KR100528118B1 - Strippable Adhesive Composition - Google Patents

Abstract

This invention provides the peelable adhesive composition characterized by containing the resin which has adhesiveness, and the compound which generate | occur | produces a gas by active energy ray irradiation.

Description

Strippable Adhesive Composition

The present invention relates to a peelable adhesive composition.

Conventionally, when processing, for example, polishing on the surface of a thin material which is easily deformed and broken by an external force such as a wafer, the thin material is fixed to a supporting substrate through an adhesive and processed. This finished material is peeled from an adhesive agent and a support base material, and the method of obtaining the processed thin plate material is performed.

The adhesive used for this purpose requires the adhesiveness which can reliably fix a thin plate material to a support base material during a processing operation, and the outstanding peelability which can peel easily a processed material from an adhesive agent and a support base material.

However, conventionally, when used for such a purpose, the adhesive composition which is excellent in both adhesiveness and peelability is not known.

It is an object of the present invention to provide an adhesive composition having excellent adhesion and peelability.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to achieve the said subject, and according to the adhesive composition containing the resin which has adhesiveness, and the compound which generate | occur | produces a gas by active energy ray irradiation, it is necessary to fix an adherend which is a material to be processed. In addition to having adhesiveness, it was found that after processing, the adherend can be easily peeled off by the gas generated by the active energy ray irradiation.

Based on these facts, the present inventors made various studies and completed the present invention.

That is, this invention provides the following peelable adhesive composition.

1. A peelable adhesive composition comprising a resin having adhesiveness and a compound that generates gas by active energy ray irradiation.

2. The peelable adhesive composition according to item 1, wherein the resin having adhesiveness is a photosensitive resin.

3. The peelable adhesive composition according to the above 1 or 2, wherein the compound which generates gas by active energy ray irradiation is quinonediazidesulfonic acid ester.

4. The compound 1 to 100 according to any one of the above items 1 to 3, wherein the use ratio of the resin having adhesiveness and the compound generating gas by active energy ray irradiation is 100 parts by weight of the compound. A peelable adhesive composition which is about a weight part.

Hereinafter, the peelable adhesive composition of this invention is demonstrated in detail.

Peelable Adhesive Composition

The peelable adhesive composition of this invention contains the resin which has adhesiveness, and the compound which generate | occur | produces a gas by active energy ray irradiation. Therefore, a to-be-adhered body adhere | attached using this composition can generate | occur | produce a gas by irradiating an active energy ray, such as an ultraviolet-ray, to this adhesive layer, and can easily peel an adhesive layer and a to-be-adhered body with the generated gas.

It is preferable that resin which has adhesiveness is resin which has adhesiveness at the temperature of about -50- + 150 degreeC, especially about -40- + 120 degreeC. In addition, it is preferable that this adhesiveness is the range of adhesive force (kgf / cm <^2> ), for example about 5-40, especially about 7-30.

The resin having tackiness may be a thermoplastic resin or a curable resin. Examples of the thermoplastic resin include acrylic resins, urethane resins, polyester resins, novolac phenols and their derivatives, polyvinyl phenols and their derivatives, silicones and their derivatives, and the like. Moreover, as curable resin, what introduce | transduced a polymerizable unsaturated group into any of these resins is contained, for example.

Moreover, as said curable resin, the photosensitive resin which has adhesiveness in the photosensitive resin composition which has adhesiveness which hardens by active energy rays, such as an ultraviolet-ray mentioned later, can also be used. In this case, a photoinitiator, a photosensitizer, etc. can be added suitably as needed.

As a compound which generate | occur | produces a gas by active energy ray irradiation, quinonediazide sulfonic-acid ester can be used preferably, for example.

Quinone diazide sulfonic acid ester is a photosensitive compound which produces | generates nitrogen gas by active energy ray irradiation, and enables peeling of an adhesive layer by the bubble by the generated nitrogen gas.

As the quinone diazide sulfonic acid ester, esters of polyhydroxy benzophenone with 1,2-quinone diazide sulfonic acids such as 1,2-benzoquinone diazide sulfonic acid and 1,2-naphthoquinone diazide sulfonic acid are preferable. Can be used.

