CN108349107A - Ceramic green sheet manufacturing process stripping film - Google Patents
Ceramic green sheet manufacturing process stripping film Download PDFInfo
- Publication number
- CN108349107A CN108349107A CN201680063814.7A CN201680063814A CN108349107A CN 108349107 A CN108349107 A CN 108349107A CN 201680063814 A CN201680063814 A CN 201680063814A CN 108349107 A CN108349107 A CN 108349107A
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- China
- Prior art keywords
- stripping film
- green sheet
- ceramic green
- manufacturing process
- peeling agent
- Prior art date
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Classifications
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
Abstract
The present invention provides a kind of ceramic green sheet manufacturing process stripping film 1A, it is the ceramic green sheet manufacturing process stripping film 1A for having base material 11 and being arranged in the peeling agent layer 12 of the side of base material 11, peeling agent layer 12 is cured by the remover combination containing melmac and polysiloxane, it is 3.5~7.0GPa from the tectorial elastic modulus of peeling agent layer 12 measured with the face of 11 opposite side of base material by nano indentation test.According to ceramic green sheet manufacturing process stripping film 1A, polysiloxane can be inhibited to be migrated from peeling agent layer to ceramic green sheet.
Description
Technical field
The present invention relates to the stripping films used in a kind of process of manufacture ceramic green sheet.
Background technology
It in the past, will be ceramic in order to manufacture the laminated ceramic product as laminated ceramic capacitor or multilayer ceramic substrate
Raw cook is molded, and the obtained ceramic green sheet of multi-disc is laminated, and is burnt into.
Ceramic green sheet is formed by the way that the ceramic slurry containing ceramic materials such as barium titanate, titanium oxide to be coated on stripping film
Type.Following fissility is required stripping film：The thin ceramics that can will be molded on the stripping film by peeling force appropriate
Raw cook is removed in the case where not deforming, being broken etc. from the stripping film.In addition, in coating ceramic slurry and making it dry
When, in order not to generate the defect of pin hole, uneven thickness etc. on ceramic green sheet, the face of coating ceramic slurry is required stripping film
(the face contacted with ceramic slurry ceramic green sheet；Hereinafter sometimes referred to " release surface ") flatness.
The example of such stripping film is disclosed in patent document 1 and 2.About the stripping film disclosed in patent document 1,
The layer formed by ultraviolet curing resin is arranged on base material, organopolysiloxane is set above and carries out addition reaction
And the polyorganosiloxane resin layer formed is as peeling agent layer.Stripping film disclosed in patent document 2 will be by that will contain (methyl)
Acrylate component and utilize (methyl) acryloyl group and/or vinyl and the coating solution of the modified silicon oil of modification in base
On material, make the curing of coating and manufacture, forms the layer of the solidfied material containing (methyl) acrylate component on base material as a result,
And the layer for containing polysiloxane polymer ingredient is formed above as peeling agent layer.
Existing technical literature
Patent document
Patent document 1：Japanese Patent No. 5675246
Patent document 2：Japanese Patent No. 5423975
Invention content
The technical problem to be solved in the present invention
However, the polysiloxane ingredient in remover combination, be easily transferred to sometimes ceramic green sheet and remover
On the face of layer contact.Face after polysiloxanes transfer generates slip, and adherence is caused to decline.If using such polysiloxanes at
The stripping film that partial volume easily shifts manufactures laminated ceramic product to manufacture ceramic green sheet using the ceramic green sheet, then to
When the ceramic green sheet of stacking applies forces against each other, laminated ceramic product interlayer it some times happens that face direction offset.If hair
Raw such offset, then in obtained laminated ceramic product, the positional precision of electrode etc. declines, and becomes to be unable to get stacking
The properties of product of ceramic product.Therefore, seek a kind of polysiloxane ingredient to the few stripping film of the transfer of ceramic green sheet.
But stripping film recorded in patent document 1 and 2 inhibits the transfer of polysiloxane ingredient with being unable to fully.
The present invention is given this fact and carries out that its purpose is to provide one kind capable of inhibiting poly-organosilicon
Oxygen alkane is migrated from peeling agent layer to the ceramic green sheet manufacturing process stripping film of ceramic green sheet.
Solve the technological means of technical problem
In order to achieve the above objectives, first, the present invention provides a kind of ceramic green sheet manufacturing process stripping film, to have
Base material and ceramic green sheet manufacturing process stripping film in the peeling agent layer of the side of the base material is set, which is characterized in that institute
It states peeling agent layer by the remover combination containing melmac and polysiloxane to be cured, passes through nano impress
Experiment is 3.5~7.0GPa (inventions from the tectorial elastic modulus of the peeling agent layer measured with the face of the base material opposite side
1)。
Foregoing invention (invention 1), peeling agent layer, table are formed by using the remover combination containing polysiloxane
Face free energy is moderately low, and fissility when stripping film is removed from ceramic green sheet is excellent.In addition, in peeling agent layer,
By make tectorial elastic modulus as above range in a manner of and so that melmac is cured sufficiently, be put into the mesh
Polysiloxane in shape structure is firmly fettered, and polysiloxane can be inhibited to be migrated from peeling agent layer to ceramic green
Piece.
In addition, usually " melmac " refers to containing there are many melamine compound and/or the melamine chemical combination
The mixture of syncytiam made of object condensation.In the present specification, " melmac " this term refers to said mixture
Or the aggregation of a kind of melamine compound.In addition, in the present specification, substance made of which is cured
Referred to as " melamine cured object ".
In foregoing invention (invention 1), the matter average molecular weight of the polysiloxane is preferably 500~20000 (inventions
2)。
In foregoing invention (invention 1,2), relative to 100 mass parts of melmac, the polysiloxane exists
Content in the remover combination is preferably 0.1~30 mass parts (invention 3).
In foregoing invention (invention 1~3), the melmac contained by the preferably described remover combination contains
There are methylated melamine and/or imino group melamine methylol (invention 4).
In foregoing invention (invention 1~4), preferably resin is further equipped between the base material and the peeling agent layer
Layer (invention 5).
In foregoing invention (invention 5), the preferably described resin layer is by containing active energy ray-curable ingredient or thermosetting
The resin combination solidification of the property changed ingredient forms (invention 6).
In foregoing invention (invention 6), the preferably described active energy ray-curable ingredient is polyfunctional acrylic ester (hair
It is bright 7).
In foregoing invention (invention 1~7), preferably further has and be arranged in the base material and the peeling agent layer phase
The second resin layer (invention 8) tossed about.
Description of the drawings
Fig. 1 be the first embodiment of the present invention is related to ceramic green sheet manufacturing process stripping film sectional view.
Fig. 2 is the sectional view for the ceramic green sheet manufacturing process stripping film that second embodiment of the present invention is related to.
Fig. 3 is the sectional view for the ceramic green sheet manufacturing process stripping film that third embodiment of the present invention is related to.
Specific implementation mode
Hereinafter, embodiments of the present invention will be described.
[ceramic green sheet manufacturing process stripping film]
As shown in Figure 1, the ceramic green sheet manufacturing process that first embodiment is related to (is hereinafter sometimes referred to simply as with stripping film 1A
" stripping film 1A ") composition have base material 11 and peeling agent layer 12.
