WO2016208469A1 - セラミックグリーンシート製造工程用剥離フィルム - Google Patents

セラミックグリーンシート製造工程用剥離フィルム Download PDF

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Publication number
WO2016208469A1
WO2016208469A1 PCT/JP2016/067796 JP2016067796W WO2016208469A1 WO 2016208469 A1 WO2016208469 A1 WO 2016208469A1 JP 2016067796 W JP2016067796 W JP 2016067796W WO 2016208469 A1 WO2016208469 A1 WO 2016208469A1
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WO
WIPO (PCT)
Prior art keywords
ceramic green
release agent
green sheet
release
polyorganosiloxane
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PCT/JP2016/067796
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English (en)
French (fr)
Japanese (ja)
Inventor
森　裕一
佐藤　慶一
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リンテック株式会社
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Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020177023942A priority Critical patent/KR20180020946A/ko
Priority to SG11201710776UA priority patent/SG11201710776UA/en
Priority to CN201680005002.7A priority patent/CN107148348A/zh
Publication of WO2016208469A1 publication Critical patent/WO2016208469A1/ja
Priority to PH12017502383A priority patent/PH12017502383A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness

Definitions

  • the present invention relates to a release film used in a process for producing a ceramic green sheet.
  • a ceramic green sheet is formed, and a plurality of obtained ceramic green sheets are laminated and fired.
  • the ceramic green sheet is formed by coating a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film.
  • the release film is required to have releasability that allows the release film to be peeled off from the thin ceramic green sheet formed on the release film with an appropriate peeling force without causing cracks or breakage.
  • the release film is generally composed of a base material and a release agent layer provided on one surface of the base material.
  • the release agent layer there is a layer made of an ultraviolet curable compound.
  • This release agent layer is formed by applying a release agent composition containing an ultraviolet curable compound on a substrate and curing the composition by irradiation with ultraviolet rays.
  • ultraviolet curable compounds whose curing is inhibited by oxygen.
  • curing in the vicinity of the surface of the release agent layer on the side opposite to the substrate surface in contact with the ceramic slurry / ceramic green sheet; hereinafter may be referred to as “release surface”). It may be insufficient.
  • the release agent layer is not sufficiently cured, the elasticity of the release agent layer is lowered. As a result, the peeling force required for peeling the release sheet from the ceramic green sheet formed on the release surface is increased.
  • Patent Document 1 discloses a release film provided with a release agent layer containing a thermosetting compound such as melamine resin and polysiloxane (polyorganosiloxane).
  • a release agent layer containing a thermosetting compound such as melamine resin and polysiloxane (polyorganosiloxane).
  • the release agent layer contains polyorganosiloxane, the release force can be reduced to some extent.
  • the melamine resin condenses by heating and can be cured without the above-described inhibition by oxygen. Therefore, the above-mentioned problem peculiar when an ultraviolet curable compound is used can be avoided.
  • the “melamine resin” means a mixture containing at least one of a plurality of types of melamine compounds and a polynuclear product formed by condensation of one or more types of melamine compounds.
  • the phrase “melamine resin” means the above mixture or an aggregate of one kind of melamine compounds.
  • what the said melamine resin hardened shall be called "melamine hardened
  • Such a shift is considered to be caused by, for example, accumulation of a shift in the stacking position in the stacking process, a shift due to thermocompression bonding in the thermocompression bonding process, a shift due to shrinkage in the sintering process, and the like.
  • the present invention has been made in view of such a situation, and exhibits a good releasability and is a peel for ceramic green sheet manufacturing process in which the migration of polyorganosiloxane from the release agent layer to the ceramic green sheet is suppressed.
  • the object is to provide a film.
  • the present invention is a release film for a ceramic green sheet manufacturing process, comprising a base material and a release agent layer provided on one side of the base material, the release agent The layer was formed from a release agent composition containing a polyorganosiloxane having at least one hydroxyl group in one molecule and a melamine resin having a total acid value of 0.030 to 0.154 mg KOH / g.
  • a release film for a ceramic green sheet manufacturing process (Invention 1).
  • the release agent layer comprises a polyorganosiloxane having at least one hydroxyl group in one molecule and a melamine resin having a total acid value of 0.030 to 0.154 mg KOH / g.
