CN110499116A - Bonding sheet - Google Patents
Bonding sheet Download PDFInfo
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- CN110499116A CN110499116A CN201910411223.XA CN201910411223A CN110499116A CN 110499116 A CN110499116 A CN 110499116A CN 201910411223 A CN201910411223 A CN 201910411223A CN 110499116 A CN110499116 A CN 110499116A
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- Prior art keywords
- adhesive
- heat
- adhesive phase
- substrate
- methyl
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- 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
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
[project] provides a kind of bonding sheet, has heat-peelable adhesive band, and the heat-peelable adhesive band has substrate and adhesive phase, and adhesive phase is not easily susceptible to the influence of the heat applied from substrate side, even if adhesive phase is also unlikely to deteriorate for roll-to-roll process.[solution] bonding sheet of the invention successively has: the 1st adhesive phase, the 1st substrate, the 2nd adhesive phase and the 2nd substrate, 1st adhesive phase and the 1st substrate constitute heat-peelable adhesive band, 2nd adhesive phase and the 2nd substrate constitute laminated portions A, and laminated portions A is configured in a manner of it can remove from the heat-peelable adhesive band.
Description
Technical field
The present invention relates to bonding sheets.
Background technique
As the bonding used in process for manufacturing electronic component etc. for the purpose for being fixed temporarily processed product
Band, it is known to show adhesiveness when being fixed temporarily, be shown as fissility easily when not needing be fixed by heating
The adhesive tape (for example, patent document 1) of fissility.The adhesive that such adhesive tape is generally configured with substrate and is set on substrate
Layer.In addition, after substrate and adhesive phase stacking are formed laminated body, which is supplied sometimes when manufacturing above-mentioned adhesive tape
In inspection operation, adhesive phase manufacturing procedure.The above-mentioned stacking with conveying roller conveying strip is mostly used in such process greatly
The so-called roll-to-roll process of body.At this point, generate sometimes as with frictional heat caused by the contact of conveying roller etc., the spy of adhesive phase
Property occur it is rotten.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-131507 bulletin
Summary of the invention
Problems to be solved by the invention
The present invention is made to solve the problems, such as above-mentioned existing, it is intended that providing a kind of bonding sheet, this is viscous
It closes piece and has the heat-peelable adhesive band with substrate and adhesive phase, adhesive phase is not easily susceptible to the heat applied from substrate side
It influences, even if adhesive phase is also unlikely to deteriorate for roll-to-roll process.
The solution to the problem
Bonding sheet of the invention successively has: the 1st adhesive phase, the 1st substrate, the 2nd adhesive phase and the 2nd substrate, and the 1st
Adhesive phase and the 1st substrate constitute heat-peelable adhesive band, and the 2nd adhesive phase and the 2nd substrate constitute laminated portions A, should
Laminated portions A is configured in a manner of it can remove from the heat-peelable adhesive band.
In 1 embodiment, above-mentioned laminated portions A with a thickness of 10 μm or more.
In 1 embodiment, the gel fraction of above-mentioned 2nd adhesive phase is 20 weight of weight %~100 %.
In 1 embodiment, to poly terephthalic acid second two after above-mentioned laminated portions A is heated 30 minutes at 100 DEG C
The bonding force A2 of alcohol ester film is relative to normality bonding force A1 of the laminated portions A to pet film
10 times or less.
In 1 embodiment, above-mentioned laminated portions A is to the normality bonding force A1 of pet film
0.05N/20mm~5N/20mm.
According to another aspect of the present invention, it is supplied to the delivery method of heat-peelable adhesive band.The delivery method is to have
The delivery method of the heat-peelable adhesive band of 1st substrate and the 1st adhesive phase, the delivery method include: by A layers of laminated portions
It is laminated on the 1st substrate side, the heat-peelable adhesive band with laminated portions A is conveyed.
The effect of invention
In accordance with the invention it is possible to provide a kind of bonding sheet, has the heat-peelable adhesive with substrate and adhesive phase
Band, adhesive phase is not easily susceptible to the influence of the heat applied from substrate side, even if adhesive phase is not also variable for roll-to-roll process
Matter.
Detailed description of the invention
Fig. 1 is the schematic cross-section of the bonding sheet of an embodiment of the invention.
Description of symbols
10 heat-peelable adhesive bands
11 the 1st adhesive phases
12 the 1st substrates
20 laminated portions A
21 the 2nd adhesive phases
22 the 2nd substrates
100 bonding sheets
Specific embodiment
A. the overall structure of bonding sheet
Fig. 1 is the schematic cross-section of the bonding sheet of an embodiment of the invention.Bonding sheet 100 successively has: the 1st is viscous
Mixture layer 11, the 1st substrate 12, the 2nd adhesive phase 21 and the 2nd substrate 22.1st adhesive phase 11 and the 1st substrate 12 constitute hot soarfing
Release adhesive tape 10.2nd adhesive phase 21 and the 2nd substrate 22 constitute laminated portions A20.Laminated portions A20 with can from hot soarfing from
The mode that type adhesive tape 10 is removed configures.Although it is not shown, but bonding sheet can also contain other any suitable layers.
In the present invention, has laminated portions A20 in 12 side of the 1st substrate of heat-peelable adhesive band 10, so as to protect
1st adhesive phase 11 is from the warm that applies from 12 side of the 1st substrate (being essentially the side laminated portions A20).More specifically, it is needing
By heat-peelable adhesive band 10 for roll-to-roll process (for example, the inspection of adhesive level, processing of adhesive level etc.)
In the case where, by heat-peelable adhesive band 10 with the heat-peelable adhesive with the laminated portions A20 for being configured at 12 side of the 1st substrate
The form of band 10 (that is, bonding sheet 100) for the technique, thus, it is possible to protect the 1st adhesive phase 11 be not subjected to due to conveying
Temperature rises caused by friction of roller etc. influences.When completing heat-peelable adhesive band 10 by defined process, laminated section
A20 is divided to be stripped, heat-peelable adhesive band 10 for example can be used as being fixed temporarily in electronic component manufacturing process and be used with band.
According to the present invention, by having the laminated portions A20 being laminated in a releasable manner, so as to prevent heat-peelable adhesive band
The heat deterioration of 10 adhesive phase (that is, the 1st adhesive phase), and as heat-peelable adhesive band 10, it can be made and meet reality
The thickness appropriate of the purposes on border.Heat-peelable adhesive band 10 can be with band laminated portions during until for use
The form of the heat-peelable adhesive band 10 (that is, bonding sheet 100) of A20 is taken care of.
In 1 embodiment, above-mentioned bonding sheet can be provided with strip.
B. heat-peelable adhesive band
Heat-peelable adhesive band has the feature for reducing or disappearing by heating bonding force.As such heat-releasable
The form of adhesive tape, is not particularly limited, for example, the band with the adhesive phase comprising heat-expandable microsphere, tool can be enumerated
There is the band etc. of the adhesive phase of heating curable.Use above-mentioned heat-peelable adhesive band as such as electronic component (such as ceramics
Capacitor) processing when, in the case where being fixed temporarily with piece of machining object, to the machining object implement as defined in processing when, performance
It is fixed temporarily required adhesiveness out, when after processing from machining object by heat-peelable adhesive band, by heating, bonding force is reduced
Or disappear, show good fissility.In 1 embodiment, heat-peelable adhesive band has substrate (the 1st substrate) and packet
Adhesive phase (the 1st adhesive phase) containing adhesive A and heat-expandable microsphere.Hereinafter, the representative as heat-peelable adhesive band
Example is illustrated the heat-peelable adhesive band with the 1st adhesive phase comprising heat-expandable microsphere.
Heat-expandable microsphere in 1st adhesive phase is expandable at the specified temperature.For such comprising thermal expansivity
The adhesive phase of microballoon, by heating, heat-expandable microsphere foaming, to be generated in adhesive surface (i.e. the 1st adhesive layer surface)
Bumps, bonding force are reduced or are disappeared.
