JP2004107650A - Releasable adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition having both excellent adhesion and releasability. <P>SOLUTION: This releasable adhesive composition contains a resin which has tackiness and a compound which generates gas by irradiation of active energy rays. The compound which generates the gas by the irradiation of the active energy rays preferably comprises a quinonediazidosulfonic acid ester in the releasable adhesive composition. The resin which has the tackiness and the compound which generates the gas by the irradiation of the active energy rays are contained in the releasable adhesive composition in such a ratio that about 1 to about 100 pts.wt. of the compound is contained based on 100 pts.wt. of the resin. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a peelable adhesive composition.

Conventionally, for example, when performing processing such as polishing on the surface of a thin sheet material that is easily deformed or damaged by an external force such as a wafer, the thin sheet material is fixed to a supporting base material via an adhesive and processed. There is a method of peeling the finished material from the adhesive and the supporting base material to obtain a processed sheet material.

Adhesives used in such applications include adhesives that allow the sheet material to be firmly fixed to the support substrate during processing operations, and materials that have been processed can be easily removed from the adhesive and the support substrate. It is required to have excellent releasability that can be peeled.

However, an adhesive composition excellent in both adhesiveness and peelability when used for such applications has not been known.

  An object of the present invention is to provide an adhesive composition excellent in both adhesiveness and peelability.

The present inventors have conducted intensive studies to achieve the above object, and as a result, according to an adhesive composition containing a resin having tackiness and a compound generating a gas by irradiation with active energy rays, it is a material to be processed. It has been found that, after having an adhesive property necessary for fixing the adherend, the adherend can be easily peeled off by gas generated by irradiation with active energy rays after processing.

Based on such knowledge, the present inventor has further conducted various studies and completed the present invention.

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

{1. A peelable adhesive composition comprising a resin having tackiness and a compound generating a gas upon irradiation with active energy rays.

{2. Item 2. The peelable adhesive composition according to Item 1, wherein the resin having tackiness is a photosensitive resin.

{3. Item 3. The releasable adhesive composition according to item 1 or 2, wherein the compound generating a gas upon irradiation with active energy rays is a quinonediazidesulfonic acid ester.

4. Any one of the above items 1 to 3, wherein the use ratio of the adhesive resin and the compound generating a gas by irradiation with active energy rays is about 1 to 100 parts by weight of the compound per 100 parts by weight of the resin. The peelable adhesive composition according to item 6.

Hereinafter, the peelable adhesive composition of the present invention will be described in detail.

Peelable Adhesive Composition The peelable adhesive composition of the present invention contains a resin having tackiness and a compound that generates a gas upon irradiation with active energy rays. Therefore, the adherend adhered using the present composition generates a gas by irradiating the adhesive layer with active energy rays such as ultraviolet rays, and the generated gas causes the adhesive layer to adhere to the adherend. It can be easily peeled off.

The resin having tackiness is preferably a resin having tackiness at a temperature of about −50 to + 150 ° C., particularly about −40 to + 120 ° C. Further, the adhesiveness is, for example, preferably in the range of about 5 to 40, particularly about 7 to 30 in adhesive strength (kgf / cm ² ).

(4) The adhesive resin may be either a thermoplastic resin or a curable resin. Examples of the thermoplastic resin include an acrylic resin, a urethane resin, a polyester resin, novolak phenol and its derivatives, polyvinyl phenol and its derivatives, and silicone and its derivatives. The curable resin includes, for example, those obtained by introducing a polymerizable unsaturated group into any of these resins.

硬化 Alternatively, as the curable resin, an adhesive photosensitive resin in an adhesive photosensitive resin composition that is cured by an active energy ray such as ultraviolet rays described below can be used. In this case, if necessary, a photopolymerization initiator, a photosensitizing dye, and the like can be appropriately added.

化合物 As the compound generating a gas upon irradiation with active energy rays, for example, quinonediazidesulfonic acid ester can be suitably used.

(2) Quinonediazide sulfonic acid ester is a photosensitive compound that generates nitrogen gas upon irradiation with active energy rays, and enables the adhesive layer to be peeled off by bubbles generated by the generated nitrogen gas.

