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WO2013047861A1 - Film de démoulage et son procédé de fabrication - Google Patents

Film de démoulage et son procédé de fabrication Download PDF

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Publication number
WO2013047861A1
WO2013047861A1 PCT/JP2012/075284 JP2012075284W WO2013047861A1 WO 2013047861 A1 WO2013047861 A1 WO 2013047861A1 JP 2012075284 W JP2012075284 W JP 2012075284W WO 2013047861 A1 WO2013047861 A1 WO 2013047861A1
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WO
WIPO (PCT)
Prior art keywords
mass
silicone resin
emulsion
resin composition
release
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/075284
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English (en)
Japanese (ja)
Inventor
武久　慶太
輝彦 管
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Film Solutions Ltd
Original Assignee
Teijin DuPont Films Japan Ltd
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Filing date
Publication date
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Publication of WO2013047861A1 publication Critical patent/WO2013047861A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Definitions

  • the present invention relates to a release film and a manufacturing method thereof.
  • silicone release films as process materials has shown significant growth.
  • silicone release films using polyester film as the base material have a very flat surface compared to those using paper and are less likely to generate dust. It is very useful as a process material in the field.
  • silicone used for such a silicone release film polydimethylsiloxane having an OH group at the terminal and polydimethylsiloxane having an H group at the terminal (hydrogen polydimethylsiloxane) are prepared using an organotin catalyst.
  • the mainstream is the type that makes a three-dimensional cross-linked structure (addition reaction type).
  • additional reaction type As can be seen from the silicone main chain bond and the side chain structure, such a silicone release layer has the disadvantages that it does not leak charges and is easily charged. As a result, various problems occur. For example, when coating resin on the surface of the release layer, uneven coating may occur, or the release characteristics when peeling the resin layer from the release film may deteriorate due to release discharge of the release film. is there.
  • the present invention was made in order to solve the above-described problems of the conventional release film, and is excellent in antistatic properties and release properties at the same time without separately providing an antistatic layer and a release layer. It is an object to provide a release film.
  • the present inventors diligently studied to solve the above problems. As a result, the present inventors have found that the above problem can be solved by a release layer formed using a coating liquid mainly composed of an emulsion-based silicone resin composition and a specific conductive polymer, and have reached the present invention. That is, the present invention employs the following configuration as the first aspect. 1.
  • a release film having a release layer on at least one side of a base film comprising: (I) a crosslinked silicone resin formed from an emulsion-based silicone resin composition, and (ii) a cationic polythiophene containing a repeating unit represented by the following formula (I) as a main component, and a polyanion.
  • Release film having a release layer containing a functional polymer as a constituent component (In the above formula (I), R 1 and R 2 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Alternatively, R 1 and R 2 are Represents an optionally substituted alkylene group having 1 to 12 carbon atoms.) 2.
  • the release film according to 1 above wherein the content of the conductive polymer in the release layer is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition.
  • this invention includes the following manufacturing methods. 3.
  • a cationic resin containing a silicone resin composition emulsion containing an emulsion silicone resin composition and a repeating unit represented by the formula (I) as a main component A method for producing a release film, wherein a coating liquid obtained by mixing an aqueous dispersion of a conductive polymer containing polythiophene and polyanion is applied to at least one surface of a base film and cured.
  • this invention includes the following aspects. 4).
  • the present invention provides a release film having an antistatic property and a release property at the same time without providing an antistatic layer and a release layer separately. It is desirable to provide a release film having The present inventors have intensively studied to solve the above-mentioned desirable problem. As a result, the present inventors have found that the above problems can be solved by a release layer formed by using a coating liquid mainly composed of an emulsion-based silicone resin composition, an emulsion-based silicone resin, and a specific conductive polymer. did. That is, the present invention employs the following configuration as a second aspect for solving a desirable problem. 5.
  • the cross-linked silicone resin has at least one structure selected from the group consisting of an emulsion-based silicone resin composition and a trifunctional unit siloxane and a tetrafunctional unit siloxane of 85% by mass or less based on the mass of the release layer. 5.
  • the release film as described in 5 or 6 above it comprises a silicone resin composition emulsion containing an emulsion type silicone resin composition containing dimethylsiloxane as a main constituent, and a trifunctional unit siloxane and a tetrafunctional unit siloxane.
  • a method for producing a release film in which a coating liquid obtained by mixing an aqueous dispersion of a conductive polymer containing is applied to at least one surface of a base film and cured.
  • the release film as the first aspect of the present invention has a release layer on at least one side of the base film, and the release layer has a crosslinked silicone resin as a release component and an antistatic component. Is a release film having both excellent antistatic properties and release properties at the same time.
  • the release film as the second aspect of the present invention has a release layer on at least one surface of the base film, and the release layer has a silicone resin composition and silicone as release components.
  • the cross-linked silicone resin formed from the resin and the conductive polymer as an antistatic component are present in the same layer. Excellent antistatic properties and releasability in the medium or heavy peel force region Is a mold release film.
  • each structural component which comprises the release film of this invention is demonstrated.
  • the base film used in the first and second embodiments is not particularly limited.
  • a sheet, a film, or a nonwoven fabric made of a phenol resin, an epoxy resin, an ABS resin, or the like a biaxially oriented polyester film can be preferably used from the viewpoint of excellent mechanical properties, dimensional stability, heat resistance, electrical properties, etc., and in particular, mechanical properties, heat resistance, dimensional stability.
  • the thickness of the base film is not particularly limited, but is preferably 500 ⁇ m or less. If it is thicker than 500 ⁇ m, the rigidity of the base film is too high, and the handling property tends to be poor when the conductive film is attached to a display or the like. From such a viewpoint, it is more preferably 100 ⁇ m or less, particularly preferably 50 ⁇ m or less. Moreover, it is preferable that it is 1 micrometer or more, and can have moderate intensity
  • the release layer in the first aspect of the present invention comprises a crosslinked silicone resin comprising an emulsion silicone resin composition, a cationic polythiophene containing as a main component a repeating unit represented by the above formula (I), and a polyanion Is contained as a constituent component.
