CN104640948B - Electronic building brick double-sided adhesive sheet - Google Patents

Electronic building brick double-sided adhesive sheet Download PDF

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Publication number
CN104640948B
CN104640948B CN201380048908.3A CN201380048908A CN104640948B CN 104640948 B CN104640948 B CN 104640948B CN 201380048908 A CN201380048908 A CN 201380048908A CN 104640948 B CN104640948 B CN 104640948B
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CN
China
Prior art keywords
double
sided adhesive
adhesive sheet
adhesive phase
crosslinking agent
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CN201380048908.3A
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CN104640948A (en
Inventor
那须健司
森田和明
土渕晃司
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Lintec Corp
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Lintec Corp
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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]
    • 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
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/312—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 parameters being the characterizing feature
    • 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)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of double-sided adhesive sheet, the double-sided adhesive sheet of the present invention possesses the adhesive phase for including the cross-linked structure reacted by crosslinking agent and crosslinking polymer, in one example, it is also equipped with the core that each interarea is laminated with adhesive phase, wherein, the stress-retained rate of adhesive phase is less than 40%, and crosslinking agent includes toluene di-isocyanate(TDI).It is preferred that using gel fraction as more than 10% 70% adhesive phase formed below.By such double-sided adhesive sheet, when sticky surface has high flexure plane, it is not easy to be peeling, and the possibility for producing exhaust can be reduced.

Description

Electronic building brick double-sided adhesive sheet
Technical field
The present invention relates to a kind of double-sided adhesive sheet, more specifically, it is related to one kind to reduce release and is possible to being assembled in The running of component in the devices such as hard disk brings the possibility of dysgenic gas componant, and double with excellent cohesive Face bonding sheet.
In addition, in this manual, the concept of the concept comprising adhesive tape and film in " piece "." it is assembled in the group in device Part " is also comprising such as display board not component directly related with the running of device.Can also by manufacturing process, keeping and/or make The gas componant that the double-sided adhesive sheet pasted from the component being assembled in device in is discharged referred to as " is vented ".
Background technology
The devices such as hard disk drive (in this manual, also known as " HDD "), relay, various switches, connector, motor Part is widely used in various products.Interim fixation, the fixation of component and the content of component during for assembling such as show at the purpose, this Plant the double-sided adhesive sheet being made up of the face of adhesive phase using two interareas in device.
In the material for constituting the adhesive phase that this double-sided adhesive sheet possesses, obtain gluing with excellent to realize The purpose of the bonding sheet of conjunction property, it is also possible to small to being possible to the use environment in device (for example, HDD is used comprising molecular weight In internal temperature be possible to as 70 DEG C or so) in volatilization degree material (in this manual, be also known as " low molecule amount Composition ").Also, during the composition of adhesive is changed over time, it is also possible in adhesive layer generate low-molecular-weight into Point.If this low molecular weight compositions formation is vented and diffused in device, low molecular weight compositions are possible to be attached to and are assembled in The surface of the component in device.
On the other hand, it is assembled with the generating assembly when foreign matter is piled up in its surface in the devices sometimes and operates bad possibility The component that property increases.As this component, HDD hard disk, contact portion of relay etc. can be illustrated.
The surface that above-mentioned low molecular weight compositions are attached to this component can cause the running of component bad, so device fortune Make bad, therefore to being difficult to produce exhaust from adhesive phase for the double-sided adhesive sheet requirement in device.
On this double-sided adhesive sheet with adhesive phase, there is a kind of for fixing HDD's disclosed in patent document 1 The double-sided adhesive sheet of component, it is provided with the adherend of adhesive phase by two surface sides of the plastic film substrate below 20 μm of thickness Partly and the release liner of non-organic silicon class of the both side surface that is arranged at bonding body portion is constituted, wherein, bonding body portion Thickness is less than 60 μm, and capacity when being heated 10 minutes at 120 DEG C is 1 μ g/cm2Below.
Prior art literature
Patent document 1：Japanese Patent Publication 2009-74060 publications
The content of the invention
The invention technical problem to be solved
But, after the present inventor etc. confirms, even if specify that using the double of the condition specified in above-mentioned patent document 1 that meets Face bonding sheet, for be pasted with HDD framework double-sided adhesive sheet one side (in this manual, including paste both-sided adhesive Including state before piece, also referred to as " framework sticky surface "), flexible printed circuit board is made via the double-sided adhesive sheet of the stickup When (in this manual, also known as " FPC ") is attached to the framework of HDD, in the difference of height part of the framework of HDD, send out sometimes " tilting " that raw FPC is peeled off together with double-sided adhesive sheet from its framework sticky surface.
" tilting " phenomenon is illustrated by accompanying drawing.Fig. 1 is the figure for being used to illustrate " to tilt " phenomenon, and is concept Represent to be pasted with the partial sectional view of FPC HDD framework via double-sided adhesive sheet to property.As shown in Fig. 1 (a), when with comprising When the mode of the difference of height part in the framework 1 of HDD is pasted with the laminate 4 of FPC2 and double-sided adhesive sheet 3, if producing " tilting " Phenomenon, then in the difference of height part, shown in such as Fig. 1 (b), the interface between double-sided adhesive sheet 3 and HDD framework 1 produces stripping From so as to form the state that laminate 4 is upturned in the part from framework.In this manual, this being pasted on is had The phenomenon that the double-sided adhesive sheet of the clung body of difference of height part is partially stripped from the clung body including the difference of height part referred to as " is stuck up Rise " (being partially stripped).It is used as one of method for avoiding occurring " tilting " phenomenon, it may be considered that improve double-sided adhesive sheet 3 relative In the cohesive of HDD framework 1.However, when improving the cohesive of double-sided adhesive sheet 3, from the adhesive for constituting double-sided adhesive sheet 3 The possibility that layer produces exhaust is also improved therewith, it cannot be said that be preferable solution.
Under the present situation background, even if it is an object of the invention to provide a kind of with the difference of height with such as framework of HDD When the face that part etc. is susceptible to the part for tilting is sticky surface, it is not easy to be peeling and can reduce the possibility for producing exhaust The double-sided adhesive sheet and the coating material for forming the adhesive phase that double-sided adhesive sheet possesses of property.
Technological means for solving technical problem
To achieve these goals, the present inventor etc. is studied the factor of above-mentioned tilting, as a result finds to remove Outside the recuperability of the FPC being bent to form along the face of the difference of height part of framework relative to FPC, relative to double-sided adhesive sheet Adhesive phase along the recuperability of the adhesive phase being bent to form in the face in the difference of height portion of framework be also tilt generation because One of element.