As the quinonediazidesulfonic acid ester, an esterified product of polyhydroxybenzophenone and a 1,2-quinonediazidesulfonic acid such as 1,2-benzoquinonediazidesulfonic acid and 1,2-naphthoquinonediazidesulfonic acid can be preferably used.

ポ リ The polyhydroxybenzophenone used to form this ester includes those represented by the following formula (I).

　式（Ｉ）中、ｍ及びｎはそれぞれ０〜３の整数であり、ｍ＋ｎの合計は１〜６である。

In the formula (I), m and n are each an integer of 0 to 3, and the sum of m + n is 1 to 6.

具体 Specific examples of polyhydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone.

On the other hand, 1,2-benzoquinonediazidosulfonic acid esterified with polyhydroxybenzophenone includes a compound represented by the following formula (II), and 1,2-naphthoquinonediazidosulfonic acid includes a compound represented by the following formula (III) ) Are included.

　１，２−ベンゾキノンジアジドスルホン酸の具体例としては、１，２−ベンゾキノンジアジド−４−スルホン酸等を挙げることができる。１，２−ナフトキノンジアジドスルホン酸の具体例としては、１，２−ナフトキノンジアジド−５−スルホン酸、１，２−ナフトキノンジアジド−４−スルホン酸等を挙げることができる。

Specific examples of 1,2-benzoquinonediazidesulfonic acid include 1,2-benzoquinonediazide-4-sulfonic acid. Specific examples of 1,2-naphthoquinonediazidesulfonic acid include 1,2-naphthoquinonediazide-5-sulfonic acid and 1,2-naphthoquinonediazide-4-sulfonic acid.

The esterification reaction between polyhydroxybenzophenone and 1,2-quinonediazidesulfonic acid is carried out by a method known per se, for example, by reacting polyhydroxybenzophenone with 1,2-quinonediazidosulfonic acid or a halide thereof (eg, chloride). Can be performed. In this case, the reaction ratio of the two is not particularly limited, but generally, 1,2-quinonediazidosulfonic acid is reacted at a ratio of 1 to q molecules with respect to the number q of hydroxyl groups in the polyhydroxybenzophenone. It is suitable. These polyhydroxybenzophenones and 1,2-quinonediazidosulfonic acids or their halides may be used alone or in combination of two or more.

In the adhesive composition of the present invention, the use ratio of the resin having tackiness and the compound that generates a gas by irradiation with active energy rays is generally about 1 to 100 parts by weight of the compound based on 100 parts by weight of the resin. And preferably about 5 to 50 parts by weight.

接着 The adhesive composition of the present invention can be prepared by dissolving or dispersing a resin having tackiness and a compound which generates gas by irradiation with active energy rays in a medium.

As the medium, various solvents such as water and organic solvents can be used alone or in combination of two or more. 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.

Material processing method The peelable adhesive composition of the present invention is used for bonding an adherend, which is a material to be processed, to a supporting substrate, and after processing, peeling the material from the supporting substrate. It can be used suitably as an agent.

加工 As a processing method of a material using the above-mentioned adhesive composition, the following method is preferable.

That is, (1) the non-processed surface of the material to be processed is fixed to a transparent support substrate through the peelable adhesive composition layer and the photosensitive resin composition layer having tackiness of the present invention. Process,
(2) a step of processing the fixed material,
(3) Next, from the outside of the supporting base material, by irradiating active energy rays to generate a gas, the processed material is peeled off, and a processing method of the material including a step of removing the processed material is used to process various materials. Can be suitably performed.

Process (1)
In the step (1), the material to be processed is transparently formed via the peelable adhesive composition layer and the tacky photosensitive resin composition layer of the present invention formed on the non-processed surface of the material. This is a step of fixing to a supporting substrate having properties.

材料 As the material to be processed, for example, various materials that require various processes such as polishing can be used without any particular limitation.

The material of the above material may be any material such as plastic, metal, glass, fiber, paper and the like, and the shape may be a film, plate, line, sphere, disk, cone, rectangular parallelepiped The shape may be any shape such as a shape or a shape obtained by combining these shapes. In particular, a material in a thin plate shape or the like which is easily deformed or broken by an external force and which requires processing such as polishing can be suitably used.

Specific materials include, for example, electronic materials such as wafers.