Bonding force of the above-mentioned heat-peelable adhesive band to pet film (for example, 25 μm of thickness)
(before heating) is preferably 0.1N/20mm or more, more preferably 1.0N/20mm~50N/20mm, further preferably 2.0N/20mm
~20N/20mm.When for such range, for example, can obtain being fixed temporarily used in the manufacture as electronic component using piece
Useful heat-peelable adhesive band.Bonding force refers in the environment of 23 DEG C, by according to JIS Z 0237 in this specification:
The bonding of 2000 method (laminating condition: 2kg roller is 1 time round-trip, peeling rate: 300mm/ minutes, 180 ° of peel angle) measurement
Power.
The adhesive surface of above-mentioned heat-peelable adhesive band is amplexiformed after pet film and heating
Bonding force is preferably 0.2N/20mm or less, more preferably 0.1N/20mm or less.In this specification, to heat-peelable adhesive band
Heating refers to the heating under the temperature-time that heat-expandable microsphere expansion or foaming reduce to bonding force.The heating is, for example,
The heating in 1 minute~10 minutes at 70 DEG C~270 DEG C.
The thickness of above-mentioned heat-peelable adhesive band is preferably 30 μm~500 μm, more preferably 40 μm~300 μm.
B-1. the 1st adhesive phase
The thickness of above-mentioned 1st adhesive phase is preferably 1 μm~30 μm, more preferably 1 μm~20 μm, further preferably 1 μ
M~10 μm.When for such range, the positional shift that can prevent adherend and sinking to the 1st adhesive phase can be obtained
Heat-peelable adhesive band.Scale, vernier caliper, micrometer can be used to measure in the thickness for constituting each layer of bonding sheet.In addition,
The microscopes such as electron microscope, optical microscopy, atomic force microscope can be used.In turn, can according to the difference of composition come
Differentiate the interface of adjacent layer and measures the thickness of each layer.As the method for discrimination at interface, for example, Raman spectrum point can be enumerated
The spectrum analysis such as analysis, infrared spectrum analysis, X-ray photoelectron spectroscopic analysis；Substance assistant laser desorpted ionized flight time matter
Compose the methods of mass spectrums such as (MALDI-TOFMS), time of flight secondary ion massspectrometry (TOF-SIMS).
The elasticity modulus that by Nanoindentation is obtained of above-mentioned 1st adhesive phase at 25 DEG C is preferably deficiency
100MPa, more preferably 0.1MPa~50MPa, further preferably 0.1MPa~10MPa.When for such range, it can obtain
To the positional shift that can prevent adherend and to the heat-peelable adhesive band of the 1st adhesive phase sunk to.Pass through Nanoindentation
Obtained elasticity modulus refers to, when throughout load, when continuously measuring when unloading by pressure head pressing in sample (for example, adhesive surface)
, load load and compression distance to pressure head, the elasticity modulus found out by obtained load loading-indentation depth curve.This
In specification, referred to by the elasticity modulus that Nanoindentation obtains, determination condition is set as load: 1mN, load unloading speed
Degree: 0.1mN/s, retention time: 1s and elasticity modulus obtained from being measured as described above.It should be noted that the 1st is viscous
In the case that mixture layer includes heat-expandable microsphere, the elasticity modulus of the 1st adhesive phase obtained by Nanoindentation is choosing
It selects and the elasticity modulus that the part of heat-expandable microsphere is measured by said determination method is not present.
(adhesive A)
As the adhesive A for constituting above-mentioned 1st adhesive phase, as long as effect of the invention can be obtained, can be used any
Adhesive appropriate.In 1 embodiment, as above-mentioned adhesive A, using curing adhesive, it is preferable to use active-energy
Ray curing adhesive.In another embodiment, as above-mentioned adhesive A, Pressuresensitive Adhesive is used.It is viscous as pressure sensitive
Mixture, for example, acrylic adhesives, elastomeric adhesive etc. can be enumerated.
(active energy ray curable adhesive)
As the resin material of above-mentioned active energy ray curable adhesive is constituted, for example, it is solid to enumerate ultraviolet light
Change system (adding rattan to regard work clearly, complex art center is published, (1989)), photocuring technology (technical information association compile (2000)),
Japanese Unexamined Patent Publication 2003-292916 bulletin, the resin material recorded in Japanese Patent 4151850 etc..More specifically, it can arrange
It enumerates comprising as female polymer of agent and the resin material of active energy beam reactive compounds (monomer or oligomer)
(R1), resin material (R2) comprising active energy beam reactive polymer etc..
As the above-mentioned polymer as female agent, for example, natural rubber, Oppanol, styrene can be enumerated
Butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, butyl rubber, polyisobutene
The rubber-based polymerics objects such as rubber, nitrile rubber (NBR)；Organic silicon-type polymer；Acrylic polymer etc..These polymer can
To be used singly or in combination two or more.
As above-mentioned active energy beam reactive compounds, for example, can enumerate with multiple acryloyl groups, methyl-prop
Enoyl-, vinyl, allyl, acetenyl etc. have the monomer or oligomer of the photoreactivity of the functional group of carbon-to-carbon multiple bond.
Wherein, it is preferable to use compound, more preferable use with respect to olefinically unsaturated functional group have the (first of respect to olefinically unsaturated functional group
Base) acrylic compounds.Compound with respect to olefinically unsaturated functional group is easy to generate free radical using ultraviolet light, therefore makes
When with the compound, being capable of forming can be with short time cured 1st adhesive phase.In addition, using having olefinic unsaturation function
When (methyl) acrylic compounds of group, it is capable of forming hardness (the specifically thermal expansivity with appropriateness after hardening
The hardness that microballoon can well foam) adhesive phase.As the monomer of photoreactivity or the concrete example of oligomer, three can be enumerated
Hydroxymethyl-propane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, pentaerythrite three (methyl) propylene
Acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six
(methyl) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, polyethylene glycol
Two (methyl) acrylate, carbamate (methyl) acrylate based compound etc. contain the compound of (methyl) acryloyl group；
This contains 2~5 aggressiveness of the compound of (methyl) acryloyl group；Deng.These compounds can be used alone or be applied in combination 2 kinds with
On.
In addition, epoxidized butadiene, methacrylic acid can be used as above-mentioned active energy beam reactive compounds
The monomers such as ethylene oxidic ester, acrylamide, vinylsiloxane；Or the oligomer being made of the monomer.Include these compounds
Resin material (R1) can use the high-energy rays such as ultraviolet light, electron beam and be cured.
In turn, as above-mentioned active energy beam reactive compounds, the organic salts such as salt and intramolecular can be used
The mixture of compound with multiple heterocycles.For the mixture, by active energy beam (for example, ultraviolet light, electronics
Beam) irradiation, organic salt cracks and generates ion, becomes and causes kind and cause the ring-opening reaction of heterocycle, can form three dimensional network
Shape structure.As above-mentioned organic salt, for example, salt compounded of iodine, phosphonium salt, antimonic salt, sulfonium salt, borate etc. can be enumerated.As above-mentioned
Intramolecular has the heterocycle in the compound of multiple heterocycles, can enumerate ethylene oxide, oxetanes, tetrahydrofuran
(oxolane), thiirane, aziridine etc..
It is living in the resin material (R1) of the above-mentioned polymer comprising as female agent and active energy beam reactive compounds
The content ratio of property energy-ray reactive compounds is preferably 0.1 weight relative to 100 parts by weight of polymer as female agent
Part~500 parts by weight, more preferably 1 parts by weight~300 parts by weight, further preferably 10 parts by weight~200 parts by weight.
As above-mentioned active energy beam reactive polymer, for example, can enumerate with acryloyl group, methacryl
Base, vinyl, allyl, acetenyl etc. have the polymer of the active energy beam reactive functional groups of carbon-to-carbon multiple bond.It is excellent
Using the compound (polymer) with respect to olefinically unsaturated functional group, more preferably using has acryloyl group or methacryl for choosing
(methyl) acrylic polymer of base.The concrete example of polymer as active energy-ray reactive functional groups, can
Enumerate the polymer etc. being made of multifunctional (methyl) acrylate.
Resin material (R2) comprising above-mentioned active energy beam reactive polymer can also contain above-mentioned active-energy
Ray reactive compounds (monomer or oligomer).