Polyhydroxybenzophenones used for the formation of this ester include those represented by the following formula (1).

In formula, m and n are the integers of 0-3, respectively, and the sum total of m + n is 1-6.

Specific examples of the polyhydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,3, 4,4'-tetrahydroxybenzophenone, and the like.

Meanwhile, the 1,2-benzoquinonediazidesulfonic acid esterified with polyhydroxybenzophenone includes a compound represented by the following Formula 2, and the 1,2-naphthoquinonediazidesulfonic acid is represented by the following Formula 3 Compound is included.

Specific examples of the 1,2-benzoquinone diazide sulfonic acid include 1,2-benzoquinone diazide-4-sulfonic acid. Specific examples of the 1,2-naphthoquinone diazide sulfonic acid include 1,2-naphthoquinone diazide-5-sulfonic acid and 1,2-naphthoquinone diazide-4-sulfonic acid.

The esterification reaction of the said polyhydroxy benzophenone and 1, 2- quinone diazide sulfonic acids is known by itself, for example, polyhydroxy benzophenone and 1, 2- quinone diazide sulfonic acid, or its This can be done by reacting a halide (for example chloride). Although the reaction ratio of the two substances at this time is not particularly limited, generally 1,2-quinonediazidesulfonic acids are reacted at a ratio of 1 to q molecules with respect to the number q of hydroxyl groups in the polyhydroxybenzophenone. It is preferable to make it. These polyhydroxy benzophenones and 1,2-quinone diazide sulfonic acids or its halides may be used independently, or may mix and use two or more types.

In the adhesive composition of the present invention, the use ratio of the resin having adhesiveness and the compound generating gas by active energy ray irradiation is usually about 1 to 100 parts by weight of the compound, preferably 5 to 100 parts by weight of the resin. It is suitably about 50 weight part.

The adhesive composition of this invention can be manufactured by melt | dissolving or disperse | distributing the resin which has adhesiveness, and the compound which produces gas by active energy ray irradiation in a medium.

As a medium, various solvents, such as water and an organic solvent, can be used individually by 1 type or in combination of 2 or more types. As the organic solvent, for example, various solvents such as a hydrocarbon solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, and an amide solvent can be used.

Processing method of the material

The peelable adhesive composition of this invention can be used suitably as an adhesive agent used when peeling this material from a support base material, after adhere | attaching the to-be-adhered body which is a material to process to a support base material.

As a processing method of the material using the said adhesive composition, the following method is preferable.

That is, (1) the process of fixing the unprocessed surface of the material to be processed to the support base material which has transparency through the peelable adhesive composition layer of this invention and the photosensitive resin composition layer which has adhesiveness,

(2) processing the fixed material;

(3) Subsequently, by processing an active energy ray from outside of the supporting substrate to generate gas, processing of various materials can be preferably performed by a processing method of a material including a step of peeling and taking out the processed material. .

Process (1)

Step (1) is a step of fixing the material to be processed to the supporting substrate having transparency through the release adhesive composition layer of the present invention and the photosensitive resin composition layer having adhesiveness formed on the unprocessed surface of the material.

As the material to be processed, various materials that require various processing such as polishing can be used without particular limitation.

The material may be any one of plastic, metal, glass, fiber, and paper, and the shape may include a film, a plate, a line, a sphere, a disc, a cone, a cuboid, or a combination of these shapes. It may be any one shape. In particular, as a thin plate-like material which is easily deformed and broken by a force from the outside, a material that requires processing such as polishing can be preferably used.

As a specific material, electronic materials, such as a wafer, etc. are mentioned, for example.

As a photosensitive resin composition which has adhesiveness used at the said process (1), it consists of a photosensitive resin which has adhesiveness, a photoinitiator, a photosensitizer, etc. as needed, and hardens | cures by active energy ray irradiation, such as an ultraviolet-ray. An aqueous or organic solvent type resin composition can be used preferably.

