CN110430981A - Stripping film is used in raw cook formation - Google Patents
Stripping film is used in raw cook formation Download PDFInfo
- Publication number
- CN110430981A CN110430981A CN201880016629.1A CN201880016629A CN110430981A CN 110430981 A CN110430981 A CN 110430981A CN 201880016629 A CN201880016629 A CN 201880016629A CN 110430981 A CN110430981 A CN 110430981A
- Authority
- CN
- China
- Prior art keywords
- agent layer
- peeling agent
- stripping film
- raw cook
- substrate
- 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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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PGEAEAYLSCKCCO-UHFFFAOYSA-N benzene;n-methylmethanamine Chemical compound CNC.C1=CC=CC=C1 PGEAEAYLSCKCCO-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- CSXPRVTYIFRYPR-UHFFFAOYSA-N bis(ethenyl)-diethoxysilane Chemical compound CCO[Si](C=C)(C=C)OCC CSXPRVTYIFRYPR-UHFFFAOYSA-N 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CPBHJGWJMLDUNB-UHFFFAOYSA-N ethenoxysilane Chemical compound [SiH3]OC=C CPBHJGWJMLDUNB-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ZBVQEUUTPTVMHY-UHFFFAOYSA-N phenyl-(2-phenylphenyl)methanone Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 ZBVQEUUTPTVMHY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
Raw cook formation of the invention is the raw cook formation stripping film (1) for being used to form raw cook with stripping film, wherein, the stripping film (1) has substrate (11) and is set to the peeling agent layer (12) of the one side of above-mentioned substrate (11), above-mentioned peeling agent layer is formed by the solidfied material of remover formation material, which contains (A) energy ray-curable compound, (B) hydrophobization silica solution and (C) removing and assign ingredient.
Description
Technical field
The present invention relates to raw cook formation stripping films.
Background technique
Stripping film is usually made of substrate and peeling agent layer.Raw cook can be by applying on such stripping film by ceramic grain
Son disperses and is dissolved in adhesive resin ceramic slurry obtained from organic solvent and is dried and manufactures.In addition, made
The raw cook made is in the manufacture that can be used for ceramic capacitor after removing film stripping.
In addition, using stripping film manufacture raw cook, since the bumps on the surface of stripping film can be transferred to life
Piece, thus exist the problems such as the surface of raw cook generates pin hole.Therefore, for stripping film, it is desirable that the bumps on surface are few such
Flatness.On the other hand, with the miniaturization, densification of ceramic capacitor in recent years, it is desirable that the further filming of raw cook.
In turn, due to the further filming of raw cook, for stripping film, it is desirable that flatness further increases.
However, there are problems that the flatness for more improving stripping film then stripping film more is easy to happen adhesion.That is, stripping film is logical
It often takes care of, transport in the state of being rolled into web-like, when forming raw cook, release and use successively from the state of web-like.Therefore,
When the stripping film that this is batched is released successively, there is the substrate of the peeling agent layer for being easy to happen demoulding film surface and removing back of the membrane
Between adhesion (adherency) the problem of.Like this, the stripping film excellent for flatness, it is desirable that prevent the performance of adhesion (anti-stick
Even property).
As improve stripping film resistance to blocking technology, such as describe in patent document 1 polyester film at least
It is provided with the mold release film of the release layer containing nonactive particle on one side.In the mold release film, 10 average roughness of layer surface are demoulded
Spending (Rz) is 20~500nm.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-255704 bulletin
Summary of the invention
Problems to be solved by the invention
However, not obtaining the removing that can take into account flatness and resistance to blocking in the stripping film recorded in patent document 1
Film.
Therefore, raw cook shape excellent the purpose of the present invention is to provide a kind of flatness and with sufficient resistance to blocking
At with stripping film.
Solution to the problem
One embodiment of the present invention relates to raw cook formation with stripping film be used to form raw cook raw cook formed use
Stripping film, wherein the stripping film has substrate and is set to the peeling agent layer of the one side of above-mentioned substrate, and above-mentioned peeling agent layer is by shelling
It is formed from dosage form at the solidfied material of material, which contains (A) energy ray-curable compound, (B) is dredged
Aquation silica solution and (C) removing assign ingredient.
One embodiment of the present invention relates to raw cook formation stripping film in, above-mentioned (B) hydrophobization silica solution
Average grain diameter is preferably 10nm or more and 100nm or less.
One embodiment of the present invention relates to raw cook formation stripping film in, preferably form above-mentioned (B) dredge
In the case where the film of aquation silica solution, water is preferably 100 ° or more to the contact angle of above-mentioned film.
One embodiment of the present invention relates to raw cook formation stripping film in, the average thickness of above-mentioned peeling agent layer
Preferably 0.2 μm or more and 2 μm or less.
One embodiment of the present invention relates to raw cook formation stripping film in, the appearance of preferably above-mentioned peeling agent layer
The arithmetic average roughness Ra in face be 8nm hereinafter, and the outer surface of above-mentioned peeling agent layer maximum rising height Rp be 50nm with
Under.
According to the present invention, it is possible to provide stripping film is used in the excellent and raw cook formation with sufficient resistance to blocking of flatness.
Detailed description of the invention
Fig. 1 is the diagrammatic cross-section for showing the raw cook formation stripping film that embodiments of the present invention are related to.
Fig. 2 is in raw cook formation stripping film for being related to embodiments of the present invention, hydrophobization silica solution it is inclined
The ideograph that analysis state is conceptually illustrated.
Symbol description
The outer surface of 1 ... stripping film, 11 ... substrates, 12 ... peeling agent layers, 12A ... peeling agent layer.
Specific embodiment
Hereinafter, for enumerating embodiment, the present invention will be described.The present invention is not limited to the contents of embodiment.
The raw cook of present embodiment is formed with stripping film 1 (following " stripping film 1 ") as shown in Figure 1, having substrate 11 and setting
It is placed in the peeling agent layer 12 of the 1st face 11A of substrate 11.
(substrate)
The substrate 11 of present embodiment has the 1st face 11A and the 2nd face 11B.