  • the release layer in the second aspect of the present invention has at least one structure selected from the group consisting of an emulsion-based silicone resin composition containing dimethylsiloxane as a main constituent, and a trifunctional unit siloxane and a tetrafunctional unit siloxane.
  • a molecule is included as a constituent component.
  • the release layer in the present invention contains a cross-linked silicone resin and a conductive polymer as essential components, but when adding the conductive polymer and optional components described later, they are desired. The amount to be added may be added so that the remaining part of the release layer is a crosslinked silicone resin.
  • each structural component which comprises the mold release layer in this invention is demonstrated.
  • the silicone resin composition used in the first and second embodiments comprises a polysiloxane having at least two unsaturated groups or hydroxyl groups in one molecule, or preferably a polydimethylsiloxane.
  • the main component and a crosslinking agent made of hydrogen polysiloxane having at least two hydrogen atoms directly bonded to silicon atoms in one molecule or preferably hydrogen polydimethylsiloxane are contained as constituents.
  • the silicone resin composition is preferably composed mainly of dimethylsiloxane.
  • dimethylsiloxane as the main constituent means —Si (CH 3 ) 2
  • the ratio of the amount of dimethylsilyl group to the amount of silanol group in the polysiloxane (-Si (CH 3 ) 2 H / -Si (CH 3 ) 2 OH) (molar ratio) is usually preferably 0.5 or more and 3 or less. If the ratio is too low, unreacted silanol groups are likely to remain, and crosslinking is weakened, and transfer of unreacted components to the adherend increases, resulting in a decrease in the quality of the adherend such as an adhesive. .
  • a silicone resin composition obtained by dispersing such a silicone resin composition in a dispersion medium mainly containing water (herein, “mainly” means a proportion exceeding 50% by mass) is emulsified.
  • a coating liquid containing the product emulsion is applied to form a coating film, and the coating film is cured to form a release layer.
  • the silicone resin composition becomes a crosslinked silicone resin by such curing and exhibits releasability.
  • the silicone resin described later is also involved in the curing to become a crosslinked silicone resin, and exhibits the releasability in the middle peel force region or heavy peel force region.
  • sulfur, nitrogen, phosphorus and the like are catalyst poisons for the catalyst, but when a silicone resin composition emulsion is used, sulfur, nitrogen and the like are contained. Addition of the conductive polymer does not cause a problem in the curability of the obtained release layer.
  • the silicone resin composition is dissolved in a solvent (for example, the one dissolved in an organic solvent), and the inside of the emulsion where the silicone resin composition exists and the conductive polymer exist. It is speculated that the separation from the outside of the emulsion is greatly affected. That is, when the silicone resin composition is dissolved in a solvent, the curing reaction occurs in the solvent. Similarly, the conductive polymer present in the solvent can participate in the curing reaction and inhibits the curing. In contrast, when the silicone resin composition is in the form of an emulsion, the curing reaction takes place inside the emulsion, so that the conductive polymer existing outside the emulsion is different in the system inside and outside the emulsion.
  • a solvent for example, the one dissolved in an organic solvent
  • the silicone resin composition when the silicone resin composition is an emulsion, the curing reaction in the presence of the conductive polymer is completely different from the conventional one, and the obtained release layer is also completely different from the conventional one. It becomes.
  • the emulsion means a dispersion medium in which fine particles not mixed with the emulsion are dispersed. Such fine particles have, for example, a size ranging from about 1 ⁇ m to about 1 nm.
  • the silicone resin composition contained in the silicone resin composition emulsion is particularly referred to as “emulsion-based silicone resin composition”.
  • the silicone resin composition in the present invention is not limited to an aqueous type, but may be any type capable of forming an emulsion, but is preferably an aqueous type silicone resin composition. Since the water-based silicone resin composition is excellent in stability when formed into an emulsion, the stability of the coating material can be increased as a result. Moreover, it is preferable from an environmental viewpoint to set it as a water-based coating agent.
  • a known method can be used for emulsification (emulsification) of the silicone resin composition. For example, a silicone resin composition prepared in advance and an emulsifier (if necessary, other components) are mixed with a homogenizer, an azide.
  • thermosetting can be preferably exemplified as a method for curing the silicone resin composition, that is, a thermosetting silicone resin composition is preferable as the silicone resin composition.
  • a thermosetting silicone resin composition is preferable as the silicone resin composition.
  • an aqueous thermosetting silicone resin composition is particularly preferable.
  • the silicone resin composition includes an addition reaction type and a condensation reaction type. From the viewpoint of excellent peeling property improvement effect, the silicone resin composition is an addition reaction type (the main agent is a polysiloxane having at least two unsaturated groups in one molecule). Siloxane, preferably polydimethylsiloxane) is preferred.
  • crosslinking agent a conventionally known crosslinking agent or one recommended by the manufacturer may be preferably used as the main crosslinking agent used at the same time.
  • main agent and the crosslinking agent as described above those produced by a conventionally known method can be used as long as they satisfy the requirements of the present invention, and ready-made products can be used as they are.
  • what mixed the main ingredient and the crosslinking agent beforehand can also be used.
  • the release layer preferably contains a platinum-based catalyst.
  • the platinum-based catalyst is a catalyst for promoting the addition reaction between the main agent and the crosslinking agent, and a known catalyst can be used as the catalyst used in the addition reaction.
  • platinum-based catalysts examples include chloroplatinic acid, chloroplatinic acid alcohol solutions and aldehyde solutions, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like.
  • the amount of the platinum-based catalyst added may be any amount that is usually used, but the amount of platinum metal added is preferably 1 to 1000 ppm, more preferably 10 to 300 ppm, relative to 100 parts by mass of the main agent. When the amount is high, the strength of the release layer is increased and the cost is excellent.
  • the conductive polymer that is an essential component of the release layer in the first and second aspects of the present invention contains cationic polythiophene and a polyanion as essential components.
  • the method for producing the conductive polymer used in the present invention is not particularly limited. For example, it can be obtained by oxidative polymerization of a substance that becomes a cationic polythiophene monomer in an aqueous polyanion solution. .
  • the cationic polythiophene in the present invention contains 3,4-disubstituted thiophene represented by the following formula (I) as a main component of the repeating unit.
