TW201014892A - Ultraviolet curable-type removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the ultraviolet curable-type removable pressure-sensitive adhesive composition - Google Patents

Abstract

Disclosed is an ultraviolet curable-type removable pressure-sensitive adhesive composition that is an ultraviolet curable-type pressure-sensitive adhesive which is useful for the formation of integrated circuits such as wafers and can be brought to a film. In such a range that a reduction in strength after curing from the strength before the curing of a pressure-sensitive adhesive film useful for a dicing tape is preferable, the ultraviolet curable-type removable pressure-sensitive adhesive composition has a high holding power and can provide a cured film without any adhesive residue on the surface of a wafer upon the removability of the cured film. The ultraviolet curable-type removable pressure-sensitive adhesive composition comprises (a) an acrylic pressure-sensitive adhesive polymer, (b) a polyfunctional epoxy acrylate, (c) a photopolymerization initiator, and (d) a curing agent reactive with a hydroxyl group, a carboxyl group, or an epoxy group. Also disclosed is a pressure-sensitive adhesive sheet using the ultraviolet curable-type removable pressure-sensitive adhesive composition.

Description

[Technical Field] The present invention relates to a surface of a semiconductor wafer that is protected during the cutting process of forming a 1C package and a semiconductor wafer, and is separated by a small piece of the component. The ultraviolet curable re-peelable adhesive composition which can be used for fixing and fixing the element piece for use on the temporary fixing adhesive sheet used. [Prior Art] In recent years, in the manufacturing steps of semiconductors, chipping or cracking which occurs during dicing of thinning of a wafer is considered to be a more serious problem. For these reasons, it is mainly believed to be in the cutting process because of the high-speed rotation of the blade, causing the wafer to vibrate during cutting. The dicing tape used in the booklet and the like is designed to suppress the vibration of the wafer during cutting, and the adhesive also requires adhesion and high retention. In the above, for example, an adhesive sheet for wafer adhesion has been disclosed (Patent Document 1), which is composed of a base film and a radiation-curable adhesive layer formed thereon, wherein The radiation-curable adhesive layer is composed of a propylene-based adhesive obtained by copolymerizing an acrylate and an OH group-containing polymerizable monomer, and a radiation-polymerizable compound having two or more unsaturated bonds. 20 to 80% by weight of the radioactive polymerizable compound has four or more unsaturated bonds, and the elastic modulus after radiation hardening is lxlO9 dyn/cm2 or more. Further, there is an active light-curing type re-peelable adhesive composition (Patent Document 2) which contains a C-201014892 olefin resin latex adhesive, a polyfunctional (meth) acrylate compound, and an active light-curing interface. Further, an adhesive resin composition (Patent Document 3) is a polymer having a weight average molecular weight of 10,000 to 2,000,000 and a glass transition temperature of -100 to 100 ° C, and is polymerizable. a carbon-carbon double bond monomer, a polymerizable carbon-carbon double bond oligomer, and an adhesive resin composition formed by a starter, and cured by ultraviolet light, from ultraviolet curing to ultraviolet curing The adhesion of the adhesive layer will be 1/3 or less. Furthermore, an adhesive tape for processing a semiconductor substrate formed by using a fluoroacrylate polymer having five or more functional groups is disclosed (Patent Document 4), which is a spherical grid closed by an epoxy resin or the like. Casing tape for packaging, such as a Grid Array (BGA) or a Chip Size Package (CSP), which is used to separate the 1C package, also requires the same considerations, for example, for UV and/or Or a film made of a base resin, a radiation polymerizable compound, a radiation polymerizable polymerization initiator, and a crosslinking agent coated on the surface of the film having a penetrating electron beam, and further prepared for processing a semiconductor substrate. tape. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 6 - 201014892 DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide an ultraviolet curable re-peelable adhesive which is a film-forming ultraviolet ray which is formed on a bulk circuit such as a wafer. A hardening type adhesive which retains the force cylinder in a desired range of reduction in the strength of the adhesive film before and after hardening which is useful for the dicing tape, and does not cause paste residue on the wafer surface when the cured film is peeled off. Hardened film. In order to solve such a problem, the inventors of the present invention have found that an ultraviolet curing type re-peelable adhesive can be solved by repeating efforts to study the ultraviolet curing type re-peelable adhesive. The above-mentioned problem is characterized in that it contains (a) an acrylic acid-based adhesive polymer, (b) a polyfunctional epoxy acrylate, (c) a photopolymerization initiator, and (d) a hydroxyl group, a carboxyl group or an epoxy group. The base has a reactive hardener, thereby completing the present invention. That is, the present invention relates to an ultraviolet curable re-peelable adhesive composition characterized by (a) a acrylic acid-based adhesive polymer, (b) a polyfunctional epoxy propylene acrylate, (c) a photopolymerization initiator, a resin having reactivity with a hydroxyl group, a carboxyl group or an epoxy group, and the polyfunctional epoxy acrylate comprising any one of the following: a compound represented by the formula (1) , 201014892 [Chemical 1] Η20 = 0Η1-ε-Ο-Ρ-Χ-lO-CHji-CH-CH^OC-CR^CHij

ΊΙ T fly I II Ο O-R2 Ο (wherein R1 is a hydrogen atom or a methyl group, which may be the same or different from each other, and R2 is a hydrogen atom or a group having an ethylenically unsaturated bond, and X is a compound having at least two epoxy groups in a molecule obtained by polymerizing a re-opening ring, and when R2 is a hydrogen atom, X is a group having at least one ethylenically unsaturated bond, and η is an integer) or a formula (2) ) the compound shown, [Chem. 2] R CICIO II o H c R CICIO II o Η c