  • the polyorganosiloxane preferably has at least one organic group selected from a polyester group and a polyether group in one molecule (Invention 2).
  • At least one of the hydroxyl groups is preferably present at the end of the polyorganosiloxane (Invention 3).
  • the polyorganosiloxane preferably has a weight average molecular weight of 1,000 to 300,000 (Invention 4).
  • the melamine resin has the following general formula (a): (In the formula, X represents —H, —CH 2 —OH, or —CH 2 —O—R, and may be the same or different. R represents a carbon number of 1-8. Each represents the same or different alkyl group, and at least one X is —CH 2 —OH.) Or a polynuclear product obtained by condensing two or more of the compounds (Invention 5).
  • the release agent composition preferably further contains an acid catalyst (Invention 6).
  • the thickness of the release agent layer is preferably 0.1 to 3 ⁇ m (Invention 7).
  • the release film for a ceramic green sheet production process according to the present invention exhibits good releasability and suppresses migration of polyorganosiloxane from the release agent layer to the ceramic green sheet.
  • release film 1 ⁇ / b> A for a ceramic green sheet manufacturing process according to the first embodiment is a base material 11 and one of the base materials 11. And a release agent layer 12 laminated on the surface (the upper surface in FIG. 1).
  • the release film 1 ⁇ / b> B for the ceramic green sheet manufacturing process according to the second embodiment includes the base material 11 and the base material 11.
  • the release agent layer 12 of the release films 1A and 1B comprises a polyorganosiloxane having at least one hydroxyl group in one molecule and a melamine resin having a total acid value of 0.030 to 0.154 mg KOH / g. It is formed from the contained release agent composition.
  • the release agent composition for forming the release agent layer 12 contains polyorganosiloxane. For this reason, the surface free energy in the peeling surface of the release agent layer 12 falls moderately. Furthermore, the release agent composition contains a melamine resin. For this reason, the release agent composition can be sufficiently cured by heating, and the formed release agent layer 12 has sufficient elasticity. By these, the peeling force at the time of peeling peeling film 1A, 1B from the ceramic green sheet shape
  • the total acid value of the melamine resin contained in the release agent composition for forming the release agent layer 12 is 0.030 to 0.154 mg KOH / g.
  • the melamine resin has a relatively large number of acidic functional groups.
  • This acidic functional group is derived mainly from the hydroxyl group of the methylol group (—CH 2 —OH) in the melamine resin.
  • the polyorganosiloxane contained in the release agent composition also has at least one hydroxyl group in one molecule.
  • the total acid value of the melamine resin is 0.030 to 0.154 mg KOH / g, and 0.032 to 0.100 mg KOH / g. It is preferably 0.035 to 0.070 mg KOH / g.
  • the total acid value of the melamine resin means the mass (mg) of potassium hydroxide necessary to completely react the group capable of reacting with potassium hydroxide contained in 1 g of melamine resin.
  • the total acid value of a melamine resin shall be represented not by a theoretical value but by an actual measured value.
  • the group capable of reacting with potassium hydroxide is a methylol group (—CH 2 —OH).
  • imino groups (—NH—) and alkyl ether groups (—CH 2 —OR) do not react with potassium hydroxide.
  • the specific measuring method of the total acid value of a melamine resin is as showing in the test example mentioned later.
  • the total acid value is less than 0.030 gKOH / g, the number of hydroxyl groups in the melamine resin becomes insufficient, and the reaction between the polyorganosiloxane and the melamine resin does not proceed sufficiently.
  • the formed release agent layer 12 the amount of polyorganosiloxane that is not fixed to the melamine cured product increases, and migration of the polyorganosiloxane to the ceramic green sheet is likely to occur.
  • the melamine resin preferably contains a melamine compound represented by the following general formula (a) or a polynuclear product obtained by condensing two or more of the melamine compounds.
  • X represents —H, —CH 2 —OH, or —CH 2 —O—R.