In addition, as shown in Fig. 2, the ceramic green sheet manufacturing process that is related to of second embodiment with stripping film 1B (below sometimes
Referred to as " stripping film 1B ") the composition tree that has base material 11, be layered on a face (being in fig. 2 upper surface) for base material 11
Lipid layer 13 and the peeling agent layer 12 being layered on the face with 11 opposite side of base material of resin layer 13.
Further, as shown in figure 3, the ceramic green sheet manufacturing process that third embodiment is related to (has below with stripping film 1C
When be referred to as " stripping film 1C ") composition have base material 11, be layered on a face (being in figure 3 upper surface) for base material 11
Resin layer 13, the peeling agent layer 12 being layered on the face with 11 opposite side of base material of resin layer 13 and it is layered in the another of base material 11
The second resin layer 14 on one face (being in figure 3 lower surface).
In stripping film 1A, 1B, 1C, peeling agent layer 12 is by the remover containing melmac and polysiloxane
Composition is formed.In addition, by nano indentation test, from the overlay film of peeling agent layer 12 measured with the face of 13 opposite side of resin layer
Elasticity modulus is 3.5~7.0GPa.
In stripping film 1A, 1B, 1C, since peeling agent layer 12 uses the remover combination shape containing polysiloxane
At, therefore the surface free energy of the release surface of peeling agent layer 12 becomes moderately low value.Further, stripping film 1A, 1B, 1C has
Above-mentioned tectorial elastic modulus.As a result, by stripping film 1A, 1B, 1C from the pottery in the release surface for being molded over stripping film 1A, 1B, 1C
Peeling force when being removed on porcelain raw cook becomes moderately low value, and can play excellent fissility.
Further, in stripping film 1A, 1B, 1C, polysiloxane is put by curing melmac by shape
At mesh-like structure in.Here, curing sufficiently trimerization in a manner of so that tectorial elastic modulus is become above-mentioned range
Melamine resin, the polysiloxane being put into above-mentioned mesh-like structure are firmly fettered so that polysiloxane exists
Moving freely in cured melmac is restricted.Therefore, ceramic green sheet is molded over stripping film 1A, 1B, 1C
When in release surface, polysiloxane can be inhibited to be migrated from peeling agent layer 12 to ceramic green sheet.Stripping film will be used as a result,
When 1A, 1B, 1C and molding ceramic green sheet are laminated, the mutual adhesion of ceramic green sheet gets a promotion, in laminated ceramic product
In manufacture, it can inhibit to generate between ceramic green sheet or between electrode print face and the face for the ceramic green sheet being in contact with it
Offset.
In addition, in stripping film 1A, 1B, 1C, peeling agent layer 12 is by the remover combination shape containing melmac
At.Therefore, compared to peeling agent layer is formed using only polysiloxane the case where, can avoid the surface of peeling agent layer 12
Free energy change obtains too low.In addition, causing surface layer to cure insufficient active energy ray-curable resin not with because oxygen hinders
Together, cured by heat cure due to melmac, in peeling agent layer 12, be not only whole overlay film bullet
Property modulus gets a promotion, and in layer and in surface layer, elasticity modulus is also fully promoted.Thus, it becomes able to will deposit
It is that the polysiloxane near the surface layer of peeling agent layer 12 is fully fixed.Further, melmac with it is aftermentioned
The compatibility of resin contained by resin layer 13 is high.Therefore, in stripping film 1B, the 1C for being provided with resin layer 13, peeling agent layer
Adherence between 12 and resin layer 13 is excellent, and peeling agent layer 12 can be inhibited from the generation of the peeling on resin layer 13.
1. peeling agent layer
(1) melmac
Melmac contained by remover combination contain the following general formula (a) expression melamine compound,
Or 2 or more the melamine compound condensation made of syncytiam.
[chemical formula 1]
In formula (a), X expressions-H ,-CH2- OH or-CH2-O-R.These groups constitute above-mentioned melamine compound each other
Condensation reaction reactive group.Specifically, by making X form-NH bases for H, it can be in-N-CH2- OH bases and-N-
CH2Condensation reaction is carried out between-R bases.In addition, by making X be-CH2- OH and form-N-CH2- OH bases and by make X be-
CH2- O-R and form-N-CH2- O-R bases, can be simultaneously in-NH bases ,-N-CH2- OH bases and-N-CH2It is carried out between-O-R bases
Condensation reaction.
In above-mentioned-CH2In-O-R bases, R indicates that carbon atom number is 1~8 alkyl.The carbon atom number is preferably 1~6
It is a, particularly preferably 1~3.As carbon atom number be 1~8 alkyl, such as can enumerate methyl, ethyl, propyl, butyl,
Amyl, hexyl, octyl etc., particularly preferably methyl.
Above-mentioned X can be respectively identical, can also be different.In addition, above-mentioned R can be respectively identical, can also be different.
Usually there is following type in melamine compound：Whole Ⅹ is-CH2The full ether type of-O-R；At least one X be-
CH2- OH and the imino group methylol type that at least one X is H；At least one X is-CH2- OH and the methylol that the X for H is not present
Type；And at least one X is H and there is no be-CH2The imino-type of the X of-OH.As three contained by above-mentioned melmac
Paracyanogen amine compounds are, it is preferable to use methylated melamine (R is the full ether type of methyl), imino group melamine methylol are (sub-
Amino methylol type), melamine methylol (methylol type), the butylated melamines full ether type of butyl (R be) etc..Into
One step from being easily dissolved in organic solvent, and is easy cured angle and sets out, it is preferable to use the melamine that methylates at low temperature
Amine or imino group melamine methylol.The reaction for making blocking group be detached from especially is never needed to, reaction speed further carries
The angle risen is set out, it is preferable to use imino group melamine methylol.
Above-mentioned melmac also can contain 2~50, in addition also contain 2~30, particularly also can contain 2~
10, further also contain syncytiam made of the compound condensation that 2~5 above-mentioned formulas (a) indicate.
In the remover combination for being used to form peeling agent layer 12, the matter average molecular weight of melmac is preferably
120~10000, particularly preferably 200~5000, further preferably 1000~4000.By make matter average molecular weight be 120 with
On, melmac can be steadily crosslinked, and form smoother release surface.On the other hand, by making the matter average molecular weight be
10000 hereinafter, can inhibit the viscosity of remover combination to become excessively high, when remover combination is coated on base material 11
Coating becomes good.In addition, the matter average molecular weight in this specification is the standard measured by gel permeation chromatography (GPC) method
The value of polystyrene conversion.
(2) polysiloxane
As the polysiloxane contained by remover combination, the silicide-comprising that the following general formula (b) can be used to indicate
Close the polymer of object.
In formula (b), m be 1 or more integer.In formula (b), R1~R8Preferably alkyl or aryl, particularly preferably carbon atom
The aryl that the alkyl or carbon atom number that number is 1~8 are 6~8.It is 1~8 alkyl as carbon atom number, such as first can be enumerated
Base, ethyl, propyl, butyl, amyl, hexyl, octyl etc., the aryl for being 6~8 as carbon atom number, can enumerate phenyl, methyl
Phenyl, wherein particularly preferred methyl.
R1~R8It can be the same or different.Additionally, there are multiple R1And R2When, R1And R2It can phase between repetitive unit
It is same to can also be different.