Η C If 3 R CICIO

HC-OR* HC-OR5 HC-OR5 I I I CH2 C-Hjj CH. I I I

(wherein R3 is a hydrogen atom or a methyl group, which may be the same or different from each other, and R4 is a hydrogen atom or a methyl group, which may be the same or different from each other, and further, the benzene skeleton to which R4 is bonded is also The substituent may be substituted with another substituent, and Ri is a hydrogen atom or a group having an ethylenically unsaturated bond, and at least one of R5 has a group having an ethylenically unsaturated bond, and m is an integer of 3 -8 to 201014892 _ or a formula ( 3) Compound shown, ο ί ci ο to R c = cc

Η c - Η cl ο

Η CR (wherein R6 is a hydrogen atom or a methyl group, which may be the same or different from each other'. R7 is a hydrogen atom or a group having an ethylenically unsaturated bond, and at least one of R7 has an ethylenicity. The base of the saturated bond). Wherein X is preferably any of the following: [Chemical 4] The base represented by the formula (4) OR9

I ch2-ch-ch. (wherein R8 is a hydrogen atom or a group of a methyl unsaturated bond) or a group represented by the formula (5), and R9 is a hydrogen atom or has an ethylenic OR1 formula; R10 is a hydrogen atom or a methyl group 'R11 is a hydrogen atom or a group having an ethyl -9 - 201014892 unsaturated bond). Wherein R2, R5, R7, R9 or RU, etc. are preferably a hydrogen atom or a group represented by the formula (6), [Chem. 6]