  • These groups constitute reactive groups in the condensation reaction between the melamine compounds. Specifically, the —NH group formed when X becomes H can undergo a condensation reaction between the —N—CH 2 —OH group and the —N—CH 2 —R group. Both the —N—CH 2 —OH group formed when X becomes —CH 2 —OH and the —N—CH 2 —R group formed when X becomes —CH 2 —R are both , —NH group, —N—CH 2 —OH group and —N—CH 2 —R group can be subjected to a condensation reaction.
  • At least one X is —CH 2 —OH.
  • the presence of at least one —CH 2 —OH group enables reaction between the hydroxyl group contained in the group and the hydroxyl group of the polyorganosiloxane, and the migration of the polyorganosiloxane is suppressed as described above.
  • the melamine resin contains a polynuclear product obtained by condensing the melamine compound, the polynuclear product itself has at least one —CH 2 —OH group.
  • R represents an alkyl group having 1 to 8 carbon atoms.
  • the number of carbon atoms is preferably 1 to 6, and particularly preferably 1 to 3.
  • Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group, and a methyl group is particularly preferable.
  • the above Xs may be the same or different.
  • said R may be the same respectively, and may differ.
  • Melamine compounds generally include a full ether form in which all Xs are —CH 2 —O—R, imino methylol in which at least one X is —CH 2 —OH and at least one X is H. type, at least one X is -CH 2 -OH and and and methylol type is H X is absent, and, at least one X is not present -CH 2 -OH a and a H H imino There are types such as types.
  • the melamine resin is an imino / methylol type from the viewpoint that curling is easily suppressed and the physical property that the total acid value is 0.030 to 0.154 mgKOH / g.
  • it preferably contains a methylol type melamine compound.
  • a methylol type melamine compound it is preferable that more X is -CH 2 -OH, in particular, the number of X is a -CH 2 -OH is preferably at least two, In particular, at least three are preferable.
  • the melamine resin may contain a polynuclear product obtained by condensing 2 to 50 compounds represented by the above formula (a), and may contain a polynuclear product obtained by condensing 2 to 30 compounds.
  • a polynuclear product formed by condensation of 10 may be included, and further, a polynuclear product formed by condensation of 2 to 5 may be included.
  • the weight average molecular weight of the melamine resin is preferably 350 to 10000, particularly preferably 700 to 5000, and more preferably 1000 to 4000. Is preferred.
  • the weight average molecular weight is 350 or more, the crosslinking rate is stabilized, and a smoother release surface can be formed.
  • the weight average molecular weight is 10,000 or less, an excessive increase in the viscosity of the release agent composition is suppressed. Thereby, the applicability
  • the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the polyorganosiloxane preferably has at least one hydroxyl group in one molecule. Further, the upper limit of the number of hydroxyl groups in one molecule of polyorganosiloxane is not particularly limited, but is 20 for example. Since the release agent layer 12 of the release films 1A and 1B is formed of a release agent composition containing polyorganosiloxane, the release surface of the release agent layer 12 can exhibit good release properties. Further, since the polyorganosiloxane has the hydroxyl group, the polyorganosiloxane can be fixed to the cured melamine by a condensation reaction with the melamine resin. As a result, the migration of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheet is suppressed.
  • the structure other than the hydroxyl group in the polyorganosiloxane is particularly limited as long as it does not inhibit the above-described peelability, the condensation reaction between the polyorganosiloxane and the melamine resin, and the condensation reaction between the melamine compounds contained in the melamine resin. It is not a thing.
  • a polymer of a silicon-containing compound represented by the following general formula (b) can be used as the polyorganosiloxane.
  • m is an integer of 1 or more.
  • At least one of R 1 to R 8 is a hydroxyl group or an organic group having a hydroxyl group.
  • at least one of R 3 to R 8 is preferably a hydroxyl group or an organic group having a hydroxyl group. That is, it is preferable that at least one of the hydroxyl group or the organic group having a hydroxyl group is present at the terminal of the polyorganosiloxane. When the hydroxyl group is present at the terminal, the polyorganosiloxane easily undergoes a condensation reaction with the melamine resin, and the migration of the polyorganosiloxane is effectively suppressed.
  • At least one of the groups other than the hydroxyl group among R 1 to R 8 is preferably an organic group.
  • the other organic groups contained in R 1 to R 8 may be an organic group having a hydroxyl group, or An organic group having no hydroxyl group may be used.
