and an amino group. By utilizing this reaction, a condensation reaction promoting catalyst having a low reaction activity at room temperature can be provided. By extremely limiting the water content of the solvent and solute of the release coating agent, the compound containing an isocyanate group is not converted to an amino group unless water is present in the release coating agent solution. However, when the release film 1 is produced by applying a release coating agent to the film-like substrate 2, the isocyanate group is converted into an amino group by obtaining water from the humidity of the atmosphere (air) in the environment. By reacting, it functions as a condensation reaction promoting catalyst for polyalkoxysiloxane. Therefore, a compound containing an isocyanate group that reacts with water to be converted to an amino group, and further, a blocking agent is added to the compound, and the blocking agent dissociates from the isocyanate group only at a high temperature to control the reactivity. The method can also be used as the condensation reaction catalyst of the present invention.

  Examples of the compound containing an isocyanate group include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and the like. .

  In addition, an isocyanate block obtained by blocking an isocyanate is deblocked by heating to regenerate the isocyanate, and is particularly effective in the present invention in which the release layer is cured by heating. Examples of the isocyanate block body include 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate having a pyrazole-blocked isocyanate group as a blocking agent and methacrylic acid having a methylethylketoxime group as a blocking agent 2- (0- [ 1'-methylpropylideneamino] carboxyamino) ethyl and the like, and examples of other blocking agents include diethyl malonate and caprolactam.

  Examples of the compound containing an isocyanurate group include Asahi Kasei Chemicals' Duranate TSA-100, TSS-100, TSE-100 and the like, NK assist NY of Nikka Chemical, and the like. It is known that an isocyanurate group is a trimer of an isocyanate group and similarly reacts with water to produce an amine.

  The carboxylic acid and carbonate of the 1-4th class amine refers to a salt obtained by reacting a 1st to 3rd class amine containing a polymer type amine with carboxylic acid or carbonic acid. Examples of the carboxylic acid include ammonia, acetic acid, and the like. When acetic acid reacts with a tertiary amine, an acetate of the tertiary amine is obtained. Further, carboxylic acids and carbonates of quaternary amines can be obtained by anion exchange of quaternary ammonium salts. Primary amine is ethylenediamine, 2-aminoethanol, hexamethylenediamine, aniline, aminosilane, etc. Secondary amine is diethylamine, tertiary amine is N, N-dimethyl-2-propanamine, tetramethylethylenediamine, triethanol Examples of amines and polymer-type amines include polyethyleneimine, polyethylenediamine, and polyallylamine.

  Further, as a result of intensive studies by the present inventor, the transfer and transfer of the ionic compound to the release surface may become a problem depending on the use, but the release layer 3 in the case of using a titanium-based organometallic catalyst. Therefore, titanium-based organometallic catalysts can also be used as the condensation reaction promoting catalyst of the present invention.

  Examples of titanium-based organometallic catalysts include tetranormal butyl titanate, butyl titanate dimer, tetraisopropyl titanate, tetra (2-ethylhexyl) titanate, diisopropoxy titanium bis (acetylacetonate), isopropoxy titanium bis (ethyl acetoacetate) and the like. Is done.

  In addition, content of a condensation reaction acceleration | stimulation catalyst is a catalyst amount, and it is good in it being 0.1-20 mass parts normally with respect to a total of 100 mass parts of solid content, such as polyalkoxysiloxane.

  In addition, as a method for applying the release coating agent to the film, for example, a well-known coating technique described in Yuji Harasaki's “Coating Method” (Tsubaki Shoten, published in 1979) can be used. Specifically, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater Examples thereof include coating techniques such as an extrusion coater and a bar coater.

  Moreover, the film thickness of a mold release coating agent layer is 0.001-1.0 micron normally as a final coating film, Preferably it is 0.001-0.05 micron. When the film thickness of the release coating agent layer is less than 0.001 micron, there is a possibility that sufficient release property of the release layer 3 may not be obtained. Further, it is not preferable because it causes deterioration of the specularity of the surface of the release layer 3 and an increase in the manufacturing cost of the release film 1.