• N — C — I II , c = cr12-c-o-ch2-ch. 〇 (wherein R 12 is a hydrogen atom or a methyl group). Wherein '(a) the acrylic-based adhesive polymer 1 〇〇 mass part' preferably contains (b) a polyfunctional epoxy acrylate of 2 〇 to 2 〇〇 by mass. Preferably, the (a) acrylic adhesive polymer has a weight average molecular weight of 200,000 to 2,000,000, and the glass transition temperature is _5 (rc~1 (rc) is formed by a hydroxyl group-containing (meth)acrylic acid. Among the ester copolymers, the preferred one is (b) a reactive product of a polyfunctional epoxy acrylate epoxy acrylate and an α' oxime-ethylenically unsaturated monoisocyanate. Further, the adhesive sheet is characterized in that the ultraviolet curable re-peelable adhesive composition is used. According to the present invention, an ultraviolet curable re-peelable adhesive can be provided as a kind of wafer or the like. The integrated circuit is formed with an ultraviolet-curable adhesive having a film-forming property, and the adhesive has an excellent appearance after application. The adhesive film strength before and after hardening for the dicing tape is reduced by a low of -10, 2010, 14892. In the ideal range, the holding force is high, and when the cured film is formed by ultraviolet light, the cured film is not formed on the surface of the wafer. [Embodiment] The best mode for carrying out the invention Hereinafter, the present invention will be specifically described. (a) Acrylic: based on (d) a hydroxyl group, a carboxyl group or an epoxy group based on (d) a re-peelable adhesive composition of the present invention (hereinafter) It is preferable that the (d) hardener) is subjected to a crosslinking reaction of the olefinic acid-based adhesive polymer, and is preferably a base. (a) an acrylic adhesive polymer having an acrylic alkyl group. a copolymer of an ester or methacrylic alkyl ester and a hydroxyl group-containing (meth) acrylate. A monomer thereof, especially a hydroxyalkyl (meth) acrylate (φ (meth) acrylate Ester, 2-hydroxypropyl (meth) propylene is preferred. Acrylate (methyl (meth) acrylate, ethyl (acid ester, η-butyl) constituting the main monomer of (a) acrylic adhesive polymer (meth) acrylate, iso-butyl (ester, tert-butyl (meth) acrylate, cyclohexyl (ester, 2-ethylhexyl (meth) acrylate, lauryl enoate , stearyl (meth) acrylate, isobornyl acrylate, etc.), alkyl vinyl ether The compound (acrylic acid ray irradiation is used as a paste, and the ultraviolet ray hardening is hard to be polymerized, and it can improve the hydroxy group in the propylene, and the main monomer, in the middle, has a hydroxy 2-hydroxyethyl ester) For example, methyl) propylene methyl) propylene methyl) propylene (methyl) propyl (methyl) propyl 2-methoxyethyl -11 - 201014892 ester, 2-methoxyethyl methacrylate , 3-methoxyethyl acrylate, 3-methoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate). Further, in the aforementioned copolymer, Copolymerization with an unsaturated compound (monomer) other than the above may be carried out without departing from the gist of the present invention. Such a monomer is preferably an aromatic vinyl compound (styrene, α-methylbenzene). Ethylene, p-methylstyrene, ethylvinylbenzene, etc.), heterocyclic vinyl compound (vinylpyrrolidone, etc.), polyalkylene di@(meth)acrylate (ethylene glycol (methyl)) Acrylate, butyl succinyl (meth) acrylate, etc.), alkylamine group ( Acrylic acid n (Ν, Ν-dimethylaminoethyl (meth) acrylate, hydrazine, hydrazine-dimethylaminopropyl (meth) acrylate, etc.), vinyl ester compound vinyl acetate , vinyl acetate, vinyl propionate, vinyl versatate), acrylic acid, methacrylic acid. The copolymerization ratio (mass ratio) of the main monomer and the monomer having a hydroxyl group, #佳系99_9/0_1~70/30, and the optimum is 99.5/0.5 to 90/10. Copolymerization For example, when it is outside this range, when it is peeled off, the adhesive composition tends to have a stomach sticking to the surface. Further, in the production of the U) acrylic adhesive polymer, it is not particularly limited, but is preferably in an organic solvent, and the main monomer, the monomer having a warp group, and the polymerization initiator (azo diiso) It is preferable to mix or drip the nitrile, azobisisovaleronitrile, benzammonium benzoate, etc., and to carry out polymerization for 4 to 20 hours in a reflux state or at 50 to 90 °C. The (a) acrylic adhesive polymer obtained has an average weight of 201014892, and is preferably 200,000 to 2,000,000, preferably 200,000 to 1,500,000, and most preferably 400,000 to 100,000. When the weight average molecular weight is less than 20,000, the adhesive composition tends to remain on the surface when it is peeled off. Further, the glass transition temperature of the (a) acrylic adhesive polymer is preferably -50 to 10 ° C, and most preferably -40 to -15 ° C. (a) If the glass transition temperature of the acrylic acid-based adhesive polymer is less than -5 (TC, its compatibility with (b) polyfunctional epoxy acrylate will be poor, and after irradiation with ultraviolet rays or radiation _ Since the adhesive force at the time of re-peeling is not completely lowered, the adhesive composition tends to remain on the surface to be faced, and conversely, if it exceeds i 〇° (:, sufficient adhesion cannot be obtained). The (b) polyfunctional epoxy acrylate used in the present invention is a denatured epoxy acrylate. That is, it can be made by making the secondary hydroxyl group and the ethylene in the epoxy acrylate not The epoxy acrylate is obtained by reacting a saturated monoisocyanate with an epoxy resin and an α,/S _ unsaturated monovalent φ acid, for example, acrylic acid and/or methacrylic acid, with respect to the epoxy group. More than 80% by mole, preferably 80% by mole or more, a resin obtained by a conventional method, for example, in "The Handbook of Polyester Resin by Eiyama Ryuichiro" (edited by Nikkan Kogyo Shimbun, 1981) ) or "Painting Word Dictionary" (Edited by Color Materials Association, 199 As described above, in the epoxy acrylate, the α,θ-unsaturated monovalent acid is 50 mol% or more based on the epoxy group of the epoxy resin. Preferably, it is 80 mol% or more, and the resin obtained by the reaction thereof also contains an unreacted epoxy group. -13- 201014892 Epoxy resin, for example, bisphenol type (for example, bisphenol, bisphenol A, hydrogenation) Bisphenol A, bisphenol F, bisphenol S, bisphenol SH, bisphenol Z, 4,4·-dihydroxybenzophenone, 2,V-dihydroxybenzophenone, bis(4-hydroxyphenyl) ) bismuth, catechol, resorcinol, hydroquinone, dihydroxynaphthalene, etc., bisphenols, tetrachlorobisphenol A, etc.), novolak type (phenol novolac, cresol novolac, bisphenol A novolac) , dicyclopentadiene-phenol novolak, etc.), naphthol aralkyl type, phenol aralkyl type, tetraphenylethane type epoxy resin, cyclic aliphatic epoxy resin, triepoxypropyl three a polyisocyanate and a halogen atom such as a bromine atom introduced thereto, etc. Here, in order to completely reduce the adhesion at the time of re-peeling after irradiation with ultraviolet rays Among these, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, phenol novolak type, cresol novolac type epoxy resin, and triepoxypropyl trimeric isocyanate are preferably used. These epoxy resins may be used singly or in combination of two or more kinds of α,/8-ethylenically unsaturated monoisocyanates which are reacted with a second-order hydroxyl group in an epoxy acrylate, for example, hydrazine (methacryl oxime). Isocyanate, manufactured by Nippon Paint Co., Ltd., Karenz® (isocyanate ethyl methacrylate, manufactured by Showa Denko), Karenz AOI (isocyanate ethyl acrylate, Showa Denko), Karenz BEI (manufactured by Showa Denko) 1,1-bisacryloyloxymethylethyl isocyanate, manufactured by Showa Denko Co., Ltd.). Other polymerizable monoisocyanates, for example, m-TMI (3-isopropenyl-, monodimethylbenzyl isocyanate, manufactured by Amino Cyanide Co., Ltd.) may be used without departing from the gist of the present invention. . Among them, based on the viewpoint that the adhesion after ultraviolet curing can be sufficiently reduced, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, 1,1-bisacryl decyloxymethyl B Isocyanates are preferred. α,θ_ethylenically unsaturated monoisocyanate reacted with a hydroxyl group of a second stage in an epoxy acrylate at a ratio of 1 mole to 2 hydroxy groups in the epoxy acrylate, generally - ethylenic unsaturation The monoisocyanate is preferably 0.1 mol or more, preferably 0.3 to 0.9 mol. When the ethylenically unsaturated monoisocyanate is less than 0.1 mol, the cohesive force is lowered, and the tendency of the adhesive film to remain from the adherend after the adhesive film is removed occurs. The second-order hydroxyl group in the epoxy acrylate and the α,/5-ethylenically unsaturated monoisocyanate, the addition reaction can be carried out using the conditions of the general urethanation reaction, and if necessary, two A urethane catalyst such as butyltin dilaurate or diazobiscyclooctane (DABCO) is reacted in the presence or absence of a solvent. (b) a polyfunctional epoxy acrylate used in the present invention, which may comprise a compound represented by the formula (1), [Chemical 7] ch2 C = C R1 - C - 0 Ο - C Η 2 - C Η - C Η2 — Ο — C — CR : 11 ν 1 11

