CN118215579A - Release film for ceramic green sheet production - Google Patents
Release film for ceramic green sheet production Download PDFInfo
- Publication number
- CN118215579A CN118215579A CN202280074167.5A CN202280074167A CN118215579A CN 118215579 A CN118215579 A CN 118215579A CN 202280074167 A CN202280074167 A CN 202280074167A CN 118215579 A CN118215579 A CN 118215579A
- Authority
- CN
- China
- Prior art keywords
- ceramic green
- green sheet
- film
- release
- release layer
- 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.)
- Pending
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- 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
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
Provided is a release film for ceramic green sheet production which has excellent releasability and is less likely to cause transfer/release of a release layer and poor adhesion. The present invention relates to a release film for producing a ceramic green sheet, which has a polyester film and a release layer. Characterized in that the release layer is a layer obtained by curing a curable composition containing: a polysiloxane A having 2 or more alkenyl groups in the molecule, a polysiloxane B having 2 or more hydrosilyl groups in the molecule, and an adhesion imparting agent C, wherein the surface free energy γS (mJ/m 2) of the surface of the release layer and the hydrogen bond component γ SVh (mJ/m 2) of γS satisfy the following formulas (a) and (B). Gamma SVh/gamma S100 is less than or equal to 1.0 and less than or equal to 6.5 (a) gamma S is less than or equal to 30 (b).
Description
Technical Field
The present invention relates to a release film for producing a ceramic green sheet having a polyester film and a release layer, which can be suitably used for producing an ultra-thin ceramic green sheet or the like.
Background
Conventionally, a release film having a polyester film as a base material and a release layer laminated thereon has been used as a film for various steps. Among them, a release film for producing a ceramic green sheet is also used as a process film for producing a ceramic green sheet which requires high smoothness, such as a laminated ceramic capacitor and a ceramic substrate.
In recent years, with the miniaturization and the increase in capacity of laminated ceramic capacitors, there is a tendency that the thickness of ceramic green sheets is also thinned. The ceramic green sheet is formed by applying a slurry containing a ceramic component such as barium titanate and a binder resin to a release film, and drying the same. The ceramic green sheet obtained by printing an electrode on the molded ceramic green sheet and peeling from the release film is laminated, pressed, baked, and coated with an external electrode, thereby manufacturing a laminated ceramic capacitor.
In recent years, the thinning of ceramic green sheets has progressed, and the releasability at the time of releasing ceramic green sheets from a release film has become more important. If the peeling force is large and uneven, damage is applied to the ceramic green sheet in the peeling step, sheet defects, uneven thickness, and the like occur, and there is a problem that defects such as pinholes and sheet cracks occur. It is therefore desirable to peel the ceramic green sheet with a lower, uniform force.
As a countermeasure for light peeling of the release layer, as in patent document 1 and the like, there has been proposed a release film using, as the release layer, a silicone coating film formed by an addition reaction by heat or the like, using a polydimethylsiloxane having an alkenyl group, a polydimethylsiloxane having a hydrosilyl group, and a platinum catalyst.
In addition, as a countermeasure for improving the curability of a release layer, patent document 2 proposes a release film having a release layer obtained by curing a radical curable composition containing a polyorganosiloxane having a reactive functional group such as an acryl group and a polyfunctional (meth) acrylate.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6619200
Patent document 2: japanese patent No. 5492352
Disclosure of Invention
Problems to be solved by the invention
However, in the invention of patent document 1, it is difficult to achieve both adhesion of the release layer to the base film and release properties on the surface, and there is a possibility that the silicone coating will come off the release layer and contaminate the step in the step of producing the ceramic green sheet.
In addition, in the invention of patent document 2, if the curability is improved to such an extent that transfer of the release layer or the like can be prevented, there is a problem that sufficient releasability is not obtained when the ceramic is peeled.
Accordingly, an object of the present invention is to provide a release film for producing a ceramic green sheet, which has excellent releasability and is less likely to cause transfer/release of a release layer and poor adhesion. The present invention also provides a method for producing a ceramic green sheet using the release film.
Solution for solving the problem
The present inventors have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by controlling the ratio of the hydrogen bond component γ SVh in the surface free energy γs to a predetermined range in particular for a release layer which is cured by adding an adhesion imparting agent, and have completed the present invention.
That is, the present invention includes the following.
[1] A release film for producing a ceramic green sheet, characterized by comprising a polyester film and a release layer,
The release layer is a layer obtained by curing a curable composition containing: a polysiloxane A having 2 or more alkenyl groups in the molecule, a polysiloxane B having 2 or more hydrosilyl groups in the molecule, and an adhesion imparting agent C,
The surface free energy γs (mJ/m 2) and the hydrogen bond component γ SVh (mJ/m 2) of γs on the surface of the release layer satisfy the following formulas (a) and (b).
1.0≤γSVh/γS*100≤6.5 (a)
γS≤30 (b)
[2] The release film for ceramic green sheet production according to [1], wherein the adhesion imparting agent C is a silane coupling agent having 1 or more functional groups selected from the group consisting of vinyl groups, epoxy groups, acryl groups and methacryl groups.
[3] The release film for ceramic green sheet production according to [1] or [2], wherein the weight average molecular weight of the polysiloxane A is 300000 to 600000.
[4] The release film for ceramic green sheet production according to any one of [1] to [3], wherein a molar ratio of an amount of hydrosilyl groups of the polysiloxane B to an amount of alkenyl groups of the polysiloxane A in the curable composition satisfies the following formula (c).
1.0≤Si-H/Si-A≤3.8 (c)
Wherein Si-H represents the molar amount of hydrosilyl groups and Si-A represents the molar amount of alkenyl groups.
[5] The release film for ceramic green sheet production according to any one of [1] to [4], wherein the curable composition contains 1 to 10 mass% of the adhesion-imparting agent C, based on the total amount of the polysiloxane A and the polysiloxane B.
[6] The release film for ceramic green sheet production according to any one of [1] to [5], wherein the polyester film has a surface layer A substantially free of inorganic particles,
The release layer is laminated on the surface layer A with a thickness of 0.005 μm or more and 0.1 μm or less,
The maximum protrusion height (Sp) of the surface of the release layer is 100nm or less.
[7] A method for producing a ceramic green sheet by molding a ceramic green sheet using the release film for ceramic green sheet production described in any one of [1] to [6], wherein the molded ceramic green sheet has a thickness of 0.2 μm to 1.0 μm.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a release film for producing a ceramic green sheet which has excellent releasability and is less likely to cause transfer/release of a release layer and poor adhesion can be provided.
Detailed Description
[ Release film for ceramic Green sheet production ]
The release film for producing a ceramic green sheet of the present invention (hereinafter, may be simply referred to as "release film") may be provided on at least one side of the polyester film.
In addition, an easy-to-adhere layer, an antistatic layer, a smoothing layer, and the like may be provided between the release layer and the polyester film, but in the present invention, good adhesion is easily obtained without sandwiching the easy-to-adhere layer or the like. That is, as a preferable embodiment, a release film in which a release layer is directly provided on a polyester film can be exemplified.
The release layer is a layer obtained by curing a curable composition containing: a polysiloxane A having 2 or more alkenyl groups in the molecule, a polysiloxane B having 2 or more hydrosilyl groups in the molecule, and an adhesion imparting agent C.
The release film of the present invention is characterized in that the surface of the release layer, that is, the surface free energy γs (mJ/m 2) and the hydrogen bond component γ SVh (mJ/m 2) of γs on the surface of the release layer opposite to the polyester film satisfy the following formulas (a) and (b).
1.0≤γSVh/γS*100≤6.5 (a)
γS≤30 (b)
First, the surface characteristics of the release layer specified by the formulas (a) and (b) will be described.
(Surface Properties of Release layer)
The above-mentioned formulae (a) and (b) include the surface free energy γs and the hydrogen bond component γ SVh thereof, and a method for obtaining them will be described. The surface free energy can be obtained by dropping each solvent of water, diiodomethane, and ethylene glycol onto the release layer and measuring the angle (contact angle) formed by the drop and the release layer after a certain period of time. From the contact angle of each solvent, the surface free energy γs of the release layer and its hydrogen bond component γ SVh were calculated by calculation using the Kitazaki-Hata formula.
More specifically, a release film was fixed on a flat glass substrate, and 1.9. Mu.L of water was dropped on the release film. After the droplet was left to stand for 60 seconds, the angle formed by the droplet and the release layer was measured and set to θ 1. 0.9. Mu.L of diiodomethane was similarly dropped onto the release film. After the droplet was left to stand for 30 seconds, the angle formed by the droplet and the release layer was measured and set to θ 2. Further, 0.9. Mu.L of ethylene glycol was added dropwise to the release film. After the droplet was left to stand for 30 seconds, the angle formed by the droplet and the release layer was measured and set to θ 3.