Above-mentioned active energy ray curable adhesive can be solidified by the irradiation of active energy beam.Above-mentioned heat-releasable
In adhesive tape, before making adhesive A solidification and after amplexiforming adherend, irradiates active energy beam and solidify adhesive A, thus
The adherend can be made closely sealed.As active energy beam, for example, gamma-rays, ultraviolet light, luminous ray, infrared can be enumerated
Line (heat ray), radio wave, alpha ray, β ray, electron beam, plasma stream, ionizing ray, particle ray etc..Active energy
Can be set as according to type of the resin material used etc. by measuring the conditions such as wavelength, the exposure of ray by any suitable
Part.For example, 10~1000mJ/cm of exposure can be irradiated2Ultraviolet light, solidify adhesive A.
(acrylic adhesives)
As above-mentioned acrylic adhesives, for example, can enumerate will use one kind or two or more (methyl) alkyl acrylate
Acrylic polymer (homopolymer or copolymer) acrylic adhesive as basic polymer of the base ester as monomer component
Agent etc..As the concrete example of (methyl) alkyl acrylate, (methyl) methyl acrylate, (methyl) acrylic acid second can be enumerated
Ester, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate,
(methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (first
Base) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (first
Base) nonyl acrylate, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) third
Olefin(e) acid hendecane base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid 14
Arrcostab, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester,
(methyl) such as (methyl) octadecyl acrylate, (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base esters
Acrylic acid C1-20 Arrcostab.Wherein it is possible to which it is preferable to use (the first of the alkyl of straight-chain or branched with carbon number 4~18
Base) alkyl acrylate.
For the purpose of the modification of cohesive force, heat resistance, bridging property etc., above-mentioned acrylic polymer as needed can be with
Comprising with can unit corresponding with the other monomers ingredient of above-mentioned (methyl) alkyl acrylate copolymer.As such monomer
Ingredient, for example, acrylic acid, methacrylic acid, carboxyethyl acrylates, acrylic acid carboxyl pentyl ester, itaconic acid, Malaysia can be enumerated
The carboxyl group-containing monomers such as acid, fumaric acid, crotonic acid；The anhydride monomers such as maleic anhydride, itaconic anhydride；(methyl) dihydroxypropyl second
Ester, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, the own ester of (methyl) dihydroxypropyl, (methyl) propylene
Sour hydroxyl monooctyl ester, (methyl) dihydroxypropyl last of the ten Heavenly stems ester, (methyl) dihydroxypropyl lauryl, methacrylic acid (4- hydroxymethyl
Cyclohexyl) the hydroxyls monomer such as methyl esters；Styrene sulfonic acid, allyl sulphonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic,
The lists containing sulfonic group such as (methyl) acrylamide propane sulfonic acid, (methyl) sulfopropyl acrylate, (methyl) propane sulfonic acid
Body；(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N- butyl (methyl) acrylamide, N- methylol (first
Base) (N- substitution) the amide system monomer such as acrylamide, N- hydroxymethyl-propane (methyl) acrylamide；(methyl) acrylic-amino second
(methyl) the acrylic acid ammonia such as ester, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) tbutylaminoethylacrylate
Base Arrcostab system monomer；(methyl) alkyl acrylates such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate
Oxygroup Arrcostab system monomer；N- N-cyclohexylmaleimide, N- isopropylmaleimide, N- lauryl maleimide, N-
The maleimides amine system monomer such as phenyl maleimide；N- methyl clothing health acid imide, N- ethyl clothing health acid imide, N- butyl clothing health
Acid imide, N- octyl clothing health acid imide, N-2- ethylhexyl clothing health acid imide, N- cyclohexyl clothing health acid imide, N- lauryl clothing
The clothing health imide series monomer such as health acid imide；N- (methyl) acryloyl-oxy methylene succinimide, N- (methyl) acryloyl
The succinimides such as base -6- oxygen hexa-methylene succinimide, eight methylene succinimide of N- (methyl) acryloyl group -8- oxygen
It is monomer；Vinyl acetate, vinyl propionate, n-vinyl pyrrolidone, methyl ethylene pyrrolidones, vinylpyridine,
Vinylpiperidone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, vinyl are disliked
The vinyl such as azoles, polyvinyl morpholinone, N- vinylcarboxylic acid amide type, styrene, α-methylstyrene, N- caprolactam
It is monomer；The cyanoacrylate monomers such as acrylonitrile, methacrylonitrile；(methyl) glycidyl acrylate etc. contains epoxy group third
Alkene acrylic monomer；(methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid polypropylene glycol ester, (methyl) methoxyethyl second
The glycol system acrylate monomers such as diol ester, (methyl) methoxyethyl polypropylene glycol ester；(methyl) acrylic acid tetrahydrofurfuryl
Ester, fluorine (methyl) acrylate, organosilicon (methyl) acrylate etc. have the acrylic acid of heterocycle, halogen atom, silicon atom etc.
Ester system monomer；Hexylene glycol two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl)
Acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, trimethylolpropane tris (first
Base) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, epoxy acrylate,
The polyfunctional monomers such as polyester acrylate, urethane acrylate；The olefin-baseds list such as isoprene, butadiene, isobutene
Body；Vinyl ether monomers such as vinyl ethers etc..These monomer components can be used alone or two or more is applied in combination.
(elastomeric adhesive)
It is as above-mentioned rubber adhesive, for example, can enumerate natural rubber；Polyisoprene rubber, styrene
Butadiene (SB) rubber, styrene isoprene (SI) rubber, styrene-isoprene-styrene block copolymer
(SIS) rubber, styrene butadiene styrene block copolymer (SBS) rubber, styrene ethylene butylene benzene second
Alkene block copolymer (SEBS) rubber, styrene ethylene propylene styrene block copolymer (SEPS) rubber, benzene second
Alkene ethylene-propylene block copolymer (SEP) rubber, reclaimed rubber, butyl rubber, polyisobutene, their modified body etc. are closed
At rubber；Deng the elastomeric adhesive as basic polymer.
(additive)
Above-mentioned adhesive A may include any suitable additive as needed.As the additive, for example, can enumerate
Initiator, crosslinking agent, tackifier, plasticizer, pigment, dyestuff, filler, antiaging agent, conductive material, antistatic agent, purple out
Ultraviolet absorbers, light stabilizer, removing regulator, softening agent, surfactant, fire retardant, antioxidant etc..
(heat-expandable microsphere)
In 1 embodiment, above-mentioned 1st adhesive phase includes heat-expandable microsphere.It is micro- comprising thermal expansivity by heating
As a result 1st adhesive phase of ball, heat-expandable microsphere expansion or foaming generate bumps in adhesive surface, bonding force is reduced or disappeared.
Use the heat-peelable adhesive band for having such 1st adhesive phase as when being fixed temporarily material, can be easily peeled off and face
When it is fixed after adherend.
As above-mentioned heat-expandable microsphere, as long as to pass through the microballoon of heat expandable or foaming, so that it may using any
Heat-expandable microsphere appropriate.As above-mentioned heat-expandable microsphere, it is, for example, possible to use contain to pass through in flexible shell
The microballoon of expansive substance is held in heating.Such heat-expandable microsphere can by any suitable method, such as coacervation,
Interfacial polymerization etc. manufactures.
Hold expansive substance as by heating, for example, can enumerate propane, propylene, butylene, normal butane, iso-butane,
Isopentane, neopentane, pentane, n-hexane, isohexane, heptane, octane, petroleum ether, the halide of methane, tetraalkyl silane etc.
Low-boiling point liquid；The azodicarbonamide to be gasified by thermal decomposition；Deng.