Based on the discovery, the present invention first provides a kind of double-sided adhesive sheet (invention 1), and it is stress-retained that it possesses at least one of which Adhesive phase of the rate less than 40%, it is characterised in that described adhesive layer is formed comprising crosslinking agent with crosslinking polymer reaction Cross-linked structure, the crosslinking agent contains toluene di-isocyanate(TDI) class crosslinking agent.
40% is less than by the stress-retained rate of adhesive phase, the double-sided adhesive sheet made involved by foregoing invention can be reduced The recuperability of sheet material when deforming in curved manner.Even if the double-sided adhesive sheet with this characteristic is pasted on such as HDD frames The higher face of the degree of crook such as the face of difference of height part of body, adhesive phase is not easy to peel off.Also, pass through double-sided adhesive sheet Crosslinking agent involved by adhesive phase contains toluene di-isocyanate(TDI) class crosslinking agent, can be easily residual by the stress of adhesive phase Rate control is stayed in above range.
In foregoing invention (invention 1), preferably the gel fraction of described adhesive layer is less than more than 10% 70% (invention 2).The friendship containing toluene di-isocyanate(TDI) class crosslinking agent is adjusted by way of turning into above range with the gel fraction of adhesive phase Join the usage amount of agent, more easily control in above range the stress-retained rate of resulting adhesive phase.
In foregoing invention (invention 1,2), all adhesive phases that double-sided adhesive sheet possesses, preferably stress-retained rate is small In 40% (invention 3).Now, even if the higher face of the face degree of crook for being pasted on the difference of height part of such as HDD frameworks, also especially Its stripping for being not likely to produce adhesive phase.
In foregoing invention (invention 1 to 3), preferably described crosslinking polymer contains the acrylic polymer without carboxyl Compound (invention 4).At this point it is possible to further reduce the possibility that exhaust is produced from adhesive phase, even if therefore double-sided adhesive sheet Be pasted on the inside of HDD frameworks, can also more stably reduce produce the bad harsh conditions of running for causing device can Can property.
In foregoing invention (invention 4), the preferably described acrylic polymer without carboxyl is included based on alkyl Carbon number is for the construction unit of less than 4 (methyl) alkyl acrylate and based on the alkenes unsaturationization with reactive functional groups The construction unit (invention 5) of compound.By including the construction unit based on the ethylenically unsaturated compounds, it is easier to viscous improving Capacity is reduced while the adhesion characteristic of mixture layer.
In foregoing invention (invention 4,5), the preferably described acrylic polymer without carboxyl is also included based on tool There is the construction unit (invention 6) of the morpholine kind compound of alkenes unsaturated group.By including the knot based on the morpholine kind compound Structure unit, it is easier to reduce capacity while the density of cross-linked structure present in adhesive phase is improved.
In foregoing invention (invention 1 to 6), preferably described double-sided adhesive sheet possesses with two cores of interarea, and Each interarea lamination described adhesive layer (invention 7).By with this structure, even if double-sided adhesive sheet is pasted on degree of crook Higher face, adhesive phase is not easy to peel off, and can improve the operability of double-sided adhesive sheet.
In foregoing invention (invention 7), the thickness of preferably described core is less than more than 2 μm 15 μm (inventions 8).By core The thickness of material can enjoy the benefit for setting core, and more play consistently double involved by foregoing invention in the scope The function of face bonding sheet.
Second purpose of the present invention is to provide a kind of coating material (invention 9), its be used to being formed foregoing invention (invention 1 to 8) adhesive phase that the double-sided adhesive sheet involved by possesses, wherein, the coating material contains crosslinking polymer and toluene Diisocyanates crosslinking agent, and with mobility.
By using this coating material, it is easier to obtain the double-sided adhesive sheet involved by foregoing invention (invention 1 to 8).
Invention effect
Double-sided adhesive sheet involved in the present invention is relatively low due to the stress-retained rate of adhesive phase, therefore the sheet material is deformed into Recuperability during bending is low.Therefore, even if double-sided adhesive sheet involved in the present invention is pasted on into the difference of height portion such as HDD frameworks During the higher faces of degree of crook such as the face divided (in this manual, also known as " high flexure plane "), double-sided adhesive sheet is acted on With adhesive phase, direction making adhesive phase be peeled off from the sticky surface of the adhesive phase the power quilt of high flexure plane opposite side Reduce.Therefore, do not increase the content of low molecular weight compositions especially in the composition of adhesive phase, can also reduce in high flexure plane And its possibility of tilting for nearby waiting generation double-sided adhesive sheet to be come off from sticky surface.Thus, according to pair involved in the present invention Face bonding sheet, when sticky surface has high flexure plane, can also reduce produce exhaust possibility and tilt can Can both property.
Brief description of the drawings
Fig. 1 is the figure of " tilting " phenomenon for illustrating to produce in the double-sided adhesive sheet involved by prior art, and is Conceptually represent to be pasted with the partial sectional view of FPC HDD framework via double-sided adhesive sheet, Fig. 1 (a) represents that " tiltings " shows As the state before generation, Fig. 1 (b) represents the state after there is " tilting " phenomenon.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.
1. double-sided adhesive sheet
If double-sided adhesive sheet two interarea involved by an embodiment of the invention is by specific adhesive phase Face is constituted, then other structures are not particularly limited.Double-sided adhesive sheet can be constituted by the two of single adhesive phase interareas Two interareas or double-sided adhesive sheet be made up of the laminate of multiple adhesive phases and double-sided adhesive sheet two interareas by The face of one species or different types of adhesive phase is constituted.Or, can also be that double-sided adhesive sheet possesses beyond adhesive phase Component (as concrete example, core described later can be enumerated) and multiple adhesive phase clamps the structure of the components such as the core.This When, two interareas of double-sided adhesive sheet can be made up of the face of same kind of adhesive phase, it is also possible to by different types of viscous The face of mixture layer is constituted.
(1) adhesive phase
(1-1) stress-retained rate
At least one in the adhesive phase that double-sided adhesive sheet involved by present embodiment possesses be defined as below should Power residual rate is less than 40%.All adhesive phases that double-sided adhesive sheet involved by present embodiment possesses, preferably stress is residual Rate is stayed to be less than 40%.
