CN105051137A

CN105051137A - Adhesive sheet

Info

Publication number: CN105051137A
Application number: CN201480016096.9A
Authority: CN
Inventors: 平山高正; 北山和宽
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2013-03-15
Filing date: 2014-03-12
Publication date: 2015-11-11
Also published as: KR20150127088A; KR102203019B1; TWI659084B; WO2014142192A1; TW201441333A; JPWO2014142192A1

Abstract

Provided is an adhesive sheet which is able to realize excellent cutting precision and a reduction in cutting debris when cutting microcomponents such as electronic components. This adhesive sheet is provided with an adhesive layer which includes a plurality of thermally expandable microspheres and an anchoring layer which is disposed on one side of the adhesive layer, with at least one or more thermally expandable microspheres protruding from the adhesive layer and the protruding thermally expandable microspheres being embedded in the anchoring layer. In a preferred embodiment, the adhesive layer includes thermally expandable microspheres having a larger particle diameter than the thickness of the adhesive layer.

Description

Adhesive sheet

Technical field

The present invention relates to adhesive sheet.

Background technology

In the manufacture of the electronic units such as Silicon Wafer, multilayer capacitor, transparency electrode, big area is imparted in the lump and function and the substrate that obtains smallly must turn to target sizes by cutting off processing.Cut-out adds man-hour, the adhesive sheet that the machined object (substrate) that the cut-out precision using stress and vibration for preventing because adding man-hour to cause reduces is fixing.This adhesive sheet require add man-hour to the sufficient bounding force of machined object and require processing after the machined object of cut-out (electronic unit) can be made easily to peel off.As such adhesive sheet, the known adhesive sheet (such as patent documentation 1) comprising heat-expandable microsphere in tackiness agent.The adhesive sheet comprising heat-expandable microsphere makes heat-expandable microsphere expand or foaming by heating, thus bounding force reduces, and therefore, showing sufficient bounding force man-hour in above-mentioned adding, after processing by heating, electronic unit can be made easily to peel off.

In recent years, along with the light weight/miniaturization of electronic unit, requirement can realize the adhesive sheet that the more high-precision machined object cutting off processing is fixed.In addition, also require to reduce processing bits (cutting swarf) cut off and add and produce man-hour.For these requirements, think, if make the tackiness agent of formation adhesive sheet thinner, then can obtain the adhesive sheet of the minimizing that can realize higher cut-out precision and cutting swarf.But, comprise the adhesive sheet of heat-expandable microsphere owing to comprising heat-expandable microsphere, the problem that the thickness that thus there is tackiness agent is restricted.More specifically, there are the following problems to comprise the adhesive sheet of heat-expandable microsphere: when making tackiness agent thinner, heat-expandable microsphere Autoadhesive is given prominence to, and significantly reduces with the practicality such as the adaptation difference of base material or machine table.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2002-121510 publication

Summary of the invention

the problem that invention will solve

The present invention makes to solve above-mentioned existing problem, its object is to, and provides a kind of cut-out at micro-elements such as electronic units to add to realize man-hour the adhesive sheet of the minimizing of excellent cut-out precision and cutting swarf.

for the scheme of dealing with problems

Adhesive sheet of the present invention possesses: the binder layer comprising multiple heat-expandable microsphere, with the one-sided fixing layer being configured in this binder layer, at least more than one heat-expandable microsphere is given prominence to from this binder layer, and this outstanding heat-expandable microsphere is embedded in fixing layer.

In a preferred embodiment, above-mentioned binder layer comprises the heat-expandable microsphere with the particle diameter larger than the thickness of this binder layer.

In a preferred embodiment, the height of the part of giving prominence to from aforementioned binder layer of above-mentioned heat-expandable microsphere is more than 0.4 μm.

In a preferred embodiment, the sectional view in regulation region comprising the part that above-mentioned heat-expandable microsphere is given prominence to from aforementioned binder layer, the length (l1) at the interface of this binder layer and above-mentioned fixing layer is more than 1.02 with the ratio (l1/L) of the length (L) of the thickness direction projection line at this interface.

In a preferred embodiment, the median size of above-mentioned heat-expandable microsphere is 6 μm ~ 45 μm.

In a preferred embodiment, the Young's modulus that above-mentioned fixing layer utilizes Using Nanoindentation to record at 25 DEG C is more than 1MPa.

In a preferred embodiment, the thickness of above-mentioned binder layer is less than 20 μm.

In a preferred embodiment, by heating, above-mentioned heat-expandable microsphere is expanded or foaming time, the surface roughness Ra being in the face of opposition side with aforementioned fixing layer of above-mentioned binder layer is more than 3 μm.

In a preferred embodiment, the Young's modulus that above-mentioned binder layer utilizes Using Nanoindentation to record at 25 DEG C is below 1MPa.

In a preferred embodiment, also base material is possessed in the side contrary with aforementioned adhesion oxidant layer of above-mentioned fixing layer.

According to alternate manner of the present invention, also provide a kind of manufacture method of electronic unit.This manufacture method comprises: attach electronic part material on above-mentioned adhesive sheet after, carries out cut-out processing to this electronic part material.

the effect of invention

According to the present invention, by fixing layer in the one-sided configuration of the binder layer comprising heat-expandable microsphere, being embedded into by the heat-expandable microsphere outstanding from binder layer fixes in layer, the binder layer in low elasticity region can not be made thinner by the concavo-convex impact caused by heat-expandable microsphere, its result, can obtain the adhesive sheet that can realize excellent cut-out precision.In addition, according to the present invention, binder layer can be made thinner, therefore, the cut-out using adhesive sheet of the present invention to carry out the micro-elements such as electronic unit adds man-hour, can suppress the generation of cutting swarf.

Accompanying drawing explanation

Fig. 1 is the schematic cross-section of adhesive sheet preferred embodiment of the present invention.

Fig. 2 is for illustration of the schematic cross-section of binder layer with the adhesive sheet preferred embodiment of the present invention at the interface of fixing layer.

Fig. 3 is the schematic cross-section of other adhesive sheet preferred embodiment of the present invention.

Fig. 4 is the figure of the Raman mapping (Ramanmapping) obtained by thickness measurement representing embodiment 3.

Fig. 5 is the figure of the SEM image in the cross section of the adhesive sheet representing embodiment 11.

Embodiment

A. the entirety of adhesive sheet is formed

Fig. 1 is the schematic cross-section of adhesive sheet preferred embodiment of the present invention.Adhesive sheet 100 possesses binder layer 10 and is configured in the one-sided fixing layer 20 of binder layer 10.Binder layer 10 comprises multiple heat-expandable microsphere 11.In practical application, binder layer 10 also comprises tackiness agent 12.At least more than one heat-expandable microsphere 11 is given prominence to from binder layer 10, and outstanding heat-expandable microsphere 11 is embedded in fixing layer 20 in the mode in layer 20 that fixes to fix.Being embedded into by making the heat-expandable microsphere 11 given prominence to fixes in layer 20, can not by the concavo-convex impact caused by heat-expandable microsphere 11.Heat-expandable microsphere 11 can be expanded or foam by heating.Although not shown, interleaving paper can be configured to protect binder layer 10 until adhesive sheet is fed into practical application on binder layer 10.In addition, in illustrated example, although clearly show the interface 1 of binder layer 10 and fixing layer 20, interface also can for the interface being difficult to distinguish by visual, microscope etc.The composition that each layer such as can be analyzed in the interface being difficult to distinguish by visual, microscope etc. distinguishes (details will describe later).

In the present invention, fixing layer 10 by possessing, can allow that heat-expandable microsphere 11 is given prominence to from binder layer 10, thus making binder layer 10 thinner.When making the binder layer 10 in low elasticity region thinner, as cutting off the temporary fixed sheet adding man-hour to electronic unit etc., contribute to realizing excellent cut-out precision.More specifically, use the thin adhesive sheet of binder layer 10 to carry out cut-out as temporary fixed sheet to electronic unit etc. and add man-hour, the distortion of this adhesive sheet is few, therefore, it is possible to prevent: the chip after cut-out adheres to again, cut surface tilts or become S word and instability, generation chip breach etc. when cutting off.In addition, when being used as to cut off to electronic unit etc. the temporary fixed sheet adding man-hour by adhesive sheet thin for binder layer 10, the generation of cutting swarf can also be suppressed.Adhesive sheet of the present invention can play above-mentioned effect certainly needless to say in the cut-out utilizing rotating knife conventional in cutting action to carry out, it is utilizing in the cut-out in order to reduce the pressing cutting of cutting loss and the flat knife that adopts, also can play above-mentioned effect and particularly useful.In addition, even if when (such as 30 DEG C ~ 150 DEG C) cut off under heating, also can precision cut off well as mentioned above.

In addition, because the binder layer 10 of adhesive sheet of the present invention comprises heat-expandable microsphere 11, therefore, when adherend (chip after such as cutting off processing) is peeled off from adhesive sheet, heated by the temperature of the degree that can expand with heat-expandable microsphere 11 or foam, produce concavo-convex at adhesive face, thus the bounding force of this adhesive face can be made to reduce or disappear.

The height H of the part of giving prominence to from binder layer of above-mentioned heat-expandable microsphere is preferably more than 0.4 μm, be more preferably 0.4 μm ~ 80 μm, more preferably 0.6 μm ~ 80 μm.In the present invention, by possessing fixing layer, can allow that heat-expandable microsphere is given prominence to above-mentioned height, thus making the thinner thickness of binder layer.In addition, height H, when above-mentioned scope, can prevent from fixing the intensity of layer and Young's modulus reduces, thus is provided as and cuts off to electronic unit etc. the adhesive sheet that the temporary fixed sheet adding man-hour contributes to realizing more excellent cut-out precision.The height of the part of giving prominence to from binder layer of heat-expandable microsphere is preferably little than the thickness of above-mentioned fixing layer.