As the material for constituting substrate 11, it is not particularly limited, it can be mentioned, for example: by polyester resin (poly terephthalic acid
Butanediol ester resin, pet resin and polyethylene naphthalate resin etc.), polyolefin resin
The film etc. that the plastics such as (acrylic resin and polymethylpentene resin etc.) and polycarbonate are formed.Substrate 11 can be monofilm,
Or 2 layers or more of multilayer film of the same race or not of the same race.In these, from processing when or using when etc. be not likely to produce dust
Deng from the viewpoint of, preferred polyester film, more preferable biaxial tension polyethylene terephthalate film.Polyester film is used utilizing
The stripping film 1 of manufacture in the case where manufacturing raw cook, can effectively prevent the coating of the ceramic slurry as caused by dust etc. bad etc..
In substrate 11, in addition to above-mentioned such material, filler etc. can also be contained.As filler, dioxy can be enumerated
SiClx, titanium oxide, calcium carbonate, kaolin and aluminium oxide etc..They can be used alone a kind, or two or more is applied in combination.Pass through
Containing such filler, the mechanical strength of substrate 11 can be assigned, and improves the slickness at the table back side, inhibits adhesion.
For the 1st face 11A of substrate 11 and surface roughness (the arithmetic average roughness Ra of the 2nd face 11B1And Ra2And
Maximum rising height Rp1And Rp2) for, it can be the roughness range that two sides is all-purpose grade, being also possible to two sides is Gao Ping
The roughness range of sliding grade.Further, it is also possible to be one side in the 1st face 11A and the 2nd face 11B be the coarse of high smooth grade
Spend range, the roughness range that another side is all-purpose grade.2nd face 11B of the substrate 11 of uncoated peeling agent layer 12 is Gao Ping
When the roughness range of sliding grade, in general, batching for stripping film 10 can generate adhesion, but the stripping film 1 of present embodiment is not allowed
Easily stick together.
For high smooth grade, the arithmetic average roughness Ra (Ra of the 1st face 11A of substrate 111) preferably
1nm or more and 40nm are hereinafter, more preferably 2nm or more and 20nm or less.As a result, as described later, in the 1st face 11A of substrate 11
On can fill up the bumps of the 1st face 11A and form the peeling agent layer 12 that have passed through smoothing.Therefore, arithmetic average roughness Ra1In
When in above range, the smoothing effect of the outer surface 12A of peeling agent layer becomes particularly significant.
For high smooth grade, the maximum rising height Rp (Rp of the 1st face 11A of substrate 111) preferably
10nm or more and 500nm are hereinafter, more preferably 15nm or more and 350nm or less.As a result, as described later, in the 1st face of substrate 11
The upper bumps that can fill up the 1st face 11A of 11A and form the peeling agent layer 12 that have passed through smoothing.Therefore, maximum rising height Rp1
When within the above range, the smoothing effect of the outer surface 12A of peeling agent layer becomes particularly significant.
For high smooth grade, the arithmetic average roughness Ra (Ra of the 2nd face 11B of substrate 112) preferably
1nm or more and 40nm are hereinafter, more preferably 2nm or more and 20nm or less.In addition, for high smooth grade, substrate
The maximum rising height Rp (Rp of 11 the 2nd face 11B2) be preferably 10nm or more and 500nm hereinafter, more preferably 15nm or more and
350nm is hereinafter, particularly preferably 20nm or more and 300nm or less.
By using the substrate of such high smooth grade, even if stripping film 1 and on it ceramic green sheet made of film
Have passed through and batch, due to the back side (the 2nd face side 11B) of the stripping film 1 contacted with coating surface be it is smooth, ceramics
The damage that raw cook is extruded and is subject to disappears, and the quality of ceramic capacitor improves.
It should be noted that for all-purpose grade, the arithmetic average roughness Ra of the 1st face 11A of substrate 11
(Ra1) be usually 5nm or more and 80nm hereinafter, the 1st face 11A of substrate 11 maximum rising height Rp (Rp1) it is usually 100nm
Above and 700nm or less.In addition, for all-purpose grade, the arithmetic average roughness Ra of the 2nd face 11B of substrate 11
(Ra2) be usually 5nm or more and 80nm hereinafter, the 2nd face 11B of substrate 11 maximum rising height Rp (Rp2) be usually 100 with
Upper and 700nm or less.
It should be noted that in the present specification, the 1st face 11A of substrate 11 and the arithmetic average roughness of the 2nd face 11B
Ra and maximum rising height Rp is according to JIS B0601-1994 and by the surface finish measurement of Mitsutoyo K.K.'s manufacture
Instrument SV3000S4 (contact pin type) is measured and the value that finds out.Moreover, in the present specification, unless otherwise indicated, " arithmetic mean roughness
Degree and maximum rising height " refers to value obtained from measurement as described above.
The average film thickness of substrate 11 is not particularly limited, preferably 10 μm or more and 300 μm hereinafter, more preferably 15 μm with
It is upper and 200 μm or less.Thus, it is possible to make the flexibility appropriateness of stripping film 1 while making the patience relative to tearing or fracture etc.
Also especially excellent.
(peeling agent layer)
The peeling agent layer 12 of present embodiment is set on the 1st face 11A of substrate 11.Peeling agent layer 12 is formed by remover
It is formed with the solidfied material of material.Moreover, in the present embodiment, due to using (A) energy ray-curable compound therefore, removing
Oxidant layer 12 can be by irradiating active energy ray with material to peeling agent layer formation and being solidified to form it.The peeling agent layer 12 can
Flatness, fissility and resistance to blocking are assigned to stripping film 1.
Arithmetic average roughness Ra (the Ra of the outer surface 12A of peeling agent layer 120) it is preferably 15nm hereinafter, more preferably
8nm or less.In addition, the maximum rising height Rp (Rp of the outer surface of peeling agent layer 120) it is preferably 50nm hereinafter, more preferably
45nm or less.As a result, when the outer surface side 12A of peeling agent layer 12 forms raw cook, it can more be prevented securely from raw cook and generate pin hole
Or local thickness is uneven, and the surface of raw cook is made to become more high smooth.