As photosensitive resin which has adhesiveness, it is preferable that it is photosensitive resin which has adhesiveness at the temperature of about -50- + 150 degreeC, especially about -40- + 120 degreeC. In addition, it is preferable that this adhesiveness is the range of adhesive force (kgf / cm <^2> ), for example about 5-40, especially about 7-30.

The specific example of the photosensitive resin which has the said adhesiveness is illustrated below.

(i) Photosensitive resin which has polymeric groups, such as a (meth) acryloyl group, as a photosensitive group

The photosensitive resin (i) can be produced by, for example, adding a glycidyl group-containing polymerizable unsaturated compound to a carboxyl group-containing acrylic resin.

In this case, the carboxyl group-containing acrylic resin to be used includes, for example, α, β-ethylenically unsaturated acids such as acrylic acid and methacrylic acid as essential monomer components, and esters of (meth) acrylic acid, for example, methyl (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and the like; It can obtain by copolymerizing 1 or more types of unsaturated monomers chosen from styrene, (meth) acrylonitrile, (meth) acrylamide, etc.

Moreover, as glycidyl-group containing polymerizable unsaturated compound added to the said carboxyl group-containing acrylic resin, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. are mentioned, for example.

The addition reaction of the carboxyl group-containing acrylic resin and the glycidyl group-containing unsaturated compound is carried out by a known method, for example, in the presence of a catalyst such as tetraethylammonium bromide, for example, about 80 to 120 ° C. for about 1 to 5 hours. It can be performed easily by making it react.

Moreover, the said photosensitive resin (i) can also be manufactured by adding the reaction material of a hydroxyl group containing polymeric unsaturated compound and a diisocyanate compound to hydroxyl group containing acrylic resin.

As said hydroxyl group containing polymeric unsaturated compound, For example, hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate; N-methylol acrylamide etc. are mentioned.

Moreover, as a diisocyanate compound, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc. are mentioned, for example.

As the hydroxyl group-containing acrylic resin, the hydroxyl group-containing polymerizable unsaturated compound is an essential monomer component, and esters of (meth) acrylic acid, for example, methyl (meth) acrylate and ethyl (meth) Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and the like; Resin obtained by copolymerizing 1 or more types of unsaturated monomers chosen from styrene, (meth) acrylonitrile, (meth) acrylamide, etc. can be used.

The hydroxyl group-containing polymerizable unsaturated compound and the diisocyanate compound are reacted in an almost equimolar ratio. The addition reaction of the reactant obtained and hydroxyl-group containing acrylic resin can be performed by making it react at the temperature of about 50-100 degreeC in nitrogen gas atmosphere in accordance with the well-known method itself.

Moreover, in the said photosensitive resin (i), the photosensitive resin containing an allyl group as a photosensitive group can also be obtained by adding the reaction material of (meth) allyl alcohol and a diisocyanate type compound to the said hydroxyl-group containing acrylic resin.

(ii) photosensitive resin containing cinnamoyl group as photosensitive group

The photosensitive resin (ii) can be produced, for example, by reacting a hydroxyl group-containing acrylic resin with a substituted or unsubstituted cinnamic acid halide in the presence of a base, for example, in a pyridine solution.

As said hydroxyl group containing acrylic resin, what was demonstrated by said (i) can be used.

In addition, the substituted or unsubstituted cinnamic acid halide includes cinnamic acid halide which may have 1 to 3 substituents selected from nitro groups, lower alkoxy groups and the like on the benzene ring, and more specifically, for example, Cinnamic acid chloride, p-nitrocinnamic acid chloride, p-methoxycinnamic acid chloride, p-ethoxycinnamic acid chloride and the like.

The substituted or unsubstituted cinnamic acid halide can generally be used in an amount within the range of about 6 to 180 parts by weight, preferably about 30 to 140 parts by weight, per 100 parts by weight of the hydroxyl group-containing acrylic resin. The reaction of the hydroxyl group-containing acrylic resin with the substituted or unsubstituted cinnamic acid halide can be carried out by a method known per se, for example, at a temperature of about 30 to 70 ° C. in the presence of a base such as a pyridine solvent. .