" stress-retained rate " in this specification is the following value obtained.That is, thickness is formed with the adhesive of measure object It is 50 μm of adhesive phase, cuts into 50mm × 50mm and be rolled into cylindric as tension test sample.In 23 DEG C, phase In the environment of to humidity 50%, using universal tensile testing machine, stretched apart from 30mm between draw speed 200mm/min, chuck The columned tension test sample, and determine the measure object part (30mm between chuck of tension test sample Part) elongation 5% when stress A (N) and stop elongation 5 minutes after stress B (N).According to these stress A for being determined, B calculates B/A × 100 (%), regard the value as stress-retained rate (%).
If double-sided adhesive sheet is pasted on the face flexure plane high of the difference of height part in such as framework of HDD, both-sided adhesive Piece also can with along the height bend facial disfigurement, the adhesive of compression stress or tensile force effect near the bending section based on the deformation Layer.But, the stress-retained rate of the adhesive phase possessed by the double-sided adhesive sheet involved by present embodiment less than 40%, Therefore deformation when being not likely to produce stickup to be resisted in the adhesive phase near the bending point and the power restored.The adhesive phase Recuperability as making adhesive phase be played a role from the power in the remote direction of sticky surface, therefore the recuperability is low may consequently contribute to subtract The small double-sided adhesive sheet for being pasted on high flexure plane produces the possibility tilted.Stuck up from double-sided adhesive sheet generation is more stably reduced From the viewpoint of the possibility risen, the stress-retained rate of adhesive phase is preferably less than 35%, and more preferably less than 30%, especially Preferably less than 25%.
The lower limit of stress-retained rate is not particularly limited, but when stress-retained rate is too low, worry is present in adhesive phase The density (in this manual, also known as " crosslink density ") of interior cross-linked structure is especially reduced and is difficult to control to adhesion characteristic (viscosity, cohesive, releasable etc.).From from the viewpoint of the possibility for reducing this problem of generation, the stress of adhesive phase Residual rate is preferably set to more than 1%, is more preferably set as more than 10%.
(1-2) is constituted
It is that double-sided adhesive sheet involved by present embodiment possesses, viscous with the characteristic on above-mentioned stress-retained rate Mixture layer, comprising reacting to form with polymer (in this manual, also known as " crosslinking polymer ") by crosslinking agent Cross-linked structure, the polymer has the functional group i.e. reactive functional groups that can be reacted with crosslinking agent.
(i) crosslinking polymer
From from the viewpoint of further reducing the capacity from double-sided adhesive sheet, the preferred adhesive phase of present embodiment Involved crosslinking polymer is the acrylic polymer that carboxyl amount is reduced.Specifically, with regard in crosslinking polymer For the containing ratio of carboxyl, the summation of monomer for forming crosslinking polymer, the knot with carboxyl are used for relative to 100 mass parts Structure unit is preferably below 1.0 mass parts, below more preferably 0.5 mass parts.Additionally, it is preferred that crosslinking polymer is not Acrylic polymer (in this manual, also known as " not carboxylic polymer (carboxy free with carboxyl polymer)”).The similarly preferred carboxyl-content of adhesive phase for constituting the double-sided adhesive sheet of present embodiment is few, additionally, it is preferred that Contain substantially no the composition with carboxyl.Construction unit with carboxyl can enumerate acrylic acid, methacrylic acid, itaconic acid Deng.
The construction unit of crosslinking polymer is not particularly limited.Can be only by based on as with (methyl) acryloyl group Compound and its derivative (ester, acrylonitrile etc.) one or more compound acrylic compounds structure Unit is constituted, can also be comprising the construction unit based on acrylic compounds and based on the chemical combination beyond acrylic compounds The construction unit of thing.In addition, " (methyl) acryloyl group " in this specification refer to acryloyl group and methylacryloyl this two Person.It is also identical on other similar terms.Also, the compound beyond aforesaid propylene acid compounds can be by a kind of compound Constitute, it is also possible to be made up of multiple compounds.
As preferred one of aforesaid propylene acid compounds, (methyl) acrylate can be enumerated.On (methyl) Acrylate shows concrete example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid third Ester, (methyl) butyl acrylate, (methyl) 2-EHA etc. have (methyl) acrylate of linear backbone；(first Base) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, the ring pentyl ester of (methyl) acrylic acid two, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid tetrahydrofurfuryl alcohol ester, (methyl) acrylate with cyclic skeleton such as acid imide acrylate；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) third Olefin(e) acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxyls Base butyl ester, (methyl) acrylic acid 4- hydroxybutyls etc. have (methyl) acrylate of hydroxyl；(methyl) acrylic acid N- methyl ammonia (methyl) acrylate with amino such as base ethyl ester；And (methyl) glycidyl acrylate etc. (methyl) with epoxy radicals Acrylate.
Wherein, crosslinking polymer preferably comprise the carbon number based on alkyl be less than 4 (methyl) alkyl acrylate (with Under, also known as " lower alkyl ") construction unit.As this lower alkyl, (first can be specifically enumerated Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) third Olefin(e) acid N-butyl, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate etc..
Wherein, from the viewpoint that balance is suitably kept with reduction capacity of the adhesion characteristic for being easy to make raising adhesive phase Consider, preferably (methyl) n-butyl acrylate and (methyl) methyl acrylate.Lower alkyl can be used alone one kind, Can also be applied in combination two or more.
As monomer (below, also known as " its for assigning the construction unit based on the compound beyond acrylic compounds His polymerizable compound "), it can illustrate the alkene such as ethene, ENB, the vinyl carboxylates such as vinyl acetate, styrene etc. Aromatic compound with alkenes unsaturated bond.
As described later, because crosslinking agent includes toluene di-isocyanate(TDI) class compound, therefore preferred present embodiment is viscous The reactive functional groups that crosslinking polymer involved by mixture layer has are the official that can be reacted with NCO Can group.As the group beyond carboxyl in this functional group, hydroxyl, amino and amide groups can be illustrated.
The species of compound to assigning the construction unit with reactive functional groups in crosslinking polymer is no special Limit.As one, above-mentioned (methyl) acrylate with hydroxyl and (methyl) acrylic acid with amino can be enumerated Ester.(" reactive chemical combination in this manual, is also known as this ethylenically unsaturated compounds with reactive functional groups Thing "), the ethylenically unsaturated compounds containing amide groups and the alcohol with vinyl can also be illustrated.As this reactivityization The concrete example of compound, can enumerate acrylamide, N,N-DMAA, N, N- dimethylmethacryl amides, N- hydroxyls Methacrylamide, N- methylol methacrylamides, 5- hexen-1-ols, 5- hexene-3-ols, 4- amylene-1-ols etc..