If it is the peeling agent layer 12 of present embodiment, even if being then high smooth and base as described above in outer surface 12A
2nd face 11B of material 11 is also that will not stick together in the case that height is smooth.
It should be noted that aftermentioned peeling agent layer formation material when on the 1st face 11A for be coated on substrate 11, has
There is appropriate mobility.Therefore, if using such peeling agent layer formation material, substrate 11 can be easily embedded to
The bumps of 1st face 11A can keep the state of the embedment.As a result, can prevent substrate 11 it is concave-convex to peeling agent layer 12 with
The opposite outer surface side 12A of substrate 11 impacts, and the outer surface 12A of peeling agent layer 12 can be made smooth.
The average thickness of peeling agent layer 12 is preferably 0.2 μm or more and 2 μm hereinafter, more preferably 0.3 μm or more and 1.5 μm
Below.When the average thickness of peeling agent layer 12 is above-mentioned lower limit or more, the smooth of the outer surface 12A of peeling agent layer 12 can be improved
Property, it can more be prevented securely from raw cook and generate pin hole or local thickness's unevenness.On the other hand, peeling agent layer 12 with a thickness of above-mentioned
When below the upper limit, the curling of the stripping film 1 caused by the cure shrinkage of peeling agent layer 12 can be prevented, in addition, can inhibit due to volume
The 2nd face 11B of substrate 11 and the outer surface 12A of peeling agent layer 12 for taking stripping film 1 and being in contact stick together.
The elasticity modulus of peeling agent layer 12 be preferably 3.5GPa or more and 8.0GPa hereinafter, more preferably 4.0GPa or more and
8.0GPa following.When the average elastic modulus of peeling agent layer 12 is in above range, the outer surface 12A of peeling agent layer 12 is enough
Firmly, in the case where stripping film has occurred closely sealed each other, it can inhibit and be segregated in the hydrophobized silica on surface and sink to.By
This, can further improve by the imparting effect of hydrophobized silica bring resistance to blocking.
It should be noted that in the present specification, the elasticity modulus of peeling agent layer 12 uses nano-hardness tester (MTS company
System, trade name " Nano Indenter SA4 "), in maximum compression distance 100nm, the rate of straining 0.05sec of pressure head-1, displacement
Nano indentation test is carried out under conditions of amplitude 2nm, vibration frequency 45Hz, determines the envelope elasticity modulus of above-mentioned stripping film.
In addition, in the present specification, unless otherwise indicated, " elasticity modulus " refers to the value measured as described above.
(remover, which is formed, uses material)
Here, being illustrated to the peeling agent layer formation for the peeling agent layer 12 for being used to form present embodiment with material.
It is molten that the peeling agent layer formation material of present embodiment contains (A) energy ray-curable compound, (B) hydrophobic SiClx
Glue and (C) removing assign ingredient.
(energy ray-curable compound)
As (A) energy ray-curable compound of present embodiment, it is not particularly limited, it can be from conventionally known substance
Middle selection.As (A) energy ray-curable compound, monomer, oligomer and resin, the Yi Jihan of energy ray-curable can be enumerated
There are their compositions etc..
As concrete example, multifunctional (methyl) acrylate, carbamate (methyl) acrylate, polyester can be enumerated
(methyl) acrylate, polyethers (methyl) acrylate, organosilicon (methyl) acrylate etc..They can be used alone one
Kind, it can also be applied in combination two or more.
It as multifunctional (methyl) acrylate, can enumerate: 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol
Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, two (first of propylene glycol
Base) acrylate, hexylene glycol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane
Three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, glycerol three
(methyl) acrylate and (methyl) acrylic acid triallyl etc..They can be used alone, and can also be applied in combination
It is two or more.In these, since appropriate rockiness can be assigned to peeling agent layer 12, more preferably use pentaerythrite four
(methyl) acrylate or dipentaerythritol six (methyl) acrylate.
In addition, being also possible to multifunctional (methyl) acrylic acid containing functional group as multifunctional (methyl) acrylate
Ester.As used functional group, preferably hydroxyl, the hydrophobization silica solution of (B) ingredient can be made in peeling agent layer formation material
In dispersibility and optimized in the universal existence that is formed by peeling agent layer 12.Acrylic compounds as hydroxyl
The concrete example for closing object, can enumerate pentaerythrite three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, two seasons penta
Tetrol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trimethylolpropane two (methyl) acrylate,
And pentaerythrite two (methyl) acrylate etc..They can be used alone, and can also be applied in combination two or more.These
In, since appropriate rockiness can be assigned to peeling agent layer 12, more preferably use pentaerythrite three (methyl) acrylic acid
Ester.In addition, can make to remove by being crosslinked of carrying out using crosslinking agent if multifunctional (methyl) acrylate has functional group
Oxidant layer 12 is cured by the method for energy line and both systems of heating, and cured degree can be made to reach desired water
It is flat.
In addition, multifunctional (methyl) acrylate is it is also preferred that more containing EO (ethylene oxide) or PO (propylene oxide) add-on type
Function (methyl) acrylate.
EO (ethylene oxide) or PO (propylene oxide) add-on type multifunctional (methyl) acrylate refer to, are made using acrylic acid
Compound obtained from EO or PO add-on type polyalcohol is esterified.It is specific enumerable: EO or PO modified glycerol triacrylate,
The modified trimethylolpropane acrylates of EO or PO, EO or the modified pentaerythritol tetraacrylate of PO and EO or PO modified two
Six acrylate of pentaerythrite etc..They can be used alone, and can also be applied in combination two or more.In these, due to
It can be by assigning appropriate flexibility to peeling agent layer 12 to prevent the crackle or cracking of peeling agent layer 12 from therefore can make
With the modified dipentaerythritol hexaacrylate of EO or PO, EO or the modified trimethylolpropane tetra-acrylate of PO.