As the substance for constituting above-mentioned shell, for example, can enumerate by acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, α-second
The nitrile monomers such as oxygroup acrylonitrile, flumaronitrile；The carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid
Monomer；Vinylidene chloride；Vinyl acetate；(methyl) methyl acrylate, (methyl) ethyl acrylate, the positive fourth of (methyl) acrylic acid
Ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid ring
(methyl) acrylate such as own ester, (methyl) benzyl acrylate, P-carboxy ethyl acrylates；Styrene, α-methylstyrene, chlorine
The styrene monomers such as styrene；The amides such as acrylamide, substituted acrylamide, Methacrylamide, substituent methyl acrylamide
Monomer；Etc. compositions polymer.The polymer being made of these monomers can be homopolymer, or copolymer.As this
Copolymer, for example, vinylidene chloride-Methyl Methacrylate-acrylonitrile Copolymer, methyl methacrylate-propylene can be enumerated
Nitrile-methacrylonitrile copolymers, Methyl Methacrylate-acrylonitrile Copolymer, acrylonitrile-methacrylonitrile-itaconic acid copolymerization
Object etc..
As above-mentioned heat-expandable microsphere, inorganic system's foaming agent or organic system foaming agent can be used.It is sent out as inorganic system
Infusion, for example, ammonium carbonate, ammonium hydrogen carbonate, sodium bicarbonate, ammonium nilrite, sodium borohydride, various Azide species can be enumerated
Deng.In addition, as organic system foaming agent, for example, the chlorofluorinations alkane systems such as trichlorofluoromethane, dichloro list fluoromethane can be enumerated
Compound；The azo compounds such as azobis isobutyronitrile, azodicarbonamide, barium azodicarboxylate；Unifor, hexichol
The hydrazines based compound such as base sulfone -3,3 '-disulfonyl hydrazide, 4,4 '-oxygen bis- (benzene sulfonyl hydrazides), allyl bis- (sulfohydrazides)；To first Dai Ya
The semicarbazides based compounds such as phenyl sulfonyl amino urea, 4,4 '-oxygen bis- (benzenesulfonylamino ureas)；5- morpholinyl -1,2,3,4-
Three azole compounds such as thiatriazole；N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitroso is to benzene
Diformamide；Equal N- nitroso based compound etc..
Commercially available product can be used in above-mentioned heat-expandable microsphere.The concrete example of heat-expandable microsphere as commercially available product can arrange
Enumerate trade name " Matsumoto Microsphere " (grade: F-30, F-30D, F- of Matsumoto Yushi-Seiyaku Co., Ltd.
36D、F-36LV、F-50、F-50D、F-65、F-65D、FN-100SS、FN-100SSD、FN-180SS、FN-180SSD、F-
190D, F-260D, F-2800D), the trade name " Expancel " of Japan Fillite Co., Ltd. (grade: 053-40,
031-40,920-40,909-80,930-120), Kureha Kagaku Kogyo K.K.'s system " ダ イ フ ォ ー system " (grade: H750,
H850, H1100, S2320D, S2640D, M330, M430, M520), Sekisui Chemical Co., Ltd's system " ADVANCELL " (etc.
Grade: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501) etc..
Partial size before the heating of above-mentioned heat-expandable microsphere is preferably 0.5 μm~80 μm, more preferably 5 μm~45 μm, into
One step is preferably 10 μm~20 μm, particularly preferably 10 μm~15 μm.Therefore, illustrate that above-mentioned thermal expansivity is micro- with average grain diameter
When particle size before the heating of ball, preferably 6 μm~45 μm, more preferably 15 μm~35 μm.Above-mentioned partial size and average grain
Diameter is the value found out by the determination of particle size distribution in laser scattering method.
Above-mentioned heat-expandable microsphere preferably have until preferably 5 times or more, more preferable 7 times of cubical expansivity or more, into one
The intensity for the appropriateness that will not be ruptured until preferably 10 times or more of step.In the case where using such heat-expandable microsphere, by adding
Heat treatment, can be effectively reduced bonding force.
The content ratio of heat-expandable microsphere in above-mentioned 1st adhesive phase can be according to the reduction of desired bonding force
Etc. suitably setting.The content ratio of heat-expandable microsphere is relative to 100 weight of base polymer for forming the 1st adhesive phase
Part be, for example, 1 parts by weight~150 parts by weight, preferably 10 parts by weight~130 parts by weight, further preferably 25 parts by weight~
100 parts by weight.
B-2. the 1st substrate
As above-mentioned 1st substrate, for example, resin sheet, non-woven fabrics, paper, metal foil, woven fabric, sheet rubber, foaming can be enumerated
Piece, their laminated body (especially including the laminated body of resin sheet) etc..As the resin for constituting resin sheet, for example, can enumerate
Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) out
(PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, vinyl-vinyl acetate copolymer (EVA), polyamide
(nylon), fully aromatic polyamide (aromatic polyamides), polyimides (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine
It is resin, polyether-ether-ketone (PEEK) etc..As non-woven fabrics, non-woven fabrics comprising abaca etc. can be enumerated by with heat resistance
The obtained non-woven fabrics of natural fiber；The synthesis such as acrylic resin non-woven fabrics, polyvinyl resin non-woven fabrics, ester system resin non-woven fabrics
Resin non-woven fabrics etc..
The thickness of above-mentioned 1st substrate can be set according to desired intensity or flexibility and using purpose etc.
For any suitable thickness.The thickness of substrate is preferably 1000 μm or less, more preferably 1 μm~1000 μm, further preferably 1
μm~500 μm, particularly preferably 3 μm~300 μm, most preferably 5 μm~250 μm.
Surface treatment can be implemented in above-mentioned 1st substrate.As surface treatment, for example, sided corona treatment can be enumerated, at chromic acid
Reason, fire exposure, high-voltage electric shock exposure, ionization radial line processing, utilizes coating process of silane coupling agent etc. at ozone exposure.It carries out
When such surface treatment, the adaptation of the 1st adhesive phase and substrate can be improved.In particular with the painting of Organic coating materials
Cloth processing can improve adaptation and the 1st adhesive phase is not susceptible to fastening destruction in removing, therefore preferably.Surface treatment
Layer can be formed in the surface of the 1st adhesive phase side.
As above-mentioned Organic coating materials, for example, can enumerate plastics applies note in material II (published by CMC, (2004)) firmly
The material of load.It is preferable to use carbamate based polymer, more preferably use polyacrylic acid ammonia carbamate, Amino-Polyester formic acid
Ester or their precursor.This is because being coated with simplicity to the coating of substrate and can industrially select many kinds of substance, energy
It is enough inexpensively to obtain.The carbamate based polymer is, for example, by the monomer of isocyanate-monomer and alcoholic hydroxy (for example, containing
The acrylic compounds of hydroxyl or the ester compounds of hydroxyl) reaction mixture formed polymer.Organic coating materials
It may include the chain extenders such as polyamines, antiaging agent, oxidation stabilizers etc. and be used as any additive.The thickness of organic coating layer does not have
It is particularly limited to, for example, 0.1 μm~10 μm or so are suitable, preferably 0.1 μm~5 μm or so, more preferable 0.5 μm~5 μm left sides
It is right.Organic coating layer can for example be formed above-mentioned Organic coating materials using any suitable print process etc..
B-3. middle layer
Heat-peelable adhesive band can be also equipped with middle layer between above-mentioned 1st adhesive phase and the 1st substrate.As composition
The material of above-mentioned middle layer, for example, organic silicon-type polymer, epoxy based polymer, polycarbonate based polymer, second can be enumerated
Alkenyl based polymer, carbamate based polymer, polyester based polymer, polyolefin polymer, gathers acrylic polymer
The polymer materials such as amide based polymer, polyimides based polymer, unsaturated hydrocarbons based polymer.Use these polymer materials
When, it is suitable for selecting monomeric species, crosslinking agent, degree of polymerization etc., so as to be readily formed the centre with above-mentioned elasticity modulus
Layer.Above-mentioned polymer material can be used alone or two or more is applied in combination.
In 1 embodiment, as the material for constituting above-mentioned middle layer, it can consolidate using by the irradiation of active energy beam
The resin material of change.When using resin material by the radiation curable of active energy beam, it is in due course and irradiates work
Property energy-ray, so as to make middle layer high elastic modulus, and also transfiguration is easy for the adjustment of elasticity modulus.Using such
When material forms middle layer, in the attaching of bonding sheet, elasticity is low, flexibility is high, treatability is excellent, after attaching, passes through photograph
Active energy beam is penetrated, the bonding sheet that can be adjusted to the elasticity modulus of above range can be obtained.
