CN103476897B - Remover combination and the shaping stripping film of ceramic green - Google Patents

Remover combination and the shaping stripping film of ceramic green Download PDF

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CN103476897B
CN103476897B CN201280015628.8A CN201280015628A CN103476897B CN 103476897 B CN103476897 B CN 103476897B CN 201280015628 A CN201280015628 A CN 201280015628A CN 103476897 B CN103476897 B CN 103476897B
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organopolysiloxane
remover combination
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thiazolinyl
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CN103476897A (en
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市川慎也
深谷知巳
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Lintec Corp
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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Abstract

The invention provides a kind of remover combination, it contains: organopolysiloxane (A), has at least 2 thiazolinyls and two side chains of at least 1 Siliciumatom in siloxane backbone have aryl in its 1 molecule; And, organopolysiloxane (B), its not there is aryl and in 1 molecule only two ends there is thiazolinyl; Organopolysiloxane (A) is 40 ~ 98 quality % relative to the solids component ratio of the total amount of organopolysiloxane (A) and organopolysiloxane (B), and the matter average molecular weight of organopolysiloxane (A) is 100000 ~ 800000.Adopt this remover combination, the coating of ceramic size can be made excellent, and meanwhile, the separability of ceramic green is also excellent.

Description

Remover combination and the shaping stripping film of ceramic green
Technical field
The stripping film that the present invention relates to remover combination and use the ceramic green of this remover combination (greensheet) shaping.
Background technology
Up to now, in order to manufacture the multilayer ceramic goods being called laminated ceramic capacitor or multilayer ceramic substrate, general by ceramic green is shaping, the ceramic green layer poststack sintering then multi-disc obtained manufactures.
Ceramic green is by being coated on stripping film shaping by the ceramic size containing the stupalith such as barium titanate or titanium oxide.As stripping film, generally use the film substrate (patent documentation 1 ~ 8) obtained through silicon-type compound lift-off processing such as polysiloxane.For this stripping film, require that there is the separability that can not break being stripped down from this stripping film by the thin ceramic green taken shape on this stripping film.
In recent years, along with miniaturization and the high performance of electronic machine, laminated ceramic capacitor or multilayer ceramic substrate are to miniaturization and multiple stratification development, and ceramic green then develops to filming.
Prior art document
Patent documentation
Patent documentation 1: JP 2002-011710 publication
Patent documentation 2: JP 2004-182836 publication
Patent documentation 3: JP 2004-216613 publication
Patent documentation 4: JP 2008-254207 publication
Patent documentation 5: JP 2009-034947 publication
Patent documentation 6: JP 2009-215428 publication
Patent documentation 7: JP 2009-227976 publication
Patent documentation 8: JP 2009-227977 publication
Summary of the invention
The problem that invention will solve
If make its dried thickness be less than 3 μm ceramic green filming, then when then coating ceramic slurry makes it dry, the following phenomenon of easy generation: the coating end of ceramic size is shunk, the thickness of this coating end is thickening, namely so-called end is shunk, and produces pin hole or crawling.In addition, when shaping ceramic green is stripped down from stripping film, the unfavorable condition such as to break easily occurring to cause due to the strength degradation of ceramic green.
And then use the electronic material of ceramic green according to its purposes, the materials such as inorganics wherein, adhesive resin, dispersion agent, organic solvent are different, and according to the kind of ceramic size used, the coating of ceramic size to stripping film changes to some extent.Therefore, for stripping film, the separability that reach the coating and ceramic green having both ceramic size is difficult.
The present invention develops in view of this present situation just, and object is, provides the shaping stripping film of ceramic green that the coating of ceramic size separability that is excellent, ceramic green simultaneously is also excellent, and is applicable to the remover combination of this stripping film.
For solving the means of problem
In order to achieve the above object, 1st aspect, the invention provides remover combination, it is characterized in that, contain: organopolysiloxane (A), in its 1 molecule, there are at least 2 thiazolinyls and two side chains of at least 1 Siliciumatom in siloxane backbone have aryl; Organopolysiloxane (B), its not there is aryl and in 1 molecule only two ends there is thiazolinyl; Above-mentioned organopolysiloxane (A) is 40 ~ 98 quality % relative to the solids component ratio of the total amount of above-mentioned organopolysiloxane (A) and above-mentioned organopolysiloxane (B), and the matter average molecular weight of above-mentioned organopolysiloxane (A) is 100000 ~ 800000(invention 1).
