CN1355833A - Pressure-sensitive adhesive tape for provisionally fixing green sheet for ceramic electronic part and process for producing ceramic electronic part - Google Patents
Pressure-sensitive adhesive tape for provisionally fixing green sheet for ceramic electronic part and process for producing ceramic electronic part Download PDFInfo
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- CN1355833A CN1355833A CN00808721A CN00808721A CN1355833A CN 1355833 A CN1355833 A CN 1355833A CN 00808721 A CN00808721 A CN 00808721A CN 00808721 A CN00808721 A CN 00808721A CN 1355833 A CN1355833 A CN 1355833A
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- adhesive tape
- self adhesive
- polymkeric substance
- binder composition
- ceramic electronic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
A pressure-sensitive adhesive tape for provisionally fixing green sheets for ceramic electronic parts which comprises a base film and a pressure-sensitive adhesive layer formed on one or both sides of the film. The pressure-sensitive adhesive layer is made of an adhesive composition comprising a pressure-sensitive adhesive and 1 to 30 wt% polymer having crystallizable side chains. The polymer is obtained mainly from an alkyl acrylate and/or an alkyl methacrylate each having a linear alkyl side chain having 16 or more carbon atoms. The pressure-sensitive adhesive tape has high tackiness when used for provisionally fixing a green sheet for ceramic electronic parts, can be easily peeled off when the work is taken out, and does not foul the work.
Description
Technical field
The present invention relates to a kind of interim adherent self adhesive tape that is used for, this self adhesive tape is used to prepare ceramic electronic component such as laminated ceramic capacitor, multilayer ceramic inductor block, resistor, ferrite (ferrites), sensor element, thermistor, varistor or piezoelectric ceramics, particularly cuts into application in the step of many small pieces at the ceramic sheet material that will give birth to (promptly being untreated).
Background technology
For example, can prepare laminated ceramic capacitor in the following manner.
Launch thinly to prepare living ceramic sheet material with the slurry of scraper ceramic powder.After many electrodes were imprinted on living sheet surface, with many sheet material laminations that these are given birth to and combine, the result formed the laminate of green sheet.Then, after beginning hot pressing this laminate, longitudinally this laminate obtains many laminated ceramic small pieces with transverse cutting with parting tool such as dicer or cutting knife type blade.These small pieces of sintering (being also referred to as " workpiece ") form outer electrode on the end face of resulting workpiece then.
In the abovementioned steps of the laminate that obtains combination and laminate is cut in the step of living small pieces, by using self adhesive tape, the small pieces of giving birth to are temporarily fixed at are used for workpiece being peeled off from the self adhesive tape of substrate surface after sheet material fixed base material and the cutting.When peeling off, need to reduce the cohesive strength between workpiece and the self adhesive tape.If cohesive strength can not reduce fully, then following point may appear.
(1) because laminate sintering not as yet itself, the bounding force between each layer may be not enough.Therefore, when when small pieces are peeled off on the self adhesive tape surface, because the strong excessively cohesive strength of self adhesive tape splitting can take place in that laminate is inner.
(2) even without splitting takes place, bonding coat also may remain in the small pieces bottom as impurity.As a result, when in the technology of small pieces being sent into subsequently, impurity can cause adhesion (blocking).Because impurity residue also carries out sintering, therefore since sintering organic materials can produce space or crack.
Therefore, reliability of products and productive rate affect adversely.
Therefore, for example disclosed by the day disclosure No.6-79812 of objection (Opposition), commonly used is a kind of self adhesive tape that comprises heat foamable type bonding coat.In the bonding coat of this self adhesive tape, contain whipping agent.As a result, by the heating self adhesive tape, whipping agent plays the effect that reduces contact area between self adhesive tape and the workpiece, thereby can easily peel off workpiece from the self adhesive tape surface after the incised layer rolled-up stock.
Yet because there is such problem in the blowing temperature height of self adhesive tape, promptly when the heating self adhesive tape, the tackiness agent of laminate inside can evaporate stains workpiece, perhaps because the hardness that the evaporation layer rolled-up stock of tackiness agent can not obtain to be scheduled to before preliminary sintering.And because foaming is inhomogeneous, cohesive strength can not fully reduce, and causes workpiece not peel off from self adhesive tape.
Disclosure of the Invention
The self adhesive tape that the present invention is used for the green sheet that provisional adhesion ceramic electronic component uses comprises a kind of base material film and at least one lip-deep a kind of bonding coat of this base material film, wherein this bonding coat comprises a kind of binder composition, this binder composition contains the crystallizable polymkeric substance of side chain of pressure sensitive adhesive and about 1-30 weight %, in binder composition.
On the two sides of base material film, provide in the situation of binder layer, can constitute binder layer to following pressure sensitive adhesive as the pressure sensitive adhesive on second, for example:
The binder composition of caoutchouc adhesive, synthetic rubber binder, phenylethylene/butadiene latex based adhesives, segmented copolymer type thermoplastic elastomer, isoprene-isobutylene rubber, polyisobutene, acryloid cement and vinyl ether co-polymer.
In one embodiment, the crystallizable polymkeric substance of this side chain comprise wherein contain 16 or the straight chained alkyl of more carbon atoms as the alkyl acrylate of side chain and/or alkyl methacrylate as main ingredient.
In one embodiment, this binder composition has such performance, and it makes this binder composition peel off from the green sheet of ceramic electronic component easily when about 35 ℃ or higher temperature.
In one embodiment, the crystallizable polymkeric substance of this side chain has temperature range and is narrower than 15 ℃ fusing point.