  • the other organic groups contained in R 1 to R 8 are organic groups having a hydroxyl group.
  • the “organic group” does not include an alkyl group described later.
  • the polyorganosiloxane represented by the formula (b) preferably has at least one organic group having a hydroxyl group or an organic group having no hydroxyl group in one molecule, particularly preferably 1 to 10, more preferably It is preferable to have 1 to 5 pieces.
  • the organic group is preferably one or more organic groups selected from a polyester group and a polyether group. Both polyester groups and polyether groups may be present in one molecule. When a polyester group or a polyether group contains a hydroxyl group, the hydroxyl group may be present at the end of these organic groups, or may be present in the side chain of these organic groups.
  • the polyorganosiloxane has the above organic group
  • the polyorganosiloxane and the melamine resin are well mixed in the release agent composition, and the phase separation of these during the curing is suppressed.
  • the condensation reaction of the polyorganosiloxane and the melamine resin as described above proceeds well, and the migration of the polyorganosiloxane is effectively suppressed.
  • groups other than those described above are preferably alkyl groups having 1 to 12 carbon atoms.
  • alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group, and a methyl group is particularly preferable.
  • R 1 to R 8 may be the same or different. When a plurality of R 1 and R 2 are present, R 1 and R 2 may be the same or different from each other.
  • the weight-average molecular weight of the polyorganosiloxane is preferably 1000 to 300,000, particularly preferably 3000 to 100,000, and more preferably 4000 to 50,000.
  • the weight average molecular weight of the polyorganosiloxane is 1000 or more, the surface free energy on the release surface of the release agent layer 12 is moderately reduced, and the peeling force when peeling the release films 1A and 1B from the ceramic green sheet is effective. Can be reduced.
  • the weight average molecular weight of the polyorganosiloxane is 300000 or less, an excessive increase in the viscosity of the release agent composition is suppressed, and the release agent composition can be easily applied to the substrate 11.
  • the content of the polyorganosiloxane in the release agent composition is preferably 0.05 to 15 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the melamine resin. Further, it is preferably 0.5 to 8 parts by mass.
  • the content of the polyorganosiloxane in the release agent composition is 0.05 parts by mass or more, the surface free energy of the release surface of the release agent layer 12 is sufficiently reduced, and an appropriate release force can be achieved. it can.
  • the content of the polyorganosiloxane in the release agent composition is 15 parts by mass or less, the content of the melamine resin can be ensured. Thereby, the elasticity of the release agent layer 12 is improved, and an appropriate peeling force can be achieved.
  • the migration of the polyorganosiloxane is suppressed due to the reaction between the polyorganosiloxane and the melamine resin as described above. For this reason, even if the release agent composition contains a relatively large amount of polyorganosiloxane, the migration of the polyorganosiloxane is sufficiently suppressed.
  • the release agent composition preferably further contains an acid catalyst.
  • an acid catalyst hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, p-toluenesulfonic acid and the like are preferable, and p-toluenesulfonic acid is particularly preferable.
  • the content of the acid catalyst in the release agent composition is preferably from 0.1 to 30 parts by weight, particularly preferably from 0.5 to 20 parts by weight, based on 100 parts by weight of the melamine resin. Is preferably 1 to 15 parts by mass.
  • the release agent composition may contain a crosslinking agent, a reaction inhibitor and the like in addition to the above components.
  • the release agent layer 12 preferably has a thickness of 0.1 to 3 ⁇ m, particularly preferably 0.2 to 2 ⁇ m, and more preferably 0.3 to 1.5 ⁇ m. It is preferable that When the thickness of the release agent layer 12 is 0.1 ⁇ m or more, the function as the release agent layer 12 can be effectively exhibited. In particular, when the release agent layer 12 containing the cured melamine is thicker than usual, the release agent layer 12 is more elastic and improved in peelability. Moreover, when the release agent layer 12 has a thickness of 3 ⁇ m or less, it is possible to suppress occurrence of blocking when the release films 1A and 1B are wound into a roll.
  • the thickness of the release agent layer 12 such as 0.1 to 3 ⁇ m is thicker than that of the normal release agent layer 12.