(iii) other photosensitive resins

As other photosensitive resin (III), prepolymers, such as polyethyleneglycol diacrylate and polypropylene glycol diacrylate, can also be used.

As a photoinitiator used as needed for the photosensitive resin composition which has adhesiveness, a conventionally well-known thing can be used, For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, Bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 2-hydroxy-2-methyl- 1-phenyl-propane-1-one, 1-hydroxy cyclohexyl phenyl ketone, p-dimethylaminobenzoic acid, 2,4-diethyl thioxanthone, isopropyl thioxanthone, etc. are mentioned. As a commercial item, for example, Lucirin TPO [Lucirin TPO, BASF Corporation make, brand name], Irg907, Irg369, Irg651, Irg819, Irg1700, Irg1800, Irg1850, Darocure 1173 [DAROCURE 1173] (above, Shiva Specialty Chemicals company make, (Trade name), Kayacure DMBI, Kayacure DETX (above, Nippon Kayaku Co., Ltd. brand name), Speed Cure ITX (SPEED CURE ITX, the Nippon Cyber Hegner company make, brand name), etc. are mentioned.

The use ratio of a photoinitiator is about 10 weight part or less with respect to 100 weight part of photosensitive resins, Preferably it exists in the range of about 0.1-5 weight part.

As a photosensitizing dye used as needed for the photosensitive resin composition which has adhesiveness, a conventionally well-known thing can be used. Specifically, for example, photosensitizing dyes such as phenothiadine dyes, anthracene dyes, colonene dyes, benzanthracene dyes, perylene dyes, pyrene dyes, merocyanine dyes, ketocoumarin dyes, Can be used. The use ratio of these photosensitizers is about 10 weight part or less with respect to 100 weight part of photosensitive resins, Preferably it exists in the range of about 0.1-5 weight part.

Moreover, an ethylenically unsaturated compound, a coloring agent, a plasticizer, a smoothing agent, etc. can be contained suitably further in the photosensitive resin composition which has adhesiveness as needed. As this ethylenically unsaturated compound, the monomer etc. which contain 1-4 ethylenically unsaturated groups can be used.

The photosensitive resin composition which has adhesiveness can be manufactured by melt | dissolving or disperse | distributing a photosensitive resin which has adhesiveness, a photoinitiator, a photosensitizing dye, etc. in a medium as needed.

As a medium, various solvents, such as water and an organic solvent, can be used 1 type or in combination of 2 or more types. As the organic solvent, for example, various solvents such as a hydrocarbon solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, and an amide solvent can be used.

The supporting substrate in the step (1) fixes the material to be processed through the peelable adhesive composition layer and the photosensitive resin composition layer having adhesiveness, so that deformation and damage are caused by such a force during processing such as polishing, for example. It is not to be. As such a support base material, the thing which can fix | immobilize the said material is used, and what has transparency to which active energy rays, such as an ultraviolet-ray, permeate | transmit is used.

Transparency of a support base material is an activity which the active energy ray irradiated from the outer side (opposite direction with respect to a peelable adhesive composition layer and the photosensitive resin composition layer) of a support base material permeate | transmits and is contained in a peelable adhesive composition layer in a process (3). This is necessary because a compound generating gas by energy ray irradiation generates gas by decomposing. However, it is not necessary to be colorless and transparent, and it may contain a coloring agent, a filler, etc. as long as it does not substantially inhibit the gas generation by the permeation | transmission of active energy ray.

By the said process (1), the laminated body by which the photosensitive resin composition layer / support base material which has the material / peelable adhesive composition layer / adhesiveness which should be processed is laminated in this order can be obtained.

This laminated body is apply | coated and dried a peelable adhesive composition on the unprocessed surface of the material to be processed, for example, forms an adhesive composition layer, apply | coats and dries the photosensitive resin composition which has adhesiveness on it, and the said resin composition layer It can be obtained by the method a of forming a and then adhering a supporting substrate thereon.

For example, the said laminated body can also be obtained by the method b which adhere | attaches what formed the peelable adhesive composition layer on the unprocessed surface of the said material, and what formed the photosensitive resin composition film which has adhesiveness on a support base material.