If adopt the stripping film using the remover combination described in foregoing invention (invention 1) to obtain, the coating of ceramic size can be made excellent, specifically, when peeling agent layer surface coated ceramic size and when making it dry, the thickness of the contraction of the coating end of ceramic size and this coating end can be suppressed thickening, namely inhibit the generation that so-called end is shunk.In addition, if adopt above-mentioned stripping film, the separability of the ceramic green that can make shaping is also excellent, only just ceramic green need can be stripped down from peeling agent layer with low peeling force.
In foregoing invention (invention 1), the matter average molecular weight of above-mentioned organopolysiloxane (B) is preferably 50000 ~ 800000(invention 2).
In foregoing invention (invention 1,2), preferably also contain platinum metals based compound as catalyzer (invention 3).
In foregoing invention (invention 1 ~ 3), preferably also containing linking agent (C) (invention 4).
In foregoing invention (invention 1 ~ 4), the thiazolinyl number contained by above-mentioned organopolysiloxane (A) is relative to the alkyl number contained by above-mentioned organopolysiloxane (A), and ratio, is preferably 0.005 ~ 0.1(invention 5).
In foregoing invention (invention 1 ~ 5), the aryl number contained by above-mentioned organopolysiloxane (A) is relative to the alkyl number contained by above-mentioned organopolysiloxane (A), and ratio, is preferably 0.01 ~ 0.5(invention 6).
In foregoing invention (invention 1 ~ 6), the thiazolinyl number contained by above-mentioned organopolysiloxane (B) is relative to the alkyl number contained by above-mentioned organopolysiloxane (B), and ratio, is preferably 0.0005 ~ 0.01(invention 7).
In foregoing invention (invention 4 ~ 7), the content of the linking agent (C) in above-mentioned remover combination, preferably can make the hydrosilyl groups number contained by linking agent (C) be calculated in molar ratio as the amount (invention 8) needed for 1.0 ~ 5.0 relative to the thiazolinyl number contained by organopolysiloxane (A) and organopolysiloxane (B).
2nd aspect, the invention provides the shaping stripping film of ceramic green, it peeling agent layer possessing base material and at least formed in the one side of above-mentioned base material, is characterized in that, above-mentioned peeling agent layer is (invention 9) that use above-mentioned remover combination (invention 1 ~ 8) to be formed.
Invention effect
Use the stripping film that obtains of remover combination of the present invention if adopted or adopt the shaping stripping film of ceramic green of the present invention, the coating of ceramic size can be made excellent, specifically, when peeling agent layer surface coated ceramic size and when making it dry, the thickness of the contraction of the coating end of ceramic size and this coating end can be suppressed thickening, namely suppress the generation that so-called end is shunk.In addition, use the stripping film that obtains of remover combination of the present invention if adopted or adopt the shaping stripping film of ceramic green of the present invention, the separability of the ceramic green that can make shaping is also excellent, only just ceramic green need can be stripped down from peeling agent layer with low peeling force.
Embodiment
Below, embodiments of the present invention are described.
Remover combination
The remover combination of present embodiment contains:
Organopolysiloxane (A), has at least 2 thiazolinyls in its 1 molecule and two side chains of at least 1 Siliciumatom in siloxane backbone has aryl; With
Organopolysiloxane (B), its not there is aryl and in 1 molecule only two ends there is thiazolinyl;
Preferably also containing linking agent (C) and/or catalyzer (D).
Organopolysiloxane (A) is the polymkeric substance of the silicon-containing compound represented by following general formula (a).
[changing 1]
In formula (a), l is the integer of more than 1.In addition, R 1and R 2for the alkyl of carbon number 1 ~ 12, such as, can enumerate, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group etc.R 1and R 2can be identical or different.R 1and R 2be preferably methyl.
In formula (a), m is the integer of more than 1.In addition, R 3and R 4for aryl, R 3and R 4can be identical or different, preferably identical.Like this, organopolysiloxane (A) be Siliciumatom in siloxane backbone two side chains on there is the structure of aryl.By this structure, when remover combination is coated on base material, in the peeling agent layer obtained, organopolysiloxane (A) is present in the substrate side of peeling agent layer more compared to organopolysiloxane (B), thinks can obtain effect described later by such structure.