  As described above, in the above-described embodiment, at least one main surface of the film-like substrate 2 having a plurality of hydroxyl groups over the entire surface of at least one main surface does not contain chlorine, sulfur, phosphorus, or aluminum. The release layer 3 mainly composed of silica obtained by hydrolyzing the polyalkoxysiloxane using a condensation reaction promoting catalyst and undergoing a condensation reaction is covalently bonded by a hydrogen bond and / or a hydrogen bond condensation reaction. Are stacked. Therefore, a release layer 3 mainly composed of silica formed by hydrolysis reaction of polyalkoxysiloxane having very low volatility among alkoxysiloxanes, which are organosilanes, is formed on the film-like substrate 2. Therefore, unlike the conventional release film, there is no possibility that the release surface of the molded body is contaminated by transferring the alkyl silane, which is a low molecular weight organosilane, or the low molecular weight cyclic siloxane, It is possible to provide a release film that can suppress contamination of the release mold.

  Further, the release layer 3 mainly composed of silica having an OH group is laminated by being directly bonded to the film-like substrate 2 by a covalent bond caused by a condensation reaction of hydrogen bonds and / or hydrogen bonds. Therefore, there is no need for an adhesive layer (anchor coat layer) for adhering the release layer 3 to the film-like substrate 2, and the substance that forms the adhesive layer is transferred to the release surface of the molded body as in the past. By doing so, it is possible to provide a release film in which the release surface is not likely to be contaminated.

  Further, the release layer 3 is formed mainly using silica obtained by hydrolysis reaction of polyalkoxysiloxane using a condensation reaction promoting catalyst which does not contain chlorine, sulfur, phosphorus and aluminum. . Therefore, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as sulfonic acid and organic phosphoric acid are not used as condensation reaction promoting catalysts. The release film 1 can be provided in which the release surface is not likely to be contaminated by transferring it to the release surface. Moreover, since an aluminum-based organometallic compound is not used as the condensation reaction promoting catalyst, there is no fear that the releasability of the release layer 3 is lowered, and a release film 1 having excellent releasability is provided. be able to.

  In addition, since a hydroxyl group is formed on at least one main surface of the film-like substrate 2, the release layer 3 mainly composed of silica obtained by hydrolysis and condensation reaction of the polyalkoxysiloxane includes: It is possible to provide a release film 1 that is reliably bonded to a film-like substrate 2 by a covalent bond resulting from a condensation reaction of hydrogen bonds and / or hydrogen bonds.

  Further, at least one main surface of the film-like substrate 2 having a plurality of hydroxyl groups over the entire surface of at least one main surface, the polyalkoxysiloxane as a main component in the solvent, chlorine, Application is performed by applying a release coating agent in which a solute containing a condensation reaction promoting catalyst not containing sulfur, phosphorus or aluminum is dissolved. Then, the coated release coating agent is heated and dried to hydrolyze a silica obtained by a hydrolysis reaction of polyalkoxysiloxane having a very low volatility among alkoxysiloxanes which are organosilanes. The release layer 3 as a main component is laminated on the film-like substrate 2 by hydrogen bonds and / or covalent bonds resulting from condensation reaction of the hydrogen bonds. Therefore, unlike the conventional release film, there is no possibility that the release surface of the molded body will be contaminated by transferring the alkylsilane, which is a low molecular weight organosilane, or the low molecular weight cyclic siloxane. The release film 1 which can suppress that a surface is contaminated can be manufactured easily.

  Further, by using a condensation-promoting catalyst containing at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate and a titanium-based organometallic compound, A mold release layer 3 that can prevent contamination of the mold release surface of the molded article by transferring a substance that forms a condensation reaction promoting catalyst to the mold release face of the molded article without impairing moldability. Can be formed on the film-like substrate 2.

  In addition, a release coating agent having a practical configuration can be provided by forming the release coating agent using any one of alcohol-based, ether-based, and ketone-based solvents.