As the resin material of the radiation curable by active energy beam, said in B-1 above-mentioned for example, can enumerate
Bright includes as female polymer of agent and the resin material of active energy beam reactive compounds (monomer or oligomer)
(R1), resin material (R2) comprising active energy beam reactive polymer etc..In 1 embodiment, for as centre
Active energy beam reactive compounds in the resin material (R1) of the materials'use of layer can be used with olefinic unsaturation
The compound of functional group.In addition, in 1 embodiment, as the active energy beam reactivity polymerization in resin material (R2)
The compound (polymer) with respect to olefinically unsaturated functional group can be used in object.
In addition, can be used as the material for constituting above-mentioned middle layer by vinyl-vinyl acetate copolymer, polypropylene
It is the hot melt system resin that the thermoplastic resins such as resin, polyamide resin are constituted.
Above-mentioned middle layer can also include any suitable additive as needed.As the additive, for example, can enumerate
Initiator, crosslinking agent, tackifier, plasticizer, pigment, dyestuff, filler, antiaging agent, conductive material, antistatic agent, purple out
Ultraviolet absorbers, light stabilizer, removing regulator, softening agent, surfactant, fire retardant, antioxidant etc..
The thickness of middle layer is preferably 1 μm~200 μm, more preferably 5 μm~50 μm, further preferably 10 μm~40 μ
m。
C. laminated portions A
As described above, laminated portions A has the 2nd adhesive phase and the 2nd substrate.Adhesive phase is usually than substrate thermal conductance
It is low.In the present invention, heat-peelable adhesive is protected using the laminated portions A comprising such adhesive phase (the 2nd adhesive phase)
Band, therefore the heat deterioration of the 1st adhesive phase (adhesive phase that heat-peelable adhesive band has) can be prevented.
Bonding force A1 (normality of the above-mentioned laminated portions A to pet film (for example, 50 μm of thickness)
Bonding force A1) it is preferably 0.04N/20mm~10N/20mm, more preferably 0.05N/20mm~5N/20mm, is more preferably
0.08N/20mm~4.5N/20mm, further preferably 0.1N/20mm~2.5N/20mm, particularly preferably 0.15N/20mm~
1.2N/20mm.When for such range, it can obtain bonding sheet (that is, above-mentioned heat-peelable adhesive band and laminated portions A
Laminated body) for defined process when laminated portions A be not easy to remove from heat-peelable adhesive band and can after defined process
The bonding sheet that easily unused laminated portions A is removed from heat-peelable adhesive band.
After above-mentioned laminated portions A is heated 30 minutes at 100 DEG C to pet film (for example,
50 μm of thickness) bonding force A2 (bonding force A2 after heating) be preferably 0.05N/20mm~10.0N/20mm, more preferably
0.08N/20mm~5.0N/20mm, further preferably 0.10N/20mm~1.5N/20mm.When for such range, for layer
Folded part A can also have desired peeling force even if the bonding sheet temperature rises when by bonding sheet for defined process.
It should be noted that bonding force is after heating at the temperature disclosed above, when the 2nd adhesive phase temperature is reduced to 23 DEG C after above-mentioned heating
The bonding force under 23 DEG C of environment.
After above-mentioned heating bonding force A2 relative to above-mentioned normality bonding force A1 be preferably 10 times or less, more preferably 5 times with
Under, further preferably 0.001 times~2.5 times, particularly preferably 0.001 times~1.8 times.When for such range, for layer
Folded part A can also have desired peeling force even if the bonding sheet temperature rises when by bonding sheet for defined process.
The thickness of above-mentioned laminated portions A is preferably 10 μm or more, more preferably 20 μm or more, be more preferably 30 μm with
Above, particularly preferably 50 μm~500 μm, most preferably 50 μm~300 μm.Laminated portions A with a thickness of 10 μm or more when, can
The heat deterioration of the 1st adhesive phase is prevented significantly.
C-1. the 2nd adhesive phase
The thickness of above-mentioned 2nd adhesive phase is preferably 1 μm~100 μm, more preferably 5 μm~80 μm, further preferably 5
μm~50 μm.When for such range, the heat deterioration of the 1st adhesive phase can be prevented significantly.
Representative above-mentioned 2nd adhesive phase is comprising taking defined polymer as the adhesive B of basic polymer.As
Above-mentioned adhesive B, it is also preferred that using Pressuresensitive Adhesive.As Pressuresensitive Adhesive used in the 2nd adhesive phase, for example,
Acrylic adhesives, elastomeric adhesive, vinyl alkyl ethers system adhesive, organic silicon-type adhesive, polyester can be enumerated
It is adhesive, polyamide-based adhesive, carbamate system adhesive, Styrene-diene block copolymer system adhesive etc..Its
In, preferably acrylic adhesives or organic silicon-type adhesive.It should be noted that above-mentioned adhesive can be used alone or
Two or more is applied in combination.
As acrylic adhesives contained in the 2nd adhesive phase, for example, using the bonding illustrated in B-1 above-mentioned
Agent.
As organic silicon-type adhesive contained in the 2nd adhesive phase, any suitable adhesive can be used.As upper
Organic silicon-type adhesive is stated, for example, it is preferable to make using organic silicon rubber or organic siliconresin that will include organopolysiloxane etc.
For the organic silicon-type adhesive of basic polymer.As the base polymer for constituting organic silicon-type adhesive, can be used will be upper
State base polymer obtained from organic silicon rubber or organic siliconresin crosslinking.It should be noted that in this specification, it is " organic
Differentiation criterion " the design of material and function of technical information association adhesive (film band) of silicon rubber " and " organic siliconresin "
Property assigns page 222~228 of the 1st edition September in 2009 30 days ".That is, " organic silicon rubber " refers to by two organosiloxanes (D unit)
The organosilicon of the linear chain structure of composition, the organic silicon rubber have the viscosity of such as 10000Pas or so." organic siliconresin "
Refer to comprising three organic half siloxanes (triorganosilhemioxane, M unit) and esters of silicon acis (Q unit) and there is branch
The organosilicon of structure.
The gel fraction of above-mentioned 2nd adhesive phase is preferably 20 weight of weight %~100 %, more preferably 30 weight %~99
Weight %, further preferably 50 weight of weight %~99 %.When for such range, the bonding force rising after heating is pressed down
System, can constitute the excellent laminated portions A of fissility.Such as get off and measures gel fraction.
<gel fraction measuring method>
The 2nd adhesive phase about 0.1g and precise (weight of sample) are taken, by sample net slice (trade name
" NTF-1122 ", Nitto Denko Corp's system) wrap after, impregnated at room temperature in the toluene of about 50ml 1 week.Then, will
Solvent insoluble component (content of net slice) is taken out from toluene, about 2 hours dry at 70 DEG C, the solvent after weighing drying
Insoluble component (weight after impregnation drying) calculates gel fraction (weight %) by following formula (a).
Gel fraction (weight %)=[(weight after impregnation drying)/(weight of sample)] × 100 (a)
The base polymer for constituting above-mentioned adhesive B preferably has OH base or COOH base.This is because using such base
When plinth polymer, crosslinking agent is able to use to adjust above-mentioned gel fraction.
C-2. the 2nd substrate
As above-mentioned 2nd substrate, for example, resin sheet, non-woven fabrics, paper, metal foil, woven fabric, sheet rubber, foaming can be enumerated
Piece, their laminated body (especially including the laminated body of resin sheet) etc..Preferably resin sheet.As the tree for constituting resin sheet
Rouge, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly- terephthaldehyde can be enumerated
Sour butanediol ester (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, vinyl-vinyl acetate copolymer
(EVA), polyamide (nylon), fully aromatic polyamide (aromatic polyamides), polyimides (PI), polyvinyl chloride (PVC), polyphenyl
Thioether (PPS), fluorine resin, polyether-ether-ketone (PEEK) etc..Wherein, preferably PET or PI.
The thickness of above-mentioned 2nd substrate is preferably 8 μm~400 μm, more preferably 15 μm~300 μm, particularly preferably 25 μm
~200 μm.When for such range, the heat deterioration of the 1st adhesive phase can be prevented significantly.