In one embodiment, when be heated to about 35 ℃ or when higher binder composition to the cohesive strength of stainless steel plate be its during at 23 ℃ to the cohesive strength of stainless steel plate about 10% or lower, perhaps be about 10g/25mm or lower.
In one embodiment, the weight-average molecular weight of described polymkeric substance is about 3000-about 25000.
The method that the present invention prepares ceramic electronic component may further comprise the steps: the laminate of living ceramic sheet material is adhered on the base material by self adhesive tape; Laminate is cut into small pieces; And peel off small pieces from the surface of base material and also heat self adhesive tape simultaneously, wherein self adhesive tape comprises a kind of base material film and at least one lip-deep bonding coat of this base material film, this bonding coat comprises a kind of binder composition, this binder composition contains the crystallizable polymkeric substance of side chain of pressure sensitive adhesive and about 1-30 weight %, in binder composition, wherein the crystallizable polymkeric substance of this side chain comprise wherein contain 16 or the straight chained alkyl of more carbon atoms as the alkyl acrylate of side chain and/or alkyl methacrylate as main ingredient, and wherein when be heated to about 35 ℃ or when higher binder composition to the cohesive strength of stainless steel plate be its during at 23 ℃ to the cohesive strength of stainless steel plate about 10% or lower.
Use self adhesive tape, will be printed on the laminate that the ceramic green sheet material of electrode obtains thereon by lamination and be fixed on the base material, cut then.Because self adhesive tape provides good viscosity, so laminate can not be stripped from the moment.Remove in the workpiece from self adhesive tape after the incised layer rolled-up stock, with self adhesive tape be heated to setting temperature or on the time, make workpiece easily to peel off from self adhesive tape.
Particularly, because the binder composition in the self adhesive tape contains pressure sensitive adhesive and in the crystallizable polymkeric substance of side chain of about 1-30 weight % of binder composition, wherein the crystallizable polymkeric substance of this side chain comprise wherein contain 16 or the straight chained alkyl of more carbon atoms as the alkyl acrylate of side chain and/or alkyl methacrylate as main ingredient, this polymkeric substance becomes crystalline or amorphous by change temperature slightly from optional temperature in the reversible mode, thereby makes the viscosity generation material alterations of small pieces.
Therefore, when binder layer is heated to predetermined temperature or on the time, the cohesive strength of binder layer reduces rapidly.Therefore, be adhered to the green sheet that is used for ceramic electronic component on the self adhesive tape and after carrying out cutting operation, can heat self adhesive tape, the result reduces it significantly and is used for the viscosity of the green sheet of ceramic electronic component, thereby small pieces (ceramic electronic component) can be easily and tape stripping.
This paper employed " green sheet that is used for ceramic electronic component " had both comprised green sheet, comprise substantially the laminate of the green sheet of being made up of pottery again, it is used for the production process of ceramic electronic component such as laminated ceramic capacitor, multilayer ceramic inductor block, resistor, ferrite, sensor element, thermistor, varistor or piezoelectric ceramics.
According to the present invention, can control the viscosity of the self adhesive tape of interim adhesion ceramic electronic component green sheet simply by the temperature that changes self adhesive tape.Therefore, when interim adhesion ceramic electronic component green sheet, can obtain big cohesive strength; When wanting workpiece to remove, can easily peel off by heating.Because workpiece does not tarnish, so can improve the reliability of ceramic electronic component.
Particularly, by using weight-average molecular weight for about 3, the side chain crystallizable polymers of 000-about 25,000 can be adhered to the tackiness agent of usefulness temporarily, and its viscosity significantly reduces when heating and changes along with time lapse hardly.
Implement best mode of the present invention
(base material film)
According to the present invention, the example that can be used for the employed base material film of provisional adhesion self adhesive tape comprises the sheet material of being made up of the synthetic resin film of the about 500 μ m of the about 5-of single or multiple lift thickness, described synthetic resins such as polyethylene, polypropylene, polyester, polymeric amide, polycarbonate, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethene-polypropylene copolymer, polyvinyl chloride.
In order to improve the bounding force with bonding coat, can carry out Corona discharge Treatment, Cement Composite Treated by Plasma, impact (blast) processing, chemical milling processing, prime treatment etc. to the surface of base material film.
On at least one surface of this base material film, the bonding coat that lamination is made up of binder composition as described below.
This binder composition can contain side chain crystallizable polymers and the pressure sensitive adhesive that the melting temperature scope is narrower than 15 ℃.The character of this tackiness agent makes the green sheet of itself and ceramic electronic component or other material have viscosity and in temperature T 1 time bonding with it, and than T1 high about 15 ℃ or more temperature T 2 time, the viscosity of the green sheet of itself and ceramic electronic component or other material significantly reduces.
(pressure sensitive adhesive)
The example of contained pressure sensitive adhesive comprises for example following tackiness agent in the binder composition:
Caoutchouc adhesive; The phenylethylene/butadiene latex based adhesives; ABA segmented copolymer type thermoplastic elastomer (wherein A represents thermoplastic polystyrene end block, and B represents rubber intermediate block such as polyisoprene, polyhutadiene or gathers (ethylene/butylene)); Isoprene-isobutylene rubber; Polyisobutene; Acryloid cement such as polyacrylic ester and vinyl-acetic ester/acrylate copolymer; And vinyl ether co-polymer such as polyvinyl methyl ether, polyvinyl ethyl ether and polyvinyl isobutyl ether.