The sectional view in regulation region comprising the part that above-mentioned heat-expandable microsphere is given prominence to from above-mentioned binder layer, binder layer and the fixing length (l1) at interface of layer are preferably more than 1.02 with the ratio (l1/L) of the length (L) of the thickness direction projection line at this interface, are more preferably 1.05 ~ 5.In the present invention, by possessing fixing layer, can allow that heat-expandable microsphere is given prominence to above-mentioned interface shape, thus making the thinner thickness of binder layer.In addition, (l1/L), when above-mentioned scope, can prevent from fixing the intensity of layer and Young's modulus reduces, thus is provided as and cuts off to electronic unit etc. the adhesive sheet that the temporary fixed sheet adding man-hour contributes to realizing more excellent cut-out precision.It should be noted that, the thick line l1 shown in the schematic cross-section of Fig. 2 is binder layer and the interface fixing layer.

The bounding force when adhesive face of adhesive sheet of the present invention (i.e. binder layer with the face fixing layer and be in opposition side) being attached at pet film (such as thickness 25 μm) is preferably more than 0.2N/20mm, is more preferably 0.2N/20mm ~ 20N/20mm, more preferably 2N/20mm ~ 10N/20mm.When such scope, can obtain as electronic unit etc. being cut off to the useful adhesive sheet of the temporary fixed sheet that adds man-hour.In this specification sheets, bounding force refer to utilize based on JISZ0237:2000 method (measure temperature: 23 DEG C, laminating condition: 1,2kg roller back and forth, peeling rate: 300mm/min, peel angle 180 °) bounding force that records.

The adhesive face of adhesive sheet of the present invention is attached at pet film (such as thickness 25 μm) and bounding force after heating is preferably below 0.2N/20mm, is more preferably below 0.1N/20mm.In this specification sheets, the heating that temperature/time that bounding force reduces with heat-expandable microsphere expansion or foaming carries out is referred to the heating of adhesive sheet.This heating is such as the heating of 1 minute ~ 10 minutes at 70 DEG C ~ 270 DEG C.

The ratio (a2/a1) of the bounding force (a2) after the bounding force (bounding force (a1) before heating) when the adhesive face of adhesive sheet of the present invention being attached at pet film (such as thickness 25 μm) and heating is preferably less than 0.5, is more preferably less than 0.1.(a2/a1) lower limit is preferably 0.0001, is more preferably 0.0005.

As mentioned above, adhesive sheet of the present invention by heating at an established temperature, produces concavo-convex at binder layer with the face (i.e. adhesive face) fixing layer and be in opposition side.The surface roughness Ra of the adhesive face after adhesive sheet heating of the present invention is preferably more than 3 μm, is more preferably more than 5 μm.When such scope, bounding force after the heating can be obtained and reduce or disappear and the adhesive sheet that adherend is easily peeled off can be made.It should be noted that, the surface roughness Ra of adhesive face refers to the surface roughness Ra of the adhesive face of the adhesive sheet after heating under the state not having adherend.Surface roughness Ra can measure based on JISB0601:1994.

Fig. 2 is the schematic cross-section of other adhesive sheet preferred embodiment of the present invention.The side contrary with binder layer 10 that adhesive sheet 200 is fixing layer 20 also possesses base material 30.It should be noted that, although not shown, other the binder layer or bond layer that are applicable to arbitrarily can be set in the side contrary with fixing layer 20 of base material 30.In addition, adhesive sheet of the present invention can at the outside of base material 30 configuration interleaving paper until be fed into practical application.When the outside of base material 30 configuration interleaving paper, this interleaving paper can be attached at base material by the tackiness agent be applicable to arbitrarily.Having illustrated in Fig. 2 and be formed with binder layer 10 at base material 30 one-sided and fix the form of layer 20, but also can form binder layer 10 in the both sides of base material 30 and fix layer 20, such as, be the such formation of binder layer/fixing layer/base material/fixing layer/binder layer.

B. layer is fixed

The Young's modulus that above-mentioned fixing layer utilizes Using Nanoindentation to record at 25 DEG C is preferably more than 1MPa, is more preferably 1MPa ~ 5000MPa, more preferably 1MPa ~ 3500MPa, be particularly preferably 1MPa ~ 1000MPa, most preferably be 10MPa ~ 600MPa.The adhesive sheet with the layer showing such Young's modulus such as can obtain by forming the fixing layer formed by the material different from binder layer.The Young's modulus utilizing Using Nanoindentation to record refers to, when load, unloading time ground METHOD FOR CONTINUOUS DETERMINATION by the load to pressure head time pressure head pressing in sample (such as adhesive face) and compression distance, the Young's modulus obtained by the load obtained-compression distance curve.In this specification sheets, the Young's modulus utilizing Using Nanoindentation to record refers to and condition determination is set to load: 1mN, load/discharge rate: 0.1mN/s, hold-time: 1s carry out measuring the Young's modulus obtained as mentioned above.

By possessing the fixing layer that the Young's modulus that utilizes Using Nanoindentation to record is more than 1MPa as mentioned above, can be provided as and the adhesive sheet that the temporary fixed sheet adding man-hour contributes to realizing excellent cut-out precision is cut off to electronic unit etc.And then by making the Young's modulus utilizing Using Nanoindentation to record of fixing layer be below 5000MPa, this fixing layer can follow the concavo-convex of the heat-expandable microsphere given prominence to from binder layer, is coated to this heat-expandable microsphere with the form embedding this heat-expandable microsphere.In addition, the overall necessary flexibility (such as can follow the flexibility of the degree of adherend) of adhesive sheet can not be damaged, the adhesive sheet helping realize excellent cut-out precision can be provided.

The tensile modulus of above-mentioned fixing layer at 25 DEG C is preferably more than 1MPa, is more preferably 1MPa ~ 5000MPa, more preferably 1MPa ~ 1000MPa.When such scope, the effect same with the effect of the above-mentioned explanation about the Young's modulus utilizing Using Nanoindentation to record can be obtained.It should be noted that, tensile modulus can measure based on JISK7161:2008.

The modulus in flexure of above-mentioned fixing layer at 25 DEG C is preferably more than 1MPa, is more preferably 1MPa ~ 5000MPa, more preferably 1MPa ~ 1000MPa.When such scope, the effect same with the effect of the above-mentioned explanation about the Young's modulus utilizing Using Nanoindentation to record can be obtained.It should be noted that, modulus in flexure can measure based on JISK7171:2008.

The thickness of above-mentioned fixing layer can be set as value applicable arbitrarily according to the concavo-convex amount of the heat-expandable microsphere given prominence to from binder layer (height of outstanding part).Fix the thickness that the heat-expandable microsphere given prominence to from binder layer preferably can all be coated to by the thickness of layer, such as, be greater than 0.4 μm and be less than 200 μm, be preferably 0.6 μm ~ 100 μm, be more preferably 0.6 μm ~ 45 μm.It should be noted that, in this specification sheets, fix the thickness of layer and refer to and be in distance the face of opposition side from the interface forming the material fixing layer 20 and the tackiness agent 12 forming binder layer 10 to what fix layer with this interface as shown in Figure 1.That is, for the part that heat-expandable microsphere 11 is given prominence to from binder layer 10, not as the evaluation object of the thickness of fixing layer.Cut off adhesive sheet and face is cut off in visual observation time, form the material fixing layer 20 and the interface of tackiness agent 12 forming binder layer 10 clear and definite when, the thickness fixing layer can use ruler, vernier callipers, micrometer to measure.In addition, the microscopes such as electron microscope, opticmicroscope, atomic force microscope also can be used to measure the thickness fixing layer.And then, can also interface be distinguished by the difference of the composition fixing layer and binder layer and measure the thickness fixing layer.Such as, the spectroscopic analysis such as Raman spectrum analysis, Infrared spectroscopy, X-ray electron spectroscopic analysis can be passed through; The mass spectrums such as Matrix-assisted laser desorption ionization instrument (MALDI-TOFMS), time of flight secondary ion massspectrometry instrument (TOF-SIMS) etc. analysis forms the composition of the material fixing layer and the tackiness agent forming binder layer, distinguishes interface and measure the thickness fixing layer according to the difference of this composition.Like this by spectroscopic analysis or mass spectrum distinguish the method at interface when visual or use microscopic examination time be difficult to distinguish interface be useful.

As the material forming above-mentioned fixing layer, such as, can list: the polymer materialss such as silicon-type polymkeric substance, epoxy polymkeric substance, polycarbonate based polymer, vinyl polymers, acrylic polymers, carbamate based polymer, Polyester polymkeric substance (such as polyethylene terephthalate), polyolefin polymkeric substance, polyamide-based polymkeric substance, polyimide based polymer, unsaturated hydrocarbons based polymer.When using these polymer materialss, suitably select monomeric species, linking agent, the polymerization degree etc., thus easily can form the fixing layer with above-mentioned Young's modulus.In addition, the affinity of above-mentioned polymer materials and heat-expandable microsphere, the tackiness agent forming binder layer and base material is excellent.Above-mentioned polymer materials can be used alone or combinationally uses two or more.

As the material forming above-mentioned fixing layer, the resin material that can be solidified (high elastic coefficient) by the irradiation of active energy beam also can be used.When utilizing such material to form fixing layer, the adhesive sheet that energy is following can be obtained, namely, described adhesive sheet is low elasticity when the attaching of adhesive sheet and flexibility is high, and operability is excellent, after attaching, by irradiating active energy beam, the Young's modulus of above-mentioned scope can be adjusted to.As active energy beam, such as, can list: gamma ray, ultraviolet, visible rays, infrared rays (invisible heat), radiowave, alpha-ray, β ray, electron rays, plasma flow, ionizing ray, particle ray etc.The postradiation Young's modulus utilizing above-mentioned Using Nanoindentation to record of active energy beam of the fixing layer that the resin material that can be solidified by the irradiation by active energy beam is formed is preferably in above-mentioned scope.In addition, the postradiation above-mentioned tensile modulus of the preferred active energy beam of fixing layer that the resin material that can be solidified by the irradiation by active energy beam is formed and/or modulus in flexure are in above-mentioned scope.

The resin material of (high elastic coefficient) can be solidified as the irradiation by active energy beam, such as can list ultraviolet Line harden システ system (add rattan clear Visual Zhu, Gross He Ji Intraoperative センター development is capable, (1989)), photo-hardening Ji Intraoperative (Ji Intraoperative Qing Reported Association can Knitting (2000)), the resin material recorded in Japanese Unexamined Patent Publication 2003-292916 publication, No. 4151850, Japanese Patent etc.More specifically, can list comprise as the polymkeric substance of host and active energy beam reactive compounds (monomer or oligopolymer) resin material (R1), comprise the resin material (R2) etc. of active energy beam reactive polymer.