  • R 1 And R 2 Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 1 And R 2 Together represent an optionally substituted alkylene group having 1 to 12 carbon atoms.
  • R 1 And R 2 are independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1 And R 2 As a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group and an ethyl group are particularly preferable.
  • R 1 And R 2 are optionally substituted alkylene groups having 1 to 12 carbon atoms
  • examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, -An alkylene group such as an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,4-butylene group, a 2,3-butylene group, and a 1,2-cyclohexylene group.
  • ⁇ , ⁇ -alkylene groups such as a methylene group, 1,2-ethylene group, 1,2-propylene group, and 2,3-butylene group are particularly preferable.
  • Examples of such ⁇ , ⁇ -alkylene groups are derived from 1,2-dibromoalkanes obtained by bromination of ⁇ -olefins such as ethene, propene, hexene, octene, decene, dodecene, and styrene. Can do.
  • ⁇ -olefins such as ethene, propene, hexene, octene, decene, dodecene, and styrene.
  • a substituent in the said alkylene group a C1-C12 alkyl group and a phenyl group are preferable, and especially a methyl group, an ethyl group, and a propyl group are preferable.
  • the cationic polythiophene in the present invention may contain only 3,4-disubstituted thiophene represented by the above formula (I) as a repeating unit, or 3,4-disubstituted thiophene as a main component of the repeating unit. And other monomers that can be polymerized therewith as secondary components.
  • the “main component” means that the proportion of the repeating unit of the 3,4-disubstituted thiophene represented by the above formula (I) is 50 mol% with respect to the entire repeating unit constituting the cationic polythiophene. It means that it is in the range of 100 mol% or less.
  • the polythiophene as described above exhibits a cationic property.
  • Such cationic polythiophene can be obtained, for example, by oxidative polymerization of 3,4-disubstituted thiophene, which is a monomer, by the method described in JP-A-1-313521.
  • the polyanion in the present invention is not particularly limited. Examples thereof include polymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid, and polymaleic acid, and polymeric sulfonic acids such as polystyrene sulfonic acid and polyvinyl sulfonic acid.
  • Such polyanions such as polymeric carboxylic acids and polymeric sulfonic acids may be homopolymers composed of only one type of anionic monomer, or may be copolymers composed of a plurality of types of anionic monomers. Further, it may be a copolymer of an anionic monomer and other monomers copolymerizable with the monomer. Examples of other monomers copolymerizable with an anionic monomer include acrylates and styrenes. When the polyanion is a copolymer, it is sufficient that at least one anionic monomer is contained as a copolymerization component.
  • polystyrene sulfonic acid and polystyrene sulfonic acid at least part of which is a metal salt are particularly preferable and are excellent in the effect of improving conductivity.
  • the number average molecular weight Mn of the polyanion is preferably in the range of 1,000 or more and 2,000,000 or less, and more preferably in the range of 2,000 or more and 500,000 or less, from the viewpoint of enhancing the conductivity improving effect.
  • the ratio of cationic polythiophene: polyanion is preferably 1: 1.1 to 1: 5.0, more preferably 1: 1.2 to 1.
  • the content of the conductive polymer in the release layer is preferably 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition.
  • the content is in the above numerical range, the effect of improving the releasability and antistatic property is excellent.
  • the content is too small, the effect of improving the antistatic property tends to be low. From such a viewpoint, it is more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 0.7% by mass or more.
  • the improvement effect of mold release property becomes low and it exists in the tendency for peeling force to become heavy.
  • the addition amount of the conductive polymer increases, the cost tends to increase.
  • the silicone resin in the second aspect of the present invention has at least one structure selected from the group consisting of a trifunctional unit siloxane represented by the following formula (II) and a tetrafunctional unit siloxane represented by the following formula (III). Is a polyorganosiloxane having as a main component.
  • main component means that the trifunctional unit siloxane is SiR. 3 O 3/2
  • the unit, tetrafunctional unit siloxane is SiO 2
  • numerator in total is shown, Preferably it is 70 mol% or more, More preferably, it is 90 mol% or more.
  • R 3 Is a linear or cyclic alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, nonyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group, etc.), aromatic It represents either a group (for example, a phenyl group) or an alkenyl group (for example, a vinyl group). These may have multiple types in one molecule.
  • the crosslinked silicone resin constituting the release layer is formed from the emulsion-based silicone resin composition and 85% by mass or less of the silicone resin based on the mass of the release layer. It becomes. Thereby, the peeling force of the target middle peeling force area
  • the content of the silicone resin is preferably 83% by mass or less, more preferably 82% by mass or less, and further preferably 80% by mass or less.
  • the content may be appropriately set according to the target peeling force.
  • a medium peel force region (a peel force region between a light peel force region and a heavy peel region may be referred to in this way.
  • a normal temperature peel force obtained by a measurement method described later is 60 to 200 mN / 25 mm, preferably In order to obtain a peeling force of 60 to 100 mN / 25 mm.)
  • the content of the silicone resin is preferably 38% by mass or more and less than 65% by mass, and 38% by mass or more and less than 55% by mass.
  • a silicone resin is not used if light peeling is achieved.
  • the peeling force can be finely adjusted within a range of less than 38% by mass.
  • the content is preferably 30% by mass or more, and in the range below the lower limit, the effect of increasing the peeling force is small.
  • the peeling force becomes only moderately heavy even if the content of the silicone resin is increased.
  • the content of the silicone resin is preferably 65% by mass or more, more preferably 70% by mass or more, and further 75% by mass or more. preferable.
  • the silicone resin is emulsified by being dispersed in a dispersion medium mainly composed of water (here, “mainly” means a ratio exceeding 50% by mass).
  • a silicone resin emulsion is used, a coating liquid containing the same is applied to form a coating film, and the coating film is cured to form a release layer.
  • the silicone resin reacts with the above-described silicone resin composition by such curing, takes in the crosslinked silicone resin to form a release layer, and exhibits an effect of increasing the peeling force in the release layer.
  • a conductive polymer containing sulfur, nitrogen, phosphorus, etc. is added in the same manner as described in the section of the silicone resin composition. Even so, the reaction of the silicone resin is not inhibited, and the effect of increasing the peeling force can be efficiently achieved. Moreover, it is hard to produce the problem regarding the sclerosis
  • the silicone resin contained in the silicone resin emulsion is particularly referred to as an emulsion-based silicone resin.