  Further, 1 to 100 parts by weight of polyalkylsilane may be further dissolved in 100 parts by weight of polyalkoxysiloxane in the solvent of the release coating agent. If it does in this way, the mold release property of the mold release layer 3 formed when a mold release coating agent is laminated | stacked on the film-form base material 2 can be improved.

In addition, the release film 1 used for forming a green sheet for a ceramic capacitor generally has a semi-cured green sheet as a release film unless the surface resistance is about 9 × 10 ¹² Ω / □ or less. It is known that problems due to static electricity occur when peeling from 1. However, since the polymer film containing vinyl alcohol has antistatic performance (about 10 ¹⁰ Ω / □), the release film 1 that does not require the addition of an antistatic agent can be provided.

Second Embodiment
A second embodiment of the release film of the present invention will be described with reference to FIG. FIG. 2 is a view showing a second embodiment of the release film of the present invention.

  This embodiment is different from the first embodiment described above, as shown in FIG. 2, the release layer 3 further includes a plurality of inorganic particles 4, and a plurality of inorganic particles 4 are formed on the surface of the release layer 3. This is a point where irregularities are formed. Since the other configuration is the same as that of the first embodiment described above, the description of the configuration is omitted.

  The release film 10 has a release coating agent applied to at least one main surface having a plurality of hydroxyl groups of the film-like substrate 2 having a plurality of hydroxyl groups over the entire surface of at least one main surface, When the applied release coating agent is heated and dried, the release layer 3 is formed by laminating the substrate 2 by the covalent bond resulting from the condensation reaction of hydrogen bonds and / or hydrogen bonds. At this time, a plurality of inorganic particles 4 are further added to the release coating agent of this embodiment.

  The inorganic particles 4 are preferably particles of 1 nm to 100 microns, but the size of the particles is not particularly limited. Moreover, it is preferable to select particles having good adhesion to other substances contained in various film-like base materials 2 and the release coating agent. Therefore, particles such as talc, bentonite, and silica, which are inorganic particles having OH groups that are surface functional groups that form hydrogen bonds, may be added to the solvent. In addition, it is preferable to select the particles that absorb the gas or liquid generated when molding the thermoplastic resin or the thermosetting resin because the gas or liquid can be absorbed.

Specifically, the inorganic particles 4 include talc (hydrous magnesium silicate represented by a general formula [Mg ₃ Si ₄ O ₁₀ (OH) ₂ ]), kaolin (general formula [Al ₂ Si ₂ O ₅ (OH) ₄ ]). (Hydrous aluminum silicate represented by the following formula), bentonite, mica, clay (white clay) and other natural minerals and similar synthetic mineral particles.

The inorganic particles 4 are silica (silicon dioxide represented by the general formula [SiO ₂ ]), glass, alumina (aluminum oxide represented by the general formula [Al ₂ O ₃ ]), aluminum hydroxide, zinc oxide, titanium oxide. , Iron oxide, calcium carbonate, magnesium carbonate, aluminum nitride, silicon nitride, boron nitride, calcium chloride, aluminum chloride and other silicon oxide, metal oxide, metal carbonate, metal chloride compound particles. The inorganic particles 4 can be composed of carbon compound particles such as carbon black, graphite, or carbon nanotubes.

  If comprised in this way, since the mold release layer 3 further contains the some inorganic particle 4, and the unevenness | corrugation by the some inorganic particle 4 is formed in the surface, for example, thermosetting resin which forms a laminated board etc. is used. When molding, unevenness is formed on the release surface of the thermosetting resin that is the molded body, so the adhesion strength of the adhesive surface when the thermosetting resin is further laminated on the release surface due to the anchor effect Can be improved. Moreover, the adhesive strength with respect to the to-be-released surface of a coating surface in the case of coating on a to-be-released surface can be improved. Further, for example, when a release film is used as a protective film for an adhesive or a pressure-sensitive adhesive, since unevenness is formed on the release layer 3, a contact portion between the adhesive or the pressure-sensitive adhesive and the release layer 3 is used. Therefore, it is possible to provide the release film 10 that is easier to peel off.