In the said method b, formation of a peelable adhesive composition layer can be performed similarly to the case of the method a. In addition, formation of the photosensitive resin composition film which has adhesiveness can also be performed similarly to the case of the method a, and apply | coats and drys the said photosensitive resin composition to a mold release sheet previously, and forms a photosensitive resin composition film | membrane, and then a support base material surface and a mold release sheet It can also be performed by bonding so that the said photosensitive resin composition film | membrane of a contact may contact, and crimping | bonding on the surface (opposite direction with respect to the said photosensitive resin composition film) of a release sheet, and then peeling a release sheet.

As a manufacturing method of the laminated body which the photosensitive resin composition layer / support base material which has the material / peelable adhesive composition layer / adhesiveness which is processed by the said process (1) laminated | stacked in this order is the said method a, the method b, etc. It is not limited, It can manufacture in any order, if such a laminated body can be obtained.

In the said process (1), application | coating of the peelable adhesive composition or the photosensitive resin composition which has adhesiveness can be performed using well-known coating apparatuses, such as a roller, a roll coater, a spin coater, a knife coater, a sprayer, and a hair haircut, for example. Can be. Drying conditions after application | coating can be suitably set according to the component content of each composition used.

In the said laminated body, it is preferable that the thickness of a peelable adhesive composition layer is about 1-50 micrometers normally, Preferably it is about 2-30 micrometers. Moreover, in the said laminated body, it is preferable that the thickness of the photosensitive resin composition layer which has adhesiveness is about 1-200 micrometers normally, Preferably it is about 2-100 micrometers.

Process (2)

Step (2) is a step of processing the material to be fixed fixed in step (1). In this process, various processes, such as grinding | polishing, are performed with respect to the surface which should be processed of the said material, for example. In the case of this process, since a material is reliably fixed to a support base material through a peelable adhesive composition layer and the adhesive photosensitive resin composition layer, necessary processing can be fully performed.

Process (3)

Step (3) is a step of peeling and taking out the processed material by irradiating active energy rays from the outside of the supporting substrate of the laminate after being processed in step (2) to generate gas.

In this step, the processed material / peelable adhesive composition layer / adhesive photosensitive resin composition layer / transparent support substrate having a laminate in this order is laminated on the outside of the support substrate (peelable adhesive composition layer and photosensitive resin) By irradiating an active energy ray from the opposite direction to the composition layer, the photosensitive resin composition layer is cured to reduce the stickiness of the surface or becomes non-tacky, and at the same time, peeling existing between the cured photosensitive resin composition layer surface and the material surface By decomposing the gas-generating compound by generating active gas by the active energy ray irradiation in the adhesive composition, the cured photosensitive resin composition layer surface becomes a rough surface, and the processed material can be easily peeled off.

As the active energy ray, for example, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, tungsten lamp and the like can be used as a light source. Moreover, as an irradiation amount of an active energy ray, it is preferable that it is about 500-10,000 J / m <^2> normally.

According to the present invention, the following remarkable effects can be obtained.

(a) The peelable adhesive composition of this invention has the adhesiveness required to fix in order to process the material to be processed, and has the outstanding peelability which can be easily peeled off by active energy ray irradiation after processing.

(b) According to the processing method of the material using the peelable adhesive composition of this invention, after fixing the material to be processed to the support base material which has transparency through the said peelable adhesive composition layer and the photosensitive resin composition layer which has adhesiveness, After processing, the active energy ray is irradiated only from the outside of the support substrate (opposite directions with respect to the peelable adhesive composition layer and the photosensitive resin composition layer), and the gas from the curable and peelable adhesive composition layer of the photosensitive resin composition layer. By generation, the material after processing can be peeled easily.

(c) Therefore, in the said processing method using the peelable adhesive composition of this invention, processing, such as grinding | polishing, is performed on the surface of the thin plate material which is easy to deform | transform and break by the force from the exterior, such as a wafer, for example. When it does, it can apply very preferably.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, Test Examples and Comparative Test Examples. However, the present invention is not limited to these examples. In addition, "part" and "%" represent "weight part" and "weight%" in each example.