Particularly, use acrylic pressure sensitive adhesives, the interaction with polymkeric substance be provided, make polymkeric substance under preset temperature, fully disperse, having viscosity, and when be heated to predetermined temperature or when higher this polymkeric substance have good rippability.Preferred acrylic pressure sensitive adhesives is made up of vinylformic acid (ethyl hexyl) ester, Hydroxyethyl acrylate etc. basically.Its example comprises the multipolymer of the propylene ester 2-hydroxy methacrylate that contains 80-95 parts by weight of acrylic 2-(ethyl hexyl) ester and 5-20 weight part.
(the crystallizable polymkeric substance of side chain)
The crystallizable polymkeric substance of the side chain that is contained in the binder composition preferably has temperature range and is narrower than 15 ℃ fusing point.
Term as used herein " fusing point " is meant that the equilibrium process that causes initial a part of polymkeric substance of arranging with orderly fashion becomes the temperature when unordered.
In one embodiment, the fusing point of polymkeric substance is preferably about 30 ℃-Yue 100 ℃, more preferably about 35 ℃-Yue 65 ℃.Preferred fusing occurs fast, promptly appears at less than about 15 ℃ and preferred less than in about 10 ℃ narrow relatively temperature range.Preferred polymers is crystallization promptly.For this reason, can heavily sneak into seeding agent or crystalline catalysts to polymkeric substance.
After the use, by binder layer being heated to the temperature of a little higher than use temperature, this binder layer can be easily from the sur-face peeling of the green sheet of ceramic electronic component.About 100 ℃ of the about usually 40-of Heating temperature, about 70 ℃ of preferably about 40-, more preferably from about 50-is about 70 ℃.
The crystallizable polymkeric substance of the side chain that is contained in the binder composition comprise wherein contain 16 or the straight chained alkyl of more a plurality of carbon atoms as the acrylate of side chain and/or methacrylic ester as wherein a kind of component.
As comprising 16 or the straight chained alkyl of more carbon atoms as the acrylate and/or the methacrylic ester (hereinafter being also referred to as " (methyl) acrylate ") of side chain, preferred (methyl) acrylate with the straight chained alkyl that comprises 16-22 carbon atom that uses is as (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid stearyl or (methyl) vinylformic acid docosyl ester.
And, also can use (methyl) acrylate, as (methyl) vinylformic acid triacontyl ester with the straight chained alkyl that comprises 16-30 carbon atom.
Replace or except comprise 16 or the methacrylic ester of straight chained alkyl as side chain of more carbon atoms, can also use following monomer:
At least aly be selected from following monomer: acrylate, (methyl) acrylate, acrylamide derivative, methacrylamide derivatives, vinyl ether derivative, vinyl ester derivative, or alpha-olefin or its have 16 or more carbon atoms and to small part by the derivative of fluorizated aliphatic group; And styrene derivatives etc. with alkyl of 16 or more carbon atoms.
Especially, the acrylate, (methyl) acrylate, acrylamide derivative, methacrylamide derivatives etc. that preferably have the straight chain fat base of 16 or more carbon atoms.More preferably have acrylate, (methyl) acrylate, acrylamide derivative, methacrylamide derivatives of the straight chain fat base of 14-22 carbon atom etc.The acrylate and the methacrylic ester that especially preferably have the straight chain fat base of 14-18 carbon atom.
In addition, can use and followingly have the monomer of functional group as the copolymerization component.Monomeric example with this functional group comprise be selected from following at least a: vinylformic acid, methacrylic acid, methylene-succinic acid, methylfumaric acid, citraconic acid, fumaric acid, toxilic acid, methylene-succinic acid mono alkyl ester, methylfumaric acid mono alkyl ester, citraconic acid mono alkyl ester, fumaric acid mono alkyl ester, maleic acid mono alkyl ester, vinylformic acid 2-hydroxy methacrylate, acrylamide, Methacrylamide, tertiary butyl amino-ethyl methacrylic ester etc.When using these monomers, note comprising 16 or the straight chained alkyl of more carbon atoms as the amount of the methacrylic ester of side chain, these monomeric amounts can be about 30% weight of about 1-as the raw-material whole monomer total amounts of base polymer.
List the fusing point of the side chain crystallizable polymers that obtains from the monomer of the straight chained alkyl that comprises 16-22 carbon atom below:
Used monomer fusing point (℃)
Vinylformic acid C16 alkyl ester 36
Methacrylic acid C16 alkyl ester 26
Vinylformic acid C18 alkyl ester 49
Methacrylic acid C18 alkyl ester 39
Vinylformic acid C20 alkyl ester 60
Methacrylic acid C20 alkyl ester 50
Vinylformic acid C22 alkyl ester 71
Methacrylic acid C22 alkyl ester 62
The preferred example of the polymkeric substance that is contained in the binder composition comprises:
(1) multipolymer of 80-98 parts by weight of acrylic acid stearyl, 2-20 parts by weight of acrylic acid and 2-10 weight part lauryl mercaptan;
(2) multipolymer of 5-90 parts by weight of acrylic acid docosyl ester, 5-90 parts by weight of acrylic acid stearyl, 1-10 parts by weight of acrylic acid and 2-10 weight part lauryl mercaptan; With
(3) multipolymer of 80-98 parts by weight of acrylic acid docosyl ester, 2-20 parts by weight of acrylic acid and 2-10 weight part lauryl mercaptan.
The amount of crystallizable polymers in binder composition is about 1% weight-Yue 30% weight, about 20% weight of preferably about 5%-, about 15% weight of especially preferably about 5%-.If the amount of contained polymkeric substance is less than 1% weight or be higher than 30% weight, then can not obtain the aforementioned effect that obtains by this polymkeric substance.