  In addition, a plurality of inorganic particles 4 are further added to the solvent for forming the release coating agent, so that the release layer 3 includes the plurality of inorganic particles 4 and has irregularities formed by the plurality of inorganic particles 4 on the surface. Can be easily formed on the film-like substrate 2.

  As described above, the film thickness of the release coating agent layer is usually 0.001 to 1.0 microns, preferably 0.001 to 0.05 microns as the final coating film. . However, as in the second embodiment, when the release layer 3 further includes a plurality of inorganic particles 4, the surface of the release layer 3 has irregularities formed by the inorganic particles 4. The film thickness of the mold layer 3 is not limited to the above-described film thickness, and the film thickness of the release layer 3 may be appropriately set according to the shape and size of the inorganic particles 4.

  A specific embodiment will be described with reference to FIGS. 3 and 4 are views showing an example of the release film of the present invention. In addition, this invention is not limited to the Example mentioned later.

  A. Releasability for epoxy adhesive (wiring board, CFRP, etc.)

(1) Release film The release films shown in Examples 1 to 11 in Fig. 3 were prepared as follows. Each release coating agent is prepared by adjusting the polyalkoxysilane silicate 45 or silicate 51 (adding KR500 if necessary), and each catalyst to 1% to 5% by weight of the IPA solvent. Each release coating agent was obtained by adding to 95 g of (isopropyl alcohol) or MEK (methyl ethyl ketone) and stirring at room temperature. The obtained release coating agent was allowed to stand at room temperature for 1 month, and the stability of each release coating solution was confirmed.

  Wet each obtained release coating agent on a 12 μm-thick boblon film (polyvinyl alcohol (PVA): manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) or a 21 μm-thick cellophane film (made by Phutamura Chemical Co., Ltd.) with a bar coater. Each release film was obtained by coating (coating) with a film thickness of about 10 μm, heat-treating at each predetermined temperature for 5 minutes, and drying and solidifying at room temperature for 1 day. In addition, when adding the talc which is an inorganic particle of Example 11 in FIG. 3, silicate 51 is 5g, talc SG95 is 2.5g, a catalyst is 5% by weight with respect to the silicate, and a dispersing agent is 0.00. 2 g was added to 25 g of IPA (isopropyl alcohol) as a solvent and stirred at room temperature to obtain a release coating agent.

(2) Confirmation of releasability with respect to epoxy adhesive As shown in Examples 1 to 11 in FIG. 3, various curable epoxy resins were applied to each release film prepared with each release coating agent, and the epoxy The peelability of the resin was confirmed. The peelability results of various epoxy resins in the Bobron film and the cellophane film were the same. In the “peelability” shown in the figure, “◯” indicates a case where the peelability is good, and “x” indicates a case where the peelability is poor. Further, in the “room temperature stability” shown in the figure, “◯” indicates a case where the stability is good, and “x” indicates a case where the stability is poor.

  The curable epoxy resin A is bisphenol A epoxy resin JER827 [manufactured by Japan Epoxy Resin Co., Ltd .; trade name (JER is a registered trademark): epoxy equivalent 180] (BISAEP), 5 g of phthalic anhydride NH2000 [Hitachi Chemical Industry Co., Ltd. ) Manufactured by mixing 4.5 g of 3or4-methyl-1,2,3,6-tetrahydrophthalic anhydride] and 0.05 g of 2-ethyl-4-methylimidazole. The result of having confirmed peelability after curing for 3 hours at 150 ° C. is shown.

  The curable epoxy resin B was obtained by mixing 5 g of aliphatic cyclic epoxy (Daicel Chemical, Celoxide 2021) and 5 g of ether-based polyol (PTG1000 manufactured by Hodogaya Chemical Co., Ltd.) with 0.15 g of diaminodiphenylmethane. The result of confirming the peelability after curing at 150 ° C. for 1 hour is shown.