As the polysiloxane contained by remover combination, preferably there is organic group in end or side chain.That is,
R in preferred formula (b)1~R8In at least one be organic group.In the present specification, " organic group " refers to not comprising above-mentioned
Alkyl and aryl group.As such organic group, can enumerate with repetitive structures such as polyethers, polyester, polyurethane
Organic group.In such organic group, the atom of a respective end such as polyethers, polyester, polyurethane with it is poly- organic
The end of siloxanes or the silicon atom bonding in chain.
Furthermore it is preferred that polysiloxane contains the functional group that can carry out cross-linking reaction.It can carry out cross-linking reaction
Functional group can Direct Bonding on the silicon atom of polysiloxane, can be also bonded in via above-mentioned organic group poly- organic
On siloxanes.That is, the R in preferred formula (b)1~R8In at least one be being capable of crosslinked functional group or with being capable of crosslinked official
The organic group that can be rolled into a ball.As Direct Bonding on the silicon atoms can crosslinked functional group, alkenyl (alkenyl can be enumerated
Group), hydrogen-based (hydrosilane groups), hydroxyl (silicol base) etc.；It is bonded in polysiloxane as via organic group
On functional group, hydroxyl, carboxyl, glycidyl, (methyl) acryloyl group etc. can be enumerated.Among these functional groups, especially
Preferably direct bonding hydroxyl (silicol base) on the silicon atoms or the hydroxyl via organic group.In addition, in this specification
" (methyl) acryloyl group " refer to both acryloyl group and methylacryloyl.It is also identical about other similar terms.
When the remover combination containing the polysiloxane with hydroxyl being made to be solidified to form peeling agent layer 12, trimerization
Melamine resin is chemically bonded with polysiloxane via the hydroxyl, and polysiloxane is consolidated by melamine cured object
It is fixed.Polysiloxane moving freely in peeling agent layer 12 is effectively limited as a result, can effectively inhibit poly-organosilicon
Oxygen alkane is migrated from peeling agent layer 12 to ceramic green sheet.As a result, when ceramic green sheet is laminated, can effectively inhibit in ceramic green
The offset in generating surface direction between piece or between electrode print face and the face for the ceramic green sheet being in contact with it, promotes electrode etc.
Positional precision.
The matter average molecular weight of polysiloxane is preferably 500~20000, and particularly preferably 1000~10000, further
Preferably 3000~8000.By making the matter average molecular weight of polysiloxane be 500 or more, the release surface of peeling agent layer 12
Surface free energy suitably reduces, and can be effectively reduced stripping when removing stripping film 1A, 1B, 1C from ceramic green sheet
Power.By making the matter average molecular weight of polysiloxane for 20000 hereinafter, the viscosity of remover combination can be inhibited to become
Height becomes easy coating remover combination.
Relative to 100 mass parts of melmac, the content of the polysiloxane in remover combination is preferably
0.1~30 mass parts, particularly preferably 0.3~25 mass parts, further preferably 0.5~20 mass parts.By making remover
The content of polysiloxane in composition is 0.1 mass parts or more, and the surface free energy of the release surface of peeling agent layer 12 fills
Divide ground to reduce, peeling force appropriate can be reached.On the other hand, by making containing for the polysiloxane in remover combination
Amount is below mass part for 30, can inhibit the migration of above-mentioned polysiloxane.Thereby, it is possible to prevent remover combination
Surface free energy excessively reduces, and can inhibit what is generated when the masking liquid of remover combination is coated on resin layer 13 to reject
(cissing), stripping film 1A, 1B, 1C can be manufactured well.
(3) other ingredients
It is preferred that remover combination further contains acid catalyst.As the example of acid catalyst, preferably hydrochloric acid, sulfuric acid,
Nitric acid, phosphoric acid, phosphorous acid, p-methyl benzenesulfonic acid etc., particularly preferred p-methyl benzenesulfonic acid.By making remover combination contain acid catalysis
The condensation reaction efficiency of agent, above-mentioned melmac carries out well.
Relative to 100 mass parts of melmac, the content of the acid catalyst in remover combination is preferably 0.1~
30 mass parts, particularly preferably 0.5~20 mass parts, further preferably 1~15 mass parts.
Other than mentioned component, remover combination can also contain crosslinking agent, reaction suppressor etc..
(4) thickness of peeling agent layer
The thickness of peeling agent layer 12 is preferably 5~2000nm.Especially for what is be made of base material 11 and peeling agent layer 12
For stripping film 1A, the thickness of peeling agent layer 12 is preferably 100~2000nm, particularly preferably 150~1000nm, further excellent
It is selected as 200~600nm.In addition, the stripping film 1B for being further equipped with resin layer 13 between base material 11 and peeling agent layer 12
Or for stripping film 1C, the thickness of peeling agent layer 12 is preferably 5~300nm, particularly preferably 10~250nm, further preferably
For 15~200nm.Thickness by making peeling agent layer 12 is 5nm or more, can effectively play the work(as peeling agent layer 12
Energy.In addition, by making the thickness of peeling agent layer 12 be 2000nm hereinafter, can inhibit to generate warpage.
2. base material
As long as resin layer 13 can be laminated in the base material 11 of stripping film 1A, 1B, 1C, it is not particularly limited.As the base material
11, such as can enumerate by the polyester of polyethylene terephthalate or polyethylene naphthalate etc.；Polypropylene, poly- methylpent
The polyolefin of alkene etc.；The film that the plastics of makrolon, polyvinyl acetate etc. are constituted, can be single layer, or it is of the same race or
2 layers or more of multilayer not of the same race.Wherein, preferred polyester film, particularly preferred polyethylene terephthalate film, further preferably
Biaxial stretch-formed polyethylene terephthalate film.Since polyethylene terephthalate film is in processing, when use etc., it is not easy to
Dust etc. is generated, therefore it is bad etc. to be effectively prevented the ceramic slurry coating such as caused by by dust.Further, pass through
To polyethylene terephthalate film carry out antistatic treatment, can prevent coating using organic solvent ceramic slurry when by
On fire or raising caused by electrostatic prevents from being coated with bad etc. effect.
In addition, in the base material 11, to promote and be arranged the adherence of peeling agent layer 12 or resin layer 13 on its surface
For the purpose of, it can be according to required and to surface treatment of the one or both sides execution based on oxidizing process or further provided for contouring method etc. or priming paint
Processing.As above-mentioned oxidizing process, for example, can enumerate Corona discharge Treatment, plasma discharge processing, chromium oxidation processes it is (wet
Formula), flame treatment, hot wind processing, ozone, ultraviolet treatment with irradiation etc., in addition, as further provided for contouring method, such as spray can be enumerated
Sand facture, hot spray process etc..These surface preparations can be properly selected according to the type of base material film, but usually from effect
The aspect of fruit and operability is set out, it is preferable to use Corona discharge Treatment method.
The thickness of base material 11 is usually 10~300 μm, preferably 15~200 μm, particularly preferably 20~125 μm.
3. resin layer
Stripping film of the present embodiment can also have resin layer 13 between base material 11 and peeling agent layer 12.Fig. 2 and
3 respectively indicate the stripping film 1B and 1C that have resin layer 13.For stripping film 1B, 1C, it is arranged in base material 11 and remover
Resin layer 13 between layer 12 absorbs the bumps in the face of 13 side of resin layer of base material 11.As a result, resin layer 13 with 11 phase of base material
The face tossed about has high flatness.Moreover, by the way that peeling agent layer 12 is arranged on the face of resin layer 13, to make peeling agent layer
The flatness of 12 release surface becomes excellent.