The dispersion component γ SVd, dipole component γsvp, and hydrogen bond component γ SVh of the surface free energy of the release layer were calculated from θ 1、θ2、θ3 and water, diiodomethane, and ethylene glycol γ LVnd, γ LVnp, γ LVnh, and γln (where n=1, 2, or 3 corresponds to water, diiodomethane, and ethylene glycol) described in table 1 by the following equation Kitazaki-Hata, and the total thereof was defined as the surface free energy γs of the release layer. I.e., γ SVd +γsvp+γ SVh =γs. The unit of the surface free energy and each component was "mJ/m 2".
TABLE 1
The inventors of the present invention found that when the surface free energy obtained by measuring the release layer under the above conditions satisfies the formulas (a) and (b), extremely good releasability is obtained when the release layer is coated with a ceramic slurry and dried to form a ceramic green sheet. In addition, the inequality on the lower limit side of the formula (a) is satisfied, so that the curability of the coating film is improved, and as a result, the release layer is easily formed to have sufficient strength, and the release layer is less likely to fall off.
For the excellent releasability of the ceramic green sheet, it is considered that the small amount of hydrogen bonding components in the surface free energy in the release layer contributes. That is, it is considered that the hydroxyl component in the binder contained in the ceramic green sheet is prevented from hydrogen bonding with the hydrogen component which is an unreacted component of the release layer, contributing to light releasability of the ceramic green sheet.
The ratio (γ SVh/γs×100) of the hydrogen bond component contained in the surface free energy of the release layer is preferably 6.5% or less, more preferably 6.0% or less, and even more preferably 5.0% or less. When the ratio is 6.5% or less, the peeling force becomes good, and the ceramic green sheet is less likely to be deformed or broken during peeling.
On the other hand, the lower limit of the ratio (γ SVh/γs×100) is preferably 1.0% or more, more preferably 1.2% or more. When the ratio is 1.0% or more, the unreacted vinyl group is less formed, and the coating film is likely to have sufficient strength, and the release layer is less likely to be peeled off.
In addition, the surface free energy γs of the release layer is also preferably low. This is considered to be because, when the surface free energy of the release layer is close to the surface free energy of the ceramic green sheet, the energy required for peeling the ceramic green sheet from the release layer increases, and as a result, the peelability is deteriorated. The surface free energy γs is preferably 30mJ/m 2 or less, more preferably 25mJ/m 2 or less, still more preferably 20mJ/m 2 or less.
The lower limit of the surface free energy γs is not particularly limited, but from the viewpoint of the coatability of the ceramic slurry, the surface free energy γs is preferably 12mJ/m 2 or more, more preferably 14mJ/m 2 or more.
[ Release layer ]
The material of the release layer constituting the release film is preferably a curable composition shown below for forming the release layer satisfying the above physical properties. That is, the release layer is preferably formed of a layer obtained by curing the curable composition described below.
The curable composition contains: a polysiloxane A having 2 or more alkenyl groups in the molecule, a polysiloxane B having 2 or more hydrosilyl groups in the molecule, and an adhesion imparting agent C.
(Polysiloxane A)
The polysiloxane a may have 2 or more alkenyl groups at the side chain and/or terminal, and is preferably a polyorganosiloxane having an alkenyl group at least at the side chain, more preferably a polyorganosiloxane having an alkenyl group only at the side chain. Further, a copolymer comprising a siloxane unit having an alkenyl group and a dialkylsiloxane unit or an alkylphenylsiloxane unit is preferable because it exhibits releasability and the amount of alkenyl groups in 1 molecule can be easily adjusted. The terminal silicon atom is preferably a trialkylsilane structure such as trimethylsilane.
Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms. By having such an alkenyl group, the strength of the release layer is excellent. The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, particularly preferably a vinyl group or a hexenyl group. The silicon atom bonded to the alkenyl group may be bonded to a plurality of alkenyl groups, but alkenyl groups bonded to alkyl groups are preferable. The alkyl group in this case is preferably a methyl group or the like.
In addition to the siloxane units having alkenyl groups, as the dialkylsiloxane units and the like contained in the polysiloxane a, dimethylsiloxane units, phenylmethylsiloxane units and the like can be exemplified as preferable examples.
Examples of the polysiloxane include those represented by the following structural formula (1).
In the above formula (1), l, m and n are integers of 0 or more (where m+n is 2 or more), and if l is 1000 or more and 10000 or less and m+n is in the range of 2 or more and 100 or less, sufficient releasability is exhibited, and a crosslinking reaction is suitably performed, and the strength of the release layer is improved, so that it is preferable. From the same point of view, (m+n)/(l+m+n+2) is preferably 0.006 or more and 0.03 or less, more preferably 0.01 or more and 0.024 or less.
The above formula does not refer to a block copolymer, and it merely indicates that the total count of each unit is l, m, and n. Thus, the polysiloxane in the above formula may be a random copolymer or a block copolymer.
In the present invention, as polysiloxane a, 1 kind of polysiloxane as described above may be used alone, or 1 kind of polysiloxane having 2 or more different alkenyl groups in 1 molecule may be used, or 2 or more kinds of polysiloxanes having 2 or more different structures such as alkenyl groups each different may be used in combination.
The weight average molecular weight of polysiloxane a is preferably 300000 to 600000, particularly preferably 400000 to 55000. The weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).
When the weight average molecular weight of the polysiloxane a is 300000 or more, the crosslinked release layer has appropriate coating film strength, and can more effectively prevent the coating film from falling off. When the weight average molecular weight is 600000 or less, the flatness of the dried coating film becomes good.
(Polysiloxane B)
The polysiloxane B may have 2 or more hydrosilyl groups (groups in which silicon atoms and hydrogen atoms are directly bonded) on the side chains and/or at the terminal ends, and is preferably a hydrosilyl group-containing hydrosilyl group at least on the side chains, more preferably a hydrosilyl group-containing hydrosilyl group only on the side chains. Further, the copolymer comprising a siloxane unit having a hydrosilyl group and a dialkylsiloxane unit or an alkylphenylsiloxane unit is preferable because it exhibits releasability and the amount of the hydrosilyl group in 1 molecule can be easily adjusted. The silicon atom directly bonded to the hydrogen atom may be directly bonded to a plurality of hydrogen atoms, but it is preferable that the hydrogen atom is bonded to an alkyl group. The alkyl group in this case is preferably a methyl group or the like. The terminal silicon atom is preferably a trialkylsilane structure such as trimethylsilane.
In addition to the siloxane units having hydrosilyl groups, as the dialkylsiloxane units and the like contained in the polysiloxane B, dimethylsiloxane units, phenylmethylsiloxane units and the like can be exemplified as preferable examples.
The hydrogen polysiloxane may be exemplified by, for example, a polysiloxane represented by the following structural formula (2).
In the above formula (2), o is an integer of 0 or more and p is an integer of 2 or more, and if o is 0 or more and 120 or less, p is 2 or more and 120 or less, and o+p is in the range of 2 or more and 240 or less, it is preferable to suitably carry out the crosslinking reaction and improve the strength of the release layer. From the same viewpoint, (p)/(o+p+2) is preferably 0.3 to 1.
The above formula does not refer to a block copolymer, and it merely indicates that the total count of each unit is o or p. Thus, the hydrogen polysiloxane in the above formula may be a random copolymer or a block copolymer.
As the polysiloxane B, 1 kind of the aforementioned hydrogen polysiloxane may be used alone, or 2 or more kinds of hydrogen polysiloxanes having different structures such as different numbers of hydrosilyl groups in 1 molecule may be used in combination.
The weight average molecular weight of the polysiloxane B is preferably 5000 to 100000, particularly preferably 7000 to 20000. When the weight average molecular weight of the polysiloxane B is 5000 or more, the crosslinked release layer has appropriate coating film strength, and can prevent the coating film from falling off. When the weight average molecular weight is 100000 or less, the flatness of the dried coating film becomes good.
In the present invention, the polysiloxane a and the polysiloxane B are preferably formed by addition polymerization in the presence of a platinum-based catalyst or the like described later, and are the main components of the release layer. Polyaddition as referred to herein refers to the reaction of the functional groups in the molecular terminals or molecular side chains in polysiloxane a as indicated by-Si-ch=ch 2 or-Si-R-ch=ch 2 with the functional groups in the molecular terminals or molecular side chains in polysiloxane B as indicated by H-Si to form-Si-CH 2CH2 -Si-or-Si-R-CH 2CH2 -Si-. Wherein "-" in the above functional groups means further linkage with a molecule. The reaction at this time is expressed by the reaction formula, and is shown in the following formula.
Here, R represents an alkylene group having 1 to 8 carbon atoms.
(Polysiloxane content)
The molar ratio of the amount of hydrosilyl groups of the polysiloxane B to the amount of alkenyl groups of the polysiloxane a preferably satisfies the following formula (c) in the curable composition.