O O-R2 (wherein R1 is a hydrogen atom or a methyl group which may be the same or different from each other, R2 is a hydrogen atom or a group having an ethylenically unsaturated bond, and X is at least 2 rings in the molecule. The compound of the oxy group is obtained by polymerizing and re-opening the ring. When R2 is a hydrogen atom, the X system has at least one ethylenically unsaturated bond I'V'Br'jjLimjjii ........... ... -15- 201014892, η is an integer). Here, 'R2 is a hydrogen atom or a group having an ethylenically unsaturated bond, but in all of the polyfunctional epoxy acrylates, R2 does not need to be substituted with a group having an ethylenically unsaturated bond, and R2 may also be contained in A molecule that remains in the case where the hydrogen atom is not replaced. When R2 is a hydrogen atom, it is obtained by (d) a hardening agent, (a) an acrylic adhesive polymer, and a crosslinking structure, and it is based on the point which can accelerate the fall of the adhesiveness after ultraviolet-ray irradiation. More ideal. R2 is a hydrogen atom or a group having an ethylenically unsaturated bond, and is preferably a group represented by the formula (6). [化8]

H2c = cr12-c-o-ch2-ch,-n-c-II I II

Ο HO (wherein R12 is a hydrogen atom or a methyl group). The group represented by the formula (6) can be introduced by reacting isocyanate ethyl methacrylate and isocyanate ethyl acrylate ' ® with a hydroxyl group of a second stage in an epoxy acrylate. In the formula (1), X is a group obtained by polymerizing and reopening a compound having at least two epoxy groups in the molecule, and is preferably any one of the following: a group represented by the formula (4), [ 9]

OR9

I

CHa-CH-CHjj-O -16- 201014892 (wherein R8 is a hydrogen atom or a methyl group, R9 is a hydrogen atom or a group having an ethylenically unsaturated bond) or a group represented by the formula (5), ]

OR11 I —ch2-ch-ch2

(wherein R1G is a hydrogen atom or a methyl group, and R11 is a hydrogen atom or a group having an ethylenically unsaturated bond). In order to obtain (b) a multi-functional epoxy acrylate represented by the formulas (4) and (5), the epoxy resin can be obtained by using bisphenol A, hydrogenated double brew A, bisphenol F or the like. Here, R9 and R11 are the same as R2, and are a hydrogen atom or a group having an ethylenically unsaturated bond. However, in all of the polyfunctional epoxy acrylates, R9 and R11 do not have to be ethylenic. The group of the saturated bond is substituted, and R9 and R11 may also contain a molecule remaining in the case where the hydrogen atom is not replaced. R9 and R11 are a hydrogen atom or a group having an ethylenically unsaturated bond, and it is preferred that the group represented by the above formula (6) is used. The group represented by the formula (6) can be introduced by reacting an isocyanate ethyl methacrylate or an isocyanatoethylpropionate ' with a hydroxyl group of a second stage in an epoxy acrylate. In the formula (1), η is preferably 1 to 10, preferably 1 to 5. When η is larger than 10, the compatibility with the acrylic adhesive polymer tends to be inferior. Further, in the (b) polyfunctional epoxy acrylate vinegar used in the present invention, the compound represented by the formula (2) may be contained. [11]

(wherein R is a hydrogen atom or a methyl group, which may be the same or different from each other, R4 is a hydrogen atom, a methyl group, which may be the same or different from each other, and the benzene skeleton to which R4 is bonded may have other substituents. Alternatively, R5 is a hydrogen atom or a group 'R5 having a B-unsaturated unsaturated bond, at least one of which is a group having a B-unsaturated unsaturated bond, and m is an integer). In order to obtain the (b) polyfunctional epoxy acrylate represented by the formula (2), the epoxy resin can be obtained by using a phenol novolak type, a cresol novolac type epoxy resin or the like. Here, at least one of R5 may be a group having an ethylenically unsaturated bond. When R5 is a hydrogen atom, it is obtained by (d) a hardening agent, (a) an acrylic adhesive polymer, and a crosslinked structure, and it is based on the viewpoint of speeding up the fall of adhesiveness after ultraviolet irradiation, More ideal. R5 is a group having an ethylenically unsaturated bond, and is preferably a group represented by the above formula (6). -18- 201014892 In the formula (2), m is preferably 1 to i, and 1 to 5 is optimal. When m is larger than 10, the compatibility with the acrylic adhesive polymer tends to be inferior. Further, the (b) polyfunctional epoxy acrylate used in the present invention may further contain a compound represented by the formula (3). [化 12]