Surface treatment can be implemented in above-mentioned 2nd substrate.As surface treatment, illustrate in B-2 above-mentioned for example, can enumerate
Processing.Surface-treated layer can be formed in the surface of the 2nd adhesive phase side.
D. the manufacturing method of bonding sheet
Bonding sheet of the invention can be manufactured by any suitable method.In 1 embodiment, heat-releasable is formed
After adhesive tape, with by the 2nd adhesive phase by the 2nd substrate be layered in the heat-peelable adhesive band the 1st substrate with the 1st bonding
The mode of the opposite side of oxidant layer, amplexiforms laminated portions A, and thus, it is possible to manufacture above-mentioned bonding sheet.
Above-mentioned heat-peelable adhesive band can be manufactured by any suitable method.For above-mentioned heat-peelable adhesive
Band, such as the following methods can be enumerated: directly coating (is formed comprising forming the adhesive A of the 1st adhesive phase on the 1st substrate
In the case where the 1st adhesive phase comprising heat-expandable microsphere, also include heat-expandable microsphere) adhesive phase formed with combination
The coat that coated with adhesive layers formation is formed with composition A on any suitable matrix is transferred to by the method for object A
Method etc. on 1st substrate.Adhesive phase formation composition A may include any suitable solvent.In addition, being formed swollen comprising heat
In the case where 1st adhesive phase of swollen property microballoon, it also can use the composition comprising adhesive A and form adhesive coat
Afterwards, after sprinkling heat-expandable microsphere on the adhesive coat, using laminating machine etc., which is embedded to the painting
In coating, the 1st adhesive phase comprising heat-expandable microsphere is formed.
Adhesive phase formation is with the content ratio of the heat-expandable microsphere in composition A relative to adhesive phase formation group
The solids by weight for closing object is preferably 5 weight of weight %~95 %, is more preferably 10 weight of weight %~70 %, is further excellent
It is selected as 10 weight of weight %~50 %.
Above-mentioned laminated portions A can be manufactured by any suitable method.For above-mentioned laminated portions A, such as can arrange
Enumerate following method: the adhesive phase of directly adhesive B of the coating comprising forming the 2nd adhesive phase, which is formed, on the 2nd substrate uses
The method of composition B or the coat for forming the coated with adhesive layers formation composition B on any suitable matrix turn
Print to the method etc. on the 2nd substrate.Adhesive phase formation composition B may include any suitable solvent.
As the coating method of above-mentioned each composition, any suitable coating method can be used.For example, can be coated with
After be dried and form each layer.As coating method, for example, can enumerate using multiple applications machine (multi-coater),
The coating method of die coating machine, gravure coater, applicator etc..As drying means, for example, natural drying, heating can be enumerated
It is dry etc..It is any appropriate that heating temperature in the case where heat drying may be set to according to the characteristic of the substance as dry object
Temperature.
E. the delivery method of heat-peelable adhesive band
The delivery method of heat-peelable adhesive band of the invention is the delivery method of above-mentioned heat-peelable adhesive band, packet
It includes: laminated portions A is laminated in the 1st substrate for having the above-mentioned heat-peelable adhesive band of the 1st substrate and the 1st adhesive phase
Side conveys the heat-peelable adhesive band with laminated portions A.Laminated portions A includes the 2nd adhesive phase and as described above
2 substrates.Laminated portions A with by the 2nd adhesive phase by the 2nd substrate be laminated in heat-peelable adhesive band the 1st substrate with the 1st
The mode of the opposite side of adhesive phase configures.
In 1 embodiment, above-mentioned delivery method (is essentially belt including the use of conveying roller pair heat-peelable adhesive band
The heat-peelable adhesive band of folded part A) it is conveyed.Heat-peelable adhesive band with laminated portions A preferably with laminated portions A at
It is conveyed for the mode of conveying roller side.Delivery method according to the present invention, by using laminated portions A to heat-peelable adhesive band
It is conveyed, caused temperature rising is influenced by the friction etc. with conveying roller so as to protect the 1st adhesive phase to be not subjected to.Root
According to the present invention, by having the laminated portions A20 being laminated in a releasable manner, so as to prevent heat-peelable adhesive band
The deterioration of adhesive phase (that is, the 1st adhesive phase), and as heat-peelable adhesive band, it can be made and meet actual purposes
Thickness appropriate.
[embodiment]
Hereinafter, by embodiment, specifically the present invention will be described, but the present invention is not limited to the examples.It is real
Apply it is in example evaluation method is as follows.In addition, unless otherwise specified, then " part " and " % " is weight basis in embodiment.
[embodiment 1]
By acrylic copolymer (2-EHA: acrylic acid=95 parts by weight: 5 parts by weight) 100 parts by weight,
Epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD C ") 3 parts by weight and toluene mixing, preparation are viscous
Mixture solution.In the PET film (thickness: 50 μm) as the 2nd substrate, it is coated in such a way that the thickness after drying becomes 5 μm
Above-mentioned binder solution and drying form the 2nd adhesive phase, PET isolation film (thickness: 38 μm) are fitted in the 2nd adhesive phase
On, obtain laminated portions A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 5 μm)/isolation film).
[embodiment 2]
As the 2nd substrate, instead of PET film (thickness: 50 μm), using Kapton (thickness: 50 μm), except this with
Outside, it operates similarly with example 1, obtains laminated portions A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 5 μ
M)/isolation film).
[embodiment 3]
As the 2nd substrate, instead of PET film (thickness: 50 μm), using PET film (thickness: 25 μm), in addition to this, with
Embodiment 1 operates in the same way, and obtains laminated portions A (the 2nd substrate (thickness: 25 μm)/the 2nd adhesive phase (thickness: 5 μm)/isolation
Film).
[embodiment 4]
As the 2nd substrate, instead of PET film (thickness: 50 μm), using PET film (thickness: 100 μm), in addition to this,
Operate similarly with example 1, obtain laminated portions A (the 2nd substrate (thickness: 100 μm)/the 2nd adhesive phase (thickness: 5 μm)/
Isolation film).
[embodiment 5]
The thickness of 2nd adhesive phase is set as 25 μm, in addition to this, operates similarly with example 1, obtains laminated portions
A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 25 μm)/isolation film).
[embodiment 6]
By acrylic copolymer (2-EHA: Hydroxyethyl Acrylate (weight ratio)=100:4) 100 weights
Measure part, isocyanates system crosslinking agent (Nippon Polyurethane Industry Co., Ltd. system, trade name " CORONATE
L ") 2 parts by weight, crosslinking accelerator (TOSOH Co., Ltd's system, trade name " Triethylenediamine (TEDA) ") 0.05 weight
Part and toluene mixing are measured, binder solution is prepared.In the PET film (50 μm) as the 2nd substrate, with the thickness after drying at
It is coated with above-mentioned binder solution and drying for 10 μm of modes, the 2nd adhesive phase is formed, PET isolation film (38 μm) is fitted in
On 2nd adhesive phase, laminated portions A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 10 μm)/isolation is obtained
Film).
[embodiment 7]
By acrylic copolymer (butyl acrylate: acrylic acid (weight ratio)=100:5) 100 parts by weight, isocyanates
Be crosslinking agent (Nippon Polyurethane Industry Co., Ltd. system, trade name " CORONATE L ") 2 parts by weight,
Epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD C ") 0.5 parts by weight and toluene mixing, preparation
Binder solution.In the PET film (50 μm) as the 2nd substrate, it is coated in such a way that the thickness after drying becomes 50 μm
Binder solution and drying are stated, the 2nd adhesive phase is formed, PET isolation film (38 μm) is fitted on the 2nd adhesive phase, is obtained
Laminated portions A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 50 μm)/isolation film).
[embodiment 8]
By acrylic copolymer (2-EHA: acrylic acid=95 parts by weight: 5 parts by weight) 100 parts by weight,
Epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD C ") 5 parts by weight and toluene mixing, preparation are viscous
Mixture solution.In the PET film (50 μm) as the 2nd substrate, it is coated in such a way that the thickness after drying becomes 5 μm above-mentioned viscous
Mixture solution and drying form the 2nd adhesive phase, PET isolation film (38 μm) are fitted on the 2nd adhesive phase, is laminated
Part A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 5 μm)/isolation film).