  • the silicone resin may be any silicone resin that can form an emulsion without being aqueous, but is preferably an aqueous silicone resin.
  • a water-based silicone resin is excellent in stability when formed into an emulsion, and as a result, the stability of the coating liquid can be increased.
  • emulsification (emulsification) of the silicone resin a known method described in the section of the silicone resin composition can be used.
  • thermosetting can be preferably exemplified. That is, as the silicone resin, a thermosetting silicone resin is preferable. As the silicone resin in the present invention, an aqueous thermosetting silicone resin is particularly preferable. As the silicone resin as described above, a silicone resin produced by a conventionally known method can be used as long as it satisfies the requirements of the present invention, or a ready-made product can be used as it is. Examples of the ready-made products include Asahi Kasei Wacker's trade name: CRA92, Toray Dow Corning Inc.
  • the coating liquid is allowed to contain an alkylene glycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, or polyethylene glycol.
  • a mold layer can be formed.
  • a water-soluble compound having an amide bond in the molecule and liquid at room temperature can also be used.
  • it can contain a water-soluble compound having an amide bond in the molecule and liquid at room temperature.
  • the content of these compounds is preferably 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive polymer.
  • the content is too small, the effect of improving the conductive performance tends to be low. From this viewpoint, 30 parts by mass or more is more preferable.
  • the improvement effect of the heat-and-moisture resistance of a mold release layer tends to become low. From this viewpoint, 600 parts by mass or less is more preferable.
  • “with respect to 100 parts by mass of the conductive polymer” means “with respect to 100 parts by mass of the solid content of the conductive polymer”.
  • an antioxidant In the release layer of the present invention, an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, a dye, an organic, You may mix
  • Method for producing release film> In the first aspect of the present invention, the emulsion-based silicone resin composition described above, a conductive polymer, a platinum-based catalyst that may be optionally added, and other components that may optionally be added.
  • a release liquid is formed by applying a coating liquid containing as a constituent component to a substrate film and curing the obtained coating film.
  • the release layer is formed by applying a coating liquid containing other components as optional components to the base film and curing the obtained coating film.
  • the coating liquid can be produced by uniformly mixing the above components using a stirring blade or the like.
  • the emulsion-based silicone resin as a silicone resin emulsion containing the emulsion-based silicone resin.
  • each component can be mixed uniformly and a uniform release layer can be obtained.
  • each component does not cancel its function, and a release layer having excellent release properties and antistatic properties can be obtained.
  • it can dilute using a suitable solvent.
  • the coating liquid obtained by mixing may be used as it is, but as long as the object of the present invention is not impaired, it is diluted with an appropriate solvent and adjusted to have an appropriate viscosity. It is preferable to use a coating liquid from the viewpoint of obtaining a release layer that is uniform and has a good appearance.
  • the solvent water is preferable. It may contain some alcohol. In that case, it is preferable that the amount of water exceeds 50% by mass.
  • any known coating method can be applied.
  • gravure roll coating method, reverse roll coating method, die coating method, kiss coating method, reverse kiss coating method, offset gravure method A coating method, a Mayer bar coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, a doctor blade method, and the like can be applied alone or in combination.
  • the coating liquid can contain a slight amount of a surfactant.
  • the base film can be subjected to a preliminary treatment on the surface as needed for the purpose of improving adhesion, coating property and the like before applying the coating liquid.
  • preliminary treatment for example, physical surface treatment such as corona discharge treatment, plasma discharge treatment, or coating of an organic resin or inorganic resin during or after the formation of the base film
  • Examples thereof include a chemical surface treatment for forming a coating adhesion layer.
  • the conditions for drying and curing after applying the coating liquid to the base film are preferably heated at a temperature of 100 ° C. or higher and 180 ° C. or lower for 10 seconds or longer and 120 seconds or shorter, 120 ° C. or higher and 160 ° C. It is more preferable to heat at a temperature of 20 seconds or more and 90 seconds or less at the following temperature, and heating at a temperature of 130 ° C. or more and 150 ° C. or less for 30 seconds to 60 seconds is particularly preferable.
  • the thickness of the release layer is preferably 10 nm or more and 3 ⁇ m or less. When the thickness is too thin, it is difficult to form a uniform coating film, and the peeling force tends to increase.
  • the uniformity of the peeling force tends to be inferior, and not only the effect of improving the releasability is lowered, but also the surface resistance value tends to be increased because the amount of the conductive polymer in the release layer is small.
  • the antistatic property improving effect tends to be low.
  • the strength of the release layer after storage over time tends to be low. In this respect, 50 nm or more is more preferable, 0.3 ⁇ m or more is further preferable, and 0.5 ⁇ m or more is particularly preferable.
  • it is too thick it consumes more material than necessary to exhibit antistatic performance, and it is not economical, and it causes an abnormality called blocking where the front and back stick in the state of the wound roll, and it can be used.
  • a cross-linked silicone resin aspect for example, a main agent or a substituent of a cross-linking agent in a silicone resin composition
  • an additive for example, particles
  • Addition thickness, etc., can be adjusted as appropriate to accommodate a wide range of desired peeling forces.
  • the inhibition of curing by the conductive polymer is suppressed, it is possible to obtain a peeling force in a light peeling force region.
  • it since it has antistatic property simultaneously with this mold release property, it can use suitably as a carrier sheet for manufacture of the product which has an adhesion layer, or a sheet
  • the product to be manufactured is brittle, it is useful to use a light release force when suppressing the breakage of the product at the time of peeling the carrier sheet or improving the productivity by facilitating the peeling. .
  • it is a carrier sheet for manufacturing a product having a pressure-sensitive adhesive layer or a sheet forming, and the product is erroneously peeled off from the carrier sheet especially during the use process.
  • This can be suitably used in the case where it is desired to highly suppress the error that occurs.
  • it can use suitably as a release film (carrier film) on the heavy release side of an electronic material adhesive tape such as an anisotropic conductive adhesive film or a non-carrier film.