As the resin for forming resin layer 13, as long as can be assigned to release surface in the case where not interfering the effect of the present invention
Flatness is given, is not particularly limited.Resin as formation resin layer 13 is, it is preferable to use stripping film 1B, 1C are easy to reach 3.5
The resin of this tectorial elastic modulus of~7.0GPa.Particularly preferred resin layer 13 is by the resin combination shape containing curability composition
At.The curability composition can be active energy ray-curable ingredient, or Thermocurable ingredient.
(1) active energy ray-curable ingredient
As active energy ray-curable ingredient, as long as to pass through irradiation in the case where not interfering the effect of the present invention
Active energy beam and cured ingredient, then be not particularly limited, and can be any one in monomer, oligomer or polymer
Kind, or their mixture.Especially as active energy ray-curable ingredient, it is preferable to use constituting acrylic acid tree
The ingredient of fat particularly preferably uses polyfunctional acrylic ester
As polyfunctional acrylic ester, such as 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycols can be enumerated
Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, neopentyl glycol oneself
Two acid esters two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, two (methyl) acrylic acid
Two ring pentyl esters, caprolactone modification two (methyl) acrylic acid dicyclopentenyl base ester, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylic acid
The bifunctional type of ester, two (acrylyl oxy-ethyl) isocyanuric acid esters, allylation two (methyl) cyclohexyl acrylate etc.；Three hydroxyl first
Base propane three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid are modified dipentaerythritol three (methyl)
Acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three
(acrylyl oxy-ethyl) isocyanuric acid ester, 6-caprolactone are modified three-(2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters etc.
Trifunctional type；The tetrafunctional type of two glycerine four (methyl) acrylate, pentaerythrite four (methyl) acrylate etc.；Propionic acid is modified
Five functional-types of dipentaerythritol five (methyl) acrylate etc.；Dipentaerythritol six (methyl) acrylate, caprolactone modification
Six functional-types of dipentaerythritol six (methyl) acrylate etc. etc..They can be used alone, and can also be applied in combination 2
Kind or more.As polyfunctional acrylic ester, cross-linked structure and the easy tectorial elastic modulus by stripping film 1B, 1C are formed from being easy
The angle for being set as aftermentioned value is set out, and preferably functional group number is 3~15, particularly preferably 3~6.Above-mentioned multifunctional third
Among olefin(e) acid ester, from can effectively absorb the bumps of substrate surface, reach the angle of excellent flatness in release surface,
It is preferable to use pentaerythritol triacrylate or dipentaerythritol hexaacrylates.
When forming resin layer 13 by the resin combination containing active energy ray-curable ingredient, preferred resin composition
Further contain Photoepolymerizationinitiater initiater.By containing Photoepolymerizationinitiater initiater, active energy ray-curable can be made at component efficiency
Cure well, furthermore it is possible to reduce the exposure of polymerizing curable time and active energy beam.
It as Photoepolymerizationinitiater initiater, is not particularly limited, well known Photoepolymerizationinitiater initiater can be used.Use multifunctional third
When olefin(e) acid ester is as active energy ray-curable ingredient, from the angle for promoting polymerisation, promoting curability, preferably make
With alpha-aminoalkyl benzene ketone compounds.As alpha-aminoalkyl benzene ketone compounds, such as 2- methyl-1s [4- can be enumerated
(methyl mercapto) phenyl] -2- morpholine propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1,2- diformazans
Amino -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone etc..Relative to polyfunctional acrylic ester
The content of 100 mass parts, the alpha-aminoalkyl benzene ketone compounds in resin combination is preferably 1~20 mass parts, especially excellent
It is selected as 3~15 mass parts, further preferably 5~10 mass parts.
(2) Thermocurable ingredient
As Thermocurable ingredient, if for do not interfere the present invention effect in the case of by heating it is cured at
Point, then it is not particularly limited.Especially as Thermocurable ingredient, it is preferable to use melmac, alkyd resin, asphalt mixtures modified by epoxy resin
Fat, phenol resin, urea resin, polyester resin, carbamate resins, polyimide resin, benzoPiperazine (benzoxazine)
Resin or acrylic resin particularly preferably use melmac.By using melmac, resin layer 13 and stripping
Adhesion between oxidant layer 12 gets a promotion, and can effectively inhibit peeling agent layer 12 and be peeled off from resin layer 13.In addition, passing through
Using melmac, the tectorial elastic modulus of stripping film 1B, 1C get a promotion, by stripping film 1B, 1C from ceramic green sheet
Fissility when stripping gets a promotion.
Although the melmac for being used to form resin layer 13 is not particularly limited, it is preferred that using be used to form
The melmac of peeling agent layer 12 melmac of the same race.At this point, three between resin layer 13 and peeling agent layer 12
Cymel shows high-affinity each other, and highly dense property, energy thus can be obtained between resin layer 13 and peeling agent layer 12
Enough peelings for effectively further inhibiting peeling agent layer 12.
(3) other ingredients
Other than mentioned component, resin combination can also contain crosslinking agent, reaction suppressor, antistatic agent, gluing and change
Into agent etc..
(4) thickness of resin layer
The thickness of resin layer 13 is preferably 100~3000nm, particularly preferably 300~2000nm, and further preferably 500
~1000nm.Thickness by making resin layer 13 is 100nm or more, can effectively absorb the bumps on 11 surface of base material, can
Reach the excellent flatness of release surface.In addition, by make the thickness of resin layer 13 be 3000nm hereinafter, can effectively inhibit
Stripping film 1B, 1C generate warpage.
4. the second resin layer
For stripping film 1C, in the face of base material 11 and resin layer 13 opposite side (hereinafter, sometimes referred to as " base material is carried on the back
Face ") on the second resin layer 14 is set.Since the absorption of the second resin layer 14 is present in the bumps of substrate backside, compared to base
The flatness at the material back side, the flatness higher with the face of 11 opposite side of base material of the second resin layer 14.Moreover, pottery will be formed
The stripping film 1C of porcelain raw cook batch for web-like when, since the face with high flatness of ceramic green sheet and the second resin layer 14 connects
It touches, therefore is capable of providing the higher ceramic green sheet of flatness.In addition, by the presence of the second resin layer 14, resin layer 13 and/or
The cure shrinkage of peeling agent layer 12 is offseted with the cure shrinkage of the second resin layer 14, therefore stripping film 1C generations can be inhibited to stick up
It is bent.
It is used to form the resin of the second resin layer 14, is not particularly limited.It, can as the resin for the second resin layer 14
To use the above-mentioned resin for being used to form resin layer 13 and using.In stripping film 1C, resin layer 13 and the second resin layer 14
It can be formed by homogenous resins, can also be formed by not homogenous resins.But from the angle for inhibiting warpage, preferred resin layer 13
It is formed by homogenous resins with the second resin layer 14.
The thickness of second resin layer 14 can be set in a manner of identical with resin layer 13.But it is stuck up from effectively inhibiting
The angle of bent generation is set out, and the thickness of the second resin layer 14 is relative to the total of the thickness of resin layer 13 and peeling agent layer 12
Than being preferably 0.2~2, particularly preferably 0.7~1.5, further preferably 0.8~1.2.