1.0≤Si-H/Si-A≤3.8 (c)
(Wherein Si-H represents the molar amount of hydrosilyl groups and Si-A represents the molar amount of alkenyl groups.)
That is, the release layer satisfies the formula (a), and in order to satisfy the formula, the amount of the hydrosilyl group of the polysiloxane B in the curable composition is preferably adjusted. Preferably, the amount of hydrosilyl groups of polysiloxane B is 3.8 times the molar amount of alkenyl groups of polysiloxane A. If the amount of the hydrosilyl group in the polysiloxane B is equal to or more than the amount of the alkenyl group in the polysiloxane a, the coating film tends to have sufficient strength, and the release layer is less likely to be peeled off. From this viewpoint, the above molar ratio is more preferably 1.5 or more, and still more preferably more than 2.0.
On the other hand, if the amount of the hydrosilyl group contained in the polysiloxane B is 3.8 times or less as compared with the alkenyl group contained in the polysiloxane a, the amount of the hydrogen bond component contained in the surface free energy of the release layer becomes appropriate, and the peeling property becomes good. From this viewpoint, the above molar ratio is more preferably 3.5 or less, and still more preferably 3.0 or less.
In the present invention, the mixing mass ratio (B/a) of polysiloxane B to polysiloxane a in the curable composition is preferably set to 0.5 or more and 5 or less, more preferably 0.9 or more and 3 or less, thereby satisfying the formula (c). By setting the mixing mass ratio (B/a), the polysiloxane a and the polysiloxane B appropriately react, and any one of the components can be prevented from precipitating on the surface of the release layer.
(Adhesion imparting agent C)
The release layer in the present invention contains an adhesion imparting agent C as an essential component. The adhesion imparting agent tends to migrate between the polyester film and the release layer in the stage of forming the release layer, and the adhesion between the polyester film and the release layer is improved. In this way, in the process of processing the ceramic green sheet using the release film, the release layer can be prevented from falling off from the polyester film, and as a result, the defective rate in the production of the ceramic green sheet can be reduced.
In order to provide adhesion to the silicone resin as the release layer, the adhesion-imparting agent preferably has a functional group that reacts with at least one of polysiloxane a and polysiloxane B. Specifically, it is preferable to have 1 or more functional groups selected from the group consisting of vinyl, epoxy, acryl and methacryl groups that react with hydrosilyl groups.
In addition, the adhesion imparting agent is preferably a silane coupling agent in order to impart adhesion to the polyester film. The silane coupling agent has compatibility with polysiloxane and can provide good adhesion to a polyester film (for example, effect achieved by hydrogen bonding).
The silane coupling agent is preferably a silane coupling agent represented by the following general formula.
X1 aSiR1 (4-a)
In the above general formula, X 1 represents the functional group, and a represents an integer of 1 to 3. In particular, a is preferably 1.
R 1 represents a hydrolyzable group selected from an alkoxy group, an acyloxy group, a halogen, or an alkyl group. Among them, an alkoxy group and an acyloxy group are preferable. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. The acyloxy group is preferably an acyloxy group having 2 to 11 carbon atoms, more preferably an acyloxy group having 2 to 7 carbon atoms, and particularly preferably an acetoxy group. As the halogen, a chlorine group is preferable. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms.
In the case where R 1 is as described above, the adhesion between the base film and the release layer is excellent.
In the above general formula, (4-a) R 1 are shown to be bonded to Si, and these R 1 may be the same kind of group or different kinds of groups, respectively. In the present invention, it is preferable that at least 1 of (4-a) R 1 is an alkoxy group or an acyloxy group, and it is more preferable that all R 1 are an alkoxy group or an acyloxy group.
The silane coupling agent of the general formula may be used in an amount of 1 or 2 or more in combination, or may be a reaction product obtained by reacting 2 or more silane coupling agents.
In order to improve the adhesion between the silane coupling agent and the polyester film, acetic acid, p-toluenesulfonic acid, and the like may be added to the silane coupling agent.
The amount of the adhesion-imparting agent added to the curable composition is preferably 1% by mass or more and 10% by mass or less, more preferably 2.0% by mass or more and 8.0% by mass or less, based on the total amount of the polysiloxane a and the polysiloxane B, and if 1% by mass or more, adhesion between the release layer and the substrate becomes good, and if 10% by mass or less, the excessive adhesion-imparting agent is less likely to adversely affect the release layer, and flatness and peelability become good.
(Catalyst D)
The curable composition for forming the release layer preferably further contains a catalyst D. The catalyst is not particularly limited as long as it can promote the curing reaction of the curable composition, and among them, a platinum group metal compound is preferable.
Examples of the platinum group metal compound include fine-particle platinum, fine-particle platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium, and the like. By containing the catalyst in the curable composition, the curing reaction of the curable composition can be more effectively performed.
The content of the catalyst D in the curable composition of the present embodiment is preferably about 1ppm to 1000ppm based on the total amount of solid components other than the catalyst D, from the viewpoint of adjusting the curing reaction rate to a suitable range.
(Optional component)
The curable composition may contain, in addition to the above components, a reaction inhibitor, a solvent, a silicone resin having no reactive functional group, an antistatic agent, and the like.
(Physical Properties of Release layer)
The thickness of the release layer is preferably 0.005 μm or more and 0.1 μm or less, particularly preferably 0.01 μm or more and 0.05 μm or less. When the thickness of the release layer is 0.005 μm or more, a thickness sufficient to function as the release layer is formed. On the other hand, when the thickness of the release layer is 0.1 μm or less, the coating film is less likely to fall off from the release layer.
For the surface of the release layer, it is preferable that the surface of the region has an average roughness (Sa) of 7nm or less and a maximum protrusion height (Sp) of 100nm or less so that the ceramic green sheet coated and molded thereon does not cause defects. Even more preferably, the area surface average roughness is 5nm or less and the maximum protrusion height is 80nm or less. For example, the maximum protrusion height (Sp) may be 45nm or less.
When the surface roughness of the region is 7nm or less and the maximum protrusion height is 100nm or less, the ceramic green sheet is preferably formed because defects such as pinholes are not generated and the yield is good. The smaller the area surface average roughness (Sa), the more preferable, but may be 0.1nm or more or 0.3nm or more. The smaller the maximum protrusion height (Sp), the more preferable, but may be 1nm or more or 3nm or more.
[ Polyester film ]
The polyester film used as the base film (hereinafter, may be referred to as a base) in the present invention is a film containing a polyester as a resin component, and preferably a film containing a polyester in the resin component in the maximum amount (for example, 90 mass% or more).
The polyester constituting the polyester film is not particularly limited, and a polyester which is generally used as a base material for a release film may be used as a film. The linear saturated polyester is preferably a crystalline linear saturated polyester containing an aromatic dibasic acid component and a diol component, and more preferably polyethylene terephthalate, polyethylene 2, 6-naphthalate, polybutylene terephthalate, 1, 3-propanediol terephthalate, or a copolymer containing these resins as a main component.
In particular, a polyester film formed of polyethylene terephthalate is preferable. The polyethylene terephthalate preferably has a repeating unit of 90 mol% or more, more preferably 95 mol% or more, and a small amount of other dicarboxylic acid component or diol component may be copolymerized. For example, from the viewpoint of cost, it is preferably produced from only terephthalic acid and ethylene glycol. In addition, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization agents, and the like may be added within a range that does not hinder the effect of the release film of the present invention. The polyester film is preferably a biaxially oriented polyester film because of high modulus of elasticity in both directions and the like.
The intrinsic viscosity of the polyethylene terephthalate film is preferably 0.50dl/g or more and 0.70dl/g or less, more preferably 0.52dl/g or more and 0.62dl/g or less. When the intrinsic viscosity is 0.50dl/g or more, it is preferable because many breaks do not occur in the stretching step. In contrast, in the case of 0.70dl/g or less, the cutting property is good when cutting to a predetermined product width, and no dimensional defect is generated, so that it is preferable. In addition, the raw material pellets are preferably sufficiently vacuum-dried.
In the present specification, the term "polyester film" may refer to a (laminated) polyester film having a surface layer a and a surface layer B.
The method for producing the polyester film of the present invention is not particularly limited, and a conventionally generally used method can be used. For example, it can be obtained as follows: the polyester film was obtained by melting the polyester by an extruder, extruding the melt in a film form, and cooling the melt by a rotary cooling drum to obtain an unstretched film, and biaxially stretching the unstretched film. The biaxially stretched film may be obtained by a method of sequentially biaxially stretching a uniaxially stretched film in the longitudinal direction or the transverse direction in the transverse direction or the longitudinal direction; or by simultaneously biaxially stretching an unstretched film in the longitudinal and transverse directions.
In the present invention, the stretching temperature at the time of stretching the polyester film is preferably set to be equal to or higher than the second transition temperature (Tg) of the polyester. It is preferable to stretch the sheet in each of the longitudinal and transverse directions by 1 to 8 times, particularly by 2 to 6 times.