  • the peel strength of the release film of the first aspect of the present invention is preferably 20 to 300 mN / 25 mm, more preferably 20 to 200 mN / 25 mm, and even more preferably, at room temperature peel force determined by the measurement method described later. Is 20 to 100 mN / 25 mm, particularly preferably 30 to 60 mN / 25 mm.
  • the room temperature peel force is in the above numerical range, it is excellent in releasability, for example, an appropriate peel force for an adhesive tape for electronic members, and the adhesive is deformed and becomes non-uniform when peeled. The problem can be suppressed. Moreover, it can suppress that an adhesive resin etc. turns easily in the process after apply
  • the heat peeling force required by the measurement method described later it is preferably 20 to 500 mN / 25 mm, more preferably 20 to 300 mN / 25 mm, still more preferably 20 to 200 mN / 25 mm, and particularly preferably 40 to 100 mN / 25 mm. is there.
  • the heat peeling force is in the above numerical range, it is possible to suppress the peeling of the adhesive when not intended during handling due to too light peeling, and the deformation of the adhesive during peeling due to too heavy peeling.
  • the release film of the first aspect of the present invention has a room temperature aging force determined by a measurement method described later, preferably 20 to 500 mN / 25 mm, more preferably 20 to 300 mN / 25 mm, and still more preferably 20 to 100 mN / 25 mm, particularly preferably 30 to 60 mN / 25 mm. If it is lighter than 20 mN / 25 mm, the product cast into a release film such as an adhesive resin is likely to be turned over after use with storage over time, resulting in a decrease in yield. On the other hand, if it is heavier than 500 mN / 25 mm, a product such as an adhesive resin cannot be easily peeled off from the release film in the production process.
  • the release film as the first aspect of the present invention has a heating aging peel force determined by a measurement method described later, preferably 20 to 500 mN / 25 mm, more preferably 20 to 300 mN / 25 mm, and still more preferably 20 to 200 mN. / 25 mm, particularly preferably 40 to 100 mN / 25 mm. If it is lighter than 20 mN / 25 mm, the product cast into a release film such as an adhesive resin is likely to be turned over after use with storage over time, resulting in a decrease in yield. On the other hand, if it is heavier than 500 mN / 25 mm, a product such as an adhesive resin cannot be easily peeled off from the release film in the production process.
  • the release coating film In order to have such a peeling force, the release coating film needs to be in an appropriate state.If the coating film is extremely thin, the coating film will repel, and the peeling will be heavy at the repelling part, In addition, even when the coating film is extremely thick, when it is wound up with a roll, the release layer sticks to the film wound up and laminated, and when the film is unwound from the roll, the release layer is cohesive failure Therefore, it is important to set the appropriate coating thickness range as described above. Moreover, in order to achieve the peeling force with time, it is also effective to reduce the excess hydrogen silane as a crosslinking agent. In addition, after the release layer is formed, it tends to be improved by performing a heating treatment at 40 to 60 ° C. for about 1 to 7 days.
  • the peel strength of the release film of the second aspect of the present invention is preferably 200 to 800 mN / 25 mm, more preferably 250 mN / 25 mm or more, and even more preferably 270 mN in the room temperature peel force determined by the measurement method described later. / 25 mm or more, more preferably 600 mN / 25 mm or less, further preferably 500 mN / 25 mm or less, and particularly preferably 450 mN / 25 mm or less.
  • the room temperature peel force is in the above numerical range, the release property is excellent, and for example, a peel force suitable for an electronic material adhesive tape can be obtained.
  • the release film does not float, and in the heating process Problems such as peeling of the adhesive from the substrate (Nakiwakare) can be suppressed.
  • required by the below-mentioned measuring method Preferably it is 400-900mN / 25mm, More preferably, it is 450mN / 25mm or more, More preferably, it is 800mN / 25mm or less, More preferably 700 mN / 25 mm or less.
  • the heat peeling force is in the above numerical range, it is possible to suppress unintentional peeling of the adhesive during handling due to too light peeling, and deformation of the adhesive during peeling due to excessive peeling.
  • an electronic material adhesive tape particularly as a release film for an anisotropic conductive adhesive film
  • it is in the above-mentioned peeling force range especially when connecting to the base of the anisotropic conductive film.
  • the temporary connection step an appropriate peeling force is obtained, the release film does not float, and problems such as peeling of the adhesive from the substrate (sparkling) in the heating step can be suppressed.
  • the room temperature aging peel force determined by the measurement method described later is preferably 200 to 700 mN / 25 mm, more preferably 300 to 600 mN / 25 mm.
  • the release film of the present invention has a heat aging peeling force determined by a measurement method described later, preferably 550 to 1100 mN / 25 mm, more preferably 600 to 1000 mN / 25 mm.
  • the release coating must be in an appropriate state. If the coating is extremely thin, the coating will be repelled, the peeling will be too heavy at the repelling area, and the coating will be extremely thick.
  • the release layer adheres to the film wound and laminated thereon, and when the film is unwound from the roll, the release layer coagulates and breaks. Since the moldability is impaired, it is important to set the appropriate coating thickness range as described above. Moreover, in order to achieve the peeling force with time, it is also effective to reduce the excess hydrogen silane as a crosslinking agent. In addition, after the release layer is formed, it tends to be improved by performing a heating treatment at 40 to 60 ° C. for about 1 to 7 days.
  • the room temperature residual adhesion rate of the release films of the first and second aspects of the present invention is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the room temperature residual adhesion rate is in the above numerical range, for example, in an adhesive tape for electronic members, the peeling force becomes stable over time. If it is lower than 80%, the transfer of the silicone component to the product increases, the adhesive strength is reduced and contamination with the silicone component is likely to occur, resulting in a decrease in yield.
  • a solvent-based silicone resin composition is used as the silicone resin composition used simultaneously with the conductive polymer, the room temperature residual adhesion rate cannot be increased.
  • the silicone resin composition to be used needs to be an emulsion type silicone resin composition.
  • the heat residual adhesion rate is preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more.