As above-mentioned be the polymkeric substance of host, such as can list the rubber-based polymeric things such as natural rubber, polyisobutylene rubber, styrene butadiene ribber, styrene-isoprene-styrene block copolymer rubber, regenerated rubber, isoprene-isobutylene rubber, polyisobutylene rubber, paracril (NBR); Silicon-type polymkeric substance; Acrylic polymers etc.These polymkeric substance can be used alone or combinationally use two or more.

As above-mentioned active energy beam reactive compounds, such as, can list and there is photoreactive monomer or the oligopolymer that acryl, methacryloyl, vinyl, allyl group, ethynyl etc. have the functional group of carbon-to-carbon multikey.As the concrete example of this photoreactive monomer or oligopolymer, can list: trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate etc. are containing (methyl) acryl compound, should containing 2 ~ 5 aggressiveness of (methyl) acryl compound, Deng.

In addition, as above-mentioned active energy beam reactive compounds, the monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinylsiloxane can be used; Or the oligopolymer to be made up of this monomer.The resin material (R1) comprising these compounds can utilize the high-energy rays such as ultraviolet, electron rays to be cured.

And then, as above-mentioned active energy beam reactive compounds, the mixture of the compound in the organic salts such as salt and molecule with multiple heterocycle can be used.This mixture is by the irradiation of active energy beam (such as ultraviolet, electron rays), and organic salt cracking and generate ion, this ion becomes Priming Seeds and causes the ring-opening reaction of heterocycle, thus can form 3 dimension reticulated structures.As above-mentioned organic salt, such as, can list: salt compounded of iodine, phosphonium salt, antimonic salt, sulfonium salt, borate etc.As the heterocycle had in above-mentioned molecule in the compound of multiple heterocycle, oxyethane, trimethylene oxide, tetrahydrofuran (THF), thiirane, ethylenimine etc. can be listed.

Above-mentionedly comprise as in the polymkeric substance of host and the resin material (R1) of active energy beam reactive compounds, active energy beam reactive compounds be preferably 0.1 weight part ~ 500 weight part relative to polymkeric substance 100 weight part as host containing proportional, be more preferably 1 weight part ~ 300 weight part, more preferably 10 weight part ~ 200 weight parts.

Above-mentioned comprising can comprise as the polymkeric substance of host and the resin material (R1) of active energy beam reactive compounds the additive be applicable to arbitrarily as required.As additive, such as, can list active energy beam polymerization starter, active energy beam polymerization promotor, linking agent, softening agent, vulcanizing agent etc.As active energy beam polymerization starter, according to the kind of used active energy beam, the initiator be applicable to arbitrarily can be used.Active energy beam polymerization starter can be used alone or combinationally uses two or more.Comprise as in the polymkeric substance of host and the resin material (R1) of active energy beam reactive compounds, active energy beam polymerization starter be preferably 0.1 weight part ~ 10 weight part relative to polymkeric substance 100 weight part as host containing proportional, be more preferably 1 weight part ~ 5 weight part.

As above-mentioned active energy beam reactive polymer, such as, can list and there is the polymkeric substance that acryl, methacryloyl, vinyl, allyl group, ethynyl etc. have the functional group of carbon-to-carbon multikey.As the concrete example of polymkeric substance with active energy beam reactive functional groups, can list: the polymkeric substance be made up of multifunctional (methyl) acrylate; Light cationic polymerization type polymkeric substance; Polyvinyl cinnamate etc. are containing cinnamoyl polymkeric substance; Diazotizing amino novolac resin; Polyacrylamide; Deng.In addition, as the resin material (R2) comprising active energy beam reactive polymer, the mixture of the compound that there is allylic active energy beam reactive polymer and there is thiol group can also be used.It should be noted that, as long as (when such as attaching adhesive sheet) can form the fixing layer precursor of the hardness (viscosity) with energy practical application before being cured by active energy beam irradiation, except there is the polymkeric substance of active energy beam reactive functional groups, the oligopolymer with active energy beam reactive functional groups can also be used.

The above-mentioned resin material (R2) comprising active energy beam reactive polymer can also comprise above-mentioned active energy beam reactive compounds (monomer or oligopolymer).In addition, the above-mentioned resin material (R2) comprising active energy beam reactive polymer can comprise the additive be applicable to arbitrarily as required.The concrete example of additive is same with the additive comprised as containing in the polymkeric substance of host and the resin material (R1) of active energy beam reactive compounds.Comprise in the resin material (R2) of active energy beam reactive polymer, active energy beam polymerization starter be preferably 0.1 weight part ~ 10 weight part relative to active energy beam reactive polymer 100 weight part containing proportional, be more preferably 1 weight part ~ 5 weight part.

Above-mentioned fixing layer can also comprise microballon.As this microballon, such as, glass microballon, resin microbeads etc. can be listed.When fixing layer and adding such microballon, the Young's modulus fixing layer can be improved, energy precision can be obtained better to the adhesive sheet that machined object is processed.The median size of microballon is such as 0.01 μm ~ 50 μm.The addition of microballon is such as 10 weight part ~ 200 weight parts relative to overall 100 weight part of fixing layer, is preferably 20 weight part ~ 100 weight parts.

C. binder layer

Above-mentioned binder layer preferably comprises tackiness agent and heat-expandable microsphere.

The thickness of above-mentioned binder layer is preferably less than 20 μm, be more preferably 0.1 μm ~ 20 μm, more preferably 1 μm ~ 15 μm, be particularly preferably 1 μm ~ 10 μm.When the thickness of binder layer is greater than 20 μm, as electronic unit etc. is cut off the temporary fixed sheet adding man-hour use when, have the worry producing following unfavorable condition: the chip after cut-out adheres to again, cut surface becomes unstable, produce chip breach when cutting off, produce the unfavorable conditions such as cutting swarf.In the present invention, by possessing fixing layer, can allow that heat-expandable microsphere is given prominence to from binder layer, thus binder layer can be made thinner.On the other hand, when the thickness of binder layer is less than 0.1 μm, there is the worry that can not obtain sufficient bounding force.It should be noted that, in this specification sheets, the thickness of binder layer refers to and is in distance the face of opposition side as shown in Figure 1 from the interface forming the material fixing layer 20 and the tackiness agent 12 forming binder layer 10 to binder layer with this interface.That is, for the part that heat-expandable microsphere 11 is given prominence to from binder layer 10, not as the evaluation object of the thickness of binder layer.It should be noted that, as the discriminating conduct forming material and the interface of the tackiness agent 12 of formation binder layer 10 fixing layer 20, illustrated by above-mentioned B item.

Above-mentioned binder layer preferably comprises the heat-expandable microsphere with the particle diameter larger than the thickness of this binder layer.In other words, the thickness of above-mentioned binder layer also can be less than the particle diameter of above-mentioned heat-expandable microsphere.In the present invention, due to binder layer can be made thinner, therefore, it is possible to obtain the adhesive sheet of cut-out precision as cutting off the temporary fixed sheet adding man-hour to electronic unit etc. and contribute to realizing excellence.

The Young's modulus utilizing Using Nanoindentation to record of at temperature when attaching adhesive sheet of the present invention, above-mentioned binder layer is preferably less than 100MPa, is more preferably 0.1MPa ~ 50MPa, more preferably 0.1MPa ~ 10MPa.The Young's modulus utilizing Using Nanoindentation to record of binder layer refers to that selection does not exist the part of heat-expandable microsphere and the Young's modulus of the Young's modulus, the i.e. tackiness agent that utilize the measuring method illustrated in above-mentioned B item to record.Temperature during above-mentioned attaching adhesive sheet such as at use acrylic adhesives as being 10 DEG C ~ 80 DEG C when tackiness agent, at use Styrene-diene block copolymerization system tackiness agent as being 40 DEG C ~ 120 DEG C when tackiness agent.

(tackiness agent)

As above-mentioned tackiness agent, preferably do not limit the expansion of heat-expandable microsphere or the tackiness agent of foaming when heating.As this tackiness agent, such as, can list: acrylic adhesives, elastomeric adhesive, vinyl alkyl ethers system tackiness agent, silicon-type tackiness agent, Polyester tackiness agent, polyamide-based tackiness agent, carbamate system tackiness agent, Styrene-diene block copolymerization system tackiness agent, radiation curable, in these tackiness agents, compounding fusing point is (such as with reference to Japanese Laid-Open Patent Publication 56-61468 publication, Japanese Laid-Open Patent Publication 63-17981 publication etc.) such as the creep properties modified form tackiness agents that obtains of the hot melt property resin of less than about 200 DEG C.Wherein be preferably acrylic adhesives or elastomeric adhesive.It should be noted that, above-mentioned tackiness agent can be used alone or combinationally uses two or more.

As aforesaid propylene acrylic binder, such as, can list the acrylic adhesives etc. of polymkeric substance based on the one kind or two or more acrylic polymers as monomer component (homopolymer or multipolymer) using (methyl) alkyl acrylate.As the concrete example of (methyl) alkyl acrylate, can list: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid C1-20 alkyl esters such as (methyl) vinylformic acid eicosyl ester.Wherein, (methyl) alkyl acrylate with the straight-chain of carbon number 4 ~ 18 or the alkyl of branched is preferably used.