Peeling agent layer forms the content (In to convert with solid component with (A) energy ray-curable compound in material
The content ratio in all solids ingredient in addition to solvent) it is preferably the 50 above of mass %
(hydrophobization silica solution)
The type of (B) hydrophobization silica solution as present embodiment, can enumerate alkoxysilane compound containing trialkylsilyl group in molecular structure and chlorosilane
The colloidal sol of the silicon dioxide microparticles such as compound.By (B) hydrophobization silica solution, resistance to blocking can be assigned to peeling agent layer 12.
As alkoxysilane compound containing trialkylsilyl group in molecular structure, as long as the silicon compound with water-disintegrable alkoxy, is just not particularly limited,
Such as the compound of general formula (1) expression can be enumerated.
R1 nSi(OR2)4-n···(1)
In above-mentioned general formula, R1Indicate hydrogen atom or non-hydrolyzable group.As non-hydrolyzable group, alkyl can be enumerated, taken
Substituted alkyl (substituent group: halogen atom, epoxy atom, (methyl) acryloxy etc.), alkenyl, aryl and aralkyl etc..R2It indicates
Low alkyl group (alkyl that carbon atom number is 1~10 (preferably carbon atom number is 1~4)).The integer that n is 0~2, R1And OR2Respectively
In the case where multiple, multiple R1It can be the same or different, in addition, multiple OR2It can be the same or different.
Herein, the alkoxysilane compound containing trialkylsilyl group in molecular structure indicated as above-mentioned general formula (1), can enumerate: tetramethoxy-silicane, four ethoxies
Base silane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silanes, tetraisobutoxy-silicane alkane, four sec-butoxies
Silane, four tert-butoxy silanes, trimethoxy silane hydride, triethoxysilane hydride, tripropoxy silane hydride,
Methyltrimethoxysilane, methyltriethoxysilane, methyl tripropoxy silane, three isopropoxy silane of methyl, ethyl three
Methoxy silane, ethyl triethoxysilane, propyl-triethoxysilicane, butyl trimethoxy silane, phenyl trimethoxy silicon
Alkane, phenyl triethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloxypropyl trimethoxy
Base silane, dimethyldimethoxysil,ne, aminomethyl phenyl dimethoxysilane, vinyltrimethoxysilane, three second of vinyl
Oxysilane, divinyl dimethoxysilane and divinyl diethoxy silane etc..They can be used alone,
It can also be applied in combination two or more.
In this case, as alkoxysilane compound containing trialkylsilyl group in molecular structure, if being 1 or 2 and R by the n compound for being 0 or n1For hydrogen
Inorganic silicon dioxide class solidfied material then can be obtained in the compound complete hydrolysis of atom, if partial hydrolysis, can obtain gathering organic
The mixing class solidfied material of type siloxane solidfied material or inorganic silicon dioxide class and poly organo siloxane.
On the other hand, n is 1 or 2 and R1For non-hydrolyzable group compound due to non-hydrolyzable group,
Poly organo siloxane solidfied material can be obtained by partly or completely all-hydrolytic.
As chlorosilane cpd, ethyl dichlorosilane, ethyl trichlorosilane, dimethyldichlorosilane, trichlorine can be enumerated
Silane, trim,ethylchlorosilane, dimethyldichlorosilane and methyl trichlorosilane etc..They can be used alone, can also be with
It is applied in combination two or more.
Silica solution is made of silicon dioxide microparticle is dispersed in water or organic solvent with collosol state.
Such organic solvent is not particularly limited, the molten fibre of methanol, ethyl alcohol, isopropanol, ethylene glycol, n-propyl can be enumerated
Agent, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dimethyl acetamide, propylene glycol monomethyl ether, hexamethylene, benzene and toluene etc..They can be with
One kind is used alone, can also be applied in combination two or more.In these, from boiling point it is relatively high from the viewpoint of, more preferable methyl
Isobutyl ketone, propylene glycol monomethyl ether.
(B) hydrophobization silica solution is some or all of silanol group of silica particle surface through having hydrophobicity base
Hydrophobization silica solution made of the surface modifier processing of group.
Herein, as surface modifier, can enumerate while have can be with the silanol group in silica particle surface
The functional group of reaction and the silane coupling agent of hydrophobic group.
It as the commercially available product of (B) hydrophobization silica solution, can enumerate for example: CIK Nanotech corporation
SIRPGM15WT%-E26 etc..
(B) hydrophobic degree of hydrophobization silica solution is judged by following methods: by silica solution coated on PET film, being removed molten
Agent and silica solution film is made, measure relative to the film water contact angle.
More specifically, in the case where foring the film of (B) hydrophobization silica solution, water is excellent to the contact angle of the film
It is selected as 100 ° or more.
That is, water be 100 ° or more to the contact angle of the film of silica solution value when, can determine whether that the surface of silica solution is hydrophobic
Property.
Herein, the mode conceptually illustrated for the segregation status to (B) hydrophobization silica solution is shown in Fig. 2
Figure.
In the case where the peeling agent layer formation material using present embodiment forms film, as shown in Fig. 2, can
Understand, hydrophobization silica solution P can largely be present in the outer surface 12A of peeling agent layer 12 in peeling agent layer 12, and be present in base
Ratio of the 1st face 11A of material 11 nearby and in peeling agent layer 12 is low.
Therefore, the rough surface of appropriateness can be assigned to the surface of peeling agent layer 12 by adding a small amount of hydrophobization silica solution
Degree.Therefore, even if in the case where stripping film 1 overlaps each other and have passed through the time, it is also possible to prevent the 2nd face 11B of substrate 11
Stick together between peeling agent layer 12,
I.e., it is appreciated that since addition small amount can play given resistance to blocking effect, can be formed flat
The excellent peeling agent layer of slip.
It should be noted that in the case where foring the film of (B) hydrophobization silica solution, contact angle of the water to the film
More preferably 100 ° or more and 130 ° or less.
On the other hand, it has confirmed that, in the case where foring the film of silica solution, when contact angle of the water to the film is
When the hydrophily of value, silica solution less than 100 ° improves, silica solution will not be segregated in the outer surface 12A of peeling agent layer 12, but
Exist with the state being scattered in entire peeling agent layer 12.