[embodiment 9]
By acrylic copolymer (2-EHA: acrylic acid=95 parts by weight: 5 parts by weight) 100 parts by weight,
Epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD C ") 3 parts by weight and toluene mixing, preparation are viscous
Mixture solution.In the PET film (5 μm) as the 2nd substrate, it is coated in such a way that the thickness after drying becomes 3 μm above-mentioned viscous
Mixture solution and drying form the 2nd adhesive phase, PET isolation film (38 μm) are fitted on the 2nd adhesive phase, is laminated
Part A (the 2nd substrate (thickness: 5 μm)/the 2nd adhesive phase (thickness: 3 μm)/isolation film).
[embodiment 10]
By acrylic copolymer (2-EHA: acrylic acid=95 parts by weight: 5 parts by weight) 100 parts by weight,
Epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD C ") 0.6 parts by weight and toluene mixing, preparation
Binder solution.In the PET film (50 μm) as the 2nd substrate, it is coated in such a way that the thickness after drying becomes 10 μm
Binder solution and drying are stated, the 2nd adhesive phase is formed, PET isolation film (38 μm) is fitted on the 2nd adhesive phase, is obtained
Laminated portions A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 10 μm)/isolation film).
[embodiment 11]
The thickness of 2nd adhesive phase is set as 50 μm, in addition to this, operates similarly to Example 10, obtains laminated section
Divide A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 50 μm)/isolation film).
[embodiment 12]
By acrylic copolymer (2-EHA: acrylic acid=95 parts by weight: 5 parts by weight) 100 parts by weight,
Epoxy crosslinking agent (Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD C ") 6 parts by weight and toluene mixing, preparation are viscous
Mixture solution.In the PET film (50 μm) as the 2nd substrate, it is coated in such a way that the thickness after drying becomes 3 μm above-mentioned viscous
Mixture solution and drying form the 2nd adhesive phase, PET isolation film (38 μm) are fitted on the 2nd adhesive phase, is laminated
Part A (the 2nd substrate (thickness: 50 μm)/the 2nd adhesive phase (thickness: 3 μm)/isolation film).
<evaluation>
By the laminated portions A made in embodiment and bonding sheet comprising laminated portions A and heat-peelable adhesive band for
Evaluation below.Show the result in table 1.
In addition, the bonding sheet without laminated portions A, being only made of heat-peelable adhesive band is viscous for (4) heat-releasable
The protectiveness of crossed belt is evaluated, as the result of comparative example 1.
(1) the normality bonding force of laminated portions A (the 2nd substrate/the 2nd adhesive phase)
The laminated portions A made in embodiment (the 2nd substrate/the 2nd adhesive phase) is cut into width: 20mm, length:
The size of 140mm is used as adherend according to fitting in JIS Z 0237 (2000) on the 2nd adhesive phase after isolation film stripping
Pet film (trade name " Lumirror S-10 " Toray Industries, Inc. system；Thickness:
50 μm, width: 20mm) (specifically, in temperature: 23 ± 2 DEG C and humidity: under the atmosphere of 65 ± 5%RH, keeping the roller of 2kg round-trip
Crimped to be bonded for 1 time), make sample for evaluation.The sample for evaluation is installed to the thermostat for being set as 23 DEG C
Cupping machine (Shimadzu Scisakusho Ltd's system, trade name " Shimadzu Autograph AG-120kN ") on, place 30 points
Clock.After placement, measure 23 DEG C at a temperature of by adherend in peel angle: 180 °, peeling rate (tensile speed): 300mm/
Minute under conditions of from laminated portions A remove when load, find out at this time concave-convex average load (except measurement initial stage summit with
The concave-convex average value of outer load), using the bumps average load as the bonding force (N/20mm width) of laminated portions A.
(2) bonding force after the heating of laminated portions A (the 2nd substrate/the 2nd adhesive phase)
Sample for evaluation is made in the same manner as above-mentioned (1).
Sample for evaluation is heated 30 minutes at 100 DEG C, then, is placed 30 minutes under 23 DEG C of atmosphere.Then, it will evaluate
Cupping machine (the trade name " Shimadzu Autograph AG-120kN " with the thermostat for being set as 23 DEG C is installed to sample
Shimadzu Scisakusho Ltd's system) on, it places 30 minutes.After placement, measure 23 DEG C at a temperature of by adherend in peel angle
Degree: 180 °, peeling rate (tensile speed): load when removing under conditions of 300mm/ minutes from laminated portions A is found out at this time
Concave-convex average load (except measurement initial stage summit in addition to load concave-convex average value), using the bumps average load as layer
The bonding force (N/20mm width) of folded part A.
In addition, measured value is based on, according to the fissility of benchmark evaluation laminated portions A below.It should be noted that herein
Fissility in practical usage situations, can be equivalent to by the bonding sheet being made of heat-peelable adhesive band and laminated portions A supply
Fissility in roll-to-roll process, after being risen by temperature caused by being influenced by the friction etc. with conveying roller.
〇: bonding force is 5.0N/20mm or less after heating
△: bonding force is more than 5.0N/20mm after heating
The gel fraction of (3) the 2nd adhesive phases
The adhesive phase about 0.1g and precise (weight of sample) for constituting laminated portions A are taken, by the sample net
After shape piece (trade name " NTF-1122 ", Nitto Denko Corp's system) is wrapped, 1 is impregnated at room temperature in the toluene of about 50ml
Week.Then, solvent insoluble component (content of net slice) is taken out from toluene, it is about 2 hours dry at 70 DEG C, it weighs dry
Solvent insoluble component (weight after impregnation drying) after dry calculates gel fraction (weight %) by following formula (a).
Gel fraction (weight %)=[(weight after impregnation drying)/(weight of sample)] × 100 (a)
(4) the protectiveness evaluation of heat-peelable adhesive band
With hand pressure roller by the laminated portions A made in embodiment be fitted in by the 1st substrate (PET film, thickness: 50 μm),
1st substrate surface of the heat-peelable adhesive band that middle layer and the 1st adhesive phase are constituted, obtains evaluation bonding sheet (the 1st adhesive
Layer (thermally strippable)/middle layer/the 1st substrate/the 2nd adhesive phase/the 2nd substrate).It should be noted that by as shown below
Method makes heat-peelable adhesive band.
In acrylic copolymer (butyl acrylate: Hydroxyethyl Acrylate=100 parts by weight: 3 parts by weight) 100 weight
Terpenes phenol system tackifying resin (trade name " YS Polystar T80 ", YASUHARA CHEMICAL CO., LTD. are compounded in part
System) 30 parts by weight, isocyanates system crosslinking agent (trade name " CORONATE L ", Nippon Polyurethane Industry
Co., Ltd.'s system) 1 parts by weight, be added toluene, equably mix, make binder solution, PET base material (the 1st substrate, thickness:
50 μm) on be coated with above-mentioned binder solution in such a way that the thickness after drying becomes 20 μm, form middle layer.
In turn, it is equably mixed in above-mentioned 00 parts by weight of copolymer 1 and dissolves isocyanates system crosslinking agent (trade name
" CORONATE L ", Nippon Polyurethane Industry Co., Ltd. system) 1 parts by weight, foaming agent (thermal expansivity
Microballoon；Trade name " Matsumoto Microsphere F-30D ", Matsumoto Yushi-Seiyaku Co., Ltd.'s system) 50 parts by weight and first
Gained coating liquid is coated on PET base material isolation film (38 μm) in such a way that the thickness after drying becomes 30 μm, forms the by benzene
1 adhesive phase.The adhesive phase is transferred in above-mentioned middle layer, above-mentioned heat-peelable adhesive band is obtained.
The probe bonding force for measuring and evaluating the 1st adhesive phase with sample under the following conditions, is set as C for its value0.Separately
Outside, it is heated under the following conditions from the back side of sample for evaluation (the 2nd substrate) side, the probe bonding force C after measurement heating.