The thickness of the polyester film is preferably 12 μm or more and 50 μm or less, more preferably 15 μm or more and 38 μm or less, still more preferably 19 μm or more and 33 μm or less. When the thickness of the film is 12 μm or more, the film is preferably produced, processed, and molded because it is not deformed by heat. On the other hand, if the film thickness is 50 μm or less, the amount of the film to be discarded after use is not extremely increased, and it is preferable in terms of reducing the environmental load.
The polyester film base material may be a single layer or a plurality of layers of 2 or more layers. For example, the base film may be a polyester film having a surface layer a substantially free of particles having a particle diameter of 1.0 μm or more and a surface layer B containing particles. Preferably, the surface layer A contains substantially no inorganic particles having a particle diameter of 1.0 μm or more.
In this embodiment, particles having a particle diameter of less than 1.0 μm and 1nm or more may be present in the surface layer A. By substantially not containing particles having a particle diameter of 1.0 μm or more, for example, inorganic particles, the transfer of the particle shape in the substrate to the resin sheet can be reduced, which causes defects.
In one embodiment, the surface layer a does not contain particles having a particle diameter of less than 1.0 μm, so that the transfer of the particle shape in the base material to the resin sheet can be more effectively suppressed to cause defects.
In one embodiment, the polyester film base material is preferably a laminated film having at least one surface layer a substantially free of inorganic particles. This can further effectively suppress occurrence of defects due to transfer of the particle shape in the base material to the resin sheet.
For example, the surface layer a substantially containing no particles having a particle diameter of less than 1.0 μm is preferably also substantially free of particles having a particle diameter of 1.0 μm or more.
In the present invention, the term "substantially free of particles" means that, for example, when inorganic particles smaller than 1.0 μm are used, the inorganic element content is 50ppm or less, preferably 10ppm or less, and most preferably the detection limit or less when the inorganic element is quantified by fluorescent X-ray analysis. This is because, even if particles are not positively added to the film, there is a possibility that a contaminant component derived from foreign matters, a contamination of a production line or a device in a production process of the raw material resin or the film may be peeled off and mixed into the film. The term "substantially not containing particles having a particle diameter of 1.0 μm or more" means not actively containing particles having a particle diameter of 1.0 μm or more.
In the case of a laminated polyester film having a multilayer structure of 2 or more layers, it is preferable that the surface layer B which may contain inorganic particles or the like is provided on the opposite surface of the surface layer a which does not substantially contain inorganic particles.
In the laminated structure, when the layer on the side of the release layer to be applied is an a layer, the layer on the opposite side is a B layer, and the core layer other than the a layer is a C layer, the laminated structure such as the release layer/a/B or the release layer/a/C/B is exemplified as the layer structure in the thickness direction. Of course, the C layer can also be a multi-layer structure. The surface layer B may not contain inorganic particles. In this case, in order to impart slidability for winding the film in a roll form, it is preferable to provide the surface layer B with a coating layer D containing at least inorganic particles and a binder.
In the polyester film base material of the present invention, the surface layer B on the opposite side to the side on which the release layer is applied is preferably formed, and from the viewpoints of slidability of the film and easiness of air discharge, inorganic particles are preferably contained, and silica particles and/or calcium carbonate particles are particularly preferably used. The inorganic particles contained in the surface layer B are preferably contained in an amount of 5000ppm to 15000ppm in terms of the total amount of the inorganic particles.
At this time, the area surface average roughness (Sa) of the thin film of the surface layer B is preferably in the range of 1nm to 40 nm. More preferably in the range of 5nm to 35 nm. When the total amount of silica particles and/or calcium carbonate particles is 5000ppm or more and Sa is 1nm or more, air can be uniformly released when the film is rolled up in a roll shape, and the rolled state is good and flatness is good, thereby being suitable for manufacturing an ultrathin ceramic green sheet. In addition, when the total amount of silica particles and/or calcium carbonate particles is 15000ppm or less and Sa is 40nm or less, aggregation of the lubricant is less likely to occur, and coarse protrusions are not formed, so that the quality is stable in the production of an ultra-thin ceramic green sheet, which is preferred.
As the particles contained in the B layer, not only silica and/or calcium carbonate but also inactive inorganic particles and/or heat-resistant organic particles and the like can be used, and silica particles and/or calcium carbonate particles are more preferably used from the viewpoint of transparency and cost. Further, as other usable inorganic particles, alumina-silica composite oxide particles, hydroxyapatite particles, and the like can be mentioned. Examples of the heat-resistant organic particles include crosslinked polyacrylic acid particles, crosslinked polystyrene particles, and benzoguanamine particles. In addition, in the case of using silica particles, porous colloidal silica is preferable, and in the case of using calcium carbonate particles, light calcium carbonate surface-treated with a polyacrylic polymer compound is preferable from the viewpoint of preventing the lubricant from falling off.
The average particle diameter of the inorganic particles added to the surface layer B is preferably 0.1 μm or more and 2.0 μm or less, particularly preferably 0.5 μm or more and 1.0 μm or less. When the average particle diameter of the inorganic particles is 0.1 μm or more, the release film is preferable because of good sliding properties. In addition, if the average particle diameter is 2.0 μm or less, the smoothness of the release layer surface is not adversely affected, and thus pinholes are not generated in the ceramic green sheet, which is preferable. The method for measuring the average particle diameter of the particles may be carried out by the following method: the particles of the cross section of the processed film were observed with a scanning electron microscope, and 100 particles were observed and the average value thereof was defined as the average particle diameter. The shape of the particles is not particularly limited as long as the object of the present invention is satisfied, and spherical particles or amorphous non-spherical particles may be used. The particle size of the amorphous particles can be calculated as the equivalent circle diameter. The equivalent circle diameter is a value obtained by dividing the area of the observed particle by the circumference ratio (pi), calculating the square root, and multiplying by 2.
As the surface layer a of the layer on the release layer side, it is preferable not to use a recycling material or the like in order to prevent the mixing of inorganic particles such as lubricant from the viewpoint of pinhole reduction.
The thickness ratio of the surface layer a of the layer on the release layer side is preferably 20% to 50% of the total layer thickness of the base film. If the content is 20% or more, the influence of particles contained in the surface layer B or the like from the inside of the film is less likely to occur, and the area surface average roughness Sa is preferably in the above range. If the thickness of the entire layer of the base film is 50% or less, the use ratio of the regeneration raw material in the surface layer B can be increased, and the environmental load is preferably small.
In addition, from the viewpoint of economy, the layer other than the surface layer a (the surface layer B or the intermediate layer C) may be 50 mass% or more and 90 mass% or less of film scraps or a recycling material for plastic bottles. Even in this case, the type, amount, particle diameter, and area surface average roughness (Sa) of the lubricant contained in the B layer preferably satisfy the above ranges.
In order to improve adhesion of a release layer or the like to be applied later, to prevent electrification, or the like, the surface of the surface layer a and/or the surface layer B may be provided with the coating layer D before stretching or after uniaxial stretching in the film forming step, or corona treatment or the like may be performed.
In the case where the particles are not contained in the surface layer B, the coating layer D containing the particles is preferably provided to have slipperiness on the surface layer B. The means for providing the coating layer D is not particularly limited, and is preferably provided by a so-called in-line coating method in which a polyester film is coated. In the case where the coating layer D having slipperiness is provided on the surface of the polyester film on the side where the release layer is not laminated, the polyester film may be formed of a single-layer polyester film substantially containing no inorganic particles, without having the surface layers a and B.
The area surface average roughness (Sa) of the surface layer B is preferably 40nm or less, more preferably 35nm or less, and further preferably 30nm or less. In the case where the surface of the surface layer B or the single-layer polyester film on the side where the release layer is not laminated is made to have slipperiness by the coating layer D, the Sa of the surface is preferably in the same range as the area surface average roughness (Sa) of the surface layer B, which is obtained by measuring the surface on which the coating layer D is laminated.
In the polyester film, the coating layer D on the surface on the side where the release layer is not laminated preferably contains at least a binder resin and particles.
(Binder resin of coating layer D)
The binder resin constituting the slip coat layer is not particularly limited, and specific examples of the polymer include polyester resins, acrylic resins, polyurethane resins, polyvinyl resins (polyvinyl alcohol and the like), polyalkylene glycols, polyalkylene imines, methylcellulose, hydroxycellulose, starches and the like. Among them, polyester resins, acrylic resins, and urethane resins are preferably used from the viewpoints of retention of particles and adhesion. In addition, polyester resins are particularly preferred in view of compatibility with polyester films. The polyester of the binder is preferably a copolyester in order to achieve solubility and dispersibility in a solvent and adhesion to a base film and other layers. The polyester resin may be modified with polyurethane. Further, as another preferable binder resin constituting the slip-coat layer on the polyester base film, polyurethane resin is exemplified. As the polyurethane resin, a polycarbonate polyurethane resin is exemplified. Further, the polyester resin and the polyurethane resin may be used in combination, or the other binder resins may be used in combination.