Therefore, it is appreciated that resistance to blocking can not be assigned to peeling agent layer 12.
It should be noted that measuring water in the case where foring the film of silica solution to the side of the contact angle of the film
Method will specifically describe in embodiment 1.
(B) average grain diameter of hydrophobization silica solution is preferably 10nm or more and 100nm or less.Average grain diameter is 10nm or more
When, it can further improve the resistance to blocking of peeling agent layer 12.On the other hand, when average grain diameter is 100nm or less, it can be ensured that removing
The flatness of the outer surface 12A of oxidant layer 12.
Therefore, the average grain diameter of (B) hydrophobization silica solution is preferably 10nm or more and 50nm hereinafter, further preferably
15nm or more and 40nm or less.
It should be noted that the average grain diameter of (B) hydrophobization silica solution is surveyed using laser diffraction and scattering formula size distribution
Partial size (median particle diameter D50) when the aggregate-value for determining the size distribution that device is found out is 50%.
Relative to above-mentioned 100 mass parts of (A) energy ray-curable compound, the content of (B) hydrophobization silica solution is with solid
Ingredient conversion is preferably 0.4 mass parts or more and 100 below the mass, it is more than more preferably 0.4 mass parts and 30 mass parts with
Under, even more preferably for more than 0.4 mass parts and 10 below the mass, more than particularly preferably 0.4 mass parts and 3 mass parts
Below.When content is above-mentioned lower limit or more, sufficient resistance to blocking can be assigned to peeling agent layer 12.On the other hand, content is
When below the above-mentioned upper limit, it can be ensured that the adaptation of peeling agent layer 12 and substrate 11.
(removing assigns ingredient)
(C) removing as present embodiment assigns ingredient, can enumerate for example: organo-silicon compound, fluorine compounds and length
Alkyl group modified compound etc..They can be used alone, and can also be applied in combination two or more.It removes and assigns as (C)
Ingredient is given, particularly preferred organo-silicon compound can enumerate the polysiloxane of the strand with straight-chain or branch-like.It is logical
It crosses (C) removing and assigns ingredient, the fissility of peeling agent layer 12 can be assigned.Additionally, it is preferred that polysiloxane is at the end of strand
At least any place in end and side chain has reactive functional groups, and the reactive functional groups have selected from (methyl) acryloyl
It is at least one kind of in base, vinyl, hydroxyl, thiol base and dimaleoyl imino.In addition, polysiloxane is more preferably above-mentioned
Reactive functional groups are directly or via poly organo made of the silicon atom bonding in divalent connection group and above-mentioned strand
Alkane.Above-mentioned reactive functional groups at least have 1 in 1 molecule.
In addition, link group as divalent, it can be mentioned, for example: alkylidene, alkylidene oxygroup, oxygroup, imido grpup, carbonyl and
By connection group of divalent made of these moiety combinations etc..
The carbon atom number that divalent links group is preferably 1~30, and more preferably 1~10.
In addition, two or more can be applied in combination in polysiloxane as needed.
Modified polyorganosiloxanes made of such reacted property functional group replaces are in (A) energy ray-curable compound
Cross-linked structure and fixation are imported into when solidifying by irradiating active energy ray.Can inhibit as a result, as peeling agent layer 12 at
Point raw cook from polysiloxane to the outer surface side 12A for being formed in peeling agent layer 12 transfer.
The organic group other than the reactive functional groups for assigning ingredient is removed as composition (C), can enumerate and not have fat
Identical or different kind 1 valency alkyl of race's unsaturated bond etc..
As 1 valency alkyl, preferably carbon atom number be 1~12 1 valency alkyl, the 1 valence hydrocarbon that more preferable carbon atom number is 1~10
Base.
As 1 valency alkyl, alkyl (methyl, ethyl and propyl etc.) and aryl (phenyl, tolyl etc.) etc. can be enumerated.
In addition, the above are methyl by 80 moles of % in preferably 1 valency alkyl as 1 valency alkyl.It can make peeling agent layer as a result,
12 fissility is especially excellent.
Relative to above-mentioned 100 mass parts of (A) energy ray-curable compound, (C) removing assigns the content of ingredient with solid
Ingredient conversion is preferably 0.01 mass parts or more and 20 below the mass, it is more than more preferably 0.02 mass parts and 15 mass parts with
Under, especially it is more preferably 0.05 mass parts or more and 10 below the mass.When content is above-mentioned lower limit or more, remover can be improved
The fissility of layer 12.On the other hand, when content is the above-mentioned upper limit or less, in the surface coating ceramic slurry of peeling agent layer 12,
It can inhibit the repulsion to ceramic slurry.
(Photoepolymerizationinitiater initiater)
In order to make peeling agent layer formation material solidification, peeling agent layer formation material can also draw containing (D) photopolymerization
Send out agent.It, can be effectively when irradiating active energy ray with material to peeling agent layer formation by containing (D) Photoepolymerizationinitiater initiater
Form peeling agent layer 12.Herein, Photoepolymerizationinitiater initiater refers to, is generated free radicals by the irradiation of ultraviolet light isoreactivity energy line
The compound of kind.
As (D) Photoepolymerizationinitiater initiater, it can be mentioned, for example: benzoin, benzoin methylether, benzoin ethyl ether, benzoin are different
Propyl ether, benzoin n-butylether, benzoin isobutyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2,2- dimethoxy -2- phenyl benzene
Ethyl ketone, 2,2- diethoxy -2- phenyl acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- hydroxycyclohexylphenyl
Ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl-1- acetone, 4- (2- hydroxyl-oxethyl) phenyl-2- (hydroxyl-2-
Propyl) ketone, benzophenone, to phenyl benzophenone, 4,4- diethylamino benzophenone, dichloro benzophenone, 2- methyl anthracene
Quinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyl thioxanthones, 2-chlorothioxanthone, 2,
4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, benzoin dimethylether, acetophenone dimethyl ketal, to dimethyl amine benzene first
Acid esters and oligomeric [2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] propane] etc..They can be used alone one
Kind, it can also be applied in combination two or more.