Production Example 1 Preparation of Photosensitive Resin Having Methacryloyl Group as Photosensitive Group

A mixed liquid consisting of 40 parts of methyl methacrylate, 40 parts of butyl acrylate, 20 parts of acrylic acid and 2 parts of azobisisobutyronitrile was added dropwise for 3 hours to 90 parts of propylene glycol monomethyl ether maintained at 110 ° C. under a nitrogen gas atmosphere. . After dropping, the mixture was aged for 1 hour, and a mixed solution consisting of 1 part of azobisdimethylvaleronitrile and 10 parts of propylene glycol monomethyl ether was added dropwise for 1 hour, and further aged for 5 hours to obtain an acrylic resin solution.

Subsequently, 24 parts of glycidyl methacrylate, 0.12 parts of hydroquinone and 0.6 parts of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 110 ° C for 5 hours while blowing air to obtain a glass transition temperature of 20 ° C and a number average molecular weight of about 20,000. The solution of photosensitive resin which has methacryloyl group was obtained.

Production Example 2 Preparation of Photosensitive Resin Composition

To 100 parts (solid content) of photosensitive resin obtained in Production Example 1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name "Irg907", Ciba as a photopolymerization initiator) 2 parts of specialty chemicals) and 2,4-diethyl thioxanthone (trade name "Gayacure DETX", manufactured by Nippon Kayaku Co., Ltd.) in 20 parts of propylene glycol monomethyl ether acetate were added, It stirred with the mechanical stirrer and obtained the photosensitive resin composition 1.

<Example 1>

To 100 parts (solid content) of the photosensitive resin obtained in Production Example 1, 2-hydroxy-3,4-bis (6-diazo-5) was used as a quinonediazide-based photosensitive compound which generates nitrogen gas by active energy ray irradiation. A solution in which 10 parts of 6-dihydro-5-oxo-1-naphthalenesulfonyloxy) -benzophenone was dissolved in 50 parts of propylene glycol monomethyl ether acetate was added.

In addition, as a photoinitiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (trade name "Irg907", manufactured by Ciba Specialty Chemicals, Inc.) and 2,4 -A solution obtained by dissolving 0.5 parts of diethyl thioxanthone (trade name "Gayacure DETX", manufactured by Nippon Kayaku Co., Ltd.) in 20 parts of propylene glycol monomethyl ether acetate was added, followed by stirring with a mechanical stirrer to remove the peelability of the present invention. Adhesive composition 1 was obtained.

<Example 2>

In Example 1, the amount of 2-hydroxy-3,4-bis (6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonyloxy) -benzophenone is 30 parts. A peelable adhesive composition 2 of the present invention was obtained in the same manner as in Example 1 except for the above.

<Example 3>

Example 1 WHEREIN: Except having used the same amount of copolymers of p-vinylphenol and styrene (brand name "Marukalinker CST15", the Maruzen Sekiyu Chemical Co., Ltd. product) instead of the photosensitive resin obtained in manufacture example 1, Example By the same composition as 1, the peelable adhesive composition 3 of this invention was obtained.

<Example 4>

Example 1 WHEREIN: Except having used the same amount of acrylic resin emulsion (brand name "Binibran 7043", the Nisshin Chemical Industries, Ltd. make) instead of the photosensitive resin obtained in manufacture example 1, it is the same composition as Example 1 of this invention. Peelable adhesive composition 4 was obtained.

About the adhesive composition 1-4 of this invention obtained in Examples 1-4, the adhesiveness and peelability with respect to a wafer were examined by the following test examples.

<Test Example 1>

The peelable adhesive composition 1 obtained in Example 1 was apply | coated so that the film thickness after drying might be set to 5 micrometers on a 8-inch wafer using a spin coater, and it heat-dried at 65 degreeC on the hotplate for 2 minutes.

Moreover, the photosensitive resin composition 1 obtained by the manufacture example 2 was apply | coated on the film | membrane so that the film thickness after drying might be 15 micrometers using a spin coater, and it heat-dried at 65 degreeC on the hotplate for 2 minutes. Next, the glass plate was crimped | bonded by the pressure of 0.4 Mpa as a support base material on this.