The reactive functional groups having as reactive compounds, are preferably difficult the hydroxyl changed colour because heat is waited. Therefore, reactive compounds are preferably (methyl) acrylate with hydroxyl and/or the alcohol with vinyl.
When the crosslinking polymer involved by present embodiment includes construction unit and base based on lower alkyl When the construction unit of reactive compounds, the monomer mass conversion containing ratio in the crosslinking polymer of these construction units (lower alkyl:Reactive compounds) it is preferably 90:10~99.9:0.1, more preferably 95:5~99.5:0.5.It is logical Cross and set within the range above-mentioned ratio, the adhesive phase comprising the cross-linked structure based on resulting crosslinking polymer can hold Change places the control of stress-retained rate within the above range.
Crosslinking polymer involved by present embodiment can also be included based on the morpholine class containing alkenes unsaturated group The construction unit of compound (following, also known as " morpholine kind compound ").Morpholinyl has the reaction of promotion crosslinking agent described later Function, therefore possess crosslinking promotion by the way that comprising the construction unit based on morpholine kind compound, crosslinking polymer is formed The polymer of the functional group of function.Now, compared with the situation of the crosslinking accelerator containing low-molecular-weight described later, can reduce The possibility of exhaust is produced, and the crosslink density of adhesive phase can be improved, therefore preferably.As the tool of morpholine kind compound Style, can enumerate N- polyvinyl morpholinones, N- pi-allyls morpholine, N- (methyl) acryloyl morpholine etc..In morpholine kind compound In, from the copolymerizable of the compound involved by other structures unit it is good from the viewpoint of, be adapted to also as acrylic compounds N- (methyl) acryloyl morpholine of compound.Morpholine kind compound can use one kind, can also use a variety of.
With regard to the containing ratio of the construction unit based on morpholine kind compound in the crosslinking polymer involved by present embodiment For, the control of stress-retained rate within the above range and is not allowed to be also easy to produce from the viewpoint of exhaust from easily, relative to The lower alkyl mass conversion content of construction unit of 100 mass parts based on lower alkyl and based on reactivity More than the summation of the reactive compounds mass conversion content of the construction unit of compound, preferably 2 mass parts 30 mass parts with Under, more than more preferably 4 mass parts below 25 mass parts.
Crosslinking polymer involved by present embodiment, which can also contain, removes the above-mentioned knot based on lower alkyl Beyond structure unit, the construction unit based on reactive compounds and the construction unit based on morpholine kind compound based on alkene The construction unit of the compound of class unsaturated bond.As the concrete example of the monomer for assigning this construction unit, can with it is above-mentioned The situation of other polymerizable compounds similarly illustrates alkene, vinyl carboxylates, the aromatic series with alkenes unsaturated bond.Or Person, can also illustrate that for example the glyoxaline compound etc. containing alkenes unsaturated group is same with morpholine kind compound possesses crosslinking The compound of the functional group of promotion functions.The containing ratio of the construction unit based on this compound is not particularly limited, but excessively When worry be difficult to by stress-retained rate control within the above range.Therefore, for its containing ratio, relative to 100 mass parts bases In the lower alkyl mass conversion content of the construction unit of lower alkyl and knot based on reactive compounds The summation of the reactive compounds mass conversion content of structure unit, preferred upper limit is 10 mass parts, and more preferably the upper limit is 5 mass Part.
(ii) crosslinking agent
Crosslinking agent involved by the adhesive phase of present embodiment contains selected from toluene di-isocyanate(TDI) (TDI) and its derives One or more kinds of compounds in thing are (in this manual, also known as " toluene di-isocyanate(TDI) class crosslinking agent ", separately Outside, also it is abbreviated as sometimes " TDI classes crosslinking agent ").Crosslinking agent involved by the adhesive phase of present embodiment is preferably handed over TDI classes Connection agent is principal component, is further preferably made up of TDI class crosslinking agents, is particularly preferably substantially made up of TDI.Handed over as TDI classes Join the concrete example of agent, can enumerate and polyisocyanate compounds or different obtained from addition reaction occur with trimethylolpropane etc. Cyanurate compound, biuret type compound and with known PPG and PEPA, acrylic polyol, There is the polyisocyanate of polyurethane prepolymer type obtained from addition reaction in polybutadiene polyol, polyisoprene polyol etc. Ester etc..TDI class crosslinking agents are contained by crosslinking agent, it is different with containing other polyisocyanate compounds, such as phenylenedimethylidyne two Cyanate (XDI) is compared with the situation of hexamethylene diisocyanate (HMDI) etc., even if double-sided adhesive sheet is flexed etc. and outer Power puts on adhesive phase, and stress is not easy to remain in adhesive phase.
The gel fraction of the adhesive phase involved by present embodiment is preferably less than more than 10% 70%, more preferably Less than more than 20% 60%.Make the gel fraction of adhesive phase in the scope by adjusting the consumption of above-mentioned crosslinking agent, can be easily By the control of stress-retained rate in above range.Specifically, the carrying out by adjusting in adhesive phase forms the anti-of cross-linked structure The content of crosslinking agent in the state of before answering, makes it relative to the above-mentioned crosslinking polymer of 100 mass parts, in 0.1 mass parts Scope below the mass parts of the above 10, easily can control the gel fraction of adhesive phase in above range.
(iii) other compositions
As long as stress-retained rate can then contain various composition in above range in adhesive phase.For example, friendship can be illustrated Connection accelerator；The coloured materials such as dyestuff, pigment；The antioxidants such as phenyl amines, phenol；Benzophenone, benzotriazole etc. Ultra-violet absorber；The filler composition such as talcum, titanium dioxide, silica, starch；Plasticiser；Antioxidant；Light stabilizer； Dispersant；And levelling agent.But, these compositions are preferably the composition for being not likely to produce exhaust.
(1-3) thickness
The thickness of the adhesive phase that the double-sided adhesive sheet involved by present embodiment possesses is not particularly limited.When excessively thin Worry that desired adhesion characteristic can not be obtained, worry less favorable from the aspect of processability when blocked up.Therefore, adhesive phase Thickness by adhesive layer integrally in terms of be generally selected in 4~30 μm of scope, be preferably selected in 6~25 μm of scope.
(2) core
Double-sided adhesive sheet involved by present embodiment can possess core.In a concrete example, present embodiment institute The double-sided adhesive sheet being related to possesses the core that each interarea is laminated with adhesive phase.