  • the thickness of the release agent layer 12 increases, the amount of migration of the polyorganosiloxane tends to increase, but in the release agent layer 12 of the release films 1A and 1B, the reaction between the polyorganosiloxane and the melamine resin occurs. Therefore, even when the release agent layer 12 is thick, the migration of the polyorganosiloxane is sufficiently suppressed.
  • the base material 11 of the release films 1A and 1B is not particularly limited as long as the release agent layer 12 or the resin layer 13 can be laminated.
  • Examples of the base material 11 include films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, plastics such as polycarbonate and polyvinyl acetate. These films may be a single layer or a multilayer of two or more layers of the same or different types. Among these, a polyester film is preferable, a polyethylene terephthalate film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.
  • the polyethylene terephthalate film hardly generates dust or the like during processing or use, for example, it is possible to effectively prevent a ceramic slurry coating failure due to dust or the like. Furthermore, by performing an antistatic treatment on the polyethylene terephthalate film, it is possible to increase the effect of preventing ignition due to static electricity when coating a ceramic slurry using an organic solvent or preventing defective coating.
  • a surface treatment by an oxidation method, a concavo-convex method, or the like, if desired, on one side or both sides primer treatment can be performed.
  • the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment.
  • the unevenness method include a sand blast method and a thermal spraying method.
  • the thickness of the substrate 11 is usually 10 to 300 ⁇ m, preferably 15 to 200 ⁇ m, and particularly preferably 20 to 125 ⁇ m.
  • Resin Layer The resin layer 13 provided on the release film 1B is located between the base material 11 and the release agent layer 12 as shown in FIG. By providing the resin layer 13 between the base material 11 and the release agent layer 12, irregularities on the surface of the base material 11 on the release agent layer 12 side are absorbed, and the roughness of the release surface of the release film 1B is reduced. Can do.
  • the resin forming the resin layer 13 is not particularly limited, and examples thereof include melamine resin, epoxy resin, phenol resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, and benzoxazine resin. Among these, it is preferable to form the resin layer 13 with a melamine resin.
  • a melamine resin By forming the resin layer 13 with a melamine resin, the adhesive force between the resin layer 13 and the base material 11 and between the resin layer 13 and the release agent layer 12 is improved. Furthermore, the elasticity on the peeling surface side of the release film 1B is improved, and the peeling force when peeling the release film 1B from the ceramic green sheet is appropriately reduced.
  • the melamine resin for forming the resin layer 13 is not particularly limited. However, from the viewpoint of suppressing the shrinkage of the resin layer 13 itself, the melamine resin used for forming the release agent layer 12 is preferably used as the melamine resin for the resin layer 13. That is, it is preferable to form the resin layer 13 using the composition containing the above-mentioned melamine resin.
  • the resin layer 13 may contain components other than the melamine resin together with the melamine resin, such as an epoxy resin, a phenol resin, a urea resin, a polyester resin, a urethane resin, an acrylic resin, a polyimide resin, and a benzoxazine resin.
  • a resin may be contained.
  • the content thereof is preferably 1 to 200 parts by mass, particularly preferably 10 to 150 parts by mass, with respect to 100 parts by mass of the melamine resin. It is preferably from ⁇ 100 parts by mass.
  • the resin layer 13 may contain a crosslinking agent, a reaction inhibitor, an adhesion improver, and the like.
  • the thickness of the resin layer 13 is usually 0.1 to 3 ⁇ m, preferably 0.2 to 2 ⁇ m, and particularly preferably 0.3 to 1.5 ⁇ m.
  • the release force required to release the release films 1A and 1B from the ceramic green sheet formed on the release surface of the release films 1A and 1B should be set as appropriate. However, it is preferably 2.5 to 50 mN / 20 mm, and more preferably 5 to 25 mN / 20 mm.
  • the release agent layer in the release films 1A and 1B is formed of a release agent composition containing the melamine resin and polyorganosiloxane. Therefore, it is possible to appropriately set the peeling force as 2.5 to 50 mN / 20 mm.