As aryl, phenyl, benzyl, tolyl, o-Xylol base etc. can be enumerated, wherein, preferred phenyl.
In formula (a), n is the integer of more than 1 or more than 2.R 5~ R 8at least 2 be thiazolinyl, that is, in 1 molecule at least 2 be thiazolinyl.Such as, can be R 7and R 8both sides are thiazolinyl (n is more than 1), also can be R 7and R 8in a side be thiazolinyl, R 5and R 6in a side or both be thiazolinyl (n is more than 1), work as R 7and R 8during for functional group beyond thiazolinyl, can be R 5and R 6both sides are thiazolinyl (n is more than 1), or also can be R 5and R 6in a side be thiazolinyl (n is more than 2).Being explained, can be R 5and R 6both sides are compound and the R of thiazolinyl 5and R 6in a side be that the compound of thiazolinyl is mixed in together.Each R 5can be identical or different.In addition, each R 6can be identical or different.
As thiazolinyl, vinyl, allyl group, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl etc. can be enumerated, wherein, particularly preferably vinyl.
R 5and R 6in the functional group except thiazolinyl be the alkyl of carbon number 1 ~ 12, such as can enumerate, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group etc., be preferably methyl.As R 7and R 8in functional group except thiazolinyl, can enumerate and R 5and R 6identical alkyl, silanol group, hydrosilyl groups etc.
Aryl number contained by organopolysiloxane (A), relative to the alkyl number contained by organopolysiloxane (A), ratio, is preferably 0.01 ~ 0.5, is particularly preferably 0.05 ~ 0.3.Be within the scope of this by making aryl number, can make, when remover combination is coated on base material, in the peeling agent layer obtained, organopolysiloxane (A) is present in the substrate side of peeling agent layer more compared to organopolysiloxane (B), thinks can obtain effect described later by such structure.
In addition, the thiazolinyl number contained by organopolysiloxane (A), relative to the alkyl number contained by organopolysiloxane (A), ratio, is preferably 0.005 ~ 0.1, is particularly preferably 0.01 ~ 0.05.By making thiazolinyl number have more than 2 in 1 molecule, be preferably in above-mentioned scope, the crosslinking structure that the cross-linking density that it can be made to be formed help aftermentioned effect is high.
The matter average molecular weight of organopolysiloxane (A) is necessary for 100000 ~ 800000, is preferably 150000 ~ 600000, is particularly preferably 200000 ~ 380000.Be explained, the matter average molecular weight in this specification sheets is the value by polystyrene conversion adopting gel permeation chromatography (GPC) method to measure.
If the matter average molecular weight of organopolysiloxane (A) is less than 100000, then, when being coated on base material by remover combination, film contraction etc. can occur, coating is deteriorated, and is difficult to obtain uniform condition of surface.In addition, if the matter average molecular weight of organopolysiloxane (A) is more than 800000, then the viscosity of remover combination rises, and is difficult to be dissolved in diluting solvent.
On the other hand, organopolysiloxane (B) is the polymkeric substance of the silicon-containing compound represented by following general formula (b).
[changing 2]
In formula (b), p is the integer of more than 1.In addition, R 9and R 10for the alkyl of carbon number 1 ~ 12, such as, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group etc. can not be aryl or thiazolinyl.R 9and R 10can be identical or different.R 9and R 10be preferably methyl.By making this organopolysiloxane (B) not containing aryl, when remover combination is coated on base material, in the peeling agent layer obtained, organopolysiloxane (B) be present in peeling agent layer more compared to organopolysiloxane (A) with base material opposing face side (face side of peeling agent layer), think and can obtain effect described later by such structure.
In formula (b), R 11at least 1 be thiazolinyl, and R 12at least 1 be thiazolinyl.That is, organopolysiloxane (B) has thiazolinyl at two ends.As thiazolinyl, vinyl, allyl group, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl etc. can be enumerated, wherein, particularly preferably vinyl.R 12in thiazolinyl beyond functional group be the alkyl of carbon number 1 ~ 12, such as can enumerate, methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group etc., be preferably methyl.Each R 11can be identical or different.In addition, each R 12can be identical or different.