As long as constituting the material of the core involved by present embodiment with the stretching higher than the material for constituting adhesive phase Intensity, i.e. have as the due key property of core, be not particularly limited.Preferably it is not likely to produce the material of organic gas Material.As the concrete example of the material for constituting core, the polyolefin such as polyethylene, polypropylene, poly terephthalic acid second two can be enumerated The resinous sheet materials such as the polyester such as ester, polybutylene terephthalate, polyimides, polyamide.Can also use in these trees Implement the material after the metal evaporations such as aluminium on the sheet material of fat.Or, the stationery being made up of synthetic paper, dipping paper etc., aluminium foil and Metal foils such as Copper Foil etc. can also be enumerated as the concrete example for the material for constituting core.
When using resin-made sheet material as core, for the cementability of adhesive phase for improving and being arranged on, can So that the surface treatment of oxidizing process or further provided for contouring method etc. should be being carried out on the face of side opposed with adhesive phase.It is used as above-mentioned oxidation Method, for example, can enumerate Corona discharge Treatment, chromic acid treatment (wet type), flame treatment, hot blast treatment, ozone/ultraviolet irradiation Processing etc., also, as further provided for contouring method, such as can enumerate sand-blast, solvent treatment method.These surface preparations can root Suitably selected according to the species of core, but from from the aspect of effect and operability etc., it is generally preferable to using at corona discharge Logos.Also, can also implement to set primary coat treatment (as concrete example, silane coupled treatment can be enumerated) of priming coat.
The thickness of the core involved by present embodiment is not particularly limited.Worry to be difficult to grasp core when excessively thin Make, or be difficult to enjoy the interests (can illustrate double-sided adhesive sheet not easy to break etc.) based on core is set.On the other hand, core When blocked up, worry that double-sided adhesive sheet is integrally thickening.Therefore, the thickness of core is generally preferably set in 2~50 μm or so of scope, More preferably it is set in 3~20 μm or so of scope.
In addition, the overall thickness of double-sided adhesive sheet be preferably set to 100 μm or so it is following, be more preferably set as 65 μm with Under.On the other hand, from from the viewpoint of ensuring operability, the overall thickness of double-sided adhesive sheet is preferably set to more than 10 μm, more It is preferably set to more than 20 μm.
(3) material is peeled off
Showing out for the adhesive phase of the both ends of the surface to form the double-sided adhesive sheet involved by present embodiment can be made, but it is logical Often before the use, stripping material is attached temporarily in order to protect adhesive phase.
The release surface that peel off material has fissility by possessing the supporting substrate of sheet and at least one side is constituted.The release surface Opposite with supporting substrate opposite side the one of the peeling agent layer that can be disposed on the supporting substrate surface without fissility The face of side, or the one side of the supporting substrate with fissility.
As the supporting substrate for peeling off material, such as can enumerate paper, synthetic paper, resinae film.As paper, for example may be used To enumerate glassine paper, polyethylene layer platen etc., as resinae film, for example, polyvinyl resin, acrylic resin can be enumerated Deng vistanex, the polyester resin such as polybutylene terephthalate resin, polyethylene terephthalate resin, acetic acid esters tree Films such as fat, polystyrene resin, vinyl chloride resin etc..As constitute peeling agent layer stripping treatment agent, can illustrate containing The heat-resistant powder fillers such as olefine kind resin, isoprene resinoid, butadiene type resin, chain alkyl resinoid, alcohol acids tree The stripping treatment agents such as fat, fluorine-type resin, organic silicon resin.The thickness for the peeling agent layer being formed on supporting substrate is without special Limit, when remover is coated with solution state, preferably 0.05~2.0 μm, more preferably 0.1~1.5 μm.When the poly- second of use During the thermoplastic resin such as alkene and polypropylene formation peeling agent layer, the thickness of peeling agent layer is preferably 3~50 μm, more preferably 5~ 40μm。
There is the supporting substrate of fissility as surface, acrylic resin film, polyvinyl resin film etc. can be illustrated Polyolefin resin film, and these polyolefin resin film layers are pressed on paper or the film of other films.
The thickness for peeling off the supporting substrate of material is not particularly limited, usually less than more than 15 μm 300 μm left and right.
Further, since running of the organo-silicon compound of gasification to HDD brings harmful effect, therefore preferably present embodiment Involved double-sided adhesive sheet does not contain the material of organic silicon, and the stripping material peeled off when preferably using do not contain yet it is organic The material of silicon class.
Also, when the release surface for peeling off material is pasted in two faces of double-sided adhesive sheet, make to be pasted on the stripping of its one side Material peels off stripping of the material from double-sided adhesive sheet from the stripping difficulty of double-sided adhesive sheet and the another side for being pasted on double-sided adhesive sheet Difficulty is different, i.e. using easily peelable material and re-release material as peel off material can improve double-sided adhesive sheet is pasted on sticky surface when Operability, therefore preferably.
2. adhesive phase formation coating material
The adhesive phase that double-sided adhesive sheet involved by present embodiment possesses can use the adhesive of following explanation Layer formation is formed with coating material.In addition, in this manual, " adhesive phase formation coating material " refers to containing being used for Form the composition and the material that is used in the painting process for forming adhesive phase of adhesive phase, and refer to 23 DEG C, There is the material of mobility when being placed in the environment of relative humidity 50%, be the situation of low-viscosity (mobile) liquid when not only comprising coating, Also comprising the viscoid with the viscosity of a certain degree.Also, being contained sometimes with solute is used to form adhesive phase Composition, contain sometimes as dispersate.
On the adhesive phase formation coating material involved by present embodiment, as long as containing for forming stress-retained Rate is not particularly limited in above range and the composition of adhesive phase comprising cross-linked structure, then its composition.Can be viscous to adjust Waited for the purpose of the thickness of mixture layer and contain solvent (also doubling as decentralized medium sometimes).
In specific of adhesive phase formation coating material involved by present embodiment, as assigning by this The composition of cross-linked structure that the adhesive phase that coating material is formed is included, the coating material contains comprising without carboxyl The crosslinking polymer and TDI class crosslinking agents of acrylic polymer (not carboxylic acrylic polymer).With regard to adhesive For the relation of the content of crosslinking polymer and TDI class crosslinking agents in layer formation coating material, relative to 100 mass parts , preferably be set to more than 0.1 mass parts TDI class crosslinking agents below 10 mass parts by crosslinking polymer.By preparing coating material Make above-mentioned relation in the scope, the gel fraction for forming the adhesive phase formed with coating material by adhesive phase can be realized easily Scope is stated, is easily less than 40% by the stress-retained rate control of the adhesive phase formed by the coating material now.In addition, As long as the stress-retained rate of resulting adhesive phase can contain in above range, then adhesive phase formation coating material Crosslinking agent beyond TDI class crosslinking agents.