5. the physical property of ceramic green sheet manufacturing process stripping film
It is opposite with resin layer 13 from peeling agent layer 12 by nano indentation test for stripping film 1A, 1B, 1C
The tectorial elastic modulus that the face of side measures be 3.5~7.0GPa, preferably 4.0~6.5GPa, particularly preferably 4.5~
6.3GPa.Tectorial elastic modulus by making stripping film 1A, 1B, 1C is 3.5GPa or more, can be effectively realized stripping film
Good fissility when 1A, 1B, 1C are removed from ceramic green sheet.In addition, the tectorial elastic by making stripping film 1A, 1B, 1C
Modulus is 7.0GPa hereinafter, batching for stripping film 1A, 1B, 1C becomes easy.
In addition, the measurement of the tectorial elastic modulus in this specification is carried out by nano indentation test.Specifically, sharp
Stripping film 1A, 1B, 1C that severing is 10mm × 10mm sizes are fixed on the then bottom in aluminum with biliquid class epoxy adhesive
On glass plate on seat.At this point, for stripping film 1A, 1B, it is coated on the face with 12 opposite side of peeling agent layer of base material 11 double
Liquid class epoxy adhesive fixes in the face on a glass.On the other hand, for stripping film 1C, the second resin layer 14 with
It is coated with biliquid class epoxy adhesive on the face of 11 opposite side of base material, which is fixed on a glass.Then, using small hardness
Evaluating apparatus (" the Nano Indenter SA2 " that is manufactured using MTS companies in test example), from peeling agent layer 12 and base material
The face of 11 opposite sides measures tectorial elastic modulus.
Stripping film 1A, 1B, 1C when institutes are removed from the ceramic green sheet in the release surface for being molded over stripping film 1A, 1B, 1C
The peeling force needed can suitably be set, but preferably 5~100mN/40mm, particularly preferably 7~50mN/40mm, into one
Step is preferably 10~30mN/40mm.For stripping film 1A, 1B, 1C, using the remover combination containing polysiloxane
Peeling agent layer 12 is formed, further, since stripping film 1A, 1B, 1C have elasticity appropriate, 5 can be appropriately set at
This peeling force of~100mN/40mm.
When being molded ceramic green sheet using stripping film 1A, 1B, 1C, polysiloxane can be inhibited to be moved from peeling agent layer 12
Move to ceramic green sheet.After ceramic green sheet is molded in the release surface of stripping film 1A, 1B, 1C as a result, by the ceramic green sheet
When being removed from stripping film 1A, 1B, 1C, the migration quantitative change of the polysiloxane in the face of ceramic green sheet contacted with release surface
It is low.Specifically, when being molded ceramic green sheet using stripping film 1A, 1B, 1C, being contacted with release surface for the ceramic green sheet is measured
Silicon atom ratio obtained from face is preferably smaller than 1.0 atom %, particularly preferably less than 0.5 atom %, and further preferably 0.3 is former
Sub- % or less.In addition, silicon atom ratio can for example be based on the silicon measured using X-ray photoelectron spectroscopic analysis method (XPS)
The amount (XPS countings) of atom (Si), carbon atom (C) and oxygen atom (O), is calculated by following formula.
Silicon atom ratio (atom %)=[(Si amount of element)/{ (C element amount)+(O amount of element)+(Si amount of element) }] ×
100
Silicon can not be detected (that is, not including silication by XPS in addition, the ceramic green sheet of measurement can be properly selected
Close object) ceramic green sheet, and using the silicon atom ratio as the evaluation of the amount of migration of the polysiloxane of peeling agent layer 12
Standard.
The maximum rising height Rp of the release surface of stripping film 1A, 1B, 1C is preferably 5~800nm, particularly preferably 10~
400nm, further preferably 20~200nm.For having stripping film 1B, 1C of resin layer 13, release surface
Maximum rising height Rp is preferably 5~300nm, particularly preferably 10~150nm, further preferably 20~75nm.By making
The maximum rising height Rp of release surface is above range, and the ceramic green sheet formed using stripping film 1A, 1B, 1C shows excellent
Flatness can manufacture the laminated ceramic product for showing excellent performance.For stripping film 1B, 1C, pass through tool
Standby resin layer 13, maximum rising height Rp become very small value as described above, can form the superior ceramics of flatness
Raw cook.In addition, shown in the assay method of the maximum rising height Rp of release surface test example as be described hereinafter.
6. the manufacturing method of ceramic green sheet manufacturing process stripping film
When manufacturing stripping film 1A, by the coating solution containing remover combination and organic solvent as needed in base
After on one face of material 11, by making the dried coating film and being solidified to form peeling agent layer 12.Stripping film 1A is obtained as a result,.
In addition, when manufacture stripping film 1B, by the coating solution containing resin combination and organic solvent as needed
After on a face of base material 11, by making the dried coating film and being solidified to form resin layer 13.Further, remover will be contained
After the coating solution of composition and organic solvent as needed is on the face with 11 opposite side of base material of resin layer 13, lead to
It crosses dry and heating and remover combination is made to cure, form peeling agent layer 12.Stripping film 1B is obtained as a result,.
In addition, when manufacture stripping film 1C, it will be containing the resin combination for being useful for resin layer 13 and as needed organic molten
After the coating solution of agent is on a face of base material 11, by making the dried coating film and being solidified to form resin layer 13.Into one
Step, will be containing being useful for the resin combination of the second resin layer 14 and the coating solution of organic solvent as needed in base material 11
Another face on after, by making the dried coating film and being solidified to form the second resin layer 14.Then, remover will be contained to combine
After the coating solution of object and organic solvent as needed is on the face with 11 opposite side of base material of resin layer 13, pass through drying
And heat and remover combination is made to cure, form peeling agent layer 12.Stripping film 1C is obtained as a result,.In addition, the second resin layer 14
Also it is more initially formed than resin layer 13, or can also be formed after peeling agent layer 12.
In the above-mentioned methods, when resin combination contains active energy ray-curable ingredient, by by resin group
It closes the film irradiation active energy beam that object is formed and makes its solidification.As active energy beam, electromagnetic wave can be used for example
Or the active energy beam with the quantum of energy in charge-particle beam, specifically, ultraviolet light or electron beam etc. can be used.It is special
The other easy ultraviolet light of preferred operations.Ultraviolet irradiation can be carried out, ultraviolet irradiation using high-pressure sodium lamp, xenon lamp etc.
Amount is preferably 50~1000mW/cm with illumination photometer2Left and right.In addition, light quantity is preferably 50~10000mJ/cm2, more preferably 80~
5000mJ/cm2, particularly preferably 200~2000mJ/cm2.On the other hand, the irradiation of electron beam can use electron-beam accelerator
Deng and carry out, the exposure of electron beam is preferably 10~1000krad or so.In addition, the photograph of the active energy beam to film
It penetrates, can also be carried out in the environment of the not active gases such as nitrogen.
In addition, when resin combination contains Thermocurable ingredient, made by heating the film formed by resin combination
It cures.Heating temperature at this time is preferably 90~140 DEG C, particularly preferably 110~130 DEG C.In addition, heating time is preferably
10~120 seconds or so, particularly preferably 50~70 seconds or so.
In the above-mentioned methods, as the coating method of coating fluid, gravure coating process, rod coating method, spray can be used for example
Mist rubbing method (spray coating method), method of spin coating (spin coating method), scraper for coating method
(knife coating method), rolling method, die coating methods (die coating method) etc..