The tacky photosensitive resin composition used in the above step (1) contains a tacky photosensitive resin and, if necessary, a photopolymerization initiator, a photosensitizing dye, and the like. An aqueous or organic solvent type resin composition which is cured by irradiation with an active energy ray can be suitably used.

As the photosensitive resin having tackiness, a photosensitive resin having tackiness at a temperature of about −50 to + 150 ° C., particularly about −40 to + 120 ° C., is preferable. Further, the adhesiveness is, for example, preferably in the range of about 5 to 40, particularly about 7 to 30 in adhesive strength (kgf / cm ² ).

具体 Specific examples of the photosensitive resin having the above-mentioned adhesiveness are shown below.

(i) As a photosensitive group, a photosensitive resin having a polymerizable group such as a (meth) acryloyl group The photosensitive resin (i) is, for example, a glycidyl group-containing polymerizable unsaturated compound in a carboxyl group-containing acrylic resin. It can be manufactured by adding.

The carboxyl group-containing acrylic resin used at that time is, for example, an α, β-ethylenically unsaturated acid such as acrylic acid and methacrylic acid as an essential monomer component, and (meth) acrylic acid esters, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc .; styrene, (meth) acrylonitrile, (meth) ) It can be obtained by copolymerizing at least one unsaturated monomer selected from acrylamide and the like.

グ リ Examples of the glycidyl group-containing polymerizable unsaturated compound added to the carboxyl group-containing acrylic resin include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

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

The photosensitive resin (i) can also be produced by adding a reaction product of a hydroxyl group-containing polymerizable unsaturated compound and a diisocyanate compound to a hydroxyl group-containing acrylic resin.

{Examples of the hydroxyl-containing polymerizable unsaturated compound include, for example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate; N-methylol acrylamide;

Examples of the diisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

Further, as the hydroxyl group-containing acrylic resin, the above-mentioned hydroxyl group-containing polymerizable unsaturated compound is used as an essential monomer component, and (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like; at least one non-method selected from styrene, (meth) acrylonitrile, (meth) acrylamide and the like. A resin obtained by copolymerizing a saturated monomer can be used.

The hydroxyl group-containing polymerizable unsaturated compound and the diisocyanate compound are reacted in substantially equimolar ratio. The addition reaction between the obtained reactant and the hydroxyl group-containing acrylic resin can be performed by a reaction at a temperature of about 50 to 100 ° C. in a nitrogen gas atmosphere according to a method known per se.

Further, among the above photosensitive resins (i), the photosensitive resin containing an allyl group as a photosensitive group allows a reaction product of (meth) allyl alcohol and a diisocyanate compound to be added to the hydroxyl group-containing acrylic resin. By doing so, it can also be obtained.

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

ヒ ド ロ キ シ ル As the hydroxyl group-containing acrylic resin, those described in the above (i) can be used.

Further, the substituted or unsubstituted cinnamate halides include cinnamate halides which may have 1 to 3 substituents selected from a nitro group, a lower alkoxy group and the like on a benzene ring. Specifically, for example, cinnamic acid chloride, p-nitrocinnamic acid chloride, p-methoxycinnamic acid chloride, p-ethoxycinnamic acid chloride and the like can be mentioned.

The substituted or unsubstituted cinnamic acid halide is generally used in an amount 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 between the hydroxyl-containing acrylic resin and the substituted or unsubstituted cinnamic halide can be carried out by a method known per se, for example, at about 30 to 70 ° C. in the presence of a base such as a pyridine solvent. The reaction can be carried out at a temperature.

(iii) Other photosensitive resin As the other photosensitive resin (iii), a prepolymer such as polyethylene glycol diacrylate and polypropylene glycol diacrylate can also be used as the photosensitive resin.

As the photopolymerization initiator used in the photosensitive resin composition having tackiness, if necessary, a conventionally known photopolymerization initiator can be used. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one , Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, p-dimethylaminobenzoic acid, 2,4-diethylthioxa And isopropylthioxanthone. Commercially available products include, for example, Lucirin TPO (trade name, manufactured by BASF), Irg907, Irg369, Irg651, Irg819, Irg1700, Irg1800, Irg1850, DAROCURE 1173 (trade name, manufactured by Ciba Specialty Chemicals), KAYACURE DMBI KAYACURE DETX (product name, manufactured by Nippon Kayaku Co., Ltd.), SPEED CURE ITX (product name, manufactured by Nippon SiberHegner Co., Ltd.) and the like.