The specified molecular weight of this crystallizable polymers is the important factor that used binder composition has the mode of the viscosity of temperature dependent and/or cohesive strength among decision the present invention.Especially, the lower molecular weight crystallizable polymers loses cohesive strength when heating.For example, reduced by 90% or more the test condition of the detailed cohesive strength of introduction (below) in the cohesive strength in 60 ℃ of whens heating than the cohesive strength under the room temperature (23 ℃).
Therefore, the preferably about 3000-of the weight-average molecular weight of this polymkeric substance is about 25000, and more preferably from about 4000-about 15000.If it is about 25000 that the weight-average molecular weight of this polymkeric substance surpasses, viscosity reduces the response of heating insufficient.If it is about 3000 that the weight-average molecular weight of this polymkeric substance is lower than, cohesive strength changes in fact along with taking place time lapse, and this is not preferred.
Binder composition of the present invention can be prepared as follows: in compatible solvent, mix pressure sensitive adhesive and crystallizable polymers, and to wherein adding optional component, as softening agent, tackifier, filler, linking agent etc.Regulate solid content to required viscosity, and this mixture of blend becomes uniform mixture up to it.Deaeration from mixture after the blend.
The example of tackifier comprises special rosin ester type tackifier, terpene phenolic type tackifier, petroleum resin type tackifier, high hydroxyl value rosin ester type tackifier, hydrogenated wood rosin glycerol ester type tackifier etc.
The example of linking agent comprises: isocyanate type composition such as tetramethylene diisocyanate, hexamethylene diisocyanate, by add three resulting affixtures of methylene phenylene diisocyanate or polymeric polyisocyanate in TriMethylolPropane(TMP); Epoxy compounds such as Sorbitol Powder polyglycidyl ether, Polyglycerine polyglycidyl ether, tetramethylolmethane polyglycidyl ether, two glycerine polyglycidyl ethers, glycerine polyglycidyl ether, neopentylglycol diglycidyl ether or resorcinol diglycidyl ether; Aziridine type compound such as TriMethylolPropane(TMP)-three-β-aziridine time base (aziridynyl) propionic ester, tetramethylol methane-three-β-aziridine time basic propionic ester, N, N '-hexa-methylene-1,6-two (1-aziridine carboxylic acid amides), N, N '-Toluene-2,4-diisocyanate, 4-two (1-aziridine carboxylic acid amides), N, N '-ditan-4,4 '-two (1-aziridine carboxylic acid amides) or TriMethylolPropane(TMP)-three-β-(2-methylaziridine carboxylic acid amides) propionic ester; And melamine type compound such as hexa methoxy methylol melamine.These can use separately or two or more are used in combination.The content of linking agent is preferably the 0.1-5 weight part, and 0.1-3 weight part more preferably is with respect to 100 weight part base polymer meters.
In order on base material film, to provide temperature active binder composition, general normal use knife coater, roller coating machine, calender courter, point type (comma) coating machine.According to the viscosity of the thickness and the material of coating, can use gravure coating machine or rod-type coating machine.Can apply this binder composition as the mode in the transfer printing by the shifting process from demoulding sheet sheet material.Said composition can be coated with (promptly not having other other material) only, or in suitable solvent, or as emulsion or latex-coating.Therefore, form bonding coat by binder composition.
Consideration is antipollution problem during storage or commercial distribution, preferably with spacer bonding protection bonding coat, adheres to up to bonding coat on the laminate surface of green sheet.Spacer can be by paper, plastic film such as polypropylene screen or polyester film, or thin, have a manufacturing such as flexible tinsel.Use releasing agent that spacer is carried out surface treatment if desired, make it to peel off easily.
Next, description is as the preparation method of the ceramic multilayer capacitor of ceramic electronic component.
At first, launch thinly to prepare living ceramic sheet material and to print electrode with the slurry of scraper in the sheet surface of giving birth to ceramic powder.With many sheet material laminations that these are given birth to and combine, to form the laminate of green sheet.Then, this laminate is fixed on the base material by self adhesive tape of the present invention.Because temperature lower (20 ℃ according to appointment-Yue 40 ℃) at the moment, this laminate sticks on the bonding coat of self adhesive tape fully.
Then, hot pressing and cut this laminate.At this moment, workpiece not with can factory peel off, perhaps transfer on any green sheet that needs cutting.After many ceramic layer rolled-up stock small pieces form in this way, remove resulting workpiece from self adhesive tape.Workpiece carries out pre-sintering process and sintering process then.At this moment, above-mentioned preset temperature or on the heating this self adhesive tape, thereby can easily peel off workpiece from self adhesive tape.Then, the sintering workpiece also forms outer electrode on the outer face of workpiece, thereby obtains small pieces type laminated ceramic capacitor.
About the method for heating self adhesive tape, can heat the keeper (base material) of self adhesive tape or band by following method, for example:
Band or keeper are placed on the hot plate; Top blast warm air (as warm air) thereon from airheater or moisture eliminator; It is placed in the baking oven; Steam blowing in the above; With radiowave it is heated; Or heat with lamp (infrared or far infrared).
Especially, preferably the green sheet of under the temperature of the fusing point that is lower than used polymkeric substance ceramic electronic component being used is bonded on the self adhesive tape, and peels off small pieces from the surface of self adhesive tape under the temperature that is being equal to or higher than melting point polymer after the cutting.
Power when in addition, guaranteeing preferably also that peeling force is reduced to temperature more than or equal to the fusing point of side chain crystallizable polymers about 10% or littler.Preferably when being heated to about 35 ℃ or higher temperature binder composition to the cohesive strength of stainless steel plate be its during at 23 ℃ to the cohesive strength of stainless steel plate about 10% or lower, perhaps be about 10/g/25mm or lower.