It is not particularly limited as above-mentioned organic solvent, various organic solvents can be used.Such as it can make
To headed by the hydrocarbon compound of toluene, hexane, heptane etc., isopropanol, isobutanol, acetone, ethyl acetate, methyl ethyl ketone,
Methyl iso-butyl ketone (MIBK) and their mixture etc..
7. the application method of ceramic green sheet manufacturing process stripping film
In order to manufacture ceramic green sheet, stripping film 1A, 1B, 1C can be used.Specifically, can be by peeling agent layer 12
Ceramic material of the release surface coating containing barium titanate or titanium oxide etc. ceramic slurry after, keep the ceramic slurry dry and obtain
Ceramic green sheet.It is coated with and slit extruding (slot die) coating method can be used for example or scrape sheet mode etc. and carry out.
As the example of the Binder Composition contained by ceramic slurry, butyral resinoid, acrylic compounds tree can be enumerated
Fat etc..In addition, the example as the solvent contained by ceramic slurry, can enumerate organic solvent, water class solvent etc..
For stripping film 1A, 1B, 1C, stripping is formed by using the remover combination containing polysiloxane
From oxidant layer 12, and by making stripping film 1A, 1B, 1C that there is elasticity appropriate, excellent fissility can be played.Further,
In peeling agent layer 12, since polysiloxane is put into the mesh-like structure being solidified to form by melmac,
Moving freely for polysiloxane is restricted, therefore polysiloxane can be inhibited to be migrated from peeling agent layer 12 to ceramics
Raw cook.When molding ceramic green sheet being laminated as a result, the mutual adhesion of ceramic green sheet gets a promotion, and can inhibit in ceramics
Offset is generated between raw cook.In addition, for stripping film 1B, 1C for having resin layer 13, the bumps on 11 surface of base material are set
Lipid layer 13 absorbs, and thus, it is possible to reach the excellent flatness of the release surface of peeling agent layer 12.Further, by by containing trimerization
The remover combination of melamine resin forms peeling agent layer 12, to make the adherence between peeling agent layer 12 and resin layer 13 become
Must be excellent, therefore peeling agent layer 12 can be inhibited from the generation of the peeling on resin layer 13.
The implementation described above be for easy understanding the present invention and record, rather than in order to limit the present invention
And it records.Thus, each element disclosed in the above embodiment is setting comprising the whole in the technical scope for belonging to the present invention
The objective of meter change or equipollent.
For example, between the base material 11 and peeling agent layer 12 of stripping film 1A, in the base material 11 and resin layer of stripping film 1B, 1C
Between 13, or between resin layer 13 and peeling agent layer 12, or the base material 11 of stripping film 1C and the second resin layer 14 it
Between, it may also set up other layers of antistatic layer etc..
Embodiment
Hereinafter, more specific description is carried out to the present invention by embodiment etc., but the scope of the present invention is not by these realities
Apply the restrictions such as example.
[embodiment 1]
(1) formation of resin layer
Used as the toluene of solvent, by the pentaerythritol triacrylate as active energy ray-curable ingredient
(SHIN-NAKAMURA CHEMICAL CO., LTD. manufactures, trade name：A-TMM-3L) 100 mass parts (be scaled solid at
The amount divided；It is same as below) and as Photoepolymerizationinitiater initiater 2- methyl-1s [4- (methyl mercapto) phenyl] -2- morpholine propane -1- ketone
(BASF AG manufactures, trade name：IRGACURE907, alpha-aminoalkyl benzene ketone compounds) mixing of 10 mass parts, it obtains
Solid component concentration is the coating fluid of the resin combination of 15 mass %.
Using Meyer stick #6, the coating fluid of obtained resin combination is uniformly coated to draw as the twin shaft of base material
Stretch polyethylene terephthalate film (thickness：31 μm) arithmetic average roughness Ra be 10nm and maximum rising height Rp is
On the face of 80nm.Then, film is 60 seconds dry in 80 DEG C, in a nitrogen environment (oxygen concentration is 1% or less), use no electricity
Pole light irradiation ultraviolet light (illumination：150mW/cm2, light quantity：About 350mJ/cm2) and resin combination is made to cure, it has obtained in base material
On be laminated with thickness be 500nm resin layer laminated body.
(2) formation of peeling agent layer
Used as the toluene of solvent, by imino-type methylated melamine resins (NIPPON CARBIDE
INDUSTRIES CO., INC. manufactures, trade name：MX730, matter average molecular weight：1508) 100 mass parts, polydimethylsiloxanes
(Shin-Etsu Chemical Co., Ltd.s manufacture alkane, trade name：X-62-1387, matter average molecular weight：2000) 10 mass
Part and as the p-methyl benzenesulfonic acid of acid catalyst, (Hitachi is melted into the manufacture of POLYMER companies, trade name：Drier900) 8 mass
Part mixing has obtained the coating fluid for the remover combination that solid component concentration is 2 mass %.
Using Meyer stick #6, the coating fluid of obtained remover combination is uniformly coated to the tree of above-mentioned laminated body
On the face with base material opposite side of lipid layer.Then, remover combination is made to cure in 120 DEG C of heat dryings 60 seconds film,
To form the peeling agent layer that thickness is 100nm on above-mentioned laminated body.By operating above, stripping film has been obtained.
[embodiment 2]
Used as the toluene of solvent, by imino-type methylated melamine resins (NIPPON CARBIDE
INDUSTRIES CO., INC. manufactures, trade name：MX730, matter average molecular weight：1508) 100 mass parts, hydroxyl containing polyester modification
(BYK-Chemie Japan companies manufacture the dimethyl silicone polymer of base, trade name：BYK-370, matter average molecular weight：5000)
0.1 mass parts and (Hitachi is melted into the manufacture of POLYMER companies, trade name as the p-methyl benzenesulfonic acid of acid catalyst：Drier
900) 8 mass parts mix, and are prepared for the coating fluid for the remover combination that solid component concentration is 15 mass %, use the coating
Liquid and resin layer is formd by by the film in 120 DEG C of heat dryings 60 seconds, in addition to this, with same as Example 1
Mode manufactured stripping film.
[embodiment 3]
Other than the content of the dimethyl silicone polymer in remover combination is changed to 30 mass parts, with implementation
1 identical mode of example has obtained stripping film.
[embodiment 4]
Other than the content of the dimethyl silicone polymer in remover combination is changed to 40 mass parts, with implementation
1 identical mode of example has obtained stripping film.
[embodiment 5]
In addition to by the dimethyl silicone polymer of 10 mass parts in remover combination be changed to 30 mass parts contain polyester
(BYK-Chemie Japan companies manufacture the dimethyl silicone polymer of modified hydroxyl, trade name：BYK-370, the equal molecule of matter
Amount：5000) other than, stripping film has been obtained in the same manner as example 1.
[comparative example 1]
Used as the toluene of solvent, by pentaerythritol triacrylate (SHIN-NAKAMURA CHEMICAL CO.,
LTD. it manufactures, trade name：A-TMM-3L) 100 mass parts, dimethyl silicone polymer (Shin-Etsu Chemical Co.,
Ltd. it manufactures, trade name：X-62-1387, matter average molecular weight：2000) 10 mass parts and the 2- first as Photoepolymerizationinitiater initiater
(BASF AG manufactures base -1 [4- (methyl mercapto) phenyl] -2- morpholine propane -1- ketone, trade name：IRGACURE907, α-ammonia
Base alkylbenzene ketone compounds) mixing of 10 mass parts, obtain the coating fluid that solid component concentration is 15 mass %.