For the object of the modification of force of cohesion, thermotolerance, bridging property etc., aforesaid propylene acids polymers can also comprise as required with can be corresponding with other monomer component of above-mentioned (methyl) alkyl acrylate copolymer unit.As such monomer component, such as, can list: the carboxyl group-containing monomers such as vinylformic acid, methacrylic acid, carboxy ethyl acrylate, carboxypentyl acrylate, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, the anhydride monomers such as maleic anhydride, itaconic anhydride, the hydroxyl monomers such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, (methyl) dihydroxypropyl lauryl, methacrylic acid (4-hydroxymethylcyclohexyl) methyl esters, styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) propane sulfonic acid etc. are containing sulfonic group monomer, (N-replacement) the acid amides system monomers such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, (methyl) acrylate, (methyl) vinylformic acid N, (methyl) acrylate system monomers such as N-dimethylamino ethyl ester, (methyl) tbutylaminoethylacrylate, (methyl) alkoxyalkyl acrylate system monomers such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, the maleimide system monomers such as N-N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenylmaleimide, the clothing health imide series monomers such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide, the succinimide system monomers such as N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxygen base hexa-methylene succinimide, N-(methyl) acryl-8-oxygen base eight methylene radical succinimide, the ethene base system monomer such as vinyl acetate, propionate, NVP, methyl ethylene pyrrolidone, vinyl pyridine, vinylpiperidone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, second alkene base oxazole, polyvinyl morpholinone, N-vinylcarboxylic acid amide type, vinylbenzene, alpha-methyl styrene, N-caprolactam, the cyanoacrylate monomer such as vinyl cyanide, methacrylonitrile, (methyl) glycidyl acrylates etc. are containing epoxy group(ing) acrylic monomer, the glycol system acrylate monomers such as (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, (methyl) methoxyethyl glycol ester, (methyl) methoxyethyl polypropylene glycol ester, (methyl) tetrahydrofurfuryl acrylate, fluoro (methyl) acrylate, organosilicon (methyl) acrylate etc. have the acrylic ester monomer of heterocycle, halogen atom, Siliciumatom etc., hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, epoxy acrylate, polyester acrylate, the polyfunctional monomers such as urethane acrylate, the olefinic monomers such as isoprene, divinyl, iso-butylene, the vinyl ether system monomers etc. such as vinyl ether.These monomer components can be used alone or combinationally use two or more.

As above-mentioned elastomeric adhesive, can list the elastomeric adhesive with polymkeric substance based on such as following rubber, described rubber is: natural rubber, polyisoprene rubber, styrene butadiene (SB) rubber, styrene isoprene (SI) rubber, styrene-isoprene-styrene segmented copolymer (SIS) rubber, styrene butadiene styrene segmented copolymer (SBS) rubber, styrene ethylene butylene styrene segmented copolymer (SEBS) rubber, styrene ethylene propylene styrene block copolymer (SEPS) rubber, styrene ethylene propylene segmented copolymer (SEP) rubber, regenerated rubber, isoprene-isobutylene rubber, polyisobutene, the synthetic rubber such as their modification body, Deng.

Above-mentioned tackiness agent can comprise the additive be applicable to arbitrarily as required.As this additive, such as, can list: linking agent, tackifier, softening agent (such as trimellitate system softening agent, pyromellitic ester system softening agent), pigment, dyestuff, weighting agent, anti-aging agent, electro-conductive material, static inhibitor, UV light absorber, photostabilizer, stripping conditioning agent, tenderizer, tensio-active agent, fire retardant, antioxidant etc.

As above-mentioned tackifier, use the tackifier be applicable to arbitrarily.As tackifier, such as, use tackifying resin.As the concrete example of tackifying resin, can list: rosin series tackifying resin (such as unmodified rosin, modified rosin, rosin phenol resin, rosin ester system resin etc.), terpenic series tackifying resin (such as terpenic series resin, terpenes phenol resin, styrenated terpene system resin, aromatic modified terpenic series resin, hydriding terpene system resin), hydrocarbon system tackifying resin (such as fatty family hydrocarbon resin, fat family cyclic hydrocarbon resin, fragrance family hydrocarbon resin (such as phenylethylene resin series, diformazan benzene series resin etc.), aliphatic/aromatic through-stone oleo-resinous, aliphatics/alicyclic through-stone oleo-resinous, hydrogenated hydrocarbon resins, coumarone system resin, coumarone indene system resin etc.), phenol system tackifying resin (such as alkyl phenol resin, dimethylbenzene diaion, resole, phenolic varnish etc.), ketone system tackifying resin, polyamide-based tackifying resin, epoxy tackifying resin, elastic system tackifying resin etc.Wherein be preferably rosin series tackifying resin, terpenic series tackifying resin or hydrocarbon system tackifying resin (phenylethylene resin series etc.).Tackifier can be used alone or combinationally use two or more.

Above-mentioned tackifier can use commercially available product.As the concrete example of the tackifier of commercially available product, can list: the terpene phenol resin such as the trade(brand)name " Tamanol901 " that the trade(brand)name " YSpolystarS145 " that YASUHARACHEMICALCO., LTD. manufacture, " MightyAceK140 ", Huang Chuan KCC manufacture; The rosin phenol resins such as the trade(brand)name " Tamanol361 " that the trade(brand)name " SUMILITERESINPR-12603 " that Sumitomo Bakelite Co manufactures, Huang Chuan KCC manufacture; The alkyl phenol resin such as trade(brand)name " Tamanol1010R ", " Tamanol200N " that Huang Chuan KCC manufactures; The alicyclic ring family stable hydrocarbon resins etc. such as the trade(brand)name " AlconP-140 " that Huang Chuan KCC manufactures.

The addition of above-mentioned tackifier is preferably 5 weight part ~ 100 weight parts relative to base polymer 100 weight part, is more preferably 10 weight part ~ 50 weight parts.

As above-mentioned linking agent, such as, can list: isocyanate-based linking agent, epoxy linking agent, melamine series linking agent, peroxidation system linking agent and Urea Series linking agent, metal alkoxide system linking agent, metal chelator system linking agent, metal-salt system linking agent, carbodiimide system linking agent, oxazoline system linking agent, ethylenimine system linking agent, amine system linking agent etc.Wherein be preferably isocyanate-based linking agent or epoxy linking agent.

As the concrete example of above-mentioned isocyanate-based linking agent, can list: the lower aliphatic such as tetramethylene diisocyanate, hexamethylene diisocyanate polyisocyanates; The alicyclic isocyanate classes such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate; 2,4 toluene diisocyanate, 4, the aromatic isocyanate such as 4 '-diphenylmethanediisocyanate, xylylene diisocyanate class; The isocyanate addition products such as the isocyanuric acid ester body (Nippon Polyurethane Industry Co., Ltd.'s manufacture, trade(brand)name " CORONATEHX ") of TriMethylolPropane(TMP)/tolylene diisocyanate 3 aggressiveness affixture (Nippon Polyurethane Industry Co., Ltd.'s manufacture, trade(brand)name " CORONATEL "), TriMethylolPropane(TMP)/hexamethylene diisocyanate 3 aggressiveness affixture (Nippon Polyurethane Industry Co., Ltd.'s manufacture, trade(brand)name " CORONATEHL "), hexamethylene diisocyanate; Deng.The content of isocyanate-based linking agent can be set to according to target bounding force the amount be applicable to arbitrarily, and relative to base polymer 100 weight part, representational is 0.1 weight part ~ 20 weight part, is more preferably 0.5 weight part ~ 10 weight part.

As aforementioned epoxy system linking agent, such as, can list: N, N, N ', N '-four glycidyl group-m-xylene diamine, diglycidylaniline, (Mitsubishi Gas Chemical Co., Ltd manufactures two (N, the N-glycidyl-amino methyl) hexanaphthene of 1,3-, trade(brand)name " TETRADC "), (chemistry society of common prosperity society manufactures 1,6-hexanediol diglycidyl ether, trade(brand)name " Epolight1600 "), (chemistry society of common prosperity society manufactures neopentylglycol diglycidyl ether, trade(brand)name " Epolight1500NP "), (chemistry society of common prosperity society manufactures ethylene glycol diglycidylether, trade(brand)name " Epolight40E "), (chemistry society of common prosperity society manufactures propylene glycol diglycidylether, trade(brand)name " Epolight70P "), (NOF Corp manufactures polyethyleneglycol diglycidylether, trade(brand)name " EPIOLE-400 "), (NOF Corp manufactures polypropylene glycol diglycidyl ether, trade(brand)name " EPIOLP-200 "), (NagaseChemteXCorporation manufactures Sorbitol Powder polyglycidyl ether, trade(brand)name " DenacolEX-611 "), (NagaseChemteXCorporation manufactures glycerine polyglycidyl ether, trade(brand)name " DenacolEX-314 "), tetramethylolmethane polyglycidyl ether, (NagaseChemteXCorporation manufactures Polyglycerine polyglycidyl ether, trade(brand)name " DenacolEX-512 "), sorbitan polyglycidyl ether, TriMethylolPropane(TMP) polyglycidyl ether, hexanodioic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl group-three (2-hydroxyethyl) isocyanuric acid ester, resorcinol diglycidyl ether, bis-phenol-S-diglycidylether, there is in molecule the epoxy system resin etc. of more than 2 epoxy group(ing).The content of epoxy linking agent can be set as amount applicable arbitrarily according to target bounding force, representational, relative to base polymer 100 weight part, is 0.01 weight part ~ 10 weight part, is more preferably 0.03 weight part ~ 5 weight part.

(heat-expandable microsphere)

As above-mentioned heat-expandable microsphere, as long as the microballoon being expanded by heating energy or foam, the heat-expandable microsphere be applicable to arbitrarily just can be used.As above-mentioned heat-expandable microsphere, such as, can use by being contained in the microballoon having and obtain in elastic shell in the expansive material of heating appearance.Such heat-expandable microsphere can utilize method, such as coacervation, the interfacial polymerization etc. be applicable to arbitrarily to manufacture.

Hold expansive material as by heating, such as, can list: the low-boiling point liquid such as halogenide, tetraalkyl silane of propane, propylene, butylene, normal butane, Trimethylmethane, iso-pentane, neopentane, Skellysolve A, normal hexane, isohexane, heptane, octane, sherwood oil, methane; The Cellmic C 121 gasified by pyrolysis; Deng.