By make organopolysiloxane (B) in its 1 molecule only two ends there is thiazolinyl, the crosslinking structure that the cross-linking density that helps aftermentioned effect is low can be formed.
Thiazolinyl number contained by organopolysiloxane (B) is preferably 0.0005 ~ 0.01 relative to the alkyl number ratio contained by organopolysiloxane (B), is particularly preferably 0.001 ~ 0.005.
The matter average molecular weight of organopolysiloxane (B) is preferably 50000 ~ 800000, is particularly preferably 100000 ~ 700000, and more preferably 300000 ~ 500000.
If the matter average molecular weight of organopolysiloxane (B) is less than 50000, be then likely difficult to be formed with the crosslinking structure that the cross-linking density that helps aftermentioned effect is low.In addition, if the matter average molecular weight of organopolysiloxane (B) is more than 800000, then the viscosity of remover combination rises, and is likely difficult to be dissolved in diluting solvent.And the solidified nature of remover combination is deteriorated, and siloxanes also likely increases to the transfer amount of ceramic green.
Organopolysiloxane (A) is 40 ~ 98 quality % relative to the solids component ratio of the total amount of organopolysiloxane (A) and organopolysiloxane (B), is preferably 50 ~ 95 quality %.If the solids component ratio of organopolysiloxane (A) is outside above-mentioned scope, even if then the coating of ceramic size is good, the separability of ceramic green also can significantly decline.
As linking agent (C), as long as can make organopolysiloxane (A) and/or organopolysiloxane (B) that crosslinked linking agent occurs, just be not particularly limited, be preferably beyond organopolysiloxane (A) and organopolysiloxane (B), there is the organopolysiloxane that at least 2 are bonded to the hydrogen atom on Siliciumatom in 1 molecule.As this organopolysiloxane, such as, can enumerate the dimethyl siloxane-methyl hydride siloxane copolymers, the methylhydrogen polysiloxanes of trimethylsiloxy end-blocking, poly-(silicon hydride sesquioxyalkane) etc. of the dimethyl siloxane-methyl hydride siloxane copolymers of dimethylhydridosiloxy end-blocking, trimethylsiloxy end-blocking.
Matter average molecular weight as the organopolysiloxane of linking agent (C) is preferably 100 ~ 5000, is particularly preferably 500 ~ 2000.
The content of the linking agent (C) in the remover combination of present embodiment preferably can make: the number of the cross-linking functional group such as the hydrosilyl groups contained by linking agent (C) is calculated in molar ratio as the amount needed for 1.0 ~ 5.0 relative to the number of the thiazolinyl contained by organopolysiloxane (A) and organopolysiloxane (B), is particularly preferably and can makes the amount of this mol ratio needed for 1.5 ~ 3.0.
Linking agent (C) is cross-linked owing to can make organopolysiloxane (A) and/or organopolysiloxane (B), therefore can give stable separability to the peeling agent layer obtained.
As catalyzer (D), as long as the remover combination of present embodiment can be made to solidify, be just not particularly limited, wherein, preferred platinum group metal based compound.As platinum metals based compound, such as, can enumerate, the olefin(e)complex, palladium, rhodium etc. of microgranular platinum, the microgranular platinum be adsorbed in carbon powder carrier, Platinic chloride, alcohol modification Platinic chloride, Platinic chloride.By making remover combination contain this catalyzer (D), the curing reaction of this remover combination can be made more effectively to carry out.
The content of catalyzer (D) in the remover combination of present embodiment, relative to the total amount of the composition beyond catalyzer (D), is preferably about 1 ~ 1000ppm.
The remover combination of present embodiment, except mentioned component (A) ~ (D), can also contain reaction suppressor, adaptation rising agent etc.