(wherein R6 is a hydrogen atom or a methyl group which may be the same or different from each other, and R7 is a hydrogen atom or a group having an ethylenically unsaturated bond, and at least one of R7 has an ethylenically unsaturated bond. base). In order to obtain (b) a polyfunctional epoxy acrylate represented by the formula (2), an epoxy resin can be obtained by using triglycidyltrimeric isocyanate. Here, at least one of R7 may be a group having an ethylenically unsaturated bond. When R7 is a hydrogen atom, it is obtained by (d) a hardening agent (a) an acrylic adhesive polymer and a crosslinked structure, and it is based on the viewpoint of speeding up the viscosity reduction after ultraviolet irradiation, and More ideal. R7 is a group having an ethylenically unsaturated bond, and is preferably a group represented by the above formula (6). (b) The amount of the polyfunctional epoxy acrylate to be used is generally in the range of 40 to 150 parts by mass, based on 100 parts by mass of the (a) acrylic adhesive polymer. (b) Polyfunctional propylene propylene-19- 201014892 When the amount of the acid ester used is less than 20 parts by mass, the three-dimensional network of the adhesive layer by irradiation with active light may be incomplete, so that it is relative to the wafer. Then the degree of force reduction will be too small and not ideal. On the other hand, when the amount is more than 200 parts by mass, the plasticization of the adhesive layer is remarkable, the cohesive force is lowered, and the necessary adhesive force cannot be obtained when the semiconductor wafer is cut, which is not preferable. In the ultraviolet curable re-peelable adhesive composition of the present invention, if necessary, it may contain (c) a photopolymerization initiator, and active light may be used in the coexistence of (c) photopolymerization initiator. . (C) photopolymerization initiator used, for example, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, Michler's ketone, thioxanthone chloride, dodecyl thioxanthene Ketone, dimethyl thioxanthone, diethyl thioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, 1-hydroxy monocyclohexyl phenyl ketone, 2-hydroxy-2-methyl 1-phenylpropane-1-pyrene and the like. Among them, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one are particularly excellent in terms of surface hardenability. Preferably. (c) The amount of the photopolymerization initiator to be used is preferably in the range of 0.1 to 5 parts by mass based on 100 parts by mass of the (b) polyfunctional acrylate. (C) When the amount of the photopolymerization initiator used is less than 0.1 part by mass, the curing speed of the adhesive composition due to irradiation with active light is slowed, and the degree of decrease in adhesion is too small. On the other hand, when the amount is more than 5 parts by mass, it is not only impossible to see the effect of matching with it, but the photopolymerization initiator is likely to remain on the surface of the wafer, or the photopolymerization initiator used is used for the photosensitive region. The range becomes larger, and the result of the sensitivity is relatively increased. Amines which can be used, preferably -20- 201014892 are, for example, N,N-dimethylethanolamine, N-methyldiethanolamine and the like. When the amine is used, it is the same amount as (c) the photopolymerization initiator. Further, the (d) hardener used in the present invention is, for example, 2,4-methylphenylene diisocyanate, 2, 6-Methylphenyl diisocyanate, hydrogenated phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, diphenylmethane-4 , 4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, tetramethylbenzene dimethyl diisocyanate, 1,5-naphthalene diisocyanate, trishydroxyl a phenylene diisocyanate adduct of a propane, a phenylene diisocyanate adduct of trimethylolpropane, a triphenylmethane triisocyanate, a methylene bis(4-phenylmethane) triisocyanate, etc. Isocyanate-based compound, bisphenol A·epichlorohydrin type epoxy resin, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, glycerol diepoxypropyl ether, Glycerol triepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, sorbitol polyepoxypropyl Ether, polyglycerol polyepoxypropyl φ ether, pentaerythritol polyepoxypropyl erythritol, diglycerol polyepoxypropyl ether and other epoxy compounds, tetramethylol methane - trin 0 Aziridine propionate, trimethylolpropane-tri-ten-azetidine propionate, N,N'-diphenylmethane-4,4,-bis(1-azetidinylcarboxyl Aziridine compound, hexamethoxymethyl melamine, hexaethoxymethyl, etc., such as decylamine, N,N'-hexamethyl aceto-1,6-bis(anthracene-azepine carboxy oxime) a tripolychlorinated compound such as melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexaethoxyoxymethyl melamine or hexahexyloxymethyl melamine, among which trishydroxyl The methyl benzene-21-201014892 diisocyanate adduct of methyl propane is preferred from the viewpoint of good reactivity with the propylene-based polymer. (d) A curing agent which is not particularly limited as long as it is reactive with a hydroxyl group, a carboxyl group or an epoxy group, and is not limited to those which react with other functional groups. For example, when the (a) acrylic adhesive polymer has an amine group, the amine group can also react with the (d) hardener. (d) The amount of the curing agent to be used is preferably from 5 to 10 parts by mass based on 100 parts by mass of the total of (a) the acrylic adhesive polymer and (b) the multifunctional epoxy acrylate. And 0.1 to 5 parts by mass is the best. (d) If the amount of the hardener used is less than 5 parts by mass, the adhesive composition may remain on the surface to cause contamination when it is peeled off after irradiation with ultraviolet rays or