As the material forming above-mentioned shell, such as can list the polymkeric substance be made up of following substances, described material is: the nitrile monomers such as vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, α-ethoxy propylene nitrile, flumaronitrile; The carboxylic acid monomers such as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid; Vinylidene chloride; Vinyl acetate; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, β-acryloxypropionic acid etc. (methyl) acrylate; The styrene monomers such as vinylbenzene, alpha-methyl styrene, chloro-styrene; The amide monomers such as acrylamide, substituted acrylamide, Methacrylamide, substituent methyl acrylamide; Deng.The polymkeric substance be made up of these monomers can be homopolymer, also can be multipolymer.As this multipolymer, such as, can list: vinylidene chloride-Methyl Methacrylate-acrylonitrile Copolymer, methyl methacrylate-vinyl cyanide-methacrylonitrile copolymers, Methyl Methacrylate-acrylonitrile Copolymer, vinyl cyanide-methacrylonitrile-itaconic acid copolymer etc.

As above-mentioned heat-expandable microsphere, inorganic system whipping agent or organic system whipping agent can be used.As inorganic system whipping agent, such as, can list: volatile salt, bicarbonate of ammonia, sodium bicarbonate, ammonium nitrite, sodium borohydride, various trinitride classes etc.In addition, as organic system whipping agent, such as, can list: the chlorofluorination such as Trichloromonofluoromethane, Dichloromonofluoromethane alkane based compound; The Azo such as Diisopropyl azodicarboxylate, Cellmic C 121, Barium azodicarboxylate; P-toluene sulfonyl hydrazide, sulfobenzide-3,3 '-disulfonyl hydrazide, 4, the hydrazine based compounds such as the two sulfonyl hydrazides of 4 '-OBSH, allyl group; P-toluenesulfonyl Urea,amino-, 4, the Urea,amino-based compounds such as 4 '-oxo two (BENZENESUFONYLAMINO urea); Three azole compounds such as 5-morpholinyl-1,2,3,4-sulfo-triazole; N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitrosoterephthalamine; Deng N-nitroso-group based compound etc.

Above-mentioned heat-expandable microsphere also can use commercially available product.As the concrete example of the heat-expandable microsphere of commercially available product, can list: trade(brand)name " the MatsumotoMicrosphere " (model: F-30 that Matsumoto Yushi-Seiyaku Co., Ltd. manufactures, F-30D, F-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), JapanFilliteCo., Ltd. trade(brand)name " the Expancel " (model: 053-40 manufactured, 031-40, 920-40, 909-80, 930-120), " DAIFOAM " (model: H750 that Kureha Kagaku Kogyo K.K. manufactures, H850, H1100, S2320D, S2640D, M330, M430, M520), " ADVANCELL " (model: EML101 that Sekisui Chemical Co., Ltd manufactures, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501) etc.

Particle diameter before the heating of above-mentioned heat-expandable microsphere is preferably 0.5 μm ~ 80 μm, be more preferably 5 μm ~ 45 μm, more preferably 10 μm ~ 20 μm, be particularly preferably 10 μm ~ 15 μm.Therefore, when the particle size before the heating of above-mentioned heat-expandable microsphere is described with median size, is preferably 6 μm ~ 45 μm, is more preferably 15 μm ~ 35 μm.Above-mentioned particle diameter and median size are the values utilizing the particle size distribution method in laser scattering method to obtain.

Above-mentioned heat-expandable microsphere preferably have until cubical expansivity reach preferably more than 5 times, more preferably more than 7 times, further preferably more than 10 times just break be applicable to intensity.When using such heat-expandable microsphere, effectively can reduce bounding force by heat treated.

Suitably can setting according to the reduction etc. of target bounding force containing proportional of the heat-expandable microsphere of above-mentioned binder layer.Heat-expandable microsphere containing proportional relative to forming base polymer 100 weight part of binder layer, be such as 1 weight part ~ 150 weight part, be preferably 10 weight part ~ 130 weight parts, be more preferably 25 weight part ~ 100 weight parts.

D. base material

As above-mentioned base material, such as, can list: resin sheet, non-woven fabrics, paper, tinsel, weave cotton cloth, sheet rubber, foamed sheet, their duplexer (especially comprising the duplexer of resin sheet) etc.As the resin forming resin sheet, such as, can list: polyethylene terephthalate (PET), PEN (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polymeric amide (nylon), fully aromatic polyamide (aromatic poly amide), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine resin, polyether-ether-ketone (PEEK) etc.As non-woven fabrics, can list: the non-woven fabrics that the non-woven fabrics etc. comprising Manila hemp is formed by the natural fiber with thermotolerance; The synthetic resins non-woven fabrics etc. such as acrylic resin non-woven fabrics, polyvinyl resin non-woven fabrics, ester system resin non-woven fabrics.

The thickness of above-mentioned base material can be set as thickness applicable arbitrarily according to target strength or flexibility and application target etc.The thickness of base material is preferably less than 1000 μm, be more preferably 1 μm ~ 1000 μm, more preferably 1 μm ~ 500 μm, be particularly preferably 3 μm ~ 300 μm, most preferably be 5 μm ~ 250 μm.

Above-mentioned base material can implement surface treatment.As surface treatment, such as, can list: corona treatment, chromic acid process, ozone exposure, fire exposure, high-voltage electric shock exposure, ionization radial line process, utilize the coating process etc. of silane coupling agent.Carry out such surface-treated words, the adaptation fixing layer and base material can be improved.Especially utilize the coating process of Organic coating materials to improve adaptation and fix layer when heating and peeling off and not easily fastening destruction occurs, so preferably.

As above-mentioned Organic coating materials, such as, can list the material recorded in プラスチックハードコート material II (CMC publication, (2004)).Preferred use carbamate based polymer, more preferably uses polyacrylate and amino manthanoate, polyester urethane or their precursor.This is because, easy and industrially can select many kinds of substance and can obtain at an easy rate to the coating of base material/be coated with.This carbamate based polymer is such as the polymkeric substance formed with the reaction mixture containing alcohol hydroxyl group monomer (such as hydroxy acryl acid compounds or hydroxyl ester cpds) by isocyanate-monomer.Organic coating materials can comprise the chainextenders such as polyamines, anti-aging agent, oxidation stabilizer etc. as any additive.The thickness of organic coating layer is not particularly limited, such as, be 0.1 μm ~ about 10 μm be applicable, is preferably 0.1 μm ~ about 5 μm, is more preferably 0.5 μm ~ about 5 μm.

E. the manufacture method of adhesive sheet

As the manufacture method of adhesive sheet of the present invention, such as can list: after (1) forms adhesive coated layer at mould release film (interleaving paper) the above-mentioned tackiness agent of upper coating, waited by compacting in this adhesive coated layer and embed above-mentioned heat-expandable microsphere, form binder layer, and on this binder layer, form the method that (stacked) fixes layer; (2) on mould release film, coating comprises the binder layer formation composition of above-mentioned tackiness agent and heat-expandable microsphere and forms adhesive coated layer, and on this adhesive coated layer, form the method that (stacked) fixes layer; (3) on mould release film, above-mentioned tackiness agent is coated with and after forming adhesive coated layer, this adhesive coated layer is formed (stacked) and fixes layer, then, mould release film is peeled off, from adhesive coated layer with the method fixing face (adhesive face) side that layer is in opposition side and to embed by suppress grade above-mentioned heat-expandable microsphere; (4) formed on mould release film and fix layer, heat-expandable microsphere is set in its one side, so in this installation surface the method etc. of coating adhesive.In the method for above-mentioned (1) ~ (4), by adhesive coated layer is dry, can form binder layer, this drying can be carried out on the opportunity be applicable to arbitrarily.This drying can be carried out before embedding heat-expandable microsphere, also can carry out after embedding heat-expandable microsphere.In addition, can carry out before formation fixes layer, also can carry out after formation fixes layer.Embed when carrying out drying after heat-expandable microsphere, preferably not easily to expand with heat-expandable microsphere or the temperature that foams carries out drying.After above-mentioned (1) and the operation shown in (2), mould release film can be peeled off, also can retain mould release film to protect adhesive face till adhesive sheet is supplied to practical application.

When adhesive sheet of the present invention possesses base material, this adhesive sheet can be in the face of opposition side what fix layer with binder layer after the operation of above-mentioned (1) ~ (4), attaches base material via the caking agent be applicable to arbitrarily or tackiness agent.In addition, also can make base material respectively and fix the duplexer of layer and the duplexer of mould release film and binder layer (or adhesive coated layer), their duplexer is fitted.

As the method forming above-mentioned fixing layer, can list: (i) makes the polymer materials that illustrates in above-mentioned B item or resin material heat fusing and obtain film like molding by extrusion molding, this molding is laminated in the method for above-mentioned binder layer (or adhesive coated layer) or base material; (ii) resin solution comprising above-mentioned polymer materials or resin material is coated above-mentioned binder layer (or adhesive coated layer) or base material, make thereafter the method for its drying; (iii) the fixing layer formation composition comprising monomer, oligopolymer or the macromonomer that can form above-mentioned polymer materials or resin material is coated above-mentioned binder layer (or adhesive coated layer) or base material, make fixing layer formation composition be polymerized the method etc. of (being such as polymerized by heating, active energy beam irradiation etc.).Utilize the method for being somebody's turn to do (iii), the usage quantity of solvent and/or heat energy can be reduced.It should be noted that, (ii) in method, also resin solution can be coated on other mould release film, make thereafter it dry and obtain the molding of film like, afterwards, this molding is laminated in above-mentioned binder layer (or adhesive coated layer) or base material.In addition, (iii) in method, also can fixing layer formation composition be coated on other mould release film, thereafter make it dry and form fixing layer precursor, this precursor is laminated in above-mentioned binder layer (or adhesive coated layer) or base material, makes thereafter it be polymerized.

Such as, in the method for above-mentioned (iii), when forming the fixing layer be made up of epoxy polymkeric substance, following method can be adopted: coating comprises 2, after the fixing layer formation composition of the epoxy compoundss such as 2-(4-hydroxy phenyl) propane diglycidylether, two (4-hydroxy phenyl) methane and solidifying agent applicable arbitrarily, carry out the method heating (such as 60 DEG C ~ 120 DEG C).

Such as, in the method for above-mentioned (iii), when forming the fixing layer be made up of carbamate based polymer, following method can be adopted: after coating comprises the fixing layer formation composition of the isocyanate compound such as tolylene diisocyanate, hexamethylene diisocyanate and the polyol compound such as polyether glycol, polyester polyol, carry out the method heating (such as 60 DEG C ~ 120 DEG C).