Composition that adhesive phase formation coating material be able to should contain according to adhesive phase and contain coloured material, antioxygen The compositions such as agent, ultra-violet absorber.
The preparation method of adhesive phase formation coating material is not limited, and only is mixed for forming adhesive phase sometimes Composition, the composition is also mixed and be prepared with solvent (also doubling as decentralized medium sometimes) sometimes.It is viscous when used for being formed When the composition of mixture layer includes the composition that should be dissolved in solvent, solvent can also be heated so that the composition is suitably molten Solution.
3. the manufacture method of double-sided adhesive sheet
The manufacture method of double-sided adhesive sheet involved by present embodiment is not particularly limited.Double-sided adhesive sheet can be enumerated One concrete example of manufacture method is as follows.
First, the first laminate and the second laminate as the laminate for peeling off material and adhesive phase are prepared.
In order to prepare the first laminate, above-mentioned adhesive phase formation is coated on to the stripping of the first stripping material with coating material On the face of surface side, the film of adhesive phase formation coating material is formed on material is peeled off.Its coating method is not particularly limited, Existing known method can be used, such as stick coating method, scraper for coating method, rolling method, scraper plate rubbing method, mold rubbing method. Then, the adhesive phase formation peeled off on material is dried with the film of coating material, obtains adhesive phase lamination in first Peel off the first laminate on material.The drying condition is arbitrary, can be positioned over room temperature, can also be heated to above-mentioned film Such as 80 DEG C or so.Drying time suitably sets according to thickness and drying temperature of film etc..For example, working as above-mentioned painting When film is heated to 80 DEG C, the heat time can be set to below a few minutes degree.Pasted on the adhesive face of first laminate Close core and obtain one side bonding sheet.
Then, the second laminate being made up of in the adhesive phase in its release surface the second stripping material and lamination is formed.Its Forming method is identical with the situation of the first laminate, therefore omits the description.
The face of the core side of so obtained one side bonding sheet is pasted with the face of the adhesive phase side of the second laminate Close, so as to first stripping material and second stripping material be pasted on respectively adhesive phase state obtain successively lamination adhesive phase, The double-sided adhesive sheet of core, adhesive phase.
Here, the first stripping material and the second stripping material can be identical structure, or different structures.As above institute State, if by one of them make easily peelable material, another make re-release material, the excellent double-sided adhesive of operating property can be made Close piece.
In addition, passing through the back tender for the adhesive phase for being appropriately setting for being formed in the first laminate and the second laminate The drying condition (specifically, can illustrate film being heated to more than 60 DEG C Zuo You) of sequence, can carry out the crosslinking in film Agent and the reaction of crosslinking polymer.In order to replace so entering in the drying process of the adhesive phase for forming each laminate Row cross-linking reaction, or, in order to also fully carry out cross-linking reaction in addition to this drying process, can be for forming each lamination After the drying process of the adhesive phase of body, such as several days standing etc. in the environment of 23 DEG C, relative humidity 50% supporting is set Raw operation.When health operation is carried out, its implementation period be it is arbitrary, can be in the adhesive phase for forming each laminate Carried out immediately after drying process, it is also possible to implementing to make the first laminate and the second laminate directly or the lamination via core Process formation double-sided adhesive sheet after carry out.
4. the application method of double-sided adhesive sheet
Double-sided adhesive sheet involved by present embodiment is used to attach the component being assembled in the devices such as HDD, relay In other assemblies (can also be interim close to).
Here, device preferably comprises its surfaces of deterrent such as the electric contact component in hard disk and magnetic head, relay in HDD At least a portion adheres to the component of foreign matter.When device include this component when, if using common double-sided adhesive sheet make component that This is attached, then the material and/or its presoma for forming above-mentioned foreign matter (as their concrete example, can enumerate carboxylic acid etc. organic Inorganic matters such as class material, organosilicon compound etc.) released as exhaust from adhesive phase of the double-sided adhesive sheet etc. Put, the possibility for being attached to the surface of the component of the above-mentioned foreign matter attachment of deterrent is high.But, the double-sided adhesive involved by present embodiment Close piece due to the possibility that release forms the exhaust of these foreign matters and its presoma can be reduced therefore above-mentioned different deterrent is assembled with Can also suitably it be used in the device of the component of thing attachment.
In case of this device is HDD and FPC is attached to HDD framework (hreinafter referred to as " framework "), to this The application method of the double-sided adhesive sheet involved by implementation method is specifically described.The adhesive phase of double-sided adhesive sheet now Sticky surface is the surface (framework sticky surface) and the surface of FPC of the framework of HDD.
Framework is that the component formed by carrying out die casting or punching press to metal group materials such as aluminium alloys is implemented for improving Obtained from the surface treatment of corrosion resistance and outward appearance.As the concrete example of surface treatment, anodic oxidation can be enumerated, using containing Electrophoretic painting of the coating of epoxylite etc..Therefore, the face structure of framework sticky surface layer as formed by being surface-treated by this Into.Also, the sticky surface of framework and on-plane surface, it is concavo-convex with existing according to rigid purpose of framework etc. is improved in many cases Face.That is, framework sticky surface has the flexure plane high in the face such as difference of height part sometimes.
On the other hand, in many cases, FPC is typically by such as metal foils such as the resinae such as Kapton film and copper Laminate (sometimes with adhering agent layer) is constituted, and its interarea is made up of the face of resinae film.Generally, the thickness of FPC is 10 μm The thickness of left and right to hundreds of μm or so, and with a certain degree of flexibility.Therefore, even if framework sticky surface is flexure plane high, FPC also can be with approximately along its shape distortion.But, because FPC has metal foil as conductive component, if therefore making FPC The minimum bending radius of the bending section office of FPC became when being bent in the way of along the shape of the flexure plane high of framework sticky surface Small, then the metal foil can cause broken string in the portion fractures.Therefore, FPC is in order to prevent the minimum bending radius from becoming too small And there is the modulus of elasticity in static bending more than to a certain degree.