Pass through formula (C/C0) × 100 calculate probe bonding force residual rate.
It being influenced by the heat from the back side, when the foaming of heat-expandable microsphere starts, the value for bonding force of popping one's head in becomes smaller, with
Probe bonding force residual rate also become smaller.Therefore, the size based on probe bonding force residual rate, it is viscous according to benchmark evaluation below
Close the protectiveness of the heat-peelable adhesive band in piece.
〇: probe bonding force residual rate is 80% or more
△: probe bonding force residual rate is 70% or more and less than 80%
×: probe bonding force residual rate is less than 70%
It should be noted that the heat-peelable adhesive band made as described above is used directly as evaluation in comparative example
Adhesive tape, for above-mentioned evaluation.
Heating means
It is placed in such a way that the 2nd substrate (in comparative example be the 1st substrate) becomes hot plate side and is heated to 90 DEG C of hot plate, into
And the top of self-evaluation adhesive tape loaded in such a way that the band is uniformly in contact with hot plate glass weight (140mm × 140mm ×
10mm).It maintains the state 20 seconds, evaluation is heated with adhesive tape.
Probe bonding force measuring method
Using adhesive test machine TAC-II (RHESCA corporation), probe bonding force is evaluated under the following conditions.It will pull out
Value of the peak load (gf) applied when out as probe bonding force.
The diameter 10mm of metal probe
The press-in speed of probe 30mm/ minutes
Load 50gf
The indentation time 0.5 second
It extracts speed 30mm/ minutes
(5) estimation of stability of laminated portions A
It is operated in the same way with above-mentioned (4), makes evaluation adhesive tape.
Evaluation is cut into the size of 20mm × 100mm with adhesive tape.By the evaluation adhesive tape of strip with laminated section
After dividing the side A to curve half relative to length direction as the mode of inside, it is stretched to original state.
Creased portion is observed by visual observation, according to benchmark evaluation below.
〇: it is not confirmed between the 1st substrate surface of heat-peelable adhesive band and the 2nd adhesive level of laminated portions A
Float
△: confirming a part between the 1st substrate surface and the 2nd adhesive phase and float, but practical permissible
×: floating for the degree not allowed on practical is confirmed between the 1st substrate surface and the 2nd adhesive phase
[table 1]
Claims (10)
1. a kind of bonding sheet, successively has: the 1st adhesive phase, the 1st substrate, the 2nd adhesive phase and the 2nd substrate,
1st adhesive phase and the 1st substrate constitute heat-peelable adhesive band,
2nd adhesive phase and the 2nd substrate constitute laminated portions A,
Laminated portions A is configured in a manner of it can remove from the heat-peelable adhesive band.
2. bonding sheet according to claim 2, wherein the laminated portions A with a thickness of 10 μm or more.
3. bonding sheet according to claim 1 or 2, wherein the 1st adhesive phase with a thickness of 1 μm~30 μm.
4. bonding sheet according to claim 1 or 2, wherein the 1st adhesive phase passes through nano impress at 25 DEG C
The elasticity modulus that method obtains is less than 100MPa.
5. bonding sheet according to claim 1 or 2, wherein the gel fraction of the 2nd adhesive phase be 20 weight %~
100 weight %.
6. bonding sheet according to claim 1 or 2, wherein the 2nd adhesive phase with a thickness of 1 μm~100 μm.
7. bonding sheet according to claim 1 or 2, wherein the 2nd substrate with a thickness of 8 μm~400 μm.
8. bonding sheet according to claim 1 or 2, wherein after heating the laminated portions A 30 minutes at 100 DEG C
It is thin to polyethylene terephthalate relative to laminated portions A to the bonding force A2 of pet film
The normality bonding force A1 of film is 10 times or less.
9. bonding sheet according to claim 1 or 2, wherein the laminated portions A is thin to polyethylene terephthalate
The normality bonding force A1 of film is 0.05N/20mm~5N/20mm.
10. a kind of delivery method of heat-peelable adhesive band, the heat-peelable adhesive band have the 1st substrate and the 1st adhesive
Layer,
The delivery method includes: that laminated portions A is laminated in the 1st substrate side, to the heat-peelable adhesive with laminated portions A
Band is conveyed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-095561 | 2018-05-17 | ||
| JP2018095561A JP7133355B2 (en) | 2018-05-17 | 2018-05-17 | Adhesive sheet |
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| Publication Number | Publication Date |
|---|---|
| CN110499116A true CN110499116A (en) | 2019-11-26 |
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ID=68585556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910411223.XA Pending CN110499116A (en) | 2018-05-17 | 2019-05-16 | Bonding sheet |
Country Status (3)
| Country | Link |
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| JP (1) | JP7133355B2 (en) |
| CN (1) | CN110499116A (en) |
| TW (1) | TW201946994A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017091515A1 (en) | 2015-11-24 | 2017-06-01 | University Of Washington | Photosensitive medical tape |
| WO2020264291A1 (en) | 2019-06-28 | 2020-12-30 | University Of Washington | Apparatus, system, and method for activating a low-adhesion state of thermal-sensitive tape |
| KR20230061511A (en) * | 2020-12-07 | 2023-05-08 | 닛토덴코 가부시키가이샤 | adhesive sheet |
| JP2023039829A (en) * | 2021-09-09 | 2023-03-22 | 日東電工株式会社 | Adhesive sheet for temporarily fixing electronic component |
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| CN1674235A (en) * | 2004-03-24 | 2005-09-28 | 日东电工株式会社 | Method and device for separating a reinforcing-plate fixed to a reinforced semiconductor wafer |
| CN102592503A (en) * | 2010-10-15 | 2012-07-18 | 精工电子有限公司 | Adhesive label, method of producing the same, and apparatus for producing the same |
| US20150299521A1 (en) * | 2012-11-02 | 2015-10-22 | Nitto Denko Corporation | Thermally debondable tape |
| CN107075323A (en) * | 2014-11-13 | 2017-08-18 | Dic株式会社 | Double-sided adhesive tape, article and separation method |
| WO2017170451A1 (en) * | 2016-03-30 | 2017-10-05 | 三井化学東セロ株式会社 | Semiconductor device manufacturing method |
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| JP5258128B2 (en) * | 2001-01-24 | 2013-08-07 | 日東電工株式会社 | Manufacturing method of heat-peelable pressure-sensitive adhesive sheet |
| JP5362332B2 (en) * | 2008-11-19 | 2013-12-11 | 日東電工株式会社 | Surface protection sheet and use thereof |
| CN103827241A (en) * | 2011-09-20 | 2014-05-28 | 日东电工株式会社 | Heat-releasable adhesive sheet for cutting electrical component and electrical component cutting method |
| CN104629639B (en) * | 2015-01-26 | 2019-04-23 | 东莞市华诚宇丰电子科技有限公司 | A kind of hot soarfing is from interim positioning film |
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2018
- 2018-05-17 JP JP2018095561A patent/JP7133355B2/en active Active
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- 2019-05-06 TW TW108115530A patent/TW201946994A/en unknown
- 2019-05-16 CN CN201910411223.XA patent/CN110499116A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1674235A (en) * | 2004-03-24 | 2005-09-28 | 日东电工株式会社 | Method and device for separating a reinforcing-plate fixed to a reinforced semiconductor wafer |
| CN102592503A (en) * | 2010-10-15 | 2012-07-18 | 精工电子有限公司 | Adhesive label, method of producing the same, and apparatus for producing the same |
| US20150299521A1 (en) * | 2012-11-02 | 2015-10-22 | Nitto Denko Corporation | Thermally debondable tape |
| CN107075323A (en) * | 2014-11-13 | 2017-08-18 | Dic株式会社 | Double-sided adhesive tape, article and separation method |
| WO2017170451A1 (en) * | 2016-03-30 | 2017-10-05 | 三井化学東セロ株式会社 | Semiconductor device manufacturing method |
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| Publication number | Publication date |
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| TW201946994A (en) | 2019-12-16 |
| JP7133355B2 (en) | 2022-09-08 |
| JP2019199561A (en) | 2019-11-21 |
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