radiation, especially In the temporary application of the semiconductor wafer cutting step, there will be a flaw in the adhesive composition remaining on the wafer. Conversely, if it exceeds 10 parts by mass, the curing will begin before the irradiation of ultraviolet rays or radiation. Unfavorable tendency, such as a decrease in adhesion after irradiation of ultraviolet rays or radiation. In order to form an adhesive sheet using the re-peelable adhesive composition thus constituted, the adhesive composition may be applied to a substrate by a conventional method, and then dried as necessary to form a film of generally 10%. An adhesive layer having a thickness of about 10 to 50 μm. The substrate is not particularly limited as long as it is a transparent film through which active light is transmitted, and is excellent in elongation when extended. Specifically, polyvinyl chloride, polybutene, and poly can be used. Butadiene, polyurethane, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene-22- 201014892 ene-1, polyurethane, poly A film of ethylene terephthalate or polybutylene dicarboxylate. The re-peelable adhesive composition of the present invention is preferably used as an adhesive sheet for a circular cutting step, but after the application is attached to the semiconductor crystal-adhesive sheet, the semiconductor crystal is broken by a rotating round blade. Wafer. Thereafter, the substrate side of the adhesive sheet is irradiated with active light such as ultraviolet rays to be cured. @ When the light source is irradiated with ultraviolet light, high-pressure mercury lamp, mercury lamp carbon arc lamp, xenon lamp, metal halide lamp, chemical lamp, black lamp, etc., when high-pressure mercury lamp is used, the ultraviolet radiation amount is generally 50 to mJ/cm2. It is carried out under conditions of 100 to 600 mJ/cm2. For example, when irradiated with a sub-ray, an electron beam having an amount of 50 to 1 000 KeV can be used, and an irradiation amount of 2 to 50 Mrad is desirable. When the amount of line irradiation or electron beam irradiation is excessive or insufficient, the same situation occurs when the amount of photopolymerization is excessive or insufficient. The adhesion before and after hardening varies depending on the type of substrate and the wafer, but it is 180 before JIS Z 2307. The peeling adhesive is 150 to 2500 g/25 mm, and the adhesive force after irradiation is preferably 5 to 50 g/25 mm. Then, the wafer is stretched to a certain interval by using a wafer expanding device, and then the wafer is pushed up by a needle or the like while the air needle set is picked up by an adsorption method or the like to lift the wafer on the substrate. The electrodes are connected by metal wires to form a semiconductive sheet of the product. Benzene is a crystal circle in a circular cut or an electric super cylinder. The present invention is specifically described by using the examples and comparative examples, but the present invention is not limited to the following. An embodiment. In addition, in the following description, "%" and "part", unless otherwise defined, are the meaning of the quality standard. The evaluation of the re-peelable adhesive sheet in the examples and the comparative examples below is as follows. The obtained adhesive sheet was attached to the surface of SUS3 04 using a pressure roller having a weight of lkg, and placed in a room adjusted to 23 ° C for 1 hour, and then a belt type ultraviolet irradiation device (manufactured by Eyegraphics Co., Ltd., 2KW lamp, 80 W/cm) After ultraviolet irradiation of 100 mJ/cm2 and 300 mJ/cm2, the adhesion and retention force before and after the irradiation were measured in accordance with JIS0237 by the following method. (1) Adhesion: Attach adhesive tape or adhesive sheet to the test plate or back. After applying pressure, measure the force required to peel the adhesive tape or adhesive film at an angle of 180° before and after UV irradiation. (2) Retention: At one end of the test plate, the 25x25 mm area of the test piece is brought into contact with and attached, and the unattached portion is placed on the inside and folded. Above the test piece, the roll was pressed back and forth once. After 20 minutes or more, one end of the test plate was stopped with a safety shutter, and then the test plate and the test piece were allowed to hang vertically, and a weight of 1 kg was attached to one end of the folded portion. Calculate the time from the test plate to the drop at the test temperature of 80 °C. (3) Appearance: After applying the adhesive to the substrate and drying it, the state of the adhesive layer was visually confirmed to have no elastic force, bubbles, foreign matter, etc. on the adhesive layer at 201014892. 〇: Adhesive layer in perfect condition: slightly visible to the elastic or sputum χ: Obviously visible to the elastic or sputum (4) Residue of the paste: attach the adhesive film to the adherend and irradiate it ( After 50 〇mJ/cm2), the adhesive film was peeled off to visually confirm whether or not the adhesive remained on the adherend. Φ 〇: no adhesive residue on the adherend △ '· some micro-adhesive residue on the adherent X'·remaining adhesive residue on the adherent. Manufacturing Example 1<Acrylic Adhesive (1)> In a reaction apparatus equipped with a stirrer, a temperature regulator, a reflow cooler, a dropping funnel, and a thermometer, 80 parts of η-butyl acrylate, 60 parts of ethyl acrylate, 6.3 parts of methyl methacrylate, and 1 part of acrylic acid were added. 0.8 parts of 2-hydroxyethyl acrylate and 130 parts of ethyl acetate, and 0.1 part of azobisisobutyronitrile as a polymerization initiator was added after the start of heating and refluxing, and the reaction was carried out for 3 hours at the reflux temperature of ethyl acetate. 