Therefore, if while make the laminate of double-sided adhesive sheet and FPC along the shape distortion of the flexure plane high of framework sticky surface, While the face of the adhesive phase side of the laminate is pasted on into framework sticky surface, then produced in FPC based on the elasticity of flexure Recuperability, the power makes the laminate away from frame in the bending section of double-sided adhesive sheet and the laminate of FPC and its part conduct nearby The power of body sticky surface and play a role.When this force is higher, produced sometimes between the adhesive phase and framework of double-sided adhesive sheet Peel off.
One of countermeasure for avoiding above mentioned problem is to improve framework sticky surface with adhesive phase towards framework quilt The adaptation in the face of the side in viscous face, specifically, raising forms the cohesive of the adhesive phase of the interarea of double-sided adhesive sheet i.e. Can.But, change the composition of adhesive phase in order to improve the cohesive of adhesive phase, to improve the sticky surface relative to framework Wetability, then worrying the amount of the exhaust from adhesive phase can increase.
In contrast, the adhesive layer for constituting the double-sided adhesive sheet being configured between framework and FPC is also produced and FPC identicals Recuperability, is conceived to the recuperability and also serves as making power of the FPC away from framework sticky surface play a role, if will be provided with making the stress residual Stay the double-sided adhesive sheet involved by the present embodiment of adhesive phase of the rate less than 40% to be configured between framework and FPC, then can Enough abated effects in be made up of the double-sided adhesive sheet and FPC involved by present embodiment it is laminate, make the laminate remote The power in the direction of framework sticky surface.Therefore, even if without such as improving the adhesive relative to the wetability of framework sticky surface etc. The composition change of layer, it is also possible to realize reducing framework sticky surface and both-sided adhesive on such as flexure plane high such as face of difference of height part The possibility being peeling between piece.Consequently, it is possible to the double-sided adhesive sheet involved by present embodiment can be realized reducing simultaneously Flexure plane high or its possibility for nearby tilting and reduction produce the possibility of exhaust from adhesive phase.
Embodiments described above is recorded for the ease of understanding the present invention, be not intended to limit it is of the invention and Record.Therefore, each important document disclosed in above-mentioned embodiment is intended to also set comprising all of technical scope for belonging to the present invention Meter change and equipollent.
Embodiment
Hereinafter, the present invention is further specifically described by embodiment etc., but the scope of the present invention is not limited to These embodiments etc..
(embodiment 1)
With butyl acrylate (BA), methyl acrylate (MA), acryloyl morpholine (ACMO) and acrylic acid 2- hydroxy methacrylates (HEA) for monomer component crosslinking polymer [BA/MA/ACMO/HEA=83.5/2/14/0.5, weight average molecular weight 600,000, Gu The mass % of shape thing 35] in 100 mass parts, mixed toluene diisocyanates crosslinking agent [Toyo Ink Co., Ltd.s system, commodity Name " BHS-8515 ", the mass % of solid content 37.5] 0.45 mass parts, so as to prepare adhesive phase formation coating material.
Using knife type coater, adhesive formation is coated on the first stripping material (easily peelable material) with coating material Make on the lift-off processing face of [Lintec Corporation systems, trade name " SP-PET381031 "] dried coating weight into 25g/m2, and by resulting film heat drying about two minutes at 100 DEG C, so as to obtain first peel off formed on material it is viscous First laminate of mixture layer.Then, on the face of the adhesive phase side in the first laminate, thickness is laminated as core The PET film [TORAY Induastries.Inc. systems, trade name " Lumirror S10 "] for 12 μm is spent, so as to obtain one side Bonding sheet.
Then, using knife type coater, adhesive formation is coated on the second stripping material (re-release material) with coating material The lift-off processing of [Lintec Corporation systems, trade name " SP-PET3811 "], which is discussed face to face, makes dried coating weight be 25g/ m2, and by resulting film heat drying about two minutes at 100 DEG C, so as to obtain forming adhesive on the second stripping material Second laminate of layer.Fit the second laminate on the face of the core side of the one side bonding sheet and make both-sided adhesive Adhesive tape.
(embodiment 2)
Mix toluene di-isocyanate(TDI) class crosslinking agent [the Toyo Ink Co., Ltd.s system, trade name " BHS- of 0.3 mass parts 8515 ", the mass % of solid content 37.5] adhesive formation coating material is prepared, in addition, make same as Example 1ly Make double-sided adhesive tape.
(embodiment 3)
Mix toluene di-isocyanate(TDI) class crosslinking agent [the Toyo Ink Co., Ltd.s system, trade name " BHS- of 0.6 mass parts 8515 ", the mass % of solid content 37.5] adhesive formation coating material is prepared, in addition, make same as Example 1ly Make double-sided adhesive tape.
(embodiment 4)
Mix toluene di-isocyanate(TDI) class crosslinking agent [the Toyo Ink Co., Ltd.s system, trade name " BHS- of 1.2 mass parts 8515 ", the mass % of solid content 37.5] adhesive formation coating material is prepared, in addition, make same as Example 1ly Make double-sided adhesive tape.
(embodiment 5)
With butyl acrylate (BA), methyl acrylate (MA), acrylic acid (AA), acryloyl morpholine (ACMO) and acrylic acid 2- hydroxy methacrylates (HEA) for monomer component crosslinking polymer [BA/MA/AA/ACMO/HEA=83/2/0.5/14/0.5, gather Close mean molecule quantity 600,000, the mass % of solid content 35] in 100 mass parts, mixed toluene diisocyanates crosslinking agent [Toyo Ink Co., Ltd.s system, trade name " BHS-8515 ", the mass % of solid content 37.5] 0.4 mass parts, so as to prepare adhesive phase shape Into with coating material, in addition, double-sided adhesive tape is made same as Example 1ly.
(comparative example 1)
Mix XDI class crosslinking agent [the Toyo Ink Co., Ltd.s system, trade name of 2.0 mass parts " BXX5640 ", the mass % of solid content 35.0] adhesive formation coating material is prepared, it is in addition, same as Example 1 Ground makes double-sided adhesive tape.
(comparative example 2)
Mix XDI class crosslinking agent [the Toyo Ink Co., Ltd.s system, trade name of 3.0 mass parts " BXX5640 ", the mass % of solid content 35.0] adhesive formation coating material is prepared, it is in addition, same as Example 1 Ground makes double-sided adhesive tape.
(comparative example 3)
Mix toluene di-isocyanate(TDI) class crosslinking agent [the Toyo Ink Co., Ltd.s system, trade name " BHS- of 3.0 mass parts 8515 ", the mass % of solid content 37.5] adhesive formation coating material is prepared, in addition, make same as Example 1ly Make double-sided adhesive tape.