Although laminated ceramic capacitor is illustrated as ceramic electronic component, the present invention is not limited to this.For example, in preparation fine ceramics device such as IC circuit card, ferrite, sensor element or rheostatic process, the present invention can be used as in the step that green sheet with ceramic electronic component cuts into many small pieces and is used for interim adherent self adhesive tape.
(embodiment)
Specifically describe the present invention below by illustrative embodiment.Any " umber " quoted in the following description all is meant " weight part ".
A. the preparation of polymkeric substance
(synthetic embodiment 1)
At first, 95 parts of vinylformic acid stearyl, 5 parts of vinylformic acid, 5 parts of lauryl mercaptans and 1 part of Kayaester HP-70 (Kayaku Akzo K.K) are mixed.Under 80 ℃, stir the mixture and made these monomer polymerizations in 5 hours.Its weight-average molecular weight of resulting polymkeric substance is about 8,000, and fusing point is 50 ℃.
(synthetic embodiment 2)
At first, in 150 parts of ethyl acetate/heptane (70/30), mix 92 parts of 2-EHAs, 8 parts of vinylformic acid 2-hydroxyl ethyl esters and 0.3 part of Trigonox 23-C70 (Kayaku Akzo K.K).Under 55 ℃, stirred the mixture 3 hours, and be heated to 80 ℃ then, and add 0.5 part of Kayaester HP-70.Stir this mixture and made these monomer polymerizations in 2 hours.Its weight-average molecular weight of resulting polymkeric substance about 600,000.
B. adhere to the preparation of the self adhesive tape of ceramic electronic component green sheet temporarily
(embodiment 1)
With 5 parts: above-mentioned synthetic embodiment 1 of 100 parts mixed and 2 polymkeric substance that obtained.In this polymers soln, add Coronate L45 (NIPPON Polyurethane IndustryCo., Ltd. makes), make that Coronate L45 is 0.5 part for the polymkeric substance of 100 parts of synthetic embodiment 2 as linking agent.Then, use roller coating machine to apply this polymers soln on polyethylene terephthalate (PET) film (about 100 μ m) surface, Corona discharge Treatment has been carried out on described PET film surface.Have the provisional adherent self adhesive tape that is used for of isolating sheet material thereby obtain one, this self adhesive tape has the bonding coat (thickness: about 30 μ m) of an acrylic type.
Self adhesive tape to the provisional adhesion usefulness of gained carries out following evaluation test.
(1) peeling force
According to JIS C2107, measure the peeling force of 180 degree between self adhesive tape and the SUS.Test is carried out under 23 ℃ and 60 ℃ respectively.
(2) state of peeling off of workpiece
From the SUS surface, after the release adhesive band,, measure the lip-deep foreign matter content of SUS according to TDS (thermal desorption spectrum) technology.In addition, measure by the cross section of visual inspection workpiece and exist/do not have interlaminar failure in the workpiece.The results are shown in Table 1.In table, " zero " represents good quality production, and " * " represents unacceptable product.
(embodiment 2)
Except adding CoronateL45 in the polymers soln of gained in embodiment 1 as the feasible polymkeric substance of linking agent for 100 parts of synthetic embodiment 2, Coronate L45 is 1.0 especially, prepares the self adhesive tape of provisional adhesion usefulness with the method that is similar to embodiment 1.The mode similar to embodiment 1 assessed the peeling force and the workpiece of the self adhesive tape of resulting provisional adhesion usefulness and peeled off state.The results are shown in Table 1.
(embodiment 3)
Except adding Coronate L45 in the polymers soln of gained in embodiment 1 as the feasible polymkeric substance of linking agent for 100 parts of synthetic embodiment 2, Coronate L45 is 3.0 especially, prepares the self adhesive tape of provisional adhesion usefulness with the method that is similar to embodiment 1.The mode similar to embodiment 1 assessed the peeling force and the workpiece of the self adhesive tape of resulting provisional adhesion usefulness and peeled off state.The results are shown in Table 1.
(comparing embodiment 1)
In 100 parts of above-mentioned synthetic embodiment 2, add 3 parts of Coronate L45 (NIPPON Polyurethane Industry Co., Ltd. makes) in the polymers soln of gained as linking agent.Then, use roller coating machine to apply this polymers soln on PET film (about 100 μ m) surface, Corona discharge Treatment has been carried out on described PET film surface.Have the provisional adherent self adhesive tape that is used for of isolating sheet material thereby obtain one, this self adhesive tape has the bonding coat (thickness: about 50 μ m) of an acrylic type.
The mode similar to embodiment 1 assessed the peeling force and the workpiece of the self adhesive tape of resulting provisional adhesion usefulness and peeled off state.The results are shown in Table 1.
(comparing embodiment 2)
In 100 parts of above-mentioned synthetic embodiment 2, add 6 parts of Coronate L45 (NIPPON Polyurethane Industry Co., Ltd. makes) in the polymers soln of gained as linking agent.Then, use roller coating machine to apply this polymers soln on PET film (about 100 μ m) surface, Corona discharge Treatment has been carried out on described PET film surface.Have the provisional adherent self adhesive tape that is used for of isolating sheet material thereby obtain one, this self adhesive tape has the bonding coat (thickness: about 50 μ m) of an acrylic type.
The mode similar to embodiment 1 assessed the peeling force and the workpiece of the self adhesive tape of resulting provisional adhesion usefulness and peeled off state.The results are shown in Table 1.
(comparing embodiment 3)
With respect to being purchased product (RIBAALPHA 3194MS, Nitto Denko Corporation make), assess the cohesive strength and the impurity performance of resulting self adhesive tape in the mode similar to embodiment 1.The results are shown in Table 1.