In the case where use (D) Photoepolymerizationinitiater initiater, content is converted with solid component relative to above-mentioned (A) energy line
100 mass parts of curability compound be preferably 0.5 mass parts or more and 20 below the mass, it is more than more preferably 0.2 mass parts
And 20 below the mass, especially more than more preferably 0.5 mass parts and 15 below the mass.Content within the above range when, stripping
Even the thickness from oxidant layer 12 is difficult to obtain the thickness of the range of curability due to oxygen inhibition, also available especially excellent
Curability.
The peeling agent layer formation of present embodiment with material remove above-mentioned (A) ingredient, above-mentioned (B) ingredient, above-mentioned (C) ingredient and
Other than above-mentioned (D) ingredient, other ingredients can also be contained.As other ingredients, it can be mentioned, for example crosslinking agents, antioxidant, ultraviolet
Light absorbers, antistatic agent, polymerization accelerant, polymerization inhibitor, infrared absorbent and plasticizer etc..As crosslinking agent, above-mentioned
(A) when using hydroxyl in the functional group of ingredient, polyvalent isocyanate compound, multivalence epoxide, multivalence nitrogen third can be used
Acridine compound and polyvalent metal chelate compound etc..
Using other ingredients, content is converted with solid component relative to above-mentioned (A) energy ray-curable
100 mass parts of compound be preferably 0.01 mass parts or more and 5 below the mass, more than more preferably 0.02 mass parts and 3 matter
Part is measured hereinafter, being especially more preferably 0.05 mass parts or more and 2 below the mass.
The peeling agent layer formation material of present embodiment can be by mixing above-mentioned (A1) ingredient and above-mentioned (B) ingredient etc.
And disperses and manufacture.It should be noted that can according to need when manufacture peeling agent layer is formed with material with bonding solvent.
As the solvent of present embodiment, it can be mentioned, for example: methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutyl
Alcohol, amylalcohol, ethyl cellosolve, benzene,toluene,xylene, ethylbenzene, hexamethylene, ethyl cyclohexane, ethyl acetate, butyl acetate, first
Ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, tetrahydrofuran, propylene glycol monomethyl ether and water etc..They can be used alone,
It can be applied in combination two or more.
(manufacturing method of stripping film)
Next, being illustrated to the method for the stripping film 1 for manufacturing present embodiment above-mentioned.
The stripping film 1 of present embodiment is using the method manufacture for having following processes: the substrate for preparing substrate 11 prepares
Process；Pass through coating peeling agent layer formation material and makes it dry the coating layer formation process to form coating layer；And it is logical
Cross the peeling agent layer formation process for making it be solidified to form peeling agent layer 12 coating layer irradiation active energy ray.
In substrate preparatory process, prepare substrate 11.
1st face 11A of substrate 11 can be implemented to be surface-treated.Thus, it is possible to make substrate 11 and be set to substrate 11
The adaptation of the peeling agent layer 12 in the 1st face side 11A is especially excellent.
As surface treatment, it can be mentioned, for example: Corona discharge Treatment, plasma discharge processing, chromium oxidation processes are (wet
Formula), flame treatment, hot wind processing, ozone and ultraviolet treatment with irradiation etc..These surface treatments can be according to the type of substrate 11
And it suitably selects, but, it is preferable to use Corona discharge Treatment usually from the viewpoint of effect and operability.
In coating layer formation process, by peeling agent layer formation above-mentioned with material be coated on substrate 11 the 1st face 11A,
And it makes it dry.Thus coating layer is obtained.
If the bumps of the 1st face 11A of substrate 11 can be filled using peeling agent layer formation material above-mentioned.Its
As a result, the outer surface 12A of peeling agent layer 12 can be made smooth.
As the method for coating peeling agent layer formation material, it can be mentioned, for example: gravure coating process, stick coating method, spray coating method,
Spin-coating method, air knife coating method, rolling method, knife coating, horizontal roller coating method and die coating method etc..
As the method for dry peeling agent layer formation material, it is not particularly limited, it can be mentioned, for example: pass through heated-air drying
The method etc. that furnace etc. is dried.
It as drying condition, is not particularly limited, drying temperature is preferably 50 DEG C or more and 130 DEG C hereinafter, drying time
Preferably 5 seconds or more and 1 minute or less.This prevents coating layer do not expect it is rotten, and can particularly effectively shape
At coating layer.As a result, the productivity of finally obtained stripping film 1 can be improved.In addition, drying temperature within the above range when,
In the case where peeling agent layer formation material contains solvent etc., the evaporation of solvent when can prevent with drying etc. generates coating
The warpage of layer or crack etc..
In peeling agent layer formation process, by irradiating active energy to coating layer obtained in above-mentioned coating layer formation process
Amount line simultaneously makes it be solidified to form peeling agent layer 12.
In this process, by making in above-mentioned coating layer formation process, the 1st face 11A's for being accurately embedded to substrate 11 is recessed
Convex coating layer directly solidifies in the state of keeping the flatness of its outer surface 12A.As a result, outer surface 12A foot can be obtained
Enough smooth peeling agent layers 12.In addition, can be obtained by making peeling agent layer formation material include foregoing constituent
To the peeling agent layer 12 of the electric conductivity with appropriateness.
As active energy ray, it can be mentioned, for example: electromagnetic wave (infrared ray, visible light, ultraviolet light and X-ray etc.) and particle
Beam (electron beam, ion beam, neutron beam and alpha ray etc.) etc.., it is preferable to use ultraviolet light or visible light, more preferably use in these
Ultraviolet light.Thus, it is possible to be easier and effectively form peeling agent layer 12.
It, can be when abundant shortening makes the cured solidification of coating layer in the case where using ultraviolet light as active energy ray
Between while, solidify coating layer equably.In addition, the method as irradiation active energy ray, is not particularly limited, it is available
Various conventional methods.For example, the light sources such as high-pressure mercury-vapor lamp, metal halide lamp and Excimer lamp can be used as light source
Lamp.