Such as, in the method for above-mentioned (iii), when forming the fixing layer be made up of vinyl polymers, the fixing layer formation composition comprising the vinyl compound such as vinylchlorid, vinylbenzene and initiator applicable arbitrarily can be used.

Above-mentioned fixing layer formation composition can comprise the additives such as initiator, catalyzer, UV light absorber, antioxidant as required.In addition, above-mentioned microballon can also be comprised.

When the resin material that above-mentioned fixing layer can be solidified by the irradiation by active energy beam is formed, in the irradiation carrying out active energy beam opportunity be applicable to arbitrarily, adhesive sheet can be obtained.The irradiation of active energy beam such as can be carried out after attaching adherend (machined object).The irradiation of active energy beam also can periodically be carried out.Such as, before the attaching of adherend, make its semicure, after attaching, make it solidify completely.The kind of active energy beam and irradiation dose can be set as applicable kind and amount arbitrarily according to the kind forming the resin material fixing layer.

According to above-mentioned manufacture method, the face of the mould release film side (fixing the opposition side of layer) of binder layer becomes adhesive face.Adhesive face is formed with the state connected with mould release film, therefore, does not have the outstanding and smooth of heat-expandable microsphere.On the other hand, be in the face of opposition side at binder layer with adhesive face, heat-expandable microsphere is given prominence to.In the present invention, utilize above-mentioned fixing layer to be coated to this outstanding heat-expandable microsphere, therefore, the two sides of adhesive sheet is smooth, thus can make the thinner thickness of binder layer.Adhesive sheet of the present invention like this can contribute to obtaining excellent cut-out precision and reducing cutting swarf as cutting off the temporary fixed sheet adding man-hour to electronic unit etc.

F. the using method (manufacture method of electronic unit) of adhesive sheet

According to other embodiment of the present invention, provide a kind of manufacture method of electronic unit.The manufacture method of electronic unit of the present invention comprises: on above-mentioned adhesive sheet, attach the electronic part material (substrate) obtained with big area, carries out cut-out processing to this electronic part material.

As above-mentioned electronic unit, such as, can list the parts of the semiconductor devices such as Silicon Wafer; Multilayer capacitor: transparency electrode; Deng.

In above-mentioned manufacture method, first, upload to be set up in machine table and state adhesive sheet, this adhesive sheet attaches with big area the electronic part material obtained.

Thereafter, utilize the method be applicable to arbitrarily to cut off above-mentioned electronic part material, can electronic unit be obtained.As the method that above-mentioned cut-out is processed, such as, can list the method using the cutter such as rotating knife, flat knife, use the method etc. of laser.When cutting off electronic part material by using the pressing of flat knife cutting, the generation of cutting swarf is inhibited, and yield rate improves.In the present invention, binder layer can be made thinner, therefore, even if by utilizing the pressing of flat knife cutting to cut off electronic part material, also can prevent: the chip after cut-out adheres to again, cut surface tilts or become S word and instability, generation chip breach etc. when cutting off.In addition, in the present invention, when using thin cutter to cut off, also can obtain above-mentioned effect, the manufacture loss (loss that the gap that the chip chamber after cut-out produces is brought) produced because of the thickness of cutter can be reduced.In the manufacture of the electronic unit of more miniaturization, because the number of cut surface is many, therefore, it is possible to the present invention reducing manufacture loss as described above is particularly useful.

In above-mentioned cut-out processing, can cut off under heating.Such as, above-mentioned machine table can be heated to 30 DEG C ~ 150 DEG C and carry out cut-out processing.

Embodiment

Below, utilize embodiment to be specifically described the present invention, but the present invention is not limited to these embodiments.Evaluation method in embodiment is as described below.In addition, in embodiment, unless otherwise specified, then " part " and " % " is weight basis.

(1) mensuration of the thickness of the binder layer in Raman mapping and fixing layer

By adhesive sheet slicing machine (microtome) Slice obtained in embodiment 1 ~ 3,5,6 and 12 ~ 15, prepare to measure sample.To the cross section of this mensuration sample, the alpha300RSA using WITec company to manufacture carries out the spectroscopic analysis based on Raman spectrum, (is the 1640cm of active energy beam reactive oligomers (UV1700B) in such as embodiment 3 based on coming from the peak being only added on the composition fixing layer ^-1peak) peak intensity, measure the thickness fixing layer and binder layer.With embodiment 3 for typical example, the Raman mapping in this mensuration is shown in Fig. 4.Using the clearly different face of the amount being only added on the composition fixed in layer as interface 1, using from interface 1 to binder layer with this interface 1 be in the distance the face of opposition side as binder layer thickness, be in distance the face of opposition side as the thickness fixing layer using from this interface 1 to what fix layer with this interface.

It should be noted that, the condition determination that Raman mapping measures is as described below.

Excitation wavelength: 532nm

Measure wave-number range: 300 ~ 3600cm ^-1

Grating: 600gr/mm

Object lens: × 100

Minute: 0.2 second/1 spectrum

Measurement range: 20 × 40 μm

Measure number: 100 × 200 points

Detector: EMCCD

(2) mensuration of the binder layer utilizing SEM and the thickness fixing layer

The adhesive sheet cutting edge cutter through-thickness obtained in embodiment 4,7 ~ 11,16,17 and comparative example 1 is cut off, after implementing Pt-Pd sputter process, the S3400N rough vacuum scanning electronic microscope (SEM) using HitachiHigh-TechnologiesCorporation to manufacture observes cut surface, distinguish interface 1, using from interface 1 to binder layer with this interface 1 be in the distance the face of opposition side as binder layer thickness, be in distance the face of opposition side as the thickness fixing layer using from this interface 1 to what fix layer with this interface.With embodiment 11 for typical example, the SEM image in the cross section of adhesive sheet is shown in Fig. 5.

It should be noted that, the condition determination that SEM observes is as described below.

Observe image: ESED picture

Acceleration voltage: 10kV

Multiplying power: 600 times

(3) mensuration of the projecting height (H) of heat-expandable microsphere

In embodiment 1 ~ 3,5,6 and 12 ~ 15, utilize the method same with above-mentioned (1), in embodiment 4,7 ~ 11,16,17 and comparative example 1, utilize the method same with above-mentioned (2), distinguish binder layer and fix the interface (namely comprising the interface of the raised face of outstanding heat-expandable microsphere) of layer, measuring the height of the part of giving prominence to from binder layer of heat-expandable microsphere.

(4) mensuration of binder layer and the fixing length (l1) at interface of layer and the length (L) of the thickness direction projection line at this interface

In embodiment 1 ~ 3,5,6 and 12 ~ 15, utilize the method same with above-mentioned (1), in embodiment 4,7 ~ 11,16,17 and comparative example 1, utilize the method same with above-mentioned (2), distinguish the interface (namely comprising the interface of the raised face of outstanding heat-expandable microsphere) of binder layer and fixing layer, measure binder layer and fix the length (l1) at interface of layer and the length (L) of the thickness direction projection line at this interface.The ratio (l1/L) of l1 and L is shown in Table 1.

(5) elastic modulus detection

The adhesive sheet slicing machine through-thickness obtained in embodiment and comparative example is cut off, to this cut surface, measures Young's modulus with nano-hardness tester.

More specifically, for fixing layer, using the surface (being in the face of opposition side with adhesive face) of the fixing layer almost vertical with cut surface and the cut surface apart from about 3 μm, this surface surperficial as determination object.The subsidiary software (triboscan) of the displacement-load hysteresis loop determinator obtained being pressed into probe (pressure head) to determination object carries out numerical value process, obtains Young's modulus thus.It should be noted that, illustrated in table 1 at the Young's modulus recorded apart from the cut surface surface on about 3 μm, surface (mean value measured for 3 times).

Nano impress instrument apparatus and condition determination as described below.

Device and condition determination

Device: nano-hardness tester; The Triboindenter that HysitronInc company manufactures

Measuring method: single plunging

Measure temperature: 25 DEG C

Press-in speed: about 1000nm/ second

Compression distance: about 800nm

Probe: diamond fabrication, Berkovich type (triangular pyramid type)

(6) bounding force measures

The bounding force of (make heat-expandable microsphere expand before) (before the heating)

Be cut to wide by the adhesive sheet obtained in embodiment and comparative example: the size of 20mm, length: 140mm, using the pet film as adherend, (trade(brand)name " lumirrorS-10 " Dongli Ltd. manufactures; Thick: 25 μm, wide: the 30mm) state of each outstanding 5mm in width left and right, based on JISZ0237:2009, makes the roller of 2kg reciprocal 1 time, be fitted on adhesive face by this adherend, prepare to measure sample.This mensuration sample is installed on the tensile testing machine (manufacture of trade(brand)name " Shimadzu AutographAG-120kN " Shimadzu Corporation) of band thermostatic bath, places 30 minutes.Thereafter, to measure adherend with peel angle: 180 °, the load when condition of peeling rate (draw speed): 300mm/min is peeled off from adhesive sheet along its length, obtain ultimate load (maximum value of the load except the summit at mensuration initial stage) now, the value this ultimate load obtained divided by bandwidth is as bounding force (N/20mm is wide).It should be noted that, aforesaid operations is in temperature: carry out under the atmosphere of 23 ± 3 DEG C and humidity: 65 ± 5%RH.

(bounding force (heat-expandable microsphere is expanded or foams rear) after heating)

Prepare as described above to measure sample, this mensuration sample is dropped into hot-air drier.In hot-air drier, at the maximum swelling temperature (aftermentioned) of heat-expandable microsphere, leave standstill 1 minute, then, as described above adherend is peeled off, measure bounding force.It should be noted that, drop into and operate in temperature before and after hot-air drier: carry out under the atmosphere of 23 ± 3 DEG C and humidity: 65 ± 5%RH.

(7) surface roughness measurement

For the adhesive sheet obtained in embodiment and comparative example, heat-expandable microsphere is expanded or after foaming, measures the surface roughness Ra of adhesive face.The expansion of heat-expandable microsphere or foaming leave standstill in hot-air drier at the maximum swelling temperature (aftermentioned) of heat-expandable microsphere to be carried out for 1 minute.It should be noted that, the laser microscope " OLS4000 " that the mensuration of surfaceness uses Olympus Co., Ltd to manufacture carries out.