(4) The use ratio of the photopolymerization initiator is suitably about 10 parts by weight or less, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the photosensitive resin.

光 A conventionally known photosensitizing dye can be used as necessary for the photosensitive resin composition having tackiness, if necessary. Specifically, for example, photosensitizing dyes such as phenothiazine dyes, anthracene dyes, coronene dyes, benzanthracene dyes, perylene dyes, pyrene dyes, merocyanine dyes, and ketocoumarin dyes can be used. . The proportion of these photosensitizing dyes used is about 10 parts by weight or less, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the photosensitive resin.

(4) The photosensitive resin composition having tackiness may further contain an ethylenically unsaturated compound, a coloring agent, a plasticizer, a leveling agent, and the like, as necessary. As the ethylenically unsaturated compound, a monomer containing 1 to 4 ethylenically unsaturated groups can be used.

The photosensitive resin composition having tackiness can be prepared by dissolving or dispersing a photosensitive resin having tackiness and, if necessary, a photopolymerization initiator, a photosensitizing dye, and the like in a medium. it can.

As the medium, various solvents such as water and organic solvents can be used alone or in combination of two or more. 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) is a material to be processed, fixed through a peelable adhesive composition layer and a photosensitive resin composition layer having tackiness, for example, during processing such as polishing. This is to prevent deformation and breakage by such a force. As such a support base material, a support base material that is strong enough to immobilize the material and has transparency through which active energy rays such as ultraviolet rays pass is used.

In step (3), the transparency of the support base material is such that active energy rays irradiated from the outside of the support base (opposite to the peelable adhesive composition layer and the photosensitive resin composition layer) pass therethrough. It is necessary to generate a gas by decomposing a compound that generates a gas by irradiation with active energy rays contained in the peelable adhesive composition layer. However, it is not necessary to be colorless and transparent, and a colorant, a filler, and the like may be contained as long as the generation of gas due to the transmission of active energy rays is not substantially inhibited.

に よ り By the above step (1), a laminate is obtained in which the material to be processed / the peelable adhesive composition layer / the photosensitive resin composition layer having tackiness / the support substrate are laminated in this order.

This laminate is, for example, coated on a non-processed surface of a material to be processed, a releasable adhesive composition, dried to form the adhesive composition layer, and a photosensitive resin composition having tackiness thereon. The resin composition layer is formed by applying and drying a product, and then a supporting substrate is attached thereon to obtain the resin composition layer.

Further, for example, the above-mentioned laminate is obtained by forming a peelable adhesive composition layer on the non-processed surface of the above-mentioned material, and by forming a photosensitive resin composition film having tackiness on a supporting substrate. Can also be obtained by the method b for pasting.

に お い て In the above method b, the formation of the peelable adhesive composition layer can be performed in the same manner as in the method a. The formation of the photosensitive resin composition film having adhesiveness may be performed in the same manner as in the method a, or the photosensitive resin composition may be applied to a release sheet in advance and dried to form the film. A photosensitive resin composition film is formed, and then adhered so that the surface of the support substrate and the photosensitive resin composition film on the release sheet are in contact with each other, and the surface of the release sheet (the photosensitive resin (The opposite direction to the composition film) and then peeling off the release sheet.

As a method for producing a laminate in which the material to be processed, the peelable adhesive composition layer, the photosensitive resin composition layer having tackiness, and the support substrate obtained in the above step (1) are laminated in this order. Is not limited to the above methods a and b, and may be prepared by any procedure as long as such a laminate is obtained.

In the step (1), the application of the peelable adhesive composition or the photosensitive resin composition having tackiness includes, for example, a roller, a roll coater, a spin coater, a knife coater, a spray, and a known application device such as a brush. Can be used. Drying conditions after application may be appropriately set according to the content of the components of each composition used.

に お い て In the laminate, the thickness of the peelable adhesive composition layer is usually about 1 to 50 µm, preferably about 2 to 30 µm. In the laminate, the thickness of the photosensitive resin composition layer having an adhesive property is usually about 1 to 200 μm, preferably about 2 to 100 μm.