(Crosslinking agent of coating layer D)
In the present invention, in order to form a crosslinked structure in the slip coat layer, the slip coat layer may be formed to contain a crosslinking agent. By containing the crosslinking agent, the adhesion at high temperature and high humidity can be further improved. Specific examples of the crosslinking agent include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based, carbodiimide-based, and aziridine-based. In order to promote the crosslinking reaction, a catalyst or the like may be used as needed.
(Particles in coating layer D)
In order to impart slidability to the surface, the easy-to-slip coating layer preferably contains lubricant particles. The particles may be inorganic particles or organic particles, and are not particularly limited, and examples thereof include (1) inorganic particles such as silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, zirconium oxide, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, halloysite, calcium carbonate, magnesium carbonate, calcium phosphate, magnesium hydroxide, and barium sulfate, (2) organic particles such as acrylic acid or methacrylic acid, vinyl chloride, vinyl acetate, nylon, styrene/acrylic acid, styrene/butadiene, polystyrene/acrylic acid, polystyrene/isoprene, methyl methacrylate/butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, and polyester, and silica is particularly preferably used in order to provide suitable sliding properties to the coating layer.
The average particle diameter of the particles is preferably 10nm or more, more preferably 20nm or more, and still more preferably 30nm or more. When the average particle diameter of the particles is 10nm or more, aggregation is not likely to occur, and slidability can be ensured, which is preferable.
The average particle diameter of the particles is preferably 1000nm or less, more preferably 800nm or less, and still more preferably 600nm or less. When the average particle diameter of the particles is 1000nm or less, the transparency is maintained, and the particles are not detached, which is preferable.
For example, small particles having an average particle diameter of about 10nm to 270nm, and large particles having an average particle diameter of about 300nm to 1000nm are mixed, and it is preferable to use small particles having an average particle diameter of about 30nm to 250nm, and large particles having an average particle diameter of about 350nm to 600nm in combination, in terms of keeping the area surface average roughness (Sa) and the maximum protrusion height (RP), which will be described later, small and reducing the average length (RSm) of the roughness curve element, while also achieving both sliding properties and smoothness. When small particles and large particles are mixed, the mass content of the small particles is preferably larger than the mass content of the large particles with respect to the total solid content of the coating layer.
[ Formation of Release layer ]
In the present invention, the method for forming the release layer is not particularly limited, and the following method is used: the coating liquid in which the release compound is dissolved or dispersed is spread on one surface of the polyester film of the substrate by coating or the like, and the solvent or the like is removed by drying and then cured.
The drying temperature of solvent drying when the release layer of the present invention is applied to a substrate film by solution coating is preferably 50 ℃ or higher and 120 ℃ or lower, more preferably 60 ℃ or higher and 100 ℃ or lower. The drying time is preferably 30 seconds or less, more preferably 20 seconds or less. Further, it is preferable to irradiate active energy rays to carry out the curing reaction after the solvent is dried. As the active energy rays used at this time, ultraviolet rays, electron beams, X-rays, and the like can be used, and ultraviolet rays are preferable because of easy use. The amount of the ultraviolet light to be irradiated is preferably 30mJ/cm 2 to 300mJ/cm 2, more preferably 30mJ/cm 2 to 200mJ/cm 2, in terms of light amount. The curing of the composition is preferably performed sufficiently by setting the ratio to 30mJ/cm 2 or more, and the processing speed can be improved by setting the ratio to 300mJ/cm 2 or less, so that a release film can be economically produced.
In the present invention, the surface tension of the coating liquid at the time of coating the release layer is not particularly limited, and is preferably 30mN/m or less. As described above, the surface tension improves the coatability after coating, and the irregularities on the surface of the dried coating film can be reduced.
As the coating method of the coating liquid, any known coating method can be applied, and for example, conventionally known methods such as a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a die coating method, a spray coating method, and an air knife coating method can be used.
[ Ceramic Green sheet ]
The release film for ceramic green sheet production of the present invention is suitable for ceramic green sheet production. The method for producing a ceramic green sheet according to the present invention is characterized by molding a ceramic green sheet using the release film described above, wherein the molded ceramic green sheet has a thickness of 0.2 μm to 1.0 μm.
The ceramic green sheet is not particularly limited as long as it is a ceramic-containing sheet. In one embodiment, the release film of the present invention is a release film for molding a ceramic green sheet containing an inorganic compound. As the inorganic compound, metal particles, metal oxides, minerals, and the like can be exemplified, and calcium carbonate, silica particles, aluminum particles, barium titanate particles, and the like can be exemplified. The present invention has a release layer having high smoothness, and even if these inorganic compounds are contained in a ceramic green sheet, the problems that may be caused by the inorganic compounds, such as breakage of the ceramic green sheet, and difficulty in peeling the ceramic green sheet from the release layer, can be suppressed.
The resin component forming the ceramic green sheet may be appropriately selected depending on the application. In one embodiment, the ceramic green sheet containing the inorganic compound is a ceramic green sheet. For example, the ceramic green sheet may contain barium titanate as an inorganic compound. The resin component may contain, for example, a polyvinyl butyral resin.
In one embodiment, the thickness of the ceramic green sheet is 0.2 μm or more and 1.0 μm or less.
For example, the present invention can provide a method for producing a release film for producing a ceramic green sheet containing such an inorganic compound. The method for producing a release film according to the present invention may further include a step of molding a ceramic green sheet having a thickness of 0.2 μm or more and 1.0 μm or less.
[ Ceramic Green sheet and ceramic capacitor ]
In general, a laminated ceramic capacitor has a rectangular parallelepiped ceramic body. The 1 st internal electrode and the 2 nd internal electrode are alternately arranged in the thickness direction inside the ceramic body. The 1 st internal electrode is exposed at the 1 st end face of the ceramic body. A 1 st external electrode is provided on the 1 st end face. The 1 st internal electrode is electrically connected to the 1 st external electrode at the 1 st end face. The 2 nd internal electrode is exposed at the 2 nd end face of the ceramic body. A2 nd external electrode is provided on the 2 nd end face. The 2 nd internal electrode is electrically connected to the 2 nd external electrode at the 2 nd end face.
In one embodiment, the release film of the present invention is a release film used for manufacturing such a laminated ceramic capacitor.
For example, a ceramic green sheet having a thickness of 0.2 μm or more and 1.0 μm or less can be molded by the method for manufacturing a ceramic green sheet by using the release film of the present invention.
More specifically, for example, a ceramic green sheet is manufactured as follows. First, using the release film of the present invention as a carrier film, a ceramic slurry for constituting a ceramic body is coated and dried. An ultrathin ceramic green sheet having a thickness of 0.2 μm or more and 1.0 μm or less is required. A conductive layer for constituting the 1 st or 2 nd internal electrode is printed on the coated, dried ceramic green sheet. The ceramic green sheet, the ceramic green sheet printed with the conductive layer for constituting the 1 st internal electrode, and the ceramic green sheet printed with the conductive layer for constituting the 2 nd internal electrode are suitably laminated and pressed, thereby obtaining a mother laminate. Cutting the mother laminate into a plurality of pieces to produce green ceramic bodies. The green ceramic body is obtained by firing the green ceramic body. Then, the 1 st and 2 nd external electrodes are formed, whereby the laminated ceramic capacitor can be completed.
Examples
The present invention will be described in more detail with reference to examples and comparative examples. In the present invention, physical properties and the like are measured or evaluated by the following methods. Hereinafter, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.
(Amount of functional groups of polysiloxane mixture)
Deuterated chloroform was added and dissolved in the same mixing ratio as the silicone mixture of polysiloxanes a and B to make the solid content 10 mass%, and the resulting mixed solution was added to an NMR tube. The sample to be added to the NMR tube was subjected to NMR measurement using a nuclear magnetic resonance apparatus (NMR AVANCE NEO 600, manufactured by BRUKER Co.), and the amounts of each functional group (mmol) of the alkenyl group and the hydrosilyl group were determined.
The molar ratio of alkenyl groups to hydrosilyl groups was calculated from the above measurement results using the following formula.
Molar ratio = Si-H/Si-a
(Wherein Si-H represents the molar amount of hydrosilyl groups and Si-A represents the molar amount of alkenyl groups.)
(Weight average molecular weight)
The sample solution having the sample concentration adjusted to 0.2% was filtered through a 0.2 μm membrane filter, and Gel Permeation Chromatography (GPC) was performed under the following conditions to determine the weight average molecular weight. The molecular weight was calculated by conversion to standard polystyrene.