In the case where irradiating active energy ray (ultraviolet light), for the exposure of active energy ray, accumulated light
Preferably 30mJ/cm2Above and 400mJ/cm2Hereinafter, more preferably 50mJ/cm2Above and 300mmJ/cm2Below.In addition, living
The illumination of property energy line is preferably 0.1W/cm2Above and 4.0W/cm2Below.Ultraviolet irradiation amount and illumination are in above range
When interior, coating layer can be made more evenly and effectively to solidify.
(application method of stripping film)
Next, being illustrated to the method for the stripping film 1 for using present embodiment above-mentioned.
The stripping film 1 that present embodiment can be used manufactures ceramic capacitor.It, can as the manufacturing method of ceramic capacitor
Enumerate such as following methods: the peeling agent layer 12 of stripping film 1 surface coating ceramic powder dispersed paste and drying and formed
After raw cook, it is laminated from the raw cook after the removing of stripping film 1, is fired and obtains potsherd, form electrode on the potsherd.This
The stripping film 1 of embodiment due to being not susceptible to adhesion, the outer surface 12A and substrate 11 of peeling agent layer 12 can be made
Both 2nd face 11B realize high smooth.As a result, if formed using the raw cook formed using the stripping film 1 of present embodiment
The ceramic capacitor that can prevent the high reliablity of the unfavorable condition caused by short circuit then can be obtained in ceramic capacitor.
(function and effect of embodiment)
According to the present embodiment, function and effect as described below can be played.
(1) the peeling agent layer formation containing (A) energy ray-curable compound can easily be embedded to substrate 11 with material
The 1st face 11A bumps, and the state of the embedment can be kept.As a result, the bumps of substrate 11 can be prevented to peeling agent layer 12
The outer surface 12A side opposite with substrate 11 impacts, and the outer surface 12A of peeling agent layer 12 can be made smooth.
(2) (B) hydrophobization silica solution is utilized, peeling agent layer 12 can also be assigned even if with few content adequately anti-stick
Lian Xing.Moreover, the flatness of the outer surface 12A of peeling agent layer 12 can also be kept even if using (B) hydrophobization silica solution.This
Outside, it utilizes (C) removing to assign ingredient, fissility can also be assigned to peeling agent layer 12.
The more specific example of raw cook formation stripping film as present embodiment, it can be mentioned, for example following such lifes
Piece forms the example for using stripping film, but the present invention is not limited to such examples.
An example of raw cook formation stripping film as present embodiment, can enumerate following raw cook formation stripping films: its
Have substrate and be set to above-mentioned substrate one side peeling agent layer, above-mentioned peeling agent layer by remover formation material solidification
Object is formed, which uses material to contain (A) as the acrylic compounds chemical combination of the hydroxyl of energy ray-curable compound
The organo-silicon compound of object, (B) hydrophobization silica solution and (C) as removing imparting ingredient.
An example of raw cook formation stripping film as present embodiment, can enumerate following raw cook formation stripping films: its
Have substrate and be set to above-mentioned substrate one side peeling agent layer, above-mentioned peeling agent layer by remover formation material solidification
Object is formed, which uses material to contain (A) as the acrylic compounds chemical combination of the hydroxyl of energy ray-curable compound
The organo-silicon compound and (D) Photoepolymerizationinitiater initiater of object, (B) hydrophobization silica solution, (C) as removing imparting ingredient.
[deformation of embodiment]
The present invention is not limited to embodiment above-mentioned, it can be achieved that deformation, improvement etc. in the range of the purpose of the present invention
Also it is included in the present invention.
For example, for substrate 11, being illustrated in the form of single layer structure, but unlimited in embodiment above-mentioned
Due to this.Substrate 11 can also be formed as 2 layers or more of multilayered structure of the same race or not of the same race.In addition, about peeling agent layer 12
Similarly, it is illustrated in the form of single layer structure, but not limited thereto.About peeling agent layer 12, can also be formed as same
Kind or 2 layers or more of multilayered structure not of the same race.
In addition, being provided with peeling agent layer 12 on the 1st face 11A of substrate 11 for example in embodiment above-mentioned
Raw cook formation is illustrated with stripping film, and but not limited thereto.Peeling agent layer can be set in the 2nd face side 11B of substrate 11
12。
Embodiment
Next, in conjunction with the embodiments and the present invention is described in more detail in comparative example, but the present invention is not appointed by these examples
What is limited.It should be noted that the material described below used in Examples and Comparative Examples.
((A) ingredient)
Energy ray-curable compound: pentaerythritol triacrylate, trade name " NK ESTER A-TMM-3L ", it is new in
Village's chemical industry Co. Ltd. system, 100 mass % of solid component
((B) ingredient)
Silica solution A: hydrophobization silica solution, average grain diameter 30nm, trade name " SIRPGM15WT%-E26 ", CIK
Nanotech corporation
Silica solution B: hydrophobization silica solution, average grain diameter 30nm, trade name " SIRMIBK15WT%-E83 ", CIK
Nanotech corporation
(other ingredients)
Silica solution C: silica solution, average grain diameter 100nm, trade name " SIRMIBK15WT%-K18 ", CIK Nanotech are public
Department's system
Silica solution D: silica solution, average grain diameter 30nm, trade name " OSCAL-1632 ", RiHui catalyst synthesis Co., Ltd's system
Silica solution E: silica solution, average grain diameter 15nm, trade name " MIBK-ST ", Nissan Chemical Ind Ltd's system
Silica solution F: silica solution average grain diameter 100nm, trade name " SIRMIBK-E65 ", CIK Nanotech corporation
((C) ingredient)
Removing assigns ingredient: trade name " SH-28 ", Toray Dow Corning corporation
((D) ingredient)
Photoepolymerizationinitiater initiater: trade name " Irgacure 184 ", BASF AG's system
[embodiment 1]
Firstly, prepared as substrate polyethylene terephthalate film (trade name " Lumirror U48 ",
Toray corporation, thickness: 38 μm, the arithmetic average roughness Ra (Ra in the 1st face1): 2nm, the 1st face maximum rising height Rp
(Rp1): 15nm, the 2nd face arithmetic average roughness Ra (Ra2): 2nm, the 2nd face maximum rising height Rp (Rp2): 15nm).