The measure ＞ of (test example 1) ＜ gel fractions
Second is pasted on the face of the adhesive phase side of the first laminate obtained in by embodiment or comparative example and peels off material Obtain gel fraction measure laminate.In the environment of 23 DEG C, relative humidity 50%, the gel fraction measure is placed with laminate 7 days.Then, gel fraction measure is cut to 50mm × 90mm with laminate, and peels off the first stripping agent for being pasted on the laminate And/or second stripping material and only obtain adhesive phase.Using the adhesive phase as gel fraction measurement sample determine its quality it Afterwards, wrapped up using Teflon (registration mark) eyelet fabrics (#380) made, and it is small that it is impregnated in 200ml ethyl acetate to 48 When.Then, the gel fraction measurement sample of Teflon (registration mark) eyelet fabric processed and its parcel is taken out from ethyl acetate, Dried two hours in 80 DEG C of baking oven.The gel fraction that Teflon (registration mark) eyelet fabric processed and its parcel are taken out from baking oven is surveyed Surely sample is used, the quality of the gel fraction measurement sample in Teflon (registration mark) eyelet fabric processed is determined.According to following formula, The Mass Calculation gel fraction of the sample by being determined.Show the result in table 1.
Gel fraction (%)=(sample mass before dried sample mass/dipping) × 100
The result of calculation of gel fraction is shown in table 1.
The measure ＞ of (test example 2) stress-retained rates of ＜
Using knife type coater, the adhesive formation of each embodiment and comparative example is coated on the first stripping with coating material The lift-off processing face of material (easily peelable material) [Lintec Corporation systems, trade name " SP-PET381031 "] and make dry after Coating weight be 50 μm, by resulting film heat drying about two minutes at 100 DEG C, thus obtain by first peel off material and The first laminate that adhesive phase is constituted.In the environment of 23 DEG C, relative humidity 50%, the laminate is placed 7 days.Then, By second stripping material (re-release material) fit in the first laminate adhesive phase side face, then, remove these peel off materials and Only obtain adhesive phase.The adhesive phase is rolled into it is cylindric and as tension test sample.Using universal tensile testing machine, So that, apart from 30mm, the measure object part of measure tension test sample is (between chuck between draw speed 200mm/min, chuck 30mm part) elongation 5% when stress A (N) and stop elongation 5 minutes after stress B (N).According to determined these Stress A, B calculate B/A × 100 (%), using the value as stress-retained rate (%).
The result of calculation of stress-retained rate is shown in table 1.
(test example 3) ＜ adaptation evaluation tests ＞
Respectively for embodiment and the double-sided adhesive sheet of comparative example, it is 25 μm to peel off first and peel off material and attach thickness PET film [TORAY Induastries.Inc. systems, trade name " Lumirror "], resulting laminate is cut and obtained The rectangle bonding sheet of 25mm × 100mm.Then, in the environment of 23 DEG C, relative humidity 50%, by the bonding sheet obtained by stripping The second stripping material and the face of adhesive phase exposed is pasted on by epoxy electro dipping plate (PALTEK Corporation systems) On the plane clung body of composition, make bonding area for 25mm × 50mm, and under above-mentioned environment, to what is do not pasted in bonding sheet (state for directly exposing adhesive phase) end, along from the direction application in 90 ° relative to the face pasted with plane clung body The load-carrying of 0.49N.Place 24 hours in this condition, and determine the amount come off from plane clung body by bonding sheet after 24 hours (bias), is evaluated according to following benchmark.
A：Disengaging amount：Below 10mm
B：Disengaging amount：More than 10 and less than 40mm
C：Disengaging amount：More than 40mm
Evaluation result is shown in table 1.
[table 1]
As shown in table 1, in the double-sided adhesive sheet of the embodiment for meeting condition of the invention, by gluing that the sheet material possesses The stress-retained rate of mixture layer is less than 40%, even if therefore double-sided adhesive sheet pasted with the state that bends, in the bending section and its The power of state restoration of the neighbouring double-sided adhesive sheet to be made from bending is also difficult to play a role.Therefore, the double-sided adhesive sheet of bending is not Easily peeled off from sticky surface.
Industrial applicibility
The printing sheet material of the present invention is relatively low and cohesive is excellent due to the possibility for producing exhaust, therefore, it is possible to by HDD The component that assembly surface deterrent adheres to foreign matter that is provided with the device such as relay, functions properly as close in height The component of the framework of flexure plane etc..
Description of reference numerals
1:HDD framework
2:FPC
3:Double-sided adhesive sheet
4:The laminate of FPC and double-sided adhesive sheet

Claims (7)

1. a kind of double-sided adhesive sheet, it is characterised in that it is that possess adhesive phase of the stress-retained rate of at least one of which less than 40% , double-sided adhesive sheet for being pasted on high flexure plane,
Described adhesive layer includes the cross-linked structure reacted by crosslinking agent and crosslinking polymer, and substantially not Containing the composition with carboxyl,
The crosslinking agent contains toluene di-isocyanate(TDI) class crosslinking agent,
The crosslinking polymer contains the acrylic polymer without carboxyl,
The acrylic polymer without carboxyl includes the knot based on the morpholine kind compound with alkenes unsaturated group Structure unit.
2. double-sided adhesive sheet according to claim 1, wherein,
The gel fraction of described adhesive layer is less than more than 10% 70%.
3. double-sided adhesive sheet according to claim 1, wherein,
Whole adhesive phases that double-sided adhesive sheet possesses, stress-retained rate is less than 40%.
4. double-sided adhesive sheet according to claim 1, wherein,
The acrylic polymer without carboxyl is further comprising (methyl) that the carbon number based on alkyl is less than 4 The construction unit of alkyl acrylate and the construction unit based on the ethylenically unsaturated compounds with the reactive functional groups.
5. double-sided adhesive sheet according to claim 1, wherein,
The double-sided adhesive sheet possesses the core with two interareas, and is laminated with described adhesive layer in each interarea.
6. double-sided adhesive sheet according to claim 5, wherein,
The thickness of the core is less than more than 2 μm 15 μm.
7. a kind of coating material, it is viscous that its double-sided adhesive sheet for being used to being formed in claim 1-6 described in any one possesses Mixture layer, wherein,
The coating material contains crosslinking polymer and toluene di-isocyanate(TDI) class crosslinking agent, and with mobility.
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