  The curable epoxy resin C is composed of 5 g of an aliphatic cyclic epoxy (Daicel Chemical, Celoxide 2021) and 5 g of an ether-based polyol (PTG1000 manufactured by Hodogaya Chemical Co., Ltd.) 0.15 g of a cationic polymerization initiator (Sanshin Chemical Industry, Sciade SI-60L). The result obtained by confirming peelability after curing at 110 ° C. for 1 hour on each release film is shown.

  In each of Examples 1 to 11 in FIG. 3, silicate 45: manufactured by Tama Chemical Industry Co., Ltd., silicate 51: manufactured by Fuso Chemical Industry Co., Ltd., KR500: manufactured by Shin-Etsu Chemical Co., Ltd., ethylenediamine: Tokyo Chemical Industry Industrial, 2-Aminoethanol: Tokyo Chemical Industry, Polyethylenediamine: Tokyo Chemical Industry, Isocyanate (NK Assist IS100N): Nikka Chemical Co., Ltd. Isocyanurate (NK Assist NY): Nikka Chemical ( Co., Ltd., Phosphoric acid (X40-2309A): Shin-Etsu Chemical Co., Ltd., Aluminum (DX9740): Shin-Etsu Chemical Co., Ltd., Titanium (D25): Shin-Etsu Chemical Co., Ltd., talc SG95 (2μ product): manufactured by Nippon Talc Co., Ltd. is used.

(3) Properties of release film Epoxy is an adhesive mainly used in printed circuit boards and CFRP (carbon fiber), and exhibits stronger adhesive strength than other adhesives such as polyester and polyimide. To do. The epoxy resin contains an epoxy and a curing agent. The epoxy is classified into an aromatic epoxy and an aliphatic cyclic epoxy based on bisphenol A, and the curing agent is classified into an acid anhydride, an amine, and a cationic polymerization agent. . And according to a use, the epoxy resin which has a predetermined characteristic is formed by combining these. In general, a combination of an aromatic epoxy and an acid anhydride is the most versatile epoxy resin that is difficult to release.

  In general, epoxy reacts with a hydroxyl group, but among the release coating agents of the present invention, a release film in which a release layer is formed using a phosphorus-based and aluminum-based condensation reaction promoting catalyst is an aromatic epoxy. There is a problem in the releasability in the combination of styrene and acid anhydride. This suggests that the surface state of the release layer (silica layer) varies depending on the type of condensation reaction promoting catalyst, and amine, isocyanate, isocyanurate, and titanium condensation reaction promoting catalysts are used. In the release film having the release layer formed thereon, it is considered that generation of hydroxyl groups on the surface of the release layer (silica layer) is suppressed.

  Moreover, as shown in Example 11 in FIG. 3, even when the release layer contains talc which is inorganic particles, the release layer has good release properties.

  B. Ceramic sheet release film

(1) Release film The release films shown in Examples 12 to 17 in Fig. 4 were prepared as follows. Each release coating agent is prepared by adjusting the polyalkoxysilane silicate 45 or silicate 51 (adding KR500 if necessary), and each catalyst to 1% to 5% by weight of the IPA solvent. (Isopropyl alcohol) or MEK (methyl ethyl ketone) was added to 95 g and stirred at room temperature to obtain each release coating agent.

The obtained release coating agent is subjected to a hydrophilization treatment for corona discharge treatment on a polyester (PET) film (Lumirror S10, manufactured by Toray) having a thickness of 12 μm, and a wet film thickness is applied to the treated surface by a bar coater ( Coating), and after heat treatment at 150 ° C. for 5 minutes, a release film was obtained by drying and solidifying at room temperature for 1 day. For a 12 μm-thick boblon film (polyvinyl alcohol (PVA): manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), a release coating agent was applied with a wet coat thickness of about 10 μm by a bar coater without corona discharge treatment, and 150 After heat treatment at 5 ° C. for 5 minutes, a release film was obtained by drying and solidifying at room temperature for 1 day. Since the surface resistance value of each of the obtained release films was measured to be 10 ¹¹ Ω / □ or less, it is not necessary to perform antistatic treatment necessary for the release film of the ceramic sheet for the boblon film. .