  • the heating residual adhesion rate is in the above numerical range, the silicone transfer to the adherend is low, so that it is possible to prevent the performance degradation of the pressure-sensitive adhesive or the like. If it is lower than 70%, the transfer of the silicone component to the product will increase due to long-term storage, and the adhesive strength and contamination by the silicone component will easily occur, resulting in a decrease in yield. In order to obtain such a residual adhesion rate, it is effective to use an emulsion type silicone resin composition.
  • the surface resistance value of the release layer in the first and second embodiments of the present invention is 1 ⁇ 10 5 ⁇ 1 ⁇ 10 13 It is preferable that it is ⁇ / ⁇ .
  • the surface resistance value when used as a protective film for an adhesive tape for electronic members, adhesion of dust and the like can be suppressed, the quality of the electronic members is increased, and the yield is also increased. Moreover, it becomes easy to set it as the outstanding mold release property.
  • the surface resistance value is low, the effect of suppressing the adhesion of dust and the like tends to be improved, but when it is too low, the effect of improving the releasability tends to be low.
  • the surface resistance value when the surface resistance value is high, excellent release properties are easily obtained, but when it is too high, the effect of suppressing dust adhesion tends to be low. From such a viewpoint, the surface resistance value is more preferably 1 ⁇ 10.
  • the addition amount of the conductive polymer may be adjusted, or the addition of the above-described alkylene glycol may be adjusted.
  • the surface resistance value tends to decrease.
  • an emulsion-based silicone resin composition is not used, a coating film cannot be formed well and the surface resistance value tends to be low. It is also preferable to use an emulsion type silicone resin.
  • the film cross section was observed with a transmission electron microscope LEM-2000 under the condition of an acceleration voltage of 100 kv, and the thickness of the release layer was measured. The measurement was carried out for 10 arbitrary points, and the average value thereof was defined as the thickness (unit: nm) of the release layer.
  • (2) Smear The appearance after the surface of the release layer was lightly boiled with the belly of an index finger cleaned with gauze impregnated with ethyl alcohol was confirmed and evaluated according to the following criteria. ⁇ : No change in appearance is confirmed. X: Change in appearance such as cloudiness is confirmed.
  • the sample with the tape attached is cut into 25 mm width x 150 mm length, stored at room temperature (23 ° C) for 2 hours, and then the 31B adhesive tape side is attached and fixed to an aluminum plate with a length of 50 mm width x 125 mm.
  • the release film was peeled off at a peel angle of 180 ° and a peel speed of 300 mm / min, and the peel strength was measured. This measurement was performed three times, and the average value was taken as the room temperature peeling force (unit: N / 25 mm).
  • the sample with the tape attached is cut into 25 mm width ⁇ 150 mm length and left in the room (23 ° C.) for 24 hours, and then the 31B adhesive tape side is attached and fixed to an aluminum plate with a length of 50 mm width ⁇ 125 mm. .
  • This is fixed to a tensile tester, the release film is peeled off at a peel angle of 180 ° and a peel speed of 300 mm / min, and the peel force is measured. This measurement is performed three times, and the average value is taken as the room temperature aging peel force (unit: N / 25 mm).
  • Peeling force with heating 10 cm ⁇ 20 cm release film sample was cut out, and a 25 mm width polyester adhesive tape (No.
  • 31B manufactured by Nitto Denko Corporation
  • a 2 kg ⁇ 45 mm width press roller Then, apply one reciprocating load.
  • the sample with the tape attached was cut to 25 mm width x 150 mm length, left in a dryer at 70 ° C for 20 hours, then left in a room at 23 ° C for 1 hour, and the 31B adhesive tape side was 50 mm wide.
  • this peeled polyester adhesive tape is affixed on said stainless steel plate, it is peeled, peeling force is measured, and it is set as residual adhesive force (f).
  • the measurement environment was a sample film that had been aged for 24 hours in an atmosphere of a temperature of 23 ° C. and a humidity of 55%.
  • Example 1-1 ⁇ Base film>
  • Manganese acetate is used as a transesterification catalyst
  • phosphorous acid is used as a stabilizer
  • antimony trioxide is used as a polymerization catalyst
  • 0.06% by mass of silicon oxide particles (average particle size: 1.8 ⁇ m) is used as a lubricant.
  • 23 ° C., o-chlorophenol solvent) polyethylene terephthalate pellets were dried, melted at a melting temperature of 280 to 300 ° C., and then extruded onto a rotary cooling drum having a surface temperature of 20 ° C.
  • the obtained unstretched film is preheated to a temperature of 75 ° C., then heated by an IR heater with a surface temperature of 800 ° C. from above 15 mm between low-speed and high-speed rolls, stretched 3.6 times in the machine direction, and rapidly cooled. Subsequently, the film was supplied to a transverse stretching machine and stretched 3.9 times in the transverse direction at a temperature of 120 ° C.
  • the obtained biaxially oriented film was heat-set at a temperature of 230 ° C. for 5 seconds to obtain a heat-fixed biaxially oriented polyester film having a thickness of 38 ⁇ m.
  • 3-glycidoxypropyltrimethoxysilane is used as an anchor coat layer of a release layer on one side of the polyester film at a position immediately before the uniaxially stretched film that has been longitudinally stretched enters transverse stretching.
  • a 3% by weight aqueous solution (containing 2.0% by weight of a surfactant in the solid content) was applied in an amount of 5 g / m 2 (wet) and dried.
  • Each of the agents contains —Si (CH 3 ) 2 O— units in the molecule in an amount exceeding 50 mol%.), Catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: CAT-PM-10A), diethylene glycol, and vitron P (Polyethylenedioxythiophene 0.5% by mass, conductive polymer aqueous dispersion added with 0.8% by mass polystyrene sulfonate as a dopant, manufactured by Agfa Materials, solid content 1.3% by mass) After adding and stirring at the mixing ratio shown below to obtain a coating solution, the coating solution is prepared by using the polyester film anchor coat layer obtained above.
  • the formed surface is coated by a conventional roll coat and dried at a drying temperature of 140 ° C. for 60 seconds to form a release layer having a thickness of 0.7 ⁇ m after drying. Obtained.
  • the properties of the obtained release film are shown in Table 1.
  • the inside of the parenthesis in the following shows mass ratio of each component with respect to 100 mass% of solid content of a silicone resin composition.
  • Example 1-2 A release layer was formed in the same manner as in Example 1-1 except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 1.