1 part of nitrogen diisobutyronitrile was dissolved in 4 parts of toluene and then added, further reacted at reflux temperature for 4 hours, diluted with toluene to obtain a resin fraction of 40%, a weight average molecular weight of 550,000, and a glass transition temperature of _3. 5· 2. (: an acrylic adhesive (1). Further, the weight average molecular weight is determined by a gel permeation chromatography method, and the glass transition temperature is determined by a differential scanning calorimeter (DSC). -25 - 201014892 Production Example 2 < Acrylic Adhesive (2)> In a reaction apparatus equipped with a stirrer, a temperature regulator, a reflow cooler, a dropping funnel, and a thermometer, 80 parts of η-butyl acrylate, 60 parts of methyl acrylate, and methacrylic acid were added. 6.3 parts of methyl ester, 1 part of acrylic acid, 0.8 parts of 2-hydroxyethyl acrylate and 130 parts of ethyl acetate. After the start of heating and reflux, azobisisobutyronitrile was added as a polymerization initiator. After the ester reflux temperature was carried out for 8 hours, the mixture was diluted with toluene to obtain an acrylic pressure-sensitive adhesive (2) having a resin component of 40%, a weight average molecular weight of 610,000, and a glass transition temperature of -25.3 ° C. Production Example 3 <Multifunctional Epoxy Acrylate (1)> A bisphenol A type epoxy resin (made by Asahi Kasei Epoxy Co., Ltd., trade name ARALDI) was added to a reaction apparatus equipped with a stirrer, a temperature regulator, a reflow cooler, a dropping funnel, and a thermometer. TE AER 2603, epoxy equivalent 189) 100 parts (1.0 equivalents), 37 parts of acrylic acid (1.0 moles), 0.6 parts of triphenylphosphine, 0.12 parts of methylhydroquinone, while blowing air, at 120 ° C The reaction was continued for 8 hours to obtain a reactant having an acid value of 0.5 KOH mg/g. Next, the temperature was lowered to 60 ° C, and isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name Karenz MOI) was dropped by a dropping funnel. Under a mixed droplet of 62 parts and 0.02 parts of dibutyltin dilaurate, the reaction system was kept at 70 ° C for 4 hours after the end of the dropwise addition, and the isocyanate group disappeared to obtain a polyfunctional epoxy having a weight average molecular weight of 130,000. Acrylate (1) -26- 201014892 Production Example 4 <Multifunctional Epoxy Acrylate (2) > In a reaction apparatus equipped with a stirrer, a temperature regulator, a reflow cooler, a dropping funnel, and a thermometer, cresol was added. Novolac type epoxy resin (manufactured by Tohto Kasei Epoxy Co., Ltd., trade name YD-704L, epoxy equivalent 209) 100 parts (1·〇 equivalent), 33 parts of acrylic acid (1.0 mol), triphenylphosphine 0.4 Methylhydroquinone 〇8 parts, while continuing to react at 120 ° C for 8 hours while blowing in air, to obtain a reactant having an acid value of 0.5 0 KOH mg / g. Next, the temperature was lowered to 6 (TC, isocyanate B by dropping the funnel Under the mixed droplets of 56 parts of methacrylic acid ester (manufactured by Showa Denko Co., Ltd., trade name Karenz MOI) and 0.02 parts of dibutyltin dilaurate, the reaction system was kept at 70 ° C for 4 hours after the completion of the dropping. The isocyanate group disappears to obtain a polyfunctional epoxy acrylate (2) having a weight average molecular weight of 4,000. Production Example 5 <Multifunctional Epoxy Acrylate (3) > In a reaction apparatus provided with a stirrer, a temperature regulator, a reflow cooler, a dropping funnel, and a thermometer, a trivalent having a triazine core as a skeleton was added. Epoxy compound (manufactured by Nissan Chemical Industries, Ltd., trade name TEPIC-S, epoxy equivalent 100) 100 parts (1.0 equivalent), 72 parts of acrylic acid (1.0 mole), triphenylphosphine 0.6 part, methyl group 0.12 parts of hydroquinone was obtained by continuously reacting at 120 ° C for 8 hours while blowing air to obtain a reactant having an acid value of 0.5 KOH mg / g. Next, the temperature was lowered to 60 ° C, and 70 parts of isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name Karenz MOI) and dibutyl -27-201014892 base tin dilaurate 0.02 were passed through a dropping funnel. After the completion of the dropwise addition, the reaction system was kept at 70 ° C for 4 hours to "discolor the isocyanate group" to obtain a polyfunctional epoxy acrylate (3) having a weight average molecular weight of 1,100. Example 1 <Production of Re-peelable Adhesive and Re-peelable Adhesive Sheet> In a container made of ultraviolet light, 70 parts of a propylene-based adhesive (1) was added to a plastic container, and a polyfunctional epoxy acrylate was added. (1) 30 parts, 1-hydroxy-cyclohexyl-phenyl-one (IRGACURE 1 84, manufactured by Ciba Specialty Chemicals Co., Ltd.), 1.2 parts, and a phenylene diisocyanate adduct of trimethylolpropane % methyl acetate solution (manufactured by Nippon Polyurethane Industry Co., Ltd., CORONET L-45E) 2.0 parts, stirred 'made as a re-peelable adhesive, further added to polyethylene terephthalate with a thickness of 50 μm The diol ester film was coated to have a film thickness of 20 μm after drying, and then dried by heating at 105 ° C for 2 minutes to prepare a re-peelable adhesive sheet. Then, the change in properties before and after the ultraviolet ray hardening was evaluated by the aforementioned method. The measurement results are shown in Table 1. [Example 2] In the production of the re-peelable adhesive sheet of Example 1, except that the amount of the acrylic adhesive (1) used was changed to 60 parts, and the amount of the polyfunctional epoxy acrylate (1) used was 40 parts. The rest of the adhesive sheet was produced in the same manner as in Example 1 and the performance change before and after ultraviolet curing was evaluated. The measurement results are shown in Table 1. -28-201014892 Example 3 In the production of the re-peelable adhesive sheet of Example 1, except that the amount of the acrylic adhesive (1) used was changed to 50 parts, the amount of the polyfunctional epoxy acrylate (1) was used. A re-peelable adhesive sheet was produced in the same manner as in Example 1 except for 50 parts, and the change in performance before and after ultraviolet curing was evaluated. The measurement results are shown in Table 1.