The device comprises: TOSOH HLC-8320GPC
Chromatographic column: TSKgel SuperHM-H X2+TSKgel SuperH2000 (TOSOH)
Solvent: chloroform 100%
Flow rate: 0.6 ml/min
Concentration: 0.2%
Injection amount: 20 μl of
Temperature: 40 DEG C
A detector: RI (RI)
(Thickness of mold Release layer)
The release film was resin-embedded and ultrathin-sliced using an ultramicrotome. Then, cross-sectional observation was performed using JEM2100, japan electron system, and the film thickness of the release layer was measured from the observed TEM image. If the thickness was too thin to be accurately evaluated by cross-sectional observation, the Si strength was measured by a fluorescent X-ray apparatus (ZSX PRIMUSII manufactured by Rigaku Co., ltd.), and the coating amount was calculated by a standard curve method.
(Area surface average roughness Sa of release layer, maximum protrusion height Sp)
The measurement was performed using a noncontact surface shape measuring system (VERTSCAN R H-M100) under the following conditions. The area surface average roughness (Sa) was an average value of 5 measurements, and the maximum protrusion height (Sp) was a maximum value of the measurement results of 7 measurements and 5 measurements other than the maximum value and the minimum value.
(Measurement conditions)
Measurement mode: WAVE mode
Objective lens: 50 times of
0.5 Tube lens
Measurement area 187. Mu.m.times.139. Mu.m
(Analysis conditions)
Face correction: correction for 4 times
Interpolation processing: complete interpolation
(Surface free energy of Release layer)
A release film was fixed on a flat glass substrate, 1.9. Mu.L of water was dropped onto the release film by using a contact angle meter (DM-501, manufactured by Kyowa Kagaku chemical Co., ltd.) and the droplet was left to stand for 60 seconds, and then the angle formed by the droplet and the release layer was measured, and the average value of 5 times was set to be θ 1. Similarly, 0.9. Mu.L of diiodomethane was dropped onto the release film, and after the droplet was left to stand for 30 seconds, the angle formed by the droplet and the release layer was measured, and the average value of 5 measurements was set to be θ 2. Further, 0.9. Mu.L of ethylene glycol was dropped onto the release film, the droplet was left to stand for 30 seconds, and the angle formed by the droplet and the release layer was measured, and the average value of 5 measurements was set to be θ 3.
The dispersion component γ SVd, dipole component γsvp, and hydrogen bond component γ SVh of the surface free energy of the release layer were calculated from the above-described θ 1、θ2、θ3 and the formulae given in table 2 for water, diiodomethane, and ethylene glycol, γ LVnd, γ LVnp, γ LVnh, and γln (where n=1, 2, or 3 corresponds to water, diiodomethane, or ethylene glycol), and the total thereof was defined as the surface free energy γs of the release layer. The unit of the surface free energy and each component was "mJ/m 2".
TABLE 2
γSVd+γSVp+γSVh＝γS
(Peeling force of ceramic sheet)
Slurry composition I containing the following materials was stirred and mixed for 10 minutes, and dispersed with zirconia beads having a diameter of 0.5mm using a bead mill for 10 minutes, to obtain 1 dispersion. Slurry composition II containing the following materials was then added to the 1-time dispersion in such a manner that the ratio of (slurry composition I) =3.4:1.0, and dispersion was performed 2 times for 10 minutes using a bead mill with zirconia beads having a diameter of 0.5mm, to obtain a ceramic slurry.
(Slurry composition I)
(Slurry composition II)
Next, the release surface of the obtained release film sample was coated with the dried slurry to 1.0 μm using an applicator, and dried at 60 ℃ for 1 minute, to obtain a release film with a ceramic green sheet. The obtained release film with ceramic green sheet was subjected to removal of electricity by a removal motor (KEYENCE CORPORATION, SJ-F020), and then peeled off at a peeling angle of 90℃and a peeling temperature of 25℃and a peeling speed of 10 m/min by a peeling tester (VPA-3, load cell load 0.1N, co., ltd.). As a peeling direction, a double-sided tape (No. 535A, manufactured by ridong electric Co., ltd.) was attached to the SUS plate attached to the peeling tester, and the release film was fixed to the double-sided tape so as to adhere the ceramic green sheet side thereto, and peeled off so as to stretch the release film side. The average value of the peel force of 20mm to 70mm was calculated from the obtained measured values, and the average value was used as the peel force. The measurement was performed 5 times in total, and the average value of the peel force was used.
(Pinhole evaluation of ceramic Green sheet)
A ceramic green sheet having a thickness of 1 μm was molded on the release surface of the release film in the same manner as in the evaluation of the release force of the ceramic sheet. Then, the release film is peeled from the release film with the molded ceramic green sheet to obtain a ceramic green sheet. The central region of the obtained ceramic green sheet in the film width direction was irradiated with light in the range of 25cm 2 from the surface opposite to the surface on which the ceramic slurry was applied, and the occurrence of pinholes, which was seen through the light transmission, was observed and visually determined based on the following criteria.
O: no pinholes are generated
X: generating more than 1 pinhole
(Si transfer amount to PVB sheet)
Polyvinyl butyral (S-LEC BM-S manufactured by dropsy chemical company) was applied to the release surface of the release film sample using an applicator so that the thickness of the dried resin became 1.0 μm, and dried at 60 ℃ for 1 minute, to obtain a release film with a PVB sheet. After leaving the release film with the PVB sheet standing at 23℃for 24 hours, the PVB sheet was peeled off from the release film, and the Si strength (Kcps) was measured on the surface of the PVB sheet in contact with the release film by a fluorescent X-ray apparatus (manufactured by Rigaku system ZSX PRIMUSII).
(Adhesion of Release layer to polyester substrate)
After 6 sheets of the release film sample were cut into 5cm×5cm pieces, 6 sheets of the release film sample were overlapped so that the release surface was in contact with the surface opposite to the release surface, and the film sample was subjected to pressure treatment under a load of 30MPa for 10 minutes. Then, 6 release films were peeled off, and the surface opposite to the release surface was colored red with a red universal pen (MGD-T2 manufactured by the temple chemical industry) for 6 sheets, to confirm whether or not the universal ink was repelled.
And (2) the following steps: the rejection sites were 0 sites in all 6 sheets
X: the rejection part in any one of 6 sheets is more than 1 part
(Adhesion of Release layer with time)
After a release film sample was stored in an atmosphere of 90% RH at 60℃for 3 days, the release layer was rubbed with a vibration type friction tester (manufactured by Kaiko scientific Co., ltd.) by applying a gauze (HAKUJUJI GAUZE manufactured by white cross Co., ltd.) to the contact portion between the load head and the film, and using a pearl paper (TOYOBOESTER Film P4255-35 manufactured by Toyo-yo Co., ltd.) to set the load of the head to 200gf/25mm 2 (5 mm. Times.5 mm) [0.0785MPa ], the film was reciprocated 10 times against the load head, and then the release surface was coated with a red universal pen (MGD-T2 manufactured by Temple chemical Co., ltd.) to confirm whether or not the universal ink was repelled.
And (2) the following steps: universal ink repellency
Delta: there are locations where universal ink is not repelled
X: universal ink is not repulsed
(Preparation of polyethylene terephthalate pellets (PET (I))
As the esterification reaction apparatus, a continuous esterification reaction apparatus comprising a 3-stage complete mixing tank having a stirring device, a dephlegmator, a raw material feed port and a product take-out port was used. TPA (terephthalic acid) was set to 2 tons/hr, EG (ethylene glycol) was set to 2 moles based on 1 mole of TPA, antimony trioxide was set to 160ppm based on the atoms of PET and Sb produced, and the slurries were continuously fed to the 1 st esterification reaction tank of the esterification reactor to carry out the reaction at an average residence time of 4 hours and 255℃under normal pressure. Then, the reaction product in the 1 st esterification reaction vessel was continuously taken out of the system, supplied to the 2 nd esterification reaction vessel, 8 mass% of EG distilled off from the 1 st esterification reaction vessel was supplied to the 2 nd esterification reaction vessel with respect to the produced PET, and EG solution containing magnesium acetate tetrahydrate in an amount of 65ppm with respect to the produced PET and Mg atoms and EG solution containing TMPA (trimethyl phosphate) in an amount of 40ppm with respect to the produced PET and P atoms were added thereto, and the reaction was carried out at 260℃with an average residence time of 1 hour under normal pressure. The reaction product from the 2 nd esterification reaction vessel was continuously taken out of the system and supplied to the 3 rd esterification reaction vessel, and 0.2 mass% of porous colloidal silica having an average particle diameter of 0.9 μm, which had been subjected to dispersion treatment for an average treatment time of 5 passes at a pressure of 39MPa (400 kg/cm 2) using a high-pressure dispersion machine (manufactured by Nippon Denshoku Co., ltd.) and 0.4 mass% of synthetic calcium carbonate having an average particle diameter of 0.6 μm, which had been 1 mass% of an ammonium salt of polyacrylic acid, were added as an EG slurry at 10%, and reacted at an average residence time of 0.5 hours and 260℃under normal pressure, respectively. The esterification reaction product produced in the 3 rd esterification reaction tank was continuously fed to a 3-stage continuous polycondensation reaction apparatus for polycondensation, filtered by a filter obtained by sintering stainless steel fibers having a 95% split particle diameter of 20 μm, ultrafiltered and extruded into water, cooled, and cut into chips to obtain PET chips having an intrinsic viscosity of 0.60dl/g (hereinafter abbreviated as PET (I)). The lubricant content in the PET chips was 0.6 mass%.