(8) after cutting off, small pieces separation property is evaluated

The adhesive sheet obtained in embodiment and comparative example to be fitted the laminated ceramic sheet of 40mm × 50mm (thickness 500 μm).With the shut-off device " G-CUT8AA " that UHT Corporation manufactures, the laminated ceramic sheet on adhesive sheet is cut into dice shape in the mode of the small pieces becoming 1mm × 0.5mm.By the laminated ceramic sheet on adhesive sheet diametrically the cylinder of 30mm side arrange.At the temperature (the maximum swelling temperature (aftermentioned) of heat-expandable microsphere) of regulation, heat treated is carried out with the state being arranged at cylinder, heat-expandable microsphere is expanded, thus small pieces are peeled off from adhesive sheet, the unsegregated chip number of chip chamber of counting cut-off part.Chip number when unsegregated chip number being separated completely divided by 100% and the number obtained are as index separatory.Index is less than 2% be set to ◎, index be more than 2% and be less than 5% be set to zero, index be more than 5% and be less than 15% be set to △, index is more than 15% be set to ×.

The detailed content of the composition of laminated ceramic sheet and the cut-out condition of shut-off device is as described below.

(laminated ceramic sheet)

Barium titanate powder 100 parts, polyvinyl butyral resin 15 parts, two (the 2-ethylhexyl) 6 parts of phthalic acid and two Vinlubs 2 parts are added in toluene solvant, carry out mixing and disperseing in ball-milling dispersion machine, obtain dielectric toluene solution thus.Applicator is used to be coated on the silicone release treated side of the pet film (manufacture of polyester film Co., Ltd. of Mitsubishi, trade(brand)name " MRF38 ", thickness: 38 μm) of band silicone release treated side in the mode that the thickness after solvent evaporates is 50 μm this solution, carry out drying, obtain ceramic plate.Be the mode laminated multi-layer of 500 μm with thickness by the ceramic plate obtained, obtain laminated ceramic sheet.

(cut-out condition)

Cut off temperature: 60 DEG C, the cut-out degree of depth (residual quantity apart from table top): about 20 μm

Cutter knife: " U-BLADE2 " that UHT Corporation manufactures, cutter are thick: 50 μm, point of a knife angle: 15 °

(9) cut surface cutting is evaluated

To operate equally with above-mentioned (8), laminated ceramic sheet is cut to dice shape in the mode of the small pieces becoming 1mm × 0.5mm.From the small pieces cut off, selecting any 10, observe cut surface with the magnifying glasses of 50 times, confirming with or without fragmentation (processing and the breach of laminated ceramic sheet that produces because cutting off), using the mean value of fragmentation sum that produces in 10 small pieces as index.Be 0 by index ~ be less than 10 places be set to ◎, be more than 10 and be less than 20 places be set to zero, be more than 20 and be less than 40 places be set to △, be being set to of more than 40 places ×.

Below record polymkeric substance preparation method.It should be noted that, herein, part is weight part in case of no particular description.

The preparation of [Production Example 1] polymkeric substance 1

In toluene, add butyl acrylate 100 parts, 5 parts, vinylformic acid and as after the benzoyl peroxide 0.2 part of polymerization starter, heat, obtain the toluene solution of acrylic copolymer (polymkeric substance 1).

The preparation of [Production Example 2] polymkeric substance 2

2-EHA 30 parts, ethyl propenoate 70 parts, vinylformic acid 2-hydroxy methacrylate 4 parts, N-phenylmaleimide 5 parts and as after the benzoyl peroxide 0.2 part of polymerization starter is added in toluene, heat, obtain the toluene solution of acrylic copolymer (polymkeric substance 2).

The preparation of [Production Example 3] polymkeric substance 3

2-EHA 30 parts, ethyl propenoate 70 parts, vinylformic acid 2-hydroxy methacrylate 4 parts, methyl methacrylate 5 parts and as after the benzoyl peroxide 0.2 part of polymerization starter is added in toluene, heat, obtain the toluene solution of acrylic copolymer (polymkeric substance 3).

The preparation of [Production Example 4] polymkeric substance 4

Butyl acrylate 50 parts, ethyl propenoate 50 parts, 5 parts, vinylformic acid, vinylformic acid 2-hydroxy methacrylate 0.1 part and as after the benzoyl peroxide 0.2 part of polymerization starter is added in toluene, heat, obtain the toluene solution of acrylic copolymer (polymkeric substance 4).

The preparation of [Production Example 5] polymkeric substance 5

Methyl acrylate 70 parts, 2-EHA 30 parts, 10 parts, vinylformic acid and as after the benzoyl peroxide 0.2 part of polymerization starter is added in vinyl acetic monomer, heat, obtain the ethyl acetate solution of acrylic copolymer (polymkeric substance 5).

The preparation of [Production Example 6] polymkeric substance 6

Butyl acrylate 50 moles, ethyl propenoate 50 moles, vinylformic acid 2-hydroxy methacrylate 22 moles and as after the benzoyl peroxide (be 0.2 part relative to the summation 100 parts of butyl acrylate, ethyl propenoate and vinylformic acid 2-hydroxy methacrylate) of polymerization starter is added in toluene, heat, obtain copolymer solution.Add the vinylformic acid 2-isocyanato ethyl of the amount suitable with 80 % by mole of the hydroxyl from the vinylformic acid 2-hydroxy methacrylate in this solution in this copolymer solution after, heat, to this hydroxyl addition methacrylic acid 2-isocyanato ethyl from vinylformic acid 2-hydroxy methacrylate, obtain the toluene solution at side chain with methacrylate based acrylic copolymer (polymkeric substance 6) thus.

The preparation of [Production Example 7] polymkeric substance 7

Butyl acrylate 80 moles, acryloyl morpholine 30 moles, vinylformic acid 2-hydroxy methacrylate 20 moles and as after the benzoyl peroxide (be 0.2 part relative to the summation 100 parts of butyl acrylate, acryloyl morpholine and vinylformic acid 2-hydroxy methacrylate) of polymerization starter is added in toluene; heat, obtain copolymer solution.Add the vinylformic acid 2-isocyanato ethyl of the amount suitable with 50 % by mole of the hydroxyl from the vinylformic acid 2-hydroxy methacrylate in this solution in this copolymer solution after, heat, to this hydroxyl addition methacrylic acid 2-isocyanato ethyl from vinylformic acid 2-hydroxy methacrylate, obtain the toluene solution at side chain with methacrylate based acrylic copolymer (polymkeric substance 7) thus.

[embodiment 1]

(formation of binder layer precursor layer)

By the toluene solution (polymkeric substance 2:100 part) of polymkeric substance 2 obtained in Production Example 2, (Japanese polyurethane Co., Ltd. manufactures isocyanate-based linking agent, trade(brand)name " CORONATEL ") 1 part, as terpenes phenol resin (Sumitomo Bakelite Co's manufacture of tackifier, trade(brand)name " SUMILITERESINPR12603 ") 5 parts, (Matsumoto Yushi-Seiyaku Co., Ltd. manufactures with heat-expandable microsphere, trade(brand)name " MatsumotoMicrosphereF-50D ", foaming (expansion) starting temperature: 95 DEG C ~ 105 DEG C, maximum swelling temperature: 125 DEG C ~ 135 DEG C, median size 10 μm ~ 18 μm) 40 parts of mixing, prepare mixed solution.In this mixed solution, add the solvent (toluene) same with the solvent phase in this mixed solution further, carry out viscosity adjustment until become the viscosity of easily coating.Applicator is used to coat the pet film (manufacture of polyester film Co., Ltd. of Mitsubishi Chemical, trade(brand)name " MRF38 ", thickness: 38 μm) of band silicone release treated side in the mode that the thickness after solvent evaporates (drying) is 10 μm this mixed solution, thereafter, carry out drying, this pet film is formed binder layer precursor layer.

(fixing the formation of layer precursor layer)

By the toluene solution (polymkeric substance 1:100 part) of above-mentioned polymkeric substance 1 obtained in Production Example 1, as the Dipentaerythritol Pentaacrylate of active energy beam reactive oligomers and mixture (Toagosei Co., Ltd's manufacture of dipentaerythritol acrylate, trade(brand)name " AronixM404 ") 20 parts, (Japanese polyurethane Co., Ltd. manufactures isocyanate-based linking agent, trade(brand)name " CORONATEL ") 2 parts, (BASF Japanese firm manufactures with energy-ray polymerization starter, trade(brand)name " Irgacure651 ") 3 parts of mixing, prepare mixed solution.In this mixed solution, add the solvent (toluene) same with the solvent phase in this mixed solution further, carry out viscosity adjustment until become the viscosity of easily coating.The mode being 20 μm with the thickness after solvent evaporates (drying) uses applicator to be coated the pet film (manufacture of polyester film Co., Ltd. of Mitsubishi Chemical, trade(brand)name " MRF38 ", thickness: 38 μm) of band silicone release treated side, thereafter, carry out drying, this pet film is formed and fixes layer precursor layer.

(formation of adhesive sheet 1)

By above-mentioned binder layer precursor layer and the laminating of fixing layer precursor layer.Then, use ultraviolet irradiation machine " UM810 (high-pressure mercury lamp source) " (manufacture of Dong Jing machine Co., Ltd.), carry out accumulated light 300mJ/cm from the precursor layer side fixing layer ²uviolizing.Thereafter, the pet film of band silicone release treated side is peeled off, obtain adhesive sheet 1 (thickness of binder layer: 10 μm, fix the thickness of layer: 25 μm).

[embodiment 2 ~ 15, comparative example 1]

As shown in table 1ly set the kind of polymkeric substance, linking agent, tackifier and heat-expandable microsphere when forming binder layer precursor layer and compounding amount, and as shown in table 1 setting forms the kind of polymkeric substance, active energy beam reactive oligomers, linking agent and energy-ray polymerization starter when fixing layer precursor layer and compounding amount, in addition, adhesive sheet is obtained similarly to Example 1.