  • the migration of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheet is suppressed. Specifically, after the ceramic green sheet was formed on the release surfaces of the release films 1A and 1B, when the ceramic green sheet was released from the release films 1A and 1B, it was in contact with the release surface of the ceramic green sheet. The migration amount of polyorganosiloxane on the surface is reduced. In particular, when a ceramic green sheet is formed using the release films 1A and 1B, the silicon atomic ratio obtained by measuring the surface of the ceramic green sheet that is in contact with the release surface is less than 1.0 atomic%.
  • the ceramic green sheet for measurement a ceramic green sheet in which silicon is not detected by XPS (that is, does not contain a silicon compound) is appropriately selected, and the silicon atomic ratio is determined based on the migration amount of the polyorganosiloxane in the release agent layer 12. It can be used as an evaluation standard.
  • release film 1A For example, gravure coating method, bar coating method, spray coating method, spin coating method, knife coating method, roll coating method, die coating method and the like can be used.
  • peeling film 1B when manufacturing peeling film 1B, after applying the coating liquid containing the melamine resin used as the raw material of a melamine resin to one surface of the base material 11, it is resin by drying and heating, for example. Layer 13 is formed. Furthermore, after applying the above-mentioned release agent composition and a coating solution containing an organic solvent as required to the surface of the resin layer 13 opposite to the substrate 11, the release agent composition is dried and heated. Is cured to form the release agent layer 12. Thereby, release film 1B is obtained. As these coating methods, the same coating methods as those described above can be used.
  • the organic solvent is not particularly limited, and various types can be used.
  • hydrocarbon compounds such as toluene, hexane, heptane, isopropyl alcohol, isobutyl alcohol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof are used.
  • the release agent composition coated as described above is preferably thermoset.
  • the heating temperature is preferably 90 to 140 ° C., more preferably 110 to 130 ° C.
  • the heating time is preferably about 10 to 120 seconds, particularly preferably about 50 to 70 seconds.
  • Release films 1A and 1B can be used for manufacturing ceramic green sheets. Specifically, after applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide to the release surface of the release agent layer 12, a ceramic green sheet is obtained by drying the ceramic slurry. Can do. The coating can be performed using, for example, a slot die coating method or a doctor blade method.
  • binder component contained in the ceramic slurry examples include butyral resins and acrylic resins.
  • solvent contained in the ceramic slurry examples include organic solvents and aqueous solvents.
  • the release agent layer 12 is formed of the release agent composition containing the melamine resin and polyorganosiloxane described above, whereby excellent release properties are exhibited. Furthermore, since a structure in which the polyorganosiloxane is fixed to the melamine resin is formed in the release agent layer 12, the migration of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheet is suppressed. Thereby, when the ceramic green sheets shape
  • Another layer such as an antistatic layer may be provided between the layer 13 and the release agent layer 12.
  • Example 1 100 parts by mass of imino-type methylated melamine resin (manufactured by Nippon Carbide Co., Ltd., trade name: MX-730, weight average molecular weight 1508) (amount converted as solid content, hereinafter the same) and polyether-modified hydroxyl group-containing polydimethylsiloxane (b1 ) (Manufactured by Big Chemie Japan, trade name: BYK-377, number average molecular weight (Mn) 5078, weight average molecular weight (Mw) 5993, molecular weight distribution (Mw / Mn) 1.18) 0.5 parts by mass, acid 4.0 parts by mass of p-toluenesulfonic acid (trade name: dryer 900, manufactured by Hitachi Chemical Co., Ltd.) as a catalyst was mixed in a mixed solvent of methyl ethyl ketone, isopropyl alcohol and isobutyl alcohol, and the solid content was 20% by mass.
  • a coating 100
  • the obtained coating solution was uniformly coated on a surface of a biaxially stretched polyethylene terephthalate film (thickness: 25 ⁇ m) as a base material having a maximum protrusion height Rp of 452 nm by a Mayer bar # 6. Subsequently, it heat-dried at 120 degreeC for 1 minute (s), the release agent composition was hardened, and the peeling film by which the 1.2-micrometer-thick release agent layer was laminated
  • the thickness of the base material and the release agent layer was measured using a reflective film thickness meter (manufactured by Filmetrics, product name: F20).
  • Example 2 to 4 A release film was obtained in the same manner as in Example 1 except that the mass parts of the polyether-modified hydroxyl group-containing polydimethylsiloxane (b1) was changed as shown in Table 1.