Using Meyer stick #6, obtained coating fluid is uniformly coated to the biaxial stretch-formed poly- terephthaldehyde as base material
Sour second diester film (thickness：31 μm) arithmetic average roughness Ra be 10nm and maximum rising height Rp is on the face of 80nm.It connects
It, film is 60 seconds dry in 80 DEG C, in a nitrogen environment (oxygen concentration is 1% or less), irradiated using electrodeless lamp ultraviolet
Line (illumination：150mW/cm2, light quantity：About 350mJ/cm2) and resin combination is made to cure, it has obtained being laminated with thickness on base material
For the laminated body of the peeling agent layer of 500nm.
[comparative example 2]
Used as the toluene of solvent, by addition type polysiloxane class remover (Dow Corning Toray Co., Ltd
Manufacture, trade name：CF-2172, matter average molecular weight：300000) 100 mass parts and platinum-type catalyst (Dow Corning
Toray Co., Ltd manufactures, BY24-835) mixing of 2 mass parts, it is prepared for the remover that solid component concentration is 1.5 mass %
The coating fluid of composition has manufactured stripping film in the same manner as example 1 other than having used the coating fluid.
[test example 1] (measurement of tectorial elastic modulus)
The size that the stripping film severing obtained in Examples and Comparative Examples is 10mm × 10mm is then used into biliquid
The substrate backside of the stripping film of severing is fixed on then on the glass plate of aluminum base by class epoxy adhesive.Then, it uses
Small hardness evaluating apparatus (MTS companies manufacture, Nano Indenter SA2), the maximum compression distance with pressure head is 100nm,
Rate of straining is 0.05sec-1, displacement amplitude 2nm, vibration frequency be 45Hz condition carry out nano indentation test, determine
The tectorial elastic modulus of above-mentioned stripping film.It shows the result in table 1.
[test example 2] (evaluation of polysiloxane migration)
By acrylic acid adhesive tape (NITTO DENKO CORPORATION manufactures, trade name：31B TAPE) it is attached to
In the release surface for having taken care of in room temperature the peeling agent layer of 48 hours stripping films after manufacture in Examples and Comparative Examples, and keeping
24 hours.
Then, above-mentioned adhesive tape is removed from stripping film, which is contacted with peeling agent layer surface
Face, based on using X-ray photoelectron spectroscopic analysis method (XPS) and measure silicon atom (Si), carbon atom (C) and oxygen atom
(O) amount (XPS countings), silicon atom ratio (atom %) has been calculated by following formula.
Silicon atom ratio (atom %)=[(Si amount of element)/{ (C element amount)+(O amount of element)+(Si amount of element) }] ×
100
As measurement device, the ESCA 5600 manufactured using Perkinelmer Inc., determination condition is as described below.
X-ray source：Mg standard(15kv,400W)
Take out angle：45°
Minute：3 minutes
Measure element：Silicon atom (Si), carbon atom (C), oxygen atom (O)
Then, it is based on criterion below, has rated polysiloxane migration.By silicon atom ratio and evaluation knot
Fruit is shown in Table 1.
◎ ... silicon atom ratios are less than 0.35 atom %
Zero ... silicon atom ratio is 0.35 atom % or more, is less than 0.5 atom %
△ ... silicon atom ratios are 0.5 atom % or more, are less than 1.0 atom %
× ... silicon atom ratio is 1.0 atom % or more
[test example 3] (evaluation for constituting the adherence of the interlayer of stripping film)
Use the resin layer before formation peeling agent layer in 10 Examples 1 to 5 of finger friction and comparative example 2 and base material phase
The stripping in the face (hereinafter sometimes referred to " resin layer surface ") and the stripping film obtained in Examples and Comparative Examples tossed about
Face, and visually judged whether to generate muddy (smear) under fluorescent light and fallen off (rubbing-off).Then, it is based on following
Evaluation criterion, have rated constitute stripping film interlayer adherence.It shows the result in table 1.
When zero ... any one in friction resin layer surface and release surface, does not generate muddiness and fall off, adherence
Well
At least one of × ... when at least one of friction resin layer surface and release surface, generate muddiness and fall off,
Adherence is bad
[test example 4] (measurement of peeling force)
To barium titanate (BaTiO3；SAKAI CHEMICAL INDUSTRY CO., LTD. manufactures, trade name：BT-03)
100 mass parts, polyvinyl butyral (SEKISUI CHEMICAL CO., LTD. manufactures, trade name：S-LEC B·KBM-
2) 8 mass parts and dioctyl phthalate (KANTO KAGAKU. manufactures, trade name：Dioctyl phthalate deer 1
Grade) in 1.4 mass parts, 69 mass parts of toluene and 46 mass parts of ethyl alcohol are added, so that its mixing is disperseed using ball mill, is prepared for making pottery
Porcelain slurry.
It, will be above-mentioned using spreader to having taken care of 48 hours stripping films after the manufacture in Examples and Comparative Examples in room temperature
Ceramic slurry is uniformly coated in the release surface of peeling agent layer, then, has been made it dry 1 minute in 80 DEG C using drying machine.
The ceramic green sheet that thickness is 3 μm has been obtained on stripping film as a result,.Thus the stripping film with ceramic green sheet has been manufactured.
The stripping film that this is had to ceramic green sheet, 24 hours have been stood in the environment of 23 degree of room temperature, relative humidity 50%.
Then, to the face with stripping film opposite side of ceramic green sheet, acrylic acid adhesive tape (NITTO DENKO are attached
CORPORATION. it manufactures, trade name：31B TAPE), and in this state severing in order to 20mm width.As
Determination sample.
The adhesive tape side of the determination sample is fixed on tablet, cupping machine (Shimadzu is used
Corporation is manufactured, name of product：It AG-IS500N), will with 180 ° of peel angle, 100mm/ minutes peeling rates
Stripping film is removed from ceramic green sheet, and determines the required power (peeling force of stripping；mN/20mm).Show the result in table 1
In.
[test example 5] (measurement of surface roughness)
By double faced adhesive tape attach on a glass, the stripping film that will be obtained in Examples and Comparative Examples, with remover
The face of layer opposite side becomes the mode of glass plate side, is fixed on a glass via above-mentioned double faced adhesive tape.For the stripping film
Release surface, use light interference type surface shape observation device (Brooker AXS companies manufacture, name of product：WYKO-1100),
Under PSI patterns maximum rising height (Rp is observed with 50 multiplying powers；Nm), based on 91.2 in obtained surface shape image ×
119.8 μm of range is determined.It shows the result in table 1.
[table 1]
It can clearly be learnt from table 1, for the stripping film obtained in embodiment, when being removed from ceramic green sheet,
It can be removed with peeling force appropriate.It further learns, the acrylic acid contacted with the stripping film obtained in embodiment is viscous
It in the contact surface of adhesive tape, silicon atom ratio is relatively small.That is, learning polysiloxane from peeling agent layer to using embodiment
Stripping film and the migration of ceramic green sheet that is formed receives effective inhibition.It, can when expecting manufacture laminated ceramic product as a result,
Inhibit using the migration of polysiloxane as the offset in the face direction of the interlayer of main cause, ceramic green sheet sandwich.This
Outside, it learns in the stripping film obtained in embodiment, the adherence of each layer is fully high, it is not easy to generate peeling agent layer from resin
Peeling on layer.Further, the stripping film compared to the comparative example 1 that resin layer is not arranged has been confirmed, resin layer is provided with
The maximum rising height Rp of the release surface of the stripping film obtained in embodiment is relatively low, and flatness is also better.