Process (2)
Step (2) is a step of processing the material to be processed fixed in step (1). In this step, various processes such as polishing are performed on the surface of the material to be processed. At the time of this processing, since the material is firmly fixed to the supporting base material via the peelable adhesive composition layer and the photosensitive resin composition layer having tackiness, it is necessary to perform necessary processing sufficiently. Can be.

Process (3)
Step (3) is to irradiate active energy rays to generate gas by irradiating the active material from the outside of the support base of the laminate after being processed in step (2), thereby peeling off the processed material, This is the step of taking out.

  In this step, the supporting material of the laminated body in which the processed material / the peelable adhesive composition layer / the photosensitive resin composition layer having the tackiness / the transparent supporting substrate is laminated in this order. By irradiating an active energy ray from the outside (the direction opposite to the releasable adhesive composition layer and the photosensitive resin composition layer), the photosensitive resin composition layer is cured and the surface tackiness is reduced. Or non-adhesive, and the compound that generates gas by irradiation with active energy rays in the peelable adhesive composition layer existing between the cured photosensitive resin composition layer surface and the material surface is decomposed. As a result, the cured photosensitive resin composition layer surface becomes rough, and the processed material can be easily peeled off.

As the active energy ray, for example, ultraviolet light or visible light using ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp lamp, carbon arc lamp, xenon lamp, metal halide lamp, tungsten lamp, or the like as a light source is used. Can be. In addition, the irradiation amount of the active energy ray is usually preferably about 500 to 10,000 J / m ² .

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

(a) The peelable adhesive composition of the present invention has an adhesive property necessary for fixing a material to be processed for processing, and moreover, after processing, can be easily peeled off by irradiation with active energy rays. Has excellent peelability.

(b) According to the method for processing a material using the releasable adhesive composition of the present invention, the material to be processed is interposed between the releasable adhesive composition layer and the tacky photosensitive resin composition layer. After fixing to a supporting substrate having transparency and processing, an active energy ray is applied from the outside of the supporting substrate (in a direction opposite to the peelable adhesive composition layer and the photosensitive resin composition layer). Only by irradiation, the processed material can be easily peeled off by curing the photosensitive resin composition layer and generating gas from the peelable adhesive composition layer.

(c) Therefore, the above-mentioned processing method using the peelable adhesive composition of the present invention, for example, when performing processing such as polishing on the surface of a thin plate material which is easily deformed or damaged by external force such as a wafer. Can be applied very suitably.

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 the examples. In each example, “parts” and “%” indicate “parts by weight” and “% by weight”.

Production Example 1 Production of a photosensitive resin having a methacryloyl group as a photosensitive group A mixed solution composed of 40 parts of methyl methacrylate, 40 parts of butyl acrylate, 20 parts of acrylic acid, and 2 parts of azobisisobutyronitrile was placed under a nitrogen gas atmosphere. In 90 parts of propylene glycol monomethyl ether maintained at 110 ° C. over 3 hours. After the dropwise addition, the mixture was aged for 1 hour, and a mixed solution composed of 1 part of azobisdimethylvaleronitrile and 10 parts of propylene glycol monomethyl ether was added dropwise for 1 hour, and aged for 5 hours to obtain an acrylic resin solution.

Next, 24 parts of glycidyl methacrylate, 0.12 parts of hydroquinone and 0.6 parts of tetraethylammonium bromide were added to the 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 A solution of a photosensitive resin having 20,000 methacryloyl groups was obtained.

Production Example 2 Production of photosensitive resin composition 100 parts (solid content) of the photosensitive resin obtained in Production Example 1 was treated with 2-methyl-1- [4- (methylthio) phenyl] -2- as a photopolymerization initiator. 2 parts of morpholinopropan-1-one (trade name "Irg907", manufactured by Ciba Specialty Chemicals) and 0.5 parts of 2,4-diethylthioxanthone (trade name "kayacure DETX", manufactured by Nippon Kayaku Co., Ltd.) Was dissolved in 20 parts of propylene glycol monomethyl ether acetate, and the mixture was stirred with a mechanical stirrer to obtain a photosensitive resin composition 1.