  • Example 1-3 The release layer was formed in the same manner as in Example 1-1 except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows and the coating thickness after drying was 0.5 ⁇ m. And a release film was obtained. The properties of the obtained release film are shown in Table 1.
  • Example 1-4 A release layer was formed in the same manner as in Example 1-3, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows.
  • Example 1-5 A release layer was formed in the same manner as in Example 1-1 except that the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 1.
  • silicone emulsion 400E silicone: methylpolysiloxane having vinyl group, crosslinker
  • silicone emulsion 400E silicone: methylpolysiloxane having vinyl group, crosslinker
  • crosslinker V72 made by Wacker Silicones, an emulsion of methylhydrogen polysiloxane, which reacts with double bonds in methylsiloxane, solid content concentration 50 mass
  • silane coupling agent manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-403
  • polyoxyethylene oleyl ether trade name: Emulgen 404, produced by Kao Corporation
  • Example 1-6 A release layer was formed in the same manner as in Example 1-5 except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 1.
  • Example 1-1 A release layer was formed in the same manner as in Example 1-3, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows.
  • Example 1-1 The base film in Example 1-1 was used as it was. Evaluation was performed on the surface on the side not having the anchor coat layer. In the table, aE + b represents a ⁇ 10 b .
  • Example 2-1 ⁇ Base film>
  • Manganese acetate is used as a transesterification catalyst
  • phosphorous acid is used as a stabilizer
  • antimony trioxide is used as a polymerization catalyst
  • 0.06% by mass of silicon oxide particles (average particle size: 1.8 ⁇ m) is used as a lubricant.
  • 23 ° C., o-chlorophenol solvent) polyethylene terephthalate pellets were dried, melted at a melting temperature of 280 to 300 ° C., and then extruded onto a rotary cooling drum having a surface temperature of 20 ° C. to obtain an unstretched film having a thickness of 520 ⁇ m.
  • the obtained unstretched film is preheated to a temperature of 75 ° C., then heated by an IR heater with a surface temperature of 800 ° C. from above 15 mm between low-speed and high-speed rolls, stretched 3.6 times in the machine direction, and rapidly cooled. Subsequently, the film was supplied to a transverse stretching machine and stretched 3.9 times in the transverse direction at a temperature of 120 ° C.
  • the obtained biaxially oriented film was heat-set at a temperature of 230 ° C. for 5 seconds to obtain a heat-fixed biaxially oriented polyester film having a thickness of 38 ⁇ m.
  • the obtained polyester film was subjected to corona treatment on one side.
  • Each of the agents contains —Si (CH 3 ) 2 O— units in the molecule in an amount exceeding 50 mol%.
  • Catalyst manufactured by Shin-Etsu Chemical Co., Ltd .: CAT-PM-10A
  • diethylene glycol and vitron P (polyethylenedioxythiophene 0.5% by mass, conductive polymer aqueous dispersion with 0.8% by mass polystyrene sulfonic acid added as a dopant, manufactured by Agfa Materials, solid content 1.3% by mass)
  • Silicone resin emulsion manufactured by Asahi Kasei Wacker Co., Ltd .: CRA92, solid content 50 mass%, this silicone resin is trifunctional Containing siloxane and / or tetrafunctional unit siloxane, and containing SiR 3 O 3/2 units and / or SiO 2 units in a total amount exceeding 50 mol% in the molecule
  • a release layer having a dried film thickness of 0.8 ⁇ m was formed to obtain a release film.
  • the properties of the obtained release film are shown in Table 2.
  • the inside of the parenthesis in the following shows the mass ratio of the solid content of each component with respect to 100 mass% of solid content of a silicone resin composition.
  • CAT-PM-10A 0.11 parts by mass (12.5% by mass)
  • Diethylene glycol 0.5 part by weight
  • Vitron P 3.0 part by weight (4.4% by weight)
  • CRA92 6.6 parts by mass (375% by mass)
  • the mass ratio of the silicone resin in a release layer is 76.2 mass%.
  • Example 2-2 A release layer was formed in the same manner as in Example 2-1, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows to obtain a release film.
  • the properties of the obtained release film are shown in Table 2.
  • CAT-PM-10A 0.1 part by mass (12.5% by mass)
  • Vitron P 3.0 parts by weight (4.9% by weight)
  • CRA92 6.8 parts by mass (425% by mass)
  • the mass ratio of the silicone resin in a release layer is 78.4 mass%.
  • Example 2-3 The release layer was formed in the same manner as in Example 2-1, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows and the coating thickness after drying was 1.3 ⁇ m. And a release film was obtained.
  • the properties of the obtained release film are shown in Table 2.
  • CAT-PM-10A 0.4 parts by mass (13.7% by mass)
  • Diethylene glycol 0.5 parts by weight
  • Vitron P 3.0 parts by weight (1.3% by weight)
  • CRA92 7.5 parts by mass (128.4% by mass
  • the mass ratio of the silicone resin in a release layer is 52.8 mass%.
  • Example 2-4 The release layer was formed in the same manner as in Example 2-1, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows and the coating thickness after drying was 0.4 ⁇ m. And a release film was obtained.
  • the properties of the obtained release film are shown in Table 2.
  • Diethylene glycol 0.5 parts by weight
  • Vitron P 3.0 parts by weight (19.5% by weight)
  • FZ-77 0.1 parts by mass CRA92: 3.6 parts by mass (900% by mass)
  • the mass ratio of the silicone resin in a release layer is 87.4 mass%.
  • FZ-77 is a surfactant (manufactured by Toray Dow Corning).
  • Silicone manufactured by Shin-Etsu Chemical Co., Ltd .: TPR6700, toluene solution, solid content 30% by mass
  • a solvent composed of 70 parts by mass of methyl ethyl ketone (MEK) and 30 parts by mass of toluene
  • MEK methyl ethyl ketone
  • catalyst manufactured by Shin-Etsu Chemical Co., Ltd .: CM670
  • Example 2 The sample was prepared by coating.