  • Example 5 0.5 parts by mass of polyether-modified hydroxyl group-containing polydimethylsiloxane (b1), polyester-modified hydroxyl group-containing polydimethylsiloxane (b2) (manufactured by BYK Japan, trade name: BYK-370, number average molecular weight (Mn) 2689, A release film was obtained in the same manner as in Example 1, except that the weight average molecular weight (Mw) 4283, the molecular weight distribution (Mw / Mn) 1.59) was changed to 1.0 part by mass.
  • Mw weight average molecular weight
  • Example 6 A release film was obtained in the same manner as in Example 5 except that the mass parts of the polyester-modified hydroxyl group-containing polydimethylsiloxane (b2) was changed as shown in Table 1.
  • the measurement sample is titrated with a potassium hydroxide standard 2-propanol solution using a potentiometric automatic titrator (product name: AT-610, EBU-610-20B, manufactured by Kyoto Electronics Industry Co., Ltd.) for neutralization.
  • the amount of potassium hydroxide standard 2-propanol solution required was measured.
  • the measurement was performed 3 times, and the average value was calculated. From this average value, the amount (mg) of potassium hydroxide required to neutralize 1 g of the melamine resin was calculated and used as the total acid value (mgKOH / g).
  • Table 1 The results are shown in Table 1.
  • the ceramic slurry was uniformly applied to the release surface of the release agent layer using an applicator. Then, it was made to dry at 80 degreeC with a dryer for 1 minute. As a result, a ceramic green sheet having a thickness of 3 ⁇ m was obtained on the release film. In this way, a release film with a ceramic green sheet was produced.
  • This release film with a ceramic green sheet was allowed to stand for 24 hours in an atmosphere at room temperature of 23 degrees and humidity of 50%.
  • an acrylic pressure-sensitive adhesive tape manufactured by Nitto Denko Corporation, trade name: 31B tape
  • 31B tape was applied to the surface of the ceramic green sheet opposite to the release film, and cut into a width of 20 mm in that state. This was used as a measurement sample.
  • the pressure-sensitive adhesive tape side of the measurement sample is fixed to a flat plate and peeled off from the ceramic green sheet using a tensile tester (manufactured by Shimadzu Corporation, product name: AG-IS500N) at a peeling angle of 180 ° and a peeling speed of 100 mm / min.
  • the film was peeled and the force required to peel (peeling force; mN / 20 mm) was measured.
  • peeling force peel
  • the polyorganosiloxane migration was evaluated according to the following criteria.
  • Table 1 shows the silicon atomic ratio and the evaluation results.
  • the release films obtained in the examples could be peeled with an appropriate peeling force when peeled from the ceramic green sheet. Furthermore, it was found that the ceramic green sheet formed using the release film obtained in the example has a small silicon atom ratio, and the migration of polyorganosiloxane is effectively suppressed. In particular, it can be seen that even when the amount of polyorganosiloxane in the release agent composition increases, the migration of polyorganosiloxane is suppressed. In addition, in the release sheet obtained in the Example, it was also confirmed that the maximum protrusion height Rp of the release surface was relatively low and the smoothness was excellent.
  • the release film obtained in the comparative example required a strong peeling force when peeling from the ceramic green sheet. Moreover, in the ceramic green sheet shape
  • the release film for a ceramic green sheet production process of the present invention is suitable for forming a ceramic green sheet.

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PCT/JP2016/067796 2015-06-23 2016-06-15 セラミックグリーンシート製造工程用剥離フィルム WO2016208469A1 (ja)

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SG11201710776UA SG11201710776UA (en) 2015-06-23 2016-06-15 Release film for ceramic green sheet production process
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JP7306516B2 (ja) * 2018-03-22 2023-07-11 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP7082890B2 (ja) * 2018-03-23 2022-06-09 リンテック株式会社 セラミックグリーンシート製造工程用剥離フィルム
JP6683295B1 (ja) * 2018-08-10 2020-04-15 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
WO2020196224A1 (ja) * 2019-03-26 2020-10-01 リンテック株式会社 剥離シート
CN114025960B (zh) * 2019-06-28 2024-05-24 东洋纺株式会社 陶瓷生片制造用脱模薄膜
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