By making remover combination described above according to the specified ratio containing above-mentioned organopolysiloxane (A) and organopolysiloxane (B), the peeling agent layer that the coating separability that is excellent, ceramic green simultaneously of ceramic size is also very excellent can be formed.Therefore, as long as the peeling agent layer formed by the remover combination of present embodiment, then peeling agent layer surface coated ceramic size and when making it dry, the coating end of ceramic size can be suppressed to shrink and the thickness of this coating end thickening (namely so-called end is shunk) and suppress phenomenon such as generation pin hole, crawling etc.In addition, even if when the ceramic green of the film like that intensity is low is shaping on this peeling agent layer, also under the condition of unfavorable conditions such as not cracking, break, with low-down peeling force, ceramic green can be stripped down from peeling agent layer.Although its principle is not yet clear, but as mentioned above, supposition be because, when organopolysiloxane (A) has aryl and organopolysiloxane (B) only has thiazolinyl at two ends, organopolysiloxane (A) is present in the substrate side of peeling agent layer more, and organopolysiloxane (B) is present in the side, top layer of peeling agent layer more, result, thinks the effect of end contraction, pin hole, crawling etc. of can being inhibited.。
(the shaping stripping film of ceramic green)
The shaping stripping film of ceramic green (below sometimes referred to as " stripping film ") of present embodiment, is made up of base material and the peeling agent layer that formed in the one side of base material.
As base material, be not particularly limited, any base material can be selected aptly from known base material.As this base material, such as, can enumerate, by the polyester such as polyethylene terephthalate or PEN; The polyolefine such as polypropylene or polymethylpentene; The film that the plastics such as polycarbonate, polyvinyl acetate are formed, base material can be individual layer, also can be the identical or different multilayer of more than 2 layers of kind.Wherein, preferred polyester film, particularly preferably polyethylene terephthalate film, the polyethylene terephthalate film of preferably two-way stretch further.Due to polyethylene terephthalate film adding man-hour, use time etc. in not easily produce dust etc., therefore, the ceramic size coating that can effectively prevent from such as being caused by dust etc. is bad.And then, by carrying out antistatic treatment to polyethylene terephthalate film, can improve and prevent from being coated with bad etc. effect.
In addition, in the substrate, in order to improve the adaptation with the peeling agent layer being arranged at its surface, as required, can implement to its one side or two sides the surface treatment or the undercoat process that utilize oxidation style or further provided for contouring method etc.As above-mentioned oxidation style, such as can enumerate Corona discharge Treatment, plasma discharge process, chromium oxide treatment (wet type), flame treating, hot blast process, ozonize, uviolizing process etc., in addition, as further provided for contouring method, such as, can enumerate sand-blast, spraying plating facture etc.These surface preparations can be selected according to the kind of base material film is suitable, generally speaking, from the viewpoint of effect and operability etc., preferably adopt Corona discharge Treatment method.
The thickness of base material is generally 10 ~ 300 μm, is preferably 15 ~ 200 μm, is particularly preferably 20 ~ 125 μm.
Peeling agent layer in present embodiment is formed by above-mentioned remover combination.Specifically, peeling agent layer contains the coating fluid of remover combination and organic solvent as required by coating in the one side of base material, and then drying makes it be solidified to form.As coating process, such as, can use gravure coating process, stick coating method, spraying method, spin-coating method, spread coating, rolling method, die coating methods etc.
Be not particularly limited as above-mentioned organic solvent, various organic solvent can be used.Such as can use the hydrocarbon compounds such as toluene, hexane, heptane, and acetone, ethyl acetate, butanone, methyl iso-butyl ketone (MIBK) and their mixture etc.
Preferably thermofixation is carried out to remover combination coated as mentioned above.Now, Heating temperature is preferably 90 ~ 140 DEG C, is preferably about 10 ~ 120 seconds heat-up time.
The thickness of peeling agent layer is not particularly limited, and is preferably 0.01 ~ 3 μm, is more preferably 0.03 ~ 1 μm.If the thickness of peeling agent layer is less than 0.01 μm, then owing to forming the difference of the material of peeling agent layer etc., sometimes can not give full play to the function as peeling agent layer.On the other hand, if the thickness of peeling agent layer is more than 3 μm, then, when stripping film being coiled into cylinder shape, often sticking together, sometimes producing unfavorable condition at extraction film.