On the other hand, in the contact surface for learning the acrylic acid adhesive tape contacted with the stripping film obtained in comparative example, silicon
Atom ratio is relatively large, and polysiloxane is inhibited to migrate to the ceramic green for using the stripping film and being formed with being unable to fully
Piece.In addition, the stripping film about comparative example 2, learns that the adherence of each layer is low, easy tos produce peeling.Further, about without
The stripping film of the comparative example 1 of resin layer confirms the stripping film compared to embodiment, the maximum rising height Rp highers of release surface
And flatness is lower.
Industrial applicibility
The ceramic green sheet manufacturing process stripping film of the present invention is suitable for the few ceramics of the migration of molding polysiloxane
Raw cook.
Reference sign
1A, 1B, 1C ... ceramic green sheet manufacturing process stripping film；11 ... base materials；12 ... peeling agent layers；13 ... resin layers；
14 ... second resin layers.
Claims (8)
1. a kind of ceramic green sheet manufacturing process stripping film is the stripping for having base material and being arranged in the side of the base material
The ceramic green sheet manufacturing process stripping film of oxidant layer, which is characterized in that
The peeling agent layer is cured by the remover combination containing melmac and polysiloxane,
By nano indentation test, it is from the tectorial elastic modulus of the peeling agent layer measured with the face of the base material opposite side
3.5~7.0GPa.
2. ceramic green sheet manufacturing process according to claim 1 stripping film, which is characterized in that the polysiloxane
Matter average molecular weight be 500~20000.
3. ceramic green sheet manufacturing process according to claim 1 or 2 stripping film, which is characterized in that relative to melamine
100 mass parts of polyimide resin, content of the polysiloxane in the remover combination are 0.1~30 mass parts.
4. ceramic green sheet manufacturing process described in any one of claim 1 to 3 stripping film, which is characterized in that described
The melmac contained by remover combination contains methylated melamine and/or imino group methylol melamine
Amine.
5. ceramic green sheet manufacturing process according to any one of claims 1 to 4 stripping film, which is characterized in that in institute
It states and is further equipped with resin layer between base material and the peeling agent layer.
6. ceramic green sheet manufacturing process according to claim 5 stripping film, which is characterized in that the resin layer is by containing
The resin combination of active energy ray-curable ingredient or Thermocurable ingredient cures.
7. ceramic green sheet manufacturing process according to claim 6 stripping film, which is characterized in that the active energy beam
Curability composition is polyfunctional acrylic ester.
8. ceramic green sheet manufacturing process according to any one of claims 1 to 7 stripping film, which is characterized in that into one
Step has the second resin layer with the peeling agent layer opposite side being arranged in the base material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-241388 | 2015-12-10 | ||
| JP2015241388A JP6646424B2 (en) | 2015-12-10 | 2015-12-10 | Release film for ceramic green sheet manufacturing process |
| PCT/JP2016/085309 WO2017098956A1 (en) | 2015-12-10 | 2016-11-29 | Release film for ceramic green sheet production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108349107A true CN108349107A (en) | 2018-07-31 |
| CN108349107B CN108349107B (en) | 2020-03-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680063814.7A Active CN108349107B (en) | 2015-12-10 | 2016-11-29 | Release film for ceramic green sheet production process |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JP6646424B2 (en) |
| KR (1) | KR20180093918A (en) |
| CN (1) | CN108349107B (en) |
| MY (1) | MY186971A (en) |
| PH (1) | PH12018501229A1 (en) |
| SG (1) | SG11201804742SA (en) |
| TW (1) | TWI701138B (en) |
| WO (1) | WO2017098956A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280085A (en) * | 2020-09-24 | 2021-01-29 | 浙江日久新材料科技有限公司 | Low-roughness MLCC functional release film capable of being used in tape casting and preparation method thereof |
| CN113165361A (en) * | 2018-11-22 | 2021-07-23 | Tdk株式会社 | Release film, ceramic component sheet, method for producing release film, method for producing ceramic component sheet, and method for producing laminated ceramic capacitor |
| CN115401974A (en) * | 2018-08-10 | 2022-11-29 | 东洋纺株式会社 | Release film for producing ceramic green sheet |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7259214B2 (en) * | 2018-05-31 | 2023-04-18 | 王子ホールディングス株式会社 | peelable film |
| WO2019004209A1 (en) * | 2017-06-27 | 2019-01-03 | 王子ホールディングス株式会社 | Releasable film |
| MY193296A (en) * | 2017-08-24 | 2022-10-03 | Toyo Boseki | Release film for production of ceramic green sheet |
| KR102342530B1 (en) * | 2017-09-29 | 2021-12-24 | 도요보 가부시키가이샤 | Release Film for Ceramic Green Sheet Manufacturing |
| JP6852720B2 (en) * | 2017-10-12 | 2021-03-31 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7172468B2 (en) * | 2017-11-17 | 2022-11-16 | 荒川化学工業株式会社 | Thermosetting release coating agent and release film |
| JP7306514B2 (en) * | 2018-03-22 | 2023-07-11 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7306515B2 (en) * | 2018-03-22 | 2023-07-11 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7106912B2 (en) * | 2018-03-22 | 2022-07-27 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7306516B2 (en) * | 2018-03-22 | 2023-07-11 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| JP7082890B2 (en) | 2018-03-23 | 2022-06-09 | リンテック株式会社 | Release film for ceramic green sheet manufacturing process |
| JPWO2021186939A1 (en) * | 2020-03-17 | 2021-09-23 |
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- 2016-11-29 SG SG11201804742SA patent/SG11201804742SA/en unknown
- 2016-11-29 MY MYPI2018702071A patent/MY186971A/en unknown
- 2016-11-29 CN CN201680063814.7A patent/CN108349107B/en active Active
- 2016-11-29 WO PCT/JP2016/085309 patent/WO2017098956A1/en active Application Filing
- 2016-12-06 TW TW105140204A patent/TWI701138B/en active
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2018
- 2018-06-08 PH PH12018501229A patent/PH12018501229A1/en unknown
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| CN115401974A (en) * | 2018-08-10 | 2022-11-29 | 东洋纺株式会社 | Release film for producing ceramic green sheet |
| CN113165361A (en) * | 2018-11-22 | 2021-07-23 | Tdk株式会社 | Release film, ceramic component sheet, method for producing release film, method for producing ceramic component sheet, and method for producing laminated ceramic capacitor |
| CN112280085A (en) * | 2020-09-24 | 2021-01-29 | 浙江日久新材料科技有限公司 | Low-roughness MLCC functional release film capable of being used in tape casting and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| SG11201804742SA (en) | 2018-07-30 |
| KR20180093918A (en) | 2018-08-22 |
| JP6646424B2 (en) | 2020-02-14 |
| TWI701138B (en) | 2020-08-11 |
| CN108349107B (en) | 2020-03-06 |
| MY186971A (en) | 2021-08-26 |
| PH12018501229A1 (en) | 2019-01-28 |
| TW201725117A (en) | 2017-07-16 |
| JP2017105092A (en) | 2017-06-15 |
| WO2017098956A1 (en) | 2017-06-15 |
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