Next, assigning 100 mass parts of energy line curability compound, 0.4 mass parts of silica solution A, removing to ingredient 5
Mass parts and the mixing of 5 mass parts of Photoepolymerizationinitiater initiater, are diluted using propylene glycol monomethyl ether, have obtained 15 matter of solid component
Material is used in the peeling agent layer formation of amount %.
Then, obtained peeling agent layer formation is coated on the 1st face of substrate with Meyer stick with material, is done at 70 DEG C
After dry 1 minute, high-pressure mercury light irradiation ultraviolet light (accumulated light: 300mJ/cm is used2), form peeling agent layer (thickness: 1 μ
M), raw cook formation stripping film has been obtained.
[embodiment 2~7 and the Comparative Examples 1 to 5]
Cooperate each material, in addition to this, obtained peeling agent layer similarly to Example 1 according to composition shown in table 1
Formation material.
In addition, obtained peeling agent layer formation material has been used to make life similarly to Example 1 in addition to this
Stripping film is used in piece formation.
[evaluation of silica solution and stripping film]
The evaluation (contact angle of silica solution) of silica solution and the evaluation of stripping film have been carried out by following such method
(elasticity modulus of resistance to blocking, the surface roughness of peeling agent layer and peeling agent layer).The obtained results are shown in tables 1.
(1) contact angle of silica solution
Using the silica solution used in Examples and Comparative Examples, silica solution painting is formd on flat glass substrate
Film.Then, glass substrate is stood, when making 0 degree of the inclination angle of glass substrate, dropwise addition 2 μ L of water droplet passes through when drop is static
Young formula finds out water contact angle.
(2) resistance to blocking
Stripping film is cut into the size of 100mm × 100mm, 2 or more identical stripping films are overlapped.On it to reach
10kg/m2Mode apply load, be superimposed on together after 5 days.
Under fluorescent light, it confirmed stripping film by range estimation whether there is or not adhesions.In turn, according to following benchmark evaluation resist blocking and that
Property.
A: film surface does not adhere to each other.
B: film surface is adhered to each other.
(3) surface roughness of peeling agent layer
The light interference type surface roughness meter " WYKO-1100 " manufactured using Veeco company, with PSI mode in lens times
Surface roughness (the arithmetic average roughness Ra of the peeling agent layer of stripping film is determined under conditions of 50 times of rate0And maximum protrusion
Height Rp0, unit: nm).
(4) elasticity modulus of peeling agent layer
Using nano-hardness tester (MTS corporation, trade name " Nano Indenter SA4 "), in the maximum indentation of pressure head
Depth 100nm, rate of straining 0.05sec-1, displacement amplitude 2nm, carry out nano indentation test under conditions of vibration frequency 45Hz,
Determine the envelope elasticity modulus of above-mentioned stripping film.
It can also clearly be confirmed according to result shown in table 1, the remover containing hydrophobization silica solution is being used to be formed
With under (Examples 1 to 7) the case where material, even if the 2nd face of peeling agent layer and substrate is all high smooth, also available tool
There is the raw cook formation stripping film of sufficient resistance to blocking.
Industrial applicibility
Raw cook formation stripping film of the invention can be suitable for use as the technology of forming ceramic raw cook.
Claims (5)
1. a kind of raw cook, which is formed, uses stripping film, it is used to form raw cook,
The raw cook formation has with stripping film:
Substrate and
It is set to the peeling agent layer of the one side of the substrate,
The peeling agent layer is formed by the solidfied material of remover formation material, which contains (A) energy
Line curability compound, (B) hydrophobization silica solution and (C) removing assign ingredient.
2. raw cook according to claim 1, which is formed, uses stripping film, wherein
The average grain diameter of (B) the hydrophobization silica solution is 10nm or more and 100nm or less.
3. raw cook according to claim 1 or 2, which is formed, uses stripping film, wherein
In the case where foring the film of described (B) hydrophobization silica solution, water is 100 ° or more to the contact angle of the film.
4. raw cook described in any one of claim 1 to 3, which is formed, uses stripping film, wherein
The average thickness of the peeling agent layer is 0.2 μm or more and 2 μm or less.
5. raw cook according to any one of claims 1 to 4, which is formed, uses stripping film, wherein
The arithmetic average roughness Ra of the outer surface of the peeling agent layer is 8nm hereinafter, and the outer surface of the peeling agent layer
Maximum rising height Rp is 50nm or less.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-044707 | 2017-03-09 | ||
| JP2017044707 | 2017-03-09 | ||
| PCT/JP2018/007389 WO2018163923A1 (en) | 2017-03-09 | 2018-02-28 | Peeling film for green sheet formation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110430981A true CN110430981A (en) | 2019-11-08 |
Family
ID=63448578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880016629.1A Pending CN110430981A (en) | 2017-03-09 | 2018-02-28 | Stripping film is used in raw cook formation |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7046053B2 (en) |
| KR (1) | KR102499440B1 (en) |
| CN (1) | CN110430981A (en) |
| WO (1) | WO2018163923A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120617A (en) * | 2023-02-20 | 2023-05-16 | 江苏裕兴薄膜科技股份有限公司 | MLCC release film and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6852720B2 (en) * | 2017-10-12 | 2021-03-31 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
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| CN116120617A (en) * | 2023-02-20 | 2023-05-16 | 江苏裕兴薄膜科技股份有限公司 | MLCC release film and preparation method thereof |
| CN116120617B (en) * | 2023-02-20 | 2024-09-27 | 江苏裕兴薄膜科技股份有限公司 | MLCC release film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018163923A1 (en) | 2018-09-13 |
| KR102499440B1 (en) | 2023-02-13 |
| JPWO2018163923A1 (en) | 2020-01-09 |
| KR20190119072A (en) | 2019-10-21 |
| JP7046053B2 (en) | 2022-04-01 |
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