For use stripping film described above, adopt slit die coating method or scraper plate coating method etc., by peeling agent layer surface coated ceramic size and make it dry, ceramic green is shaping.Now, the stripping film of present embodiment can suppress the generation of the thickness of the contraction of the coating end of ceramic size and this coating end thickening (namely so-called end is shunk), and can suppress the generation of pin hole or crawling.On the other hand, even if when the ceramic green of film like low for intensity is shaping on peeling agent layer, the unfavorable condition such as also can not to crack, break, as long as apply low peeling force, specifically be less than the peeling force of 13mN/100mm, just ceramic green can be stripped down from peeling agent layer.Like this, when adopting the stripping film of present embodiment, the coating of ceramic size is excellent, and meanwhile, the separability of ceramic green is also excellent.
Embodiment described above is to more easily understand the present invention, instead of in order to limit scope of the present invention.Therefore, each key element disclosed in above-mentioned embodiment is equivalent to also comprise the whole design variant and Equivalent that belong to the technology of the present invention category.
Such as, base material 1 and peeling agent layer opposition side surface or between base material 1 and peeling agent layer, can also other layers such as antistatic layer be set.
Embodiment
, further illustrate the present invention by embodiment etc. below, but scope of the present invention is not limited to these embodiments etc.
(embodiment 1)
To there are more than 2 vinyl in 1 molecule, and not containing organopolysiloxane (A) 95 mass parts that the part of vinyl is made up of dimethyl siloxane-diphenylsiloxane copolymer, not containing aryl, and in 1 molecule only two ends there is vinyl, other functional groups are organopolysiloxane (B) the 5 mass parts mixing of methyl, after adding the linking agent (C) be made up of the methylhydrogen polysiloxanes of trimethylsiloxy end-blocking, be the organic solvent diluting of principal constituent in order to toluene, preparation solid component concentration is the coating fluid of the remover combination of 1.5 quality %.Be explained, organopolysiloxane (A) is shown in table 1 relative to the solids component ratio (quality %) of the total amount of organopolysiloxane (A) and organopolysiloxane (B).
Herein, the matter average molecular weight of organopolysiloxane (A) is 360000, phenyl number (number relative to the methyl number contained by organopolysiloxane (A)) contained by organopolysiloxane (A) is calculated in molar ratio as 0.125, and the vinyl number (number relative to the methyl number contained by organopolysiloxane (A)) contained by organopolysiloxane (A) is calculated in molar ratio as 0.025.
In addition, the matter average molecular weight of organopolysiloxane (B) is 440000, and the vinyl number (number relative to the methyl number contained by organopolysiloxane (B)) contained by organopolysiloxane (B) is calculated in molar ratio as 0.0024.
On the other hand, the matter average molecular weight of linking agent (C) is 1000, and the content of the linking agent (C) in remover combination is calculated in molar ratio as the amount needed for 1.91 for making the hydrosilyl groups number contained by linking agent (C) relative to the vinyl number contained by organopolysiloxane (A) and organopolysiloxane (B).
By solids component ratio, platinum group catalyst (chemical industry society of SHIN-ETSU HANTOTAI system is added in above-mentioned coating fluid 100 mass parts, PL-50T) 7 mass parts, adopt Meyer rod coating method, the coating fluid obtained is coated on equably polymer PET (resin society of the Mitsubishi system of the two-way stretch as base material, ダ イ ア ホ イ Le T-100, thickness: 38 μm) on, be 0.1 μm to make dried thickness.Then, by hot air circulation type drying machine heat treated 60 seconds at 135 DEG C, silicone resin stripper is solidified, obtain closing at layers on substrates the stripping film having peeling agent layer.