(Preparation of polyethylene terephthalate pellets (PET (II))
On the other hand, in the production of the above-mentioned PET (I) chips, PET chips (hereinafter referred to simply as PET (II)) having an intrinsic viscosity of 0.62dl/g and containing no particles such as calcium carbonate and silica at all were obtained.
(Production of laminated film X1)
These PET chips were dried and melted at 285℃and melted by a separate melt extruder, and then 2-stage filtration was performed by sintering a stainless steel fiber having a 95% split particle size of 15 μm and a stainless steel particle having a 95% split particle size of 15 μm, and the above were joined in a feed block, and laminated so that PET (I) became a surface layer B (layer opposite to the release surface) and PET (II) became a surface layer A (layer on the release surface), and extruded (cast) at a rate of 45 m/min into a sheet form, and then electrostatically sealed/cooled on a casting drum at 30℃by an electrostatic sealing method to obtain an unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl/g. The layer ratio was adjusted so that PET (I)/(II) =60 mass%/40 mass% was obtained by calculating the discharge amount from each extruder. The unstretched sheet was then heated by an infrared heater and stretched 3.5 times in the longitudinal direction at a roll temperature of 80℃by a speed difference between rolls. Then, the resultant was guided to a tenter and stretched 4.2 times in the transverse direction at 140 ℃. Subsequently, in the heat-set zone, a heat treatment was performed at 210 ℃. Then, a relaxation treatment of 2.3% was performed at 170℃in the transverse direction, thereby obtaining a biaxially stretched polyethylene terephthalate film X1 having a thickness of 31. Mu.m. The Sa of the surface layer A of the obtained film X1 was 1nm, and the Sa of the surface layer B was 28nm.
(Production of laminated film X2)
As the laminated film X2, PET (II) was used on both the surface layer a side and the surface layer B side, and the laminated film was extruded (cast) into a sheet shape at a speed of 45 m/min, and the sheet was electrostatically adhered and cooled on a casting drum at 30 ℃ by an electrostatic adhesion method to obtain an unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl/g. The unstretched PET sheet was heated to 100℃by a heated roll set and an infrared heater, and then stretched 3.5 times in the longitudinal direction by a roll set having a difference in peripheral speed, to obtain a uniaxially stretched PET film. Next, the following slip coating liquid was applied to one side of a PET film by a bar coater, and then dried at 80 ℃ for 15 seconds. The coating amount after final stretching and drying was adjusted to be 0.1. Mu.m. Then, the film was stretched to 4.0 times in the width direction at 150℃by a tenter, heated at 230℃for 0.5 seconds while fixing the length of the film in the width direction, and further subjected to a relaxation treatment in the width direction of 3% at 230℃for 10 seconds, to obtain an in-line coated polyester film having a thickness of 31. Mu.m. The Sa of the surface layer A of the obtained film X2 was 1nm, and the Sa of the surface layer B was 14nm.
(Easily sliding coating liquid)
Example 1
A silicone mixture R1 was prepared, which was prepared by adjusting a vinyl-modified silicone resin (weight average molecular weight: 466000, in the structural formula (1), l=3120, m=46, n=0) shown in the structural formula (1) as polysiloxane a, and polymethylhydrosiloxane (weight average molecular weight: 8400, in the structural formula (2), o=3, p=65) shown in the structural formula (2) as polysiloxane B so that the molar ratio (hydrosilyl amount/alkenyl amount) became 2.0, to prepare a coating liquid M1 for forming a release layer, which was described below, containing the silicone mixture R1, the adhesion imparting agent S1, and the catalyst P1.
(Coating liquid M1 for Forming Release layer)
The release layer forming coating liquid M1 having the above composition was applied to the surface layer a of the laminated film X1 by reverse gravure so that the coating amount after drying became 0.020 μm. Then, the processing speed was adjusted so that the material was charged into the 1 st drying furnace after 0.5 seconds, and the material was continuously heated and dried at a1 st drying furnace temperature of 120℃and a2 nd drying furnace temperature of 90 ℃. After the drying step, a release film for producing a ceramic green sheet was obtained by irradiating a chill roll with ultraviolet light having an integrated light quantity of 100mJ/cm 2 by using an ultraviolet irradiator (manufactured by Heraeus Group, H bulb) and solidifying the release layer. The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 2
A release film for ceramic green sheet production was produced in the same manner as in example 1, except that a vinyl-modified silicone resin (weight average molecular weight: 495000, in formula (1), l=2820, m=60, n=0) represented by formula (1) as polysiloxane a, and a polymethylhydrosiloxane (weight average molecular weight: 8400, in formula (2), o=3, p=65) represented by formula (2) as polysiloxane B were prepared so as to adjust the molar ratio (hydrosilyl amount/alkenyl amount) to 1.0, to prepare a silicone mixture R2, which contains the silicone mixture R2, the adhesion-imparting agent S1, and the catalyst P1, to form a release layer-forming coating liquid M2 described below.
(Coating liquid M2 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 3
A release film for ceramic green sheet production was produced in the same manner as in example 1, except that a vinyl-modified silicone resin (weight average molecular weight: 52000, in formula (1), l=3700, m=40, n=0) represented by formula (1) as polysiloxane a, and a polymethylhydrosiloxane (weight average molecular weight: 8400, in formula (2), o=3, p=65) represented by formula (2) as polysiloxane B were prepared so as to adjust the molar ratio (hydrosilyl amount/alkenyl amount) to 3.0 of the silicone mixture R3, the adhesion-imparting agent S1, and the coating liquid M3 for forming a release layer described below, which was used as a catalyst, were prepared.
(Coating liquid M3 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 4
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the release layer-forming coating solution M1 was applied so that the coating amount after drying became 0.050 μm. The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 5
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the release layer-forming coating solution M1 was applied so that the coating amount after drying became 0.080 μm. The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 6
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M4 containing the silicone mixture R1, the adhesion imparting agent S2, and the catalyst P1 was applied so that the coating amount after drying became 0.020 μm.
(Coating liquid M4 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 7
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M5 containing the silicone mixture R1, the adhesion imparting agent S3 and the catalyst P1 was applied so that the coating amount after drying became 0.020 μm.
(Coating liquid M5 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 8
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M6 containing the silicone mixture R1, the adhesion imparting agent S4 and the catalyst P1 was applied so that the coating amount after drying became 0.020 μm.
(Coating liquid M6 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 9
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M7 was applied so that the coating amount after drying became 0.020 μm and the content ratio of the adhesion imparting agent S1 was different.
(Coating liquid M7 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 10
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M8 was applied so that the coating amount after drying became 0.020 μm and the content ratio of the adhesion imparting agent S1 was different.
(Coating liquid M8 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 11
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M9 was applied so that the coating amount after drying became 0.020 μm and the content ratio of the adhesion imparting agent S1 was different.
(Coating liquid M9 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 12
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M10 was applied so that the coating amount after drying became 0.020 μm and the content ratio of the adhesion imparting agent S1 was different.
(Coating liquid M10 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 13
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the release layer-forming coating liquid M1 was applied to the laminated film X2. The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 14
A release film for ceramic green sheet production was produced in the same manner as in example 1, except that a silicone mixture R4 was prepared, which was prepared by adjusting a molar ratio (hydrosilyl amount/alkenyl amount) of a vinyl-modified silicone resin (weight average molecular weight: 18000, in formula (1), i=110, m=3, n=1) shown in formula (1) and a polymethylhydrosiloxane (weight average molecular weight: 8400, in formula (2), o=3, p=65) shown in formula (2) as polysiloxane B, to 1.6, and a release layer-forming coating liquid M11 described below, which contained the silicone mixture R4, the adhesion-imparting agent S1, and the catalyst P1, was prepared.
(Coating liquid M11 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Example 15
A release film for ceramic green sheet production was produced in the same manner as in example 1, except that a vinyl-modified silicone resin (weight average molecular weight: 500000, in structural formula (1), l=3460, m=25, n=4) represented by structural formula (1) as polysiloxane a, and a polymethylhydrosiloxane (weight average molecular weight: 8400, in structural formula (2), o=3, p=65) represented by structural formula (2) as polysiloxane B were prepared so as to adjust the molar ratio (hydrosilyl amount/alkenyl amount) to 3.5 in the silicone mixture R5, the following coating liquid M12 for release layer formation containing the silicone mixture R5, the adhesion imparting agent S1, and the catalyst P1.