(2) Confirmation of releasability with respect to ceramic sheet On the release layer of each release film prepared with each release coating agent, barium titanate: 100 parts by weight, water dispersible vinyl acetate resin: 10 parts by weight, When a water-based ceramic slurry having a composition of 1 part by weight of polycarboxylic acid and 20 parts by weight of water is coated by a doctor blade method and dried and solidified, the ceramic sheet is peeled off to obtain a ceramic sheet having a thickness of 50 μm. The peelability of the ceramic sheet was confirmed.

  As shown in Examples 12 to 17 in FIG. 4, each release sheet has good peelability. In “Removability” shown in the figure, “◎” indicates that the releasability was very good, “○” indicates that the releasability was good, and “×” indicates that the releasability was good. The case where the property was poor is shown. In the “coatability” shown in the figure, “◯” indicates that the release layer of the release film was successfully coated with the aqueous ceramic slurry.

  The present invention is not limited to the above-described embodiments, and various modifications other than those described above can be made without departing from the spirit of the present invention. A release layer may be formed.

DESCRIPTION OF SYMBOLS 1,10 Release film 2 Film-like base material 3 Release layer 4 Inorganic particle

Claims (12)

A film-like substrate having a plurality of hydroxyl groups over the entire surface of at least one main surface;
A release layer laminated on at least one main surface of the substrate having the plurality of hydroxyl groups,
The release layer is mainly composed of silica obtained by hydrolysis reaction of polyalkoxysiloxane using a condensation reaction accelerating catalyst not containing chlorine, sulfur, phosphorus, and aluminum, and the plurality of hydroxyl groups. A release film, wherein the release film is formed by laminating a hydrogen bond and / or a covalent bond formed by a condensation reaction of the hydrogen bond on at least one main surface of the substrate.   The release film according to claim 1, wherein the release layer further includes a plurality of inorganic particles, and the surface has irregularities formed by the plurality of inorganic particles.   The release film according to claim 1 or 2, wherein the film-like substrate is a polymer of a vinyl monomer having at least one hydroxyl group or a cellulose.   2. The film-like substrate is a polymer film in which a hydroxyl group is formed on at least one principal surface by corona discharge treatment, plasma treatment, or hydrophilic treatment by treatment with a sodium / naphthalene complex solution. The release film in any one of thru | or 3.   A film-like substrate having a plurality of hydroxyl groups over the entire surface of at least one main surface, and at least one main surface having the plurality of hydroxyl groups, the main component of which is a polyalkoxysiloxane, chlorine, sulfur, phosphorus By applying a release coating agent formed by dissolving a solute containing a condensation reaction promoting catalyst not containing aluminum, and heating and drying, the release layer is condensed with hydrogen bonds and / or the hydrogen bonds. A method for producing a release film, wherein the film-like base material is laminated by a covalent bond by reaction.   The condensation reaction promoting catalyst contains at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate and a titanium-based organometallic compound. Item 6. A method for producing a release film according to Item 5.   The method for producing a release film according to claim 5 or 6, wherein a plurality of inorganic particles are further added to the solvent. A release coating agent that forms a release layer of a release film by being laminated on at least one main surface of a film-like substrate,
A mold release coating agent characterized in that it is formed by dissolving a solute containing a condensation reaction promoting catalyst containing polyalkoxysiloxane as a main component and not containing chlorine, sulfur, phosphorus or aluminum.   The condensation reaction promoting catalyst contains at least one of a compound containing an isocyanate group or an isocyanurate group, a carboxylic acid of a quaternary amine, a carbonate and a titanium-based organometallic compound. Item 9. A release coating agent according to Item 8.   The release coating agent according to claim 8 or 9, wherein a plurality of inorganic particles are further added to the solvent.   The release coating agent according to any one of claims 8 to 10, wherein the solvent is any one of alcohol, ether and ketone.   12. The release coating agent according to any one of 8 to 11, wherein 1 to 100 parts by weight of polyalkylsilane is further dissolved in 100 parts by weight of polyalkoxysiloxane in the solvent.

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