(embodiment 2)
By organopolysiloxane (A) 90 mass parts and the mixing of organopolysiloxane (B) 10 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A) and organopolysiloxane (B), be 1.91, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(embodiment 3)
By organopolysiloxane (A) 70 mass parts and the mixing of organopolysiloxane (B) 30 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A) and organopolysiloxane (B), be 1.95, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(embodiment 4)
By organopolysiloxane (A) 50 mass parts and the mixing of organopolysiloxane (B) 50 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A) and organopolysiloxane (B), be 2.00, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 1)
Do not use organopolysiloxane (B), only use organopolysiloxane (A) 100 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A), be 1.90, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 2)
By organopolysiloxane (A) 99 mass parts and the mixing of organopolysiloxane (B) 1 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A) and organopolysiloxane (B), be 1.90, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 3)
By organopolysiloxane (A) 30 mass parts and the mixing of organopolysiloxane (B) 70 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A) and organopolysiloxane (B), be 2.11, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 4)
By organopolysiloxane (A) 10 mass parts and the mixing of organopolysiloxane (B) 90 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A) and organopolysiloxane (B), be 2.42, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 5)
Do not use organopolysiloxane (A), only use organopolysiloxane (B) 100 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (B), be 3.00, in addition, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 6)
To there are more than 2 vinyl in 1 molecule and organopolysiloxane (B) the 5 mass parts mixing that uses of organopolysiloxane (A ') 95 mass parts be not made up of dimethyl siloxane-methyl phenylsiloxane copolymer (on a side chain of siloxane backbone, there is aryl) containing the part of vinyl and embodiment 1, after adding the linking agent (C) be made up of the methylhydrogen polysiloxanes of trimethylsiloxy end-blocking, be the organic solvent diluting of principal constituent in order to toluene, preparation solid component concentration is the coating fluid of the remover combination of 1.5 quality %.Be explained, organopolysiloxane (A ') is shown in table 1 relative to the solids component ratio (quality %) of the total amount of organopolysiloxane (A ') and organopolysiloxane (B).
Herein, the matter average molecular weight of organopolysiloxane (A ') is 390000, phenyl number (number relative to the methyl number contained by organopolysiloxane (A ')) contained by organopolysiloxane (A ') is calculated in molar ratio as 0.012, and the vinyl number (number relative to the methyl number contained by organopolysiloxane (A ')) contained by organopolysiloxane (A ') is calculated in molar ratio as 0.019.
In addition, the content of the linking agent (C) in remover combination, is calculated in molar ratio as the amount needed for 2.53 for making the hydrosilyl groups number contained by linking agent (C) relative to the vinyl number contained by organopolysiloxane (A ') and organopolysiloxane (B).
Except using above-mentioned coating fluid, operation preparation coating fluid, makes stripping film similarly to Example 1.
(comparative example 7)
By organopolysiloxane (A ') 50 mass parts and the mixing of organopolysiloxane (B) 50 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A ') and organopolysiloxane (B), be 2.57, in addition, operate same with comparative example 6 prepares coating fluid, makes stripping film.
(comparative example 8)
Do not use organopolysiloxane (B), only use organopolysiloxane (A ') 100 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A '), be 2.53, in addition, operate same with comparative example 6 prepares coating fluid, makes stripping film.
(comparative example 9)
By organopolysiloxane (A ') 10 mass parts and the mixing of organopolysiloxane (B) 90 mass parts, add linking agent (C), make hydrosilyl groups number contained by linking agent (C) relative to the vinyl number ratio contained by organopolysiloxane (A ') and organopolysiloxane (B), be 2.76, in addition, operate same with comparative example 6 prepares coating fluid, makes stripping film.
(test example 1) (evaluation of ceramic size coating)
To barium titanate (BaTiO 3; Sakai chemical industry society system, BT-03) 100 mass parts, polyvinyl butyral (ponding chemical industry society system, エ ス レ ッ Network BKBM-2) 10 mass parts and dioctyl phthalate (DOP) (Northeast chemistry society system, dioctyl phthalate (DOP) ensures purity 1 grade) add mixed solution (mass ratio 6:4) 115 mass parts of toluene and ethanol in 5 mass parts, with ball mill by its blending dispersion, preparation ceramic size.
The peeling agent layer of the stripping film (wide: 300mm) of 48 hours is preserved at normal temperatures on the surface after manufacturing in embodiment and comparative example, use the ceramic size that die type coating machine (wide 250mm) even spread is above-mentioned, dried thickness is made to be 3 μm, then, at 80 DEG C, its dry 1 minute is made with drying machine.Manufacture the stripping film volume 300m with ceramic green thus.
To the volume of the stripping film with the ceramic green 300m obtained, range estimation confirms that whether end occurs in width end is shunk.Its result, is evaluated as zero by the sample not occurring to shrink end, the sample occurring to shrink end is evaluated as ×.And then range estimation is confirmed whether to occur can be shunk by the small film of the ceramic size visually seen, so-called pin hole or due to ceramic size coating thickness inequality caused by crawling.The sample that pin hole and the crawling that can with the naked eye find out does not occur is evaluated as zero, the sample that pin hole or crawling occur is evaluated as ×.Result is shown in table 1.