Table 1
| Tackiness agent | Peeling force (g/25mm) | Workpiece is peeled off state | |||
| ??23℃ | ??60℃ | Interlaminar failure | Residual | ||
| Embodiment 1 | Heat sensitive adhesive | ??100 | 10 or lower | ????○ | ????○ |
| Embodiment 2 | Heat sensitive adhesive | ??30 | 10 or lower | ????○ | ????○ |
| Embodiment 3 | Heat sensitive adhesive | ??20 | 10 or lower | ????○ | ????○ |
| Comparative example 1 | Pressure sensitive adhesive | ??300 | ?200 | ????× | ????× |
| Comparative example 2 | Pressure sensitive adhesive | ??300 | ?100 | ????× | ????× |
| Comparative example 3 | Pressure sensitive adhesive | ??30 | ?10 | ????○ | ????× |
" zero " represents good quality production, and " * " represents unacceptable product.
The surface of comparative example 1 and 2 self adhesive tape and the separability of workpiece surface are poor, cause interlaminar failure.In comparative example 1-3, also observe the pollution on the workpiece surface.On the contrary, the resistance to crocking after the separability of embodiment 1-3 and the heating (60 ℃) is all good, and initial adhesion intensity (23 ℃) is improved.
(embodiment 4)
Below, carry out following test and study the molecular weight of side chain crystallizable polymers contained in the bonding coat and the corresponding peeling force of interim self adhesive tape that heating has this binder layer and reduce relation between the ratio.
The monomer mixture of lauryl mercaptan (polymerization retarder) gained that adds different umbers in 95 parts of vinylformic acid stearyl and 5 parts of acrylic acid mixtures was stirred 5 hours down at 80 ℃, make these monomer polymerizations.The result obtains weight-average molecular weight and is respectively 2,000,4,000,8,000,15,000 and 19,000 polymkeric substance (respectively at being shown polymkeric substance 1-5 in the table 2).
In every kind of polymkeric substance of 15 parts of above-mentioned preparations, sneak into the polymkeric substance that 85 parts of above-mentioned synthetic embodiment 2 are obtained.In these polymers solns, add Coronate L45 (NIPPONPolyurethane Industry Co., Ltd. makes), make that Coronate L45 is 0.5 part for the polymkeric substance of 100 parts of synthetic embodiment 2 as linking agent.Then, (thickness: about 50 μ m) apply this polymers soln on the surface, described polyester film surface has been carried out delustring and has been handled at polyester film to use roller coating machine.Thereby obtain to have the provisional adherent self adhesive tape that is used for of isolating sheet material, every kind of self adhesive tape all has the bonding coat (thickness: about 20 μ m) of acrylic type.
The provisional adherent self adhesive tape of gained is cut into the strip that width is 25mm, to be used as test block.
Then, the pressurization of the binder layer of aforementioned test block is adhered on the SUS plate, the surface of this plate is with the #280 polishing, and (width: 45mm, load: 2kg) to-and-fro movement thereon is 4 times to make rubber rollers under 23 ℃.After the bonding, allow test block leave standstill 20 minutes.One end of each test block is peeled off on the directions of 180 degree with the speed that 300mm/ divides, and measures the Resistance Value of feeling when peeling off, as the peeling force under 23 ℃.
In addition, being placed on the hot plate that is heated to 60 ℃ in advance, and left standstill 20 minutes with the test block that is similar to method for preparing.One end of test block is peeled off on the direction of 180 degree with the speed that 300mm/ divides, and measures the Resistance Value of feeling when peeling off, as 60 ℃ peeling force.The results are shown in Table 2 for it.
Table 2＜embodiment 4 〉
| Sample number | Molecular weight | Peeling force (g/25mm) | |
| ??23℃????60℃ | Reduced rate from 23 ℃ to 60 ℃ | ||
| Polymkeric substance 1 | ????2000 | ??60g?????5g | ??????92％ |
| Polymkeric substance 2 | ????4000 | ??150g????10g | ??????93％ |
| Polymkeric substance 3 | ????8000 | ??180g????8g | ??????96％ |
| Polymkeric substance 4 | ????15000 | ??160g????10g | ??????94％ |
| Polymkeric substance 5 | ????19000 | ??150g????30g | ??????80％ |
As known from Table 2, if the molecular weight of the crystallizable polymkeric substance of side chain is too big, peeling force does not reduce during heating, thereby causes low reduced rate.
(embodiment 5)
Below, carry out that the molecular weight of side chain crystallizable polymers contained in the bonding coat is studied in following test and because the passage of time has the relation of the peeling force of the self adhesive tape of this bonding coat between changing temporarily.
The method that is similar to embodiment 4 is cut into the strip that width is 25mm to the provisional adherent self adhesive tape that is used for of gained, to be used as test block.
Measure the peeling force of these test blocks of 23 ℃ with the method that is similar to embodiment 4.
Then, the test block of analogous products is being left in 23 ℃ isothermal/wait in the wet room 2 months, measuring the peeling force of these test blocks 23 ℃ the time with the method that is similar to embodiment 4.
The results are shown in Table 3 for it.In table 3, the velocity of variation in 2 months, with preparation after ratio that measure immediately, that be defined as 100 value represent.