It should be noted that, in embodiment 2 ~ 5,8,10,13 ~ 15 and comparative example 1, when forming fixing layer precursor layer, replace the pet film of band silicone release treated side and at the upper coating mixture of PET film (thickness: 100 μm), obtain this PET film unstripped and there is the adhesive sheet of PET film (base material).In addition, in embodiment 4 and comparative example 1, adhesive sheet is not obtained with carrying out uviolizing.

The detailed content of the linking agent recorded in table 1, tackifier, heat-expandable microsphere, active energy beam reactive oligomers, energy-ray polymerization starter is as described below.

< linking agent >

TETRADC: Mitsubishi Gas Chemical Co., Ltd's manufacture, trade(brand)name " TETRADC ", epoxy linking agent

< tackifier >

PR51732: Sumitomo Bakelite Co manufactures, trade(brand)name " SUMILITERESINPR51732 "

S145:YASUHARACHEMICALCO., LTD. manufacture, trade(brand)name " YSpolystarS145 "

U130:YASUHARACHEMICALCO., LTD. manufacture, trade(brand)name " YSpolystarU130 "

T160:YASUHARACHEMICALCO., LTD. manufacture, trade(brand)name " YSpolystarT160 "

< heat-expandable microsphere >

F-30D: Matsumoto Yushi-Seiyaku Co., Ltd.'s manufacture, trade(brand)name " MatsumotoMicrosphereF-30D ", foaming (expansion) starting temperature: 70 DEG C ~ 80 DEG C, maximum swelling temperature: 110 DEG C ~ 120 DEG C, median size 10 μm ~ 18 μm

F-65D: Matsumoto Yushi-Seiyaku Co., Ltd.'s manufacture, trade(brand)name " MatsumotoMicrosphereF-65D ", foaming (expansion) starting temperature: 105 DEG C ~ 115 DEG C, maximum swelling temperature: 145 DEG C ~ 155 DEG C, median size 12 μm ~ 18 μm

FN-180SSD: Matsumoto Yushi-Seiyaku Co., Ltd.'s manufacture, trade(brand)name " MatsumotoMicrosphereFN-180SSD ", foaming (expansion) starting temperature: 135 DEG C ~ 150 DEG C, maximum swelling temperature: 165 DEG C ~ 180 DEG C, median size 15 μm ~ 25 μm

F-260D: Matsumoto Yushi-Seiyaku Co., Ltd.'s manufacture, trade(brand)name " MatsumotoMicrosphereF-260D ", foaming (expansion) starting temperature: 190 DEG C ~ 200 DEG C, maximum swelling temperature: 250 DEG C ~ 260 DEG C, median size 20 μm ~ 35 μm

< active energy beam reactive oligomers >

UV1700B: the manufacture of Japanese synthetic chemistry Co., Ltd., trade(brand)name " purple light UV-1700B ", ultraviolet hardening urethane acrylate

UV7620EA: the manufacture of Japanese synthetic chemistry Co., Ltd., trade(brand)name " purple light UV-7620EA ", ultraviolet hardening urethane acrylate

UV3000B: the manufacture of Japanese synthetic chemistry Co., Ltd., trade(brand)name " purple light UV-3000B ", ultraviolet hardening urethane acrylate

M321: Toagosei Co., Ltd's manufacture, trade(brand)name " AronixM321 ", TriMethylolPropane(TMP) PO modified triacrylate (the average addition mole number of propylene oxide (PO): 2 moles)

UV7630B: the manufacture of Japanese synthetic chemistry Co., Ltd., trade(brand)name " purple light UV-7630B ", ultraviolet hardening urethane acrylate

< energy-ray polymerization starter >

I184:BASF company manufactures, trade(brand)name " Irgacure184 "

I2959:BASF company manufactures, trade(brand)name " Irgacure2959 "

I651:BASF company manufactures, trade(brand)name " Irgacure651 "

[embodiment 16]

By the toluene solution (polymkeric substance 1:100 part) of polymkeric substance 1 obtained in Production Example 1, (Mitsubishi Gas Chemical Co., Ltd manufactures epoxy linking agent, trade(brand)name " TETRADC ") 0.8 part, as the terpenes phenol resin (YASUHARACHEMICALCO. of tackifier, LTD. manufacture, trade(brand)name " YSpolystarS145 ") 30 parts, (Matsumoto Yushi-Seiyaku Co., Ltd. manufactures with heat-expandable microsphere, trade(brand)name " MatsumotoMicrosphereF-50D ", foaming (expansion) starting temperature: 95 DEG C ~ 105 DEG C, maximum swelling temperature: 125 DEG C ~ 135 DEG C, median size 10 μm ~ 18 μm) 30 parts of mixing, prepare mixed solution.In this mixed solution, add the solvent (toluene) same with the solvent phase in this mixed solution further, carry out viscosity adjustment until become the viscosity of easily coating.Applicator is used to coat the pet film (manufacture of polyester film Co., Ltd. of Mitsubishi Chemical, trade(brand)name " MRF38 ", thickness: 38 μm) of band silicone release treated side in the mode that the thickness after solvent evaporates (drying) is 30 μm this mixed solution, thereafter, carry out drying, this pet film is formed binder layer precursor layer.

At the matt treated side of the pet film (Dongli Ltd.'s manufacture, trade(brand)name " lumirrortypeX42 ", thickness: 50 μm) as fixing layer, by the adhesive face of hand roller laminating aforementioned adhesion oxidant layer precursor layer.Carry out autoclave process (40 DEG C, 5Kgf/cm ², 10 minutes), obtain adhesive sheet (binder layer (thickness: 30 μm)/fixing layer (polyethylene terephthalate, thickness: 50 μm)).

[embodiment 17]

By the toluene solution (polymkeric substance 4:100 part) of polymkeric substance 4 obtained in Production Example 4, (Mitsubishi Gas Chemical Co., Ltd manufactures epoxy linking agent, trade(brand)name " TETRADC ") 0.8 part, as the terpenes phenol resin (YASUHARACHEMICALCO. of tackifier, LTD. manufacture, trade(brand)name " YSpolystarS145 ") 5 parts, (Matsumoto Yushi-Seiyaku Co., Ltd. manufactures with heat-expandable microsphere, trade(brand)name " MatsumotoMicrosphereF-50D ", foaming (expansion) starting temperature: 95 DEG C ~ 105 DEG C, maximum swelling temperature: 125 DEG C ~ 135 DEG C, median size 10 μm ~ 18 μm) 30 parts of mixing, prepare mixed solution.In this mixed solution, add the solvent (toluene) same with the solvent phase in this mixed solution further, carry out viscosity adjustment until become the viscosity of easily coating.Applicator is used to coat the pet film (manufacture of polyester film Co., Ltd. of Mitsubishi Chemical, trade(brand)name " MRF38 ", thickness: 38 μm) of band silicone release treated side in the mode that the thickness after solvent evaporates (drying) is 40 μm this mixed solution, thereafter, carry out drying, this pet film is formed binder layer precursor layer.

In the pet film (one side of the DIAFIX (PG-CHI (FG, thickness 200 μm)) that Mitsubishi Plastics Inc manufactures as fixing layer, use the mixed solvent (vinyl acetic monomer: dimethyl formamide=1:10 (volume %)) of coiling rod (No. 10) coating vinyl acetic monomer and dimethyl formamide, use the adhesive face of hand roller laminating aforementioned adhesion oxidant layer precursor layer at its coated face.With hot air dryer drying 3 minutes at 80 DEG C, obtain adhesive sheet (binder layer (thickness: 40 μm)/fixing layer (polyethylene terephthalate, thickness: 200 μm)).

Table 1

As shown in Table 1, adhesive sheet of the present invention can make bounding force reduce by heating, and, add man-hour carrying out cut-out to adherend, excellent cut-out precision can be realized.

utilizability in industry

Manufacture method of the present invention and adhesive sheet can be preferred for the manufacture of the chip shape electronic components such as semi-conductor chip.

description of reference numerals

10 binder layers

11 heat-expandable microspheres

12 tackiness agents

20 fix layer

30 base materials

100,200 adhesive sheets

Claims

1. an adhesive sheet, it possesses: the binder layer comprising multiple heat-expandable microsphere, and is configured in the one-sided fixing layer of this binder layer,

At least more than one heat-expandable microsphere is given prominence to from this binder layer,

This outstanding heat-expandable microsphere is embedded in fixing layer.

2. adhesive sheet according to claim 1, wherein, described binder layer comprises the heat-expandable microsphere with the particle diameter larger than the thickness of this binder layer.

3. adhesive sheet according to claim 1 and 2, wherein, the height of the part of giving prominence to from described binder layer of described heat-expandable microsphere is more than 0.4 μm.

4. the adhesive sheet according to any one of claims 1 to 3, wherein, the sectional view in regulation region comprising the part that described heat-expandable microsphere is given prominence to from described binder layer, the length (l1) at the interface of this binder layer and described fixing layer is more than 1.02 with the ratio (l1/L) of the length (L) of the thickness direction projection line at this interface.

5. the adhesive sheet according to any one of Claims 1 to 4, wherein, the median size of described heat-expandable microsphere is 6 μm ~ 45 μm.

6. the adhesive sheet according to any one of Claims 1 to 5, wherein, the Young's modulus that described fixing layer utilizes Using Nanoindentation to record at 25 DEG C is more than 1MPa.

7. the adhesive sheet according to any one of claim 1 ~ 6, wherein, the thickness of described binder layer is less than 20 μm.

8. the adhesive sheet according to any one of claim 1 ~ 7, wherein, by heating, described heat-expandable microsphere is expanded or foaming time, the surface roughness Ra being in the face of opposition side with described fixing layer of described binder layer is more than 3 μm.

9. the adhesive sheet according to any one of claim 1 ~ 8, wherein, the Young's modulus that described binder layer utilizes Using Nanoindentation to record at 25 DEG C is less than 100MPa.

10. the adhesive sheet according to any one of claim 1 ~ 9, wherein, also possesses base material in the side contrary with described binder layer of described fixing layer.

The manufacture method of 11. 1 kinds of electronic units, it comprises: after the adhesive sheet according to any one of claim 1 ~ 10 attaches electronic part material,

Cut-out processing is carried out to this electronic part material.