  • MEK 70 parts by mass Toluene: 30 parts by mass
  • TPR6700 10 parts by mass (100% by mass)
  • CM670 0.2 mass part (6.7 mass%)
  • Vitron P 10 parts by mass (4.3% by mass)
  • CRA92 10 parts by mass (166.7% by mass)
  • the mass ratio of the silicone resin in a release layer is 60.0 mass%.
  • Examples 2-5 to 2-14 The same method as in Example 2-1 except that the mixing ratio of each component in the coating liquid for forming the release layer is as shown in Table 3 and the coating thickness after drying is as shown in Table 2.
  • a release layer was formed to obtain a release film.
  • the properties of the obtained release film are shown in Table 2.
  • aE + b represents a ⁇ 10 b .
  • Effect of the Invention it is possible to provide a release film that is excellent in antistatic properties and release properties at the same time without separately providing an antistatic layer and a release layer.
  • it can be set as the peeling force of the wide range with antistatic property.
  • the peeling force in the light peeling force region can be obtained.
  • it can use suitably as a carrier sheet used for the use for the use for which light peeling is requested
  • the peel force in the middle peel force region or heavy peel force region as well as antistatic properties.
  • it can be suitably used as a release film (carrier film) on the heavy peeling side of an electronic material adhesive tape such as an anisotropic conductive adhesive film or a non-carrier film, where heavy peeling is required.
  • the present invention it is possible to produce a release film having excellent release properties and antistatic properties by a single coating. Moreover, since the obtained film can be used suitably for manufacture of the product which has an adhesion layer, a carrier sheet for sheet formation, etc., the industrial applicability is high.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention a pour but de proposer un film de démoulage qui a d'excellentes propriétés antistatiques et une excellente aptitude au démoulage en même temps sans être doté d'une couche antistatique et d'une couche de démoulage de façon séparée. La présente invention concerne un film de démoulage, qui a une couche de démoulage sur au moins une surface d'un film de base et la couche de démoulage contenant, comme constituants, (i) une résine de silicone réticulée qui est formée à partir d'une composition de résine de silicone en émulsion et (ii) un polymère conducteur qui contient un polyanion et un polythiophène cationique qui contient une unité répétitive représentée par la formule (I) comme composant principal. (Dans la formule (I), R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle ayant 1-4 atomes de carbone, ou, en variante, R1 et R2 se combinent et représentent un groupe alkylène facultativement substitué ayant 1-12 atomes de carbone).
PCT/JP2012/075284 2011-09-26 2012-09-25 Film de démoulage et son procédé de fabrication Ceased WO2013047861A1 (fr)

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JP2015074192A (ja) * 2013-10-10 2015-04-20 帝人デュポンフィルム株式会社 異方導電性フィルム用離型フィルム
JP2016188276A (ja) * 2015-03-30 2016-11-04 信越ポリマー株式会社 導電性離型剤及びその製造方法、帯電防止フィルムの製造方法、及び帯電防止フィルム
CN109016769A (zh) * 2018-06-27 2018-12-18 深汕特别合作区昌茂粘胶新材料有限公司 一种抗静电硅胶保护膜及其制备方法
US10854357B2 (en) * 2016-07-11 2020-12-01 Shin-Etsu Polymer Co., Ltd. Coating material for forming conductive release layer, method for producing same, conductive release film, and method for producing same
CN115873516A (zh) * 2023-01-09 2023-03-31 太湖金张科技股份有限公司 一种无基材ab胶及其制备方法
JP2023055188A (ja) * 2021-10-05 2023-04-17 旭化成ワッカーシリコーン株式会社 シリコーンエマルジョン組成物及び該組成物を用いた剥離被膜の製造方法
KR102598209B1 (ko) * 2022-07-06 2023-11-06 도레이첨단소재 주식회사 이형 코팅 조성물
JP2024008379A (ja) * 2022-07-08 2024-01-19 信越ポリマー株式会社 導電性高分子分散液、導電性積層体及びその製造方法
JP2024008377A (ja) * 2022-07-08 2024-01-19 信越ポリマー株式会社 導電性高分子分散液、導電性積層体及びその製造方法
JP2024008381A (ja) * 2022-07-08 2024-01-19 信越ポリマー株式会社 導電性高分子分散液、導電性積層体及びその製造方法

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JP2003055552A (ja) * 2001-08-16 2003-02-26 Shin Etsu Chem Co Ltd 剥離紙用シリコーン組成物及び剥離紙
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015074192A (ja) * 2013-10-10 2015-04-20 帝人デュポンフィルム株式会社 異方導電性フィルム用離型フィルム
JP2016188276A (ja) * 2015-03-30 2016-11-04 信越ポリマー株式会社 導電性離型剤及びその製造方法、帯電防止フィルムの製造方法、及び帯電防止フィルム
US10854357B2 (en) * 2016-07-11 2020-12-01 Shin-Etsu Polymer Co., Ltd. Coating material for forming conductive release layer, method for producing same, conductive release film, and method for producing same
CN109016769A (zh) * 2018-06-27 2018-12-18 深汕特别合作区昌茂粘胶新材料有限公司 一种抗静电硅胶保护膜及其制备方法
JP2023055188A (ja) * 2021-10-05 2023-04-17 旭化成ワッカーシリコーン株式会社 シリコーンエマルジョン組成物及び該組成物を用いた剥離被膜の製造方法
JP7760440B2 (ja) 2021-10-05 2025-10-27 旭化成ワッカーシリコーン株式会社 シリコーンエマルジョン組成物及び該組成物を用いた剥離被膜の製造方法
KR102598209B1 (ko) * 2022-07-06 2023-11-06 도레이첨단소재 주식회사 이형 코팅 조성물
JP2024008379A (ja) * 2022-07-08 2024-01-19 信越ポリマー株式会社 導電性高分子分散液、導電性積層体及びその製造方法
JP2024008377A (ja) * 2022-07-08 2024-01-19 信越ポリマー株式会社 導電性高分子分散液、導電性積層体及びその製造方法
JP2024008381A (ja) * 2022-07-08 2024-01-19 信越ポリマー株式会社 導電性高分子分散液、導電性積層体及びその製造方法
CN115873516A (zh) * 2023-01-09 2023-03-31 太湖金张科技股份有限公司 一种无基材ab胶及其制备方法

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