Table 3＜embodiment 5 〉
| Sample number | Molecular weight | The test value of peeling force (g/25mm) | |
| After the preparation after immediately preparation February | 2 months velocity of variation | ||
| Polymkeric substance 1 | ?2000 | ??60g???????????????5g | ????-33％ |
| Polymkeric substance 2 | ?4000 | ??150g??????????????10g | ????-17％ |
| Polymkeric substance 3 | ?8000 | ??180g??????????????8g | ????-11％ |
| Polymkeric substance 4 | ?15000 | ??160g??????????????10g | ????+3％ |
| Polymkeric substance 5 | ?19000 | ??150g??????????????30g | ????-3％ |
As known from Table 3, if the molecular weight of the crystallizable polymkeric substance of side chain is little, then the viscosity of self adhesive tape reduces slightly between staging life.
Industrial applicibility
The invention provides a kind of adhesive tape and a kind of method for preparing ceramic electronic component of interim adhesion ceramic electronic component green sheet, so that the adhesion strength of adhesive tape is enough to not cause disengaging or the dislocation of small pieces, until the cutting step of green sheet is finished, and the reduction of the adhesion strength when realizing peeling off workpiece is not in order to produce interlaminar failure and not residual any residue.
Claims (9)
1. a self adhesive tape that is used for temporarily adhering to the ceramic electronic component green sheet comprises a kind of base material film and is being provided at least one lip-deep bonding coat of this base material film,
Wherein said bonding coat comprises a kind of binder composition, and this binder composition comprises the crystallizable polymkeric substance of side chain of pressure sensitive adhesive and about 1-30 weight %, in binder composition.
2. claim 1 is used for provisional adherent self adhesive tape, the crystallizable polymkeric substance of wherein said side chain comprises alkyl acrylate and/or the alkyl methacrylate as main component, this alkyl acrylate and/or alkyl methacrylate have 16 or the straight chained alkyl of more carbon atoms as side chain.
Claim 1 be used for provisional adherent self adhesive tape, wherein said binder composition has such performance, this performance makes binder composition peel off from the green sheet of ceramic electronic component easily when about 35 ℃ or higher temperature.
Claim 1 be used for provisional adherent self adhesive tape, wherein the crystallizable polymkeric substance of this side chain has temperature range and is narrower than 15 ℃ fusing point.
Claim 1 be used for provisional adherent self adhesive tape, wherein this binder composition when being heated to about 35 ℃ or higher temperature to the cohesive strength of stainless steel plate, be its in the time of 23 ℃ to the cohesive strength of stainless steel plate about 10% or lower.
Claim 1 be used for provisional adherent self adhesive tape, wherein the weight-average molecular weight of this polymkeric substance is about 3000-about 25000.
7. method for preparing ceramic electronic component, this method may further comprise the steps:
The green sheet laminate of pottery is adhered on the base material by self adhesive tape;
This laminate is cut into small pieces; And in the described self adhesive tape of heating, these small pieces are peeled off from the surface of self adhesive tape,
Wherein this self adhesive tape comprises a kind of base material film and is being provided at least one lip-deep bonding coat of this base material film, this bonding coat comprises a kind of binder composition, this binder composition contains the crystallizable polymkeric substance of side chain of pressure sensitive adhesive and the about 30 weight % of about 1-, in binder composition, and wherein this binder composition when being heated to about 35 ℃ or higher temperature to the cohesive strength of stainless steel plate be its during at 23 ℃ to the cohesive strength of stainless steel plate about 10% or lower.
8. the method for preparing ceramic electronic component of claim 7, wherein the crystallizable polymkeric substance of this side chain comprise wherein contain 16 or the straight chained alkyl of more carbon atoms as the alkyl acrylate of side chain and/or alkyl methacrylate as main ingredient.
9. the method for preparing ceramic electronic component of claim 7, wherein the weight-average molecular weight of this polymkeric substance is about 3000-about 25000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16450999A JP4391623B2 (en) | 1999-06-10 | 1999-06-10 | Temporary adhesive tape for raw sheet for ceramic electronic component and method for manufacturing ceramic electronic component |
| JP164509/99 | 1999-06-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1355833A true CN1355833A (en) | 2002-06-26 |
| CN1272396C CN1272396C (en) | 2006-08-30 |
Family
ID=15794522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008087210A Expired - Lifetime CN1272396C (en) | 1999-06-10 | 2000-06-09 | Pressure-sensitive adhesive tape for provisionally fixing green sheet for ceramic electronic part and process for producing ceramic electronic part |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4391623B2 (en) |
| KR (1) | KR100457652B1 (en) |
| CN (1) | CN1272396C (en) |
| MY (1) | MY132153A (en) |
| TW (1) | TWI265189B (en) |
| WO (1) | WO2000077113A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105073932A (en) * | 2013-04-05 | 2015-11-18 | 霓达株式会社 | Temporary fixing double-sided adhesive tape and temporary fixing method for workpiece using same |