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

Further, as photoinitiators, 2 parts and 2 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irg907”, manufactured by Ciba Specialty Chemicals) , 4-Diethylthioxanthone (trade name "kayacure @ DETX", manufactured by Nippon Kayaku Co., Ltd.) in 0.5 parts was dissolved in 20 parts of propylene glycol monomethyl ether acetate, and the mixture was stirred with a mechanical stirrer. A peelable adhesive composition 1 was obtained.

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

In Example 1, a copolymer of p-vinylphenol and styrene (trade name “Marcalinker CST15”, manufactured by Maruzen Petrochemical Co.) was used in the same amount in place of the photosensitive resin obtained in Production Example 1. By using the same composition as in Example 1, a peelable adhesive composition 3 of the present invention was obtained.

Example 1 was the same as Example 1 except that the same amount of an acrylic resin emulsion (trade name: "ViniBlan 7043", manufactured by Nissin Chemical Industry Co., Ltd.) was used in place of the photosensitive resin obtained in Production Example 1. Depending on the composition, a peelable adhesive composition 4 of the present invention was obtained.

接着 With respect to the adhesive compositions 1 to 4 of the present invention obtained in Examples 1 to 4, the adhesiveness to a wafer and the peelability were examined by the following test examples.

Test example 1
The peelable adhesive composition 1 obtained in Example 1 was applied on an 8-inch wafer using a spin coater so that the film thickness after drying was 5 μm, and was applied on a hot plate at 65 ° C. for 2 hours. Heated and dried for minutes.

Further, the photosensitive resin composition 1 obtained in Production Example 2 was applied on the film using a spin coater so that the film thickness after drying was 15 μm, and was applied at 65 ° C. on a hot plate at 65 ° C. Heated and dried for minutes. Next, a glass plate was pressed thereon as a supporting substrate at a pressure of 0.4 MPa.

Thus, a laminate was obtained in which wafer / layer of peelable adhesive composition 1 / layer of photosensitive resin composition 1 / glass plate were laminated in this order.

After fixing the wafer surface of the laminated body to a worktable with a commercially available double-sided tape, and bonding the outside of the glass plate to a spring using a suction cup, and measuring the initial adhesive force (kgf / cm ² ), UV light of 6,000 J / m ² was irradiated from the outside of the glass plate with an extra-high pressure mercury lamp. The adhesive strength after irradiation was measured in the same manner.

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

Further, the adhesive strength after UV irradiation was 1 kgf / cm ² , which was an adhesive strength capable of easily peeling the wafer from the adhesive layer, and the peelability was good. Good releasability means that the adhesive strength is 2 kgf / cm ² or less.

Test example 2
In the test example 1, the initial adhesive strength and after the UV irradiation were the same as in the test example 1 except that the peelable adhesive composition 2 obtained in the example 2 was used instead of the peelable adhesive composition 1. The adhesion was measured.

Test example 3
In the test example 1, the initial adhesive strength and after the UV irradiation were the same as in the test example 1 except that the peelable adhesive composition 3 obtained in the example 3 was used instead of the peelable adhesive composition 1. The adhesion was measured.

Test example 4
In the test example 1, the initial adhesive strength and after the UV irradiation were the same as in the test example 1 except that the peelable adhesive composition 4 obtained in the example 4 was used instead of the peelable adhesive composition 1. The adhesion was measured.

Table 1 shows the results of measuring the initial adhesive strength and the adhesive strength after UV irradiation in Test Examples 1 to 4.

Comparative test example 1
An 8-inch wafer was fixed to a glass plate as a support substrate using a commercially available double-sided tape. Next, after the wafer was polished, the wafer was peeled off from the glass plate. However, it was difficult to peel off the wafer.

Claims (4)

A peelable adhesive composition comprising a resin having tackiness and a compound generating a gas upon irradiation with active energy rays. The peelable adhesive composition according to claim 1, wherein the resin having tackiness is a photosensitive resin. The peelable adhesive composition according to claim 1 or 2, wherein the compound that generates a gas upon irradiation with active energy rays is a quinonediazidesulfonic acid ester. The use ratio of the adhesive resin and the compound that generates a gas by irradiation with active energy rays is about 1 to 100 parts by weight of the compound per 100 parts by weight of the resin. The peelable adhesive composition according to item 6.