(test example 2) (evaluation of the separability of ceramic green)
After the stripping film with ceramic green obtained same with test example 1 is left standstill 24 hours in the atmosphere of room temperature 23 DEG C, humidity 50%, be cut into the size of 100mm × 100mm, paste on one side at it and count from ceramic green face side the acrylic adhesive tape (Dong electrician society system, 31B adhesive tape) that length is 100mm.This sample is fixed on flat board, stripping film face side is contacted with this flat board, will the end avris of acrylic adhesive tape be pasted with as downside, be arranged on electronic stripping tester (society of Shimadzu Seisakusho Ltd. system, AG-IS500N) according to inclination 45 °.Then, from be pasted with acrylic adhesive tape one end limit stripping film is stripped down from ceramic green, acrylic adhesive tape side is arranged on the fixture of electronic stripping tester.In this condition, with the peeling rate of 200mm/min, acrylic adhesive tape is vertically pulled upwardly, measures the peeling force (mN/100mm) when being peeled off by ceramic green from stripping film.Result is shown in table 1.
In addition, owing to being less than 13mN/100mm as the preferred peeling force of the shaping stripping film of ceramic green, the sample therefore peeling force recorded being less than 13mN/100mm is evaluated as zero, by peeling force be that the sample of more than 13mN/100mm is evaluated as ×.Result is shown in table 1.
Find out from the result shown in table 1, the stripping film obtained in embodiment 1 ~ 4, the coating of its ceramic size is excellent, as long as and apply low peeling force and just ceramic green can be peeled off, the separability of ceramic green is also excellent.On the other hand, the stripping film obtained in comparative example 1 ~ 9, although the coating of its ceramic size is excellent, only have applying high peeling force ceramic green could be peeled off, the separability of ceramic green is poor.
Industrial applicability
Remover combination of the present invention is applicable to the peeling agent layer forming the shaping stripping film of ceramic green.In addition, the shaping stripping film of ceramic green of the present invention can be used as the excellent and stripping film that the separability of ceramic green is also very excellent of the coating of ceramic size.

Claims (6)

1. remover combination, is characterized in that, contains:
Organopolysiloxane (A), has at least 2 thiazolinyls in its 1 molecule and two side chains of at least 1 Siliciumatom in siloxane backbone has aryl, and
Organopolysiloxane (B), its not there is aryl and in 1 molecule only two ends there is thiazolinyl;
Described organopolysiloxane (A) is 40 ~ 98 quality % relative to the solids component ratio of the total amount of described organopolysiloxane (A) and described organopolysiloxane (B),
The matter average molecular weight of described organopolysiloxane (A) is 100000 ~ 380000,
The matter average molecular weight of described organopolysiloxane (B) is 50000 ~ 500000,
Described matter average molecular weight is the value by polystyrene conversion adopting gel permeation chromatography,
Aryl number contained by described organopolysiloxane (A) is relative to the alkyl number contained by described organopolysiloxane (A), and ratio is 0.05 ~ 0.5,
Thiazolinyl number contained by described organopolysiloxane (B) is relative to the alkyl number contained by described organopolysiloxane (B), and ratio is 0.0005 ~ 0.01.
2. remover combination according to claim 1, is characterized in that, also contains platinum metals based compound as catalyzer.
3. remover combination according to claim 1, is characterized in that, also containing linking agent (C).
4. remover combination according to claim 1, it is characterized in that, thiazolinyl number contained by described organopolysiloxane (A) is relative to the alkyl number contained by described organopolysiloxane (A), and ratio is 0.005 ~ 0.1.
5. remover combination according to claim 3, it is characterized in that, the content of the linking agent (C) in described remover combination is calculated in molar ratio as the amount needed for 1.0 ~ 5.0 for making the hydrosilyl groups number contained by linking agent (C) relative to the thiazolinyl number contained by organopolysiloxane (A) and organopolysiloxane (B).
6. the shaping stripping film of ceramic green, it peeling agent layer possessing base material and at least formed in the one side of described base material, is characterized in that, described peeling agent layer uses the remover combination described in any one of claim 1 ~ 5 to be formed.
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