| CN106047197A (en) * | 2015-04-14 | 2016-10-26 | 霓达株式会社 | Temperature sensitive adhesive sheet for manufacturing ceramic electronic component and method for manufacturing ceramic electronic component |
| CN106047231A (en) * | 2015-04-03 | 2016-10-26 | 霓达株式会社 | Temperature sensitive adhesive |
| CN107418461A (en) * | 2016-05-17 | 2017-12-01 | 霓达株式会社 | Response to temperature adhesive |
| CN108300370A (en) * | 2016-09-09 | 2018-07-20 | 霓达株式会社 | Thermo-sensitive bonding sheet and the manufacturing method for using its chip |
| CN110819253A (en) * | 2018-08-10 | 2020-02-21 | 日东电工株式会社 | Adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI302561B (en) * | 2004-01-28 | 2008-11-01 | Lg Chemical Ltd | Releasable adhesive composition |
| JP2006245353A (en) * | 2005-03-04 | 2006-09-14 | Nitta Ind Corp | Fastening adhesive tape, and method of manufacturing laminated ceramic capacitor |
| KR100843449B1 (en) * | 2006-08-31 | 2008-07-03 | 삼성전기주식회사 | Ceramic sheet product and its production method |
| JP5276314B2 (en) * | 2007-12-21 | 2013-08-28 | 東京応化工業株式会社 | Adhesive composition and adhesive film |
| JP5408869B2 (en) * | 2007-12-25 | 2014-02-05 | 京セラ株式会社 | Adhesive resin composition and method for producing ceramic substrate using the same |
| KR101341405B1 (en) * | 2009-07-02 | 2014-01-02 | 니타 가부시키가이샤 | Inorganic sealing film-attached adhesive tape, and method for transferring inorganic sealing film |
| JP5639446B2 (en) * | 2010-11-09 | 2014-12-10 | ニッタ株式会社 | Easy peelable adhesive sheet and easy peelable adhesive tape |
| KR20130142405A (en) * | 2012-06-19 | 2013-12-30 | 삼성디스플레이 주식회사 | Display device and method of manufacturing a display device |
| JP7271169B2 (en) * | 2018-12-27 | 2023-05-11 | 日東電工株式会社 | Adhesive sheet |
| JP7358272B2 (en) * | 2019-02-21 | 2023-10-10 | マクセル株式会社 | Adhesive tape and its usage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990013420A1 (en) * | 1989-05-11 | 1990-11-15 | Landec Labs, Inc. | Temperature-activated adhesive assemblies |
| AU1441692A (en) * | 1991-02-12 | 1992-09-07 | Landec Corporation | Temperature zone specific pressure-sensitive adhesive compositions, and adhesive assemblies and methods of use associated therewith |
| JPH09208924A (en) * | 1996-02-05 | 1997-08-12 | Nitta Ind Corp | Hold-back agent for material to be worked and installing and removing of material to be worked using the same |
| JP3717584B2 (en) * | 1996-03-14 | 2005-11-16 | ニッタ株式会社 | Easy peelable label |
| JP3717583B2 (en) * | 1996-03-14 | 2005-11-16 | ニッタ株式会社 | Easily peelable label and its peeling method |
| JP3485412B2 (en) * | 1996-03-15 | 2004-01-13 | ニッタ株式会社 | Temporary adhesive tape for laminated ceramic capacitor laminating process and method for producing laminated ceramic capacitor |
| JPH09249858A (en) * | 1996-03-19 | 1997-09-22 | Nitta Ind Corp | Tacky tape for dicing semiconductor wafer |
| JPH09270580A (en) * | 1996-03-29 | 1997-10-14 | Sumitomo Kinzoku Electro Device:Kk | Manufacture of multilayer ceramic board |
| JP3565411B2 (en) * | 1999-06-10 | 2004-09-15 | ニッタ株式会社 | Temporary adhesive tape for raw sheet for ceramic electronic component and method for producing ceramic electronic component |
-
1999
- 1999-06-10 JP JP16450999A patent/JP4391623B2/en not_active Expired - Lifetime
-
2000
- 2000-06-09 MY MYPI20002604A patent/MY132153A/en unknown
- 2000-06-09 KR KR10-2001-7015873A patent/KR100457652B1/en active IP Right Grant
- 2000-06-09 CN CNB008087210A patent/CN1272396C/en not_active Expired - Lifetime
- 2000-06-09 WO PCT/JP2000/003796 patent/WO2000077113A1/en active IP Right Grant
- 2000-06-09 TW TW089111282A patent/TWI265189B/en not_active IP Right Cessation
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105073932A (en) * | 2013-04-05 | 2015-11-18 | 霓达株式会社 | Temporary fixing double-sided adhesive tape and temporary fixing method for workpiece using same |
| CN105073932B (en) * | 2013-04-05 | 2017-09-22 | 霓达株式会社 | The method of temporarily fixing of interim fixation double-sided adhesive tape and the machined object using the adhesive tape |
| TWI636112B (en) * | 2013-04-05 | 2018-09-21 | 霓塔股份有限公司 | Double adhesive tape for temporary fixing and temporary fixing method of workpiece using the tape |
| CN106047231A (en) * | 2015-04-03 | 2016-10-26 | 霓达株式会社 | Temperature sensitive adhesive |
| CN106047231B (en) * | 2015-04-03 | 2018-05-11 | 霓达株式会社 | Thermo-sensitive adhesive |
| CN106047197A (en) * | 2015-04-14 | 2016-10-26 | 霓达株式会社 | Temperature sensitive adhesive sheet for manufacturing ceramic electronic component and method for manufacturing ceramic electronic component |
| CN107418461A (en) * | 2016-05-17 | 2017-12-01 | 霓达株式会社 | Response to temperature adhesive |
| CN108300370A (en) * | 2016-09-09 | 2018-07-20 | 霓达株式会社 | Thermo-sensitive bonding sheet and the manufacturing method for using its chip |
| CN110819253A (en) * | 2018-08-10 | 2020-02-21 | 日东电工株式会社 | Adhesive sheet |
| CN110819253B (en) * | 2018-08-10 | 2023-04-21 | 日东电工株式会社 | Pressure-sensitive adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000077113A1 (en) | 2000-12-21 |
| TWI265189B (en) | 2006-11-01 |
| CN1272396C (en) | 2006-08-30 |
| JP2000351946A (en) | 2000-12-19 |
| KR100457652B1 (en) | 2004-11-18 |
| MY132153A (en) | 2007-09-28 |
| JP4391623B2 (en) | 2009-12-24 |
| KR20020034089A (en) | 2002-05-08 |
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