This obtained the laminated body by which the layer of the wafer / peelable adhesive composition 1 / the layer of photosensitive resin composition 1 / glass plate was laminated | stacked in this order.

After fixing the wafer surface of the laminate to the workbench with commercially available double-sided tape, the outside of the glass plate was joined to the spring balance using a sucker to measure the initial adhesive force (kgf / cm ² ), and then the ultra-high pressure mercury lamp from the outside of the glass plate. UV light of 6,00 J / m ² was irradiated. It measured by making the adhesive force after irradiation the same.

The initial adhesive force was 7 kgf / cm ² , which was sufficient to fix and polish the wafer, and had good adhesion. Good adhesion means that the adhesion is 5 kgf / cm ² or more.

Moreover, the adhesive force after UV irradiation was 1 kgf / cm <^2> , and it is the adhesive force which can peel easily a wafer from an adhesive bond layer, and peelability was favorable. Good peelability means that the adhesive force is 2 kgf / cm ² or less.

<Test Example 2>

In Experiment 1, except having used the peelable adhesive composition 2 obtained in Example 2 instead of the peelable adhesive composition 1, it carried out similarly to Test Example 1, and measured the initial adhesive force and the adhesive force after UV irradiation.

<Test Example 3>

In Experiment 1, except having used the peelable adhesive composition 3 obtained in Example 3 instead of the peelable adhesive composition 1, it carried out similarly to Test Example 1, and measured the initial adhesive force and the adhesive force after UV irradiation.

<Test Example 4>

In Experiment 1, except having used the peelable adhesive composition 4 obtained in Example 4 instead of the peelable adhesive composition 1, it carried out similarly to Test Example 1, and measured the initial adhesive force and the adhesive force after UV irradiation.

In Test Examples 1 to 4, the results of measuring the initial adhesive strength and the adhesive strength after UV irradiation are shown in Table 1 below.

Comparative Test Example 1

An 8 inch wafer was fixed to a glass plate as a supporting substrate using a commercial double-sided tape. Subsequently, the wafer was peeled off from the glass plate after polishing the wafer, but peeling was difficult.

According to the present invention, the following remarkable effects can be obtained.

(a) The peelable adhesive composition of this invention has the adhesiveness required to fix in order to process the material to be processed, and has the outstanding peelability which can be easily peeled off by active energy ray irradiation after processing.

(b) According to the processing method of the material using the peelable adhesive composition of this invention, after fixing the material to be processed to the support base material which has transparency through the said peelable adhesive composition layer and the photosensitive resin composition layer which has adhesiveness, After processing, the active energy ray is irradiated only from the outside of the support substrate (opposite directions with respect to the peelable adhesive composition layer and the photosensitive resin composition layer), and the gas from the curable and peelable adhesive composition layer of the photosensitive resin composition layer. By generation, the material after processing can be peeled easily.

(c) Therefore, in the said processing method using the peelable adhesive composition of this invention, processing, such as grinding | polishing, is performed on the surface of the thin plate material which is easy to deform | transform and break by the force from the exterior, such as a wafer, for example. When it does, it can apply very preferably.

Claims (5)

A peelable adhesive composition comprising a resin having adhesiveness and a compound generating gas by active energy ray irradiation. The peelable adhesive composition of Claim 1 whose resin which is adhesive is photosensitive resin. The peelable adhesive composition of Claim 1 or 2 whose compound which generate | occur | produces a gas by active energy ray irradiation is quinone diazide sulfonic-acid ester. The peelable adhesive according to claim 1 or 2, wherein the use ratio of the resin having adhesiveness and the compound which generates gas by active energy ray irradiation is about 1 to 100 parts by weight of the compound based on 100 parts by weight of the resin. Composition. The peelable adhesive composition of Claim 3 whose use ratio of the resin which has adhesiveness, and the compound which generate | occur | produces gas by active energy ray irradiation is about 1-100 weight part of said compounds with respect to 100 weight part of said resins.