(Coating liquid M12 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Comparative example 1
A release film for ceramic green sheet production was produced in the same manner as in example 1, except that a vinyl-modified silicone resin (weight average molecular weight: 480000, in formula (1), l=3220, m=13, n=7) shown in formula (1) as polysiloxane a, and a polymethylhydrosiloxane (weight average molecular weight: 8400, in formula (2), o=3, p=65) shown in formula (2) as polysiloxane B were prepared so as to adjust the molar ratio (hydrosilyl amount/alkenyl amount) to 4.0, as silicone mixture R6, a coating liquid M13 for forming a release layer described below containing silicone mixture R6, an adhesion imparting agent S1, and a catalyst P1, were produced.
(Coating liquid M13 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Comparative example 2
A release film for ceramic green sheet production was produced in the same manner as in example 1, except that a vinyl-modified silicone resin (weight average molecular weight: 462000, in formula (1), l=2820, m=60, n=0) represented by formula (1) as polysiloxane a, and a polymethylhydrosiloxane (weight average molecular weight: 8400, in formula (2), o=3, p=65) represented by formula (2) as polysiloxane B were prepared so as to adjust the molar ratio (hydrosilyl amount/alkenyl amount) to 0.8 as silicone mixture R7, the following release layer-forming coating liquid M14 containing silicone mixture R7, adhesion-imparting agent S1, and catalyst P1.
(Coating liquid M14 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Comparative example 3
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M15 containing the silicone mixture R1, the adhesion imparting agent S4 and the catalyst P1 was applied so that the coating amount after drying became 0.020 μm.
(Coating liquid for Forming Release layer M15)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
Comparative example 4
A release film for ceramic green sheet production was obtained in the same manner as in example 1, except that the following release layer forming coating liquid M16 containing the silicone mixture R1 and the catalyst P1 and containing no adhesion imparting agent was applied so that the coating amount after drying became 0.020 μm.
(Coating liquid M16 for Forming Release layer)
The outline of the coating liquid for forming a release layer and the laminated film used at this time is shown in table 3. The results of evaluating the physical properties of the obtained release film are shown in table 4.
TABLE 3
TABLE 4
As shown in the results of table 4, in examples 1 to 15, since the release layer was a layer obtained by curing a curable composition containing polysiloxane a, polysiloxane B, and adhesion-imparting agent C, and satisfied the formulas (a) and (B), release films were obtained that were excellent in release properties, and were less likely to cause transfer/release of the release layer and poor adhesion.
In example 11, since the content ratio of the adhesion-imparting agent is too small, the effect of improving the adhesion with time is reduced, and it is found that there is a preferable lower limit value of the content ratio of the adhesion-imparting agent. In example 12, since the content ratio of the adhesion-imparting agent was too large, the peeling force was slightly increased, and it was found that there was a preferable upper limit value of the content ratio of the adhesion-imparting agent. In example 14, since the weight average molecular weight of polysiloxane a was too small, the transfer amount of the silicone to PVB was slightly increased, and it was found that there was a preferable lower limit value for the weight average molecular weight of polysiloxane a. In example 15, since the molar ratio (hydrosilyl group amount/alkenyl group amount) was slightly large, the ceramic release force was slightly high, and it was found that there was a preferable upper limit value of the molar ratio.
In contrast, in comparative example 1 in which the molar ratio (hydrosilyl group amount/alkenyl group amount) was large and exceeded the upper limit of formula (a), the peel force was increased. In comparative example 2 in which the molar ratio (amount of hydrosilyl groups/amount of alkenyl groups) is smaller than the lower limit value of formula (a), the result of offset is poor, and the release layer is transferred to the surface of the substrate opposite to the release layer, so that there is a possibility that the ceramic green sheet processing step is significantly contaminated, and the amount of Si transfer to the PVB sheet is also increased. In comparative example 3 in which the upper limit value of the formula (a) was exceeded as a result of using an unfavorable adhesion-imparting agent, the adhesion-imparting agent prevented curing, and as a result, the adhesion was poor, and the possibility of contaminating the ceramic green sheet processing step was extremely high. In comparative example 4 in which the adhesion-imparting agent was not used, the peeling force was increased, the adhesion was decreased with time, and the Si transfer amount to the PVB sheet was slightly increased.
Industrial applicability
According to the present invention, by improving the smoothness and peelability of the release layer, a release film is provided that can mold a ceramic green sheet having few defects even in an ultra-thin layer having a thickness of 1 μm or less, and thus a ceramic green sheet can be manufactured without causing any problem.
Claims (7)
1. A release film for producing a ceramic green sheet, characterized by comprising a polyester film and a release layer,
The release layer is a layer obtained by curing a curable composition containing: a polysiloxane A having 2 or more alkenyl groups in the molecule, a polysiloxane B having 2 or more hydrosilyl groups in the molecule, and an adhesion imparting agent C,
The surface free energy γS (mJ/m 2) and the hydrogen bond component γ SVh (mJ/m 2) of γS of the surface of the release layer satisfy the following formulas (a) and (b),
1.0≤γSVh/γS*100≤6.5 (a)
γS≤30(b)。
2. The release film for ceramic green sheet production according to claim 1, wherein the adhesion imparting agent C is a silane coupling agent having 1 or more functional groups selected from the group consisting of vinyl groups, epoxy groups, acryl groups, and methacryl groups.
3. The release film for ceramic green sheet production according to claim 1 or 2, wherein the polysiloxane a has a weight average molecular weight of 300000 or more and 600000 or less.
4. The release film for ceramic green sheet production according to any one of claims 1 to 3, wherein the molar ratio of the amount of hydrosilyl groups of the polysiloxane B to the amount of alkenyl groups of the polysiloxane A in the curable composition satisfies the following formula (c),
1.0≤Si-H/Si-A≤3.8 (c)
Wherein Si-H represents the molar amount of hydrosilyl groups and Si-A represents the molar amount of alkenyl groups.
5. The release film for ceramic green sheet production according to any one of claims 1 to 4, wherein the curable composition contains 1 to 10 mass% of the adhesion-imparting agent C, based on the total amount of the polysiloxane a and the polysiloxane B.
6. The release film for ceramic green sheet production according to any one of claims 1 to 5, wherein the polyester film has a surface layer A substantially free of inorganic particles,
The release layer is laminated on the surface layer A with a thickness of 0.005-0.1 μm,
The maximum protrusion height (Sp) of the surface of the release layer is 100nm or less.
7. A method for producing a ceramic green sheet, which comprises molding a ceramic green sheet using the release film for producing a ceramic green sheet according to any one of claims 1 to 6, wherein the molded ceramic green sheet has a thickness of 0.2 μm to 1.0. Mu.m.
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| JP2021181580 | 2021-11-08 | ||
| JP2021-181580 | 2021-11-08 | ||
| PCT/JP2022/039881 WO2023080026A1 (en) | 2021-11-08 | 2022-10-26 | Release film for manufacturing ceramic green sheet |
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| CN118215579A true CN118215579A (en) | 2024-06-18 |
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| JP (1) | JPWO2023080026A1 (en) |
| KR (1) | KR20240053062A (en) |
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| JP3318356B2 (en) * | 1992-06-29 | 2002-08-26 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane composition for forming release cured film |
| JP2003292895A (en) * | 2002-03-29 | 2003-10-15 | Toray Ind Inc | Polysiloxane composition and releasing film |
| WO2016052171A1 (en) * | 2014-10-03 | 2016-04-07 | 東レ株式会社 | Laminated film and method for producing same |
| KR102294022B1 (en) * | 2014-10-17 | 2021-08-27 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Heavy release additive for release sheet, organopolysiloxane composition for release sheet, and release sheet |
| JP6619200B2 (en) * | 2015-10-21 | 2019-12-11 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
| JP6957968B2 (en) * | 2017-05-17 | 2021-11-02 | 信越化学工業株式会社 | Heavy release composition for release sheet and release sheet |
| WO2019059329A1 (en) * | 2017-09-21 | 2019-03-28 | 三菱ケミカル株式会社 | Mold release film and laminate |
| WO2019088184A1 (en) * | 2017-11-02 | 2019-05-09 | 東洋紡株式会社 | Release film for producing ceramic green sheet |
| JP7641922B2 (en) * | 2019-07-02 | 2025-03-07 | モルガン アドゥヒーシブス カンパニー， エルエルシー | Silicone Compositions Containing Acrylate Curing Accelerators |
| JP7459461B2 (en) * | 2019-08-02 | 2024-04-02 | 東洋紡株式会社 | Release film for ceramic green sheet production |
| WO2021113058A1 (en) * | 2019-12-02 | 2021-06-10 | Dow Silicones Corporation | Composition for preparing a release coating |
| JP7631707B2 (en) * | 2020-08-25 | 2025-02-19 | 住友ベークライト株式会社 | Release Film |
| JP7626974B2 (en) * | 2021-03-23 | 2025-02-05 | 東洋紡株式会社 | Release Film |
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