实施 Example 4 In the production of the re-peelable adhesive sheet of Example 1, the amount of the polyfunctional epoxy acrylate (1) was 40 parts, except that the amount of the acrylic adhesive (2) was changed to 60 parts. The re-peelable adhesive sheet was produced in the same manner as in Example ,, and the change in performance before and after ultraviolet curing was evaluated. The measurement results are shown in Table 1. In the production of the re-peelable adhesive sheet of Example 1, except that the amount of the acrylic adhesive (2) used was changed to 50 parts, and the amount of the polyfunctional epoxy acrylate (1) used was 50 parts, A re-peelable adhesive sheet was produced in the same manner as in Example ,, and the change in properties before and after ultraviolet curing was evaluated. The measurement results are shown in Table 1. Example 6 In the production of the re-peelable adhesive sheet of Example 1, except that the amount of the propylene-29-201014892 acid-based adhesive (1) was changed to 70 parts of the 'polyfunctional epoxy acrylate (2) A re-peelable adhesive sheet was produced in the same manner as in Example 1 except that the amount was 30 parts, and the change in properties before and after ultraviolet curing was evaluated. The measurement results are shown in Table 1. [Example 7] In the production of the re-peelable adhesive sheet of Example 1, the amount of the acrylic adhesive (1) used was changed to 70 parts, and the amount of the polyfunctional epoxy acrylate (3) was 30 parts. Further, in the same manner as in Example 1, a re-peelable adhesive sheet was produced, and the change in properties before and after ultraviolet curing was evaluated. The measurement results are shown in Table 1. Comparative Example 1 In the production of the re-peelable adhesive sheet of Example 1, the polyfunctional epoxy acrylate (1) was changed to bisphenol A type epoxy acrylate (manufactured by Showa Polymer Co., Ltd., trade name VR). A re-peelable adhesive sheet was produced in the same manner as in Example 1 except for -77), and the change in performance before and after ultraviolet curing was evaluated. The measurement results are shown in Table 2. Comparative Example 2 In the production of the re-peelable adhesive sheet of Example 1, the polyfunctional epoxy acrylate (1) was changed to a bisphenol A-type ring except that the amount of the acrylic adhesive (1) was changed to 60 parts. A re-peelable adhesive sheet was produced in the same manner as in Example 1 except for 40 parts of the oxy acrylate, and the change in performance before and after the ultraviolet -30 - 201014892 line hardening was evaluated. The measurement results are shown in Table 2. Comparative Example 3 In the production of the re-peelable adhesive sheet of Example 1, except that the amount of the acrylic adhesive (1) was changed to 70 parts, the polyfunctional epoxy acrylate (1) was changed to dipentaerythritol hexaacrylate. A re-peelable adhesive sheet was produced in the same manner as in Example 1 except for 30 parts (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), and the change in performance before and after ultraviolet curing was evaluated. The measurement results are shown in Table 2. Comparative Example 4 In the production of the re-peelable adhesive sheet of Example 1, the polyfunctional epoxy acrylate (1) was changed to a bisphenol A-type ring except that the amount of the acrylic adhesive (1) was changed to 60 parts. A φ re-peelable adhesive sheet was produced in the same manner as in Example 1 except that 20 parts of oxy acrylate and 20 parts of dipentaerythritol hexaacrylate were used, and the change in performance before and after ultraviolet curing was evaluated. The measurement results are shown in Table 2. -31 - 201014892 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Re-peelable adhesive resin composition Acrylic poly-adhesive (1) (Bu-EA) 70 60 50 70 70 Adhesive (2) (Bu-MA) 60 50 Polyfunctional Oligomers · Monomeric Polyfunctional Epoxy Acrylates (1) 30 40 50 40 50 Polyfunctional Epoxy Acrylates (2) 30 Multifunctional Epoxy acrylate (3) 30 Bisphenol A epoxy acrylate dipentaerythritol hexaacrylate photopolymerization initiator IRGACURE 184 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Hardener CORONET L-45E 2 2 2 2 2 2 2 Re-peelable adhesive sheet Evaluation _ Adhesion (g/25mm) Before UV irradiation 1600 1900 2300 1600 1900 1500 1600 After UV irradiation 20 10 5 10 5 20 10 80 °C retention (min) >240 >240 >240 >240 >240 >240 >240 Appearance paste residue 〇〇〇〇〇〇〇-32- 201014892 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Re-peeling type Adhesive Acrylic Poly/Adhesive (1) (Bu-EA) 70 60 70 60 Adhesive (2) (Bu-MA) Polyfunctional Oligomer Monomer Polyfunctional Epoxy Acrylate (1) Functional epoxy acrylate (2) Polyfunctional epoxy acrylate (3) Bisphenol A epoxy acrylate 30 40 20 Dipentaerythritol hexaacrylate 30 20 Photopolymerization initiator IRGACURE 184 1.2 1.2 1.2 1.2 Hardener CORONET L- 45E 2 2 2 2 Adhesive strength of re-peelable adhesive sheet (g/25mm) 1600 1900 800 1200 before ultraviolet irradiation 100 20 5 5 80 °C holding force (min) 20 2 >240 10 Appearance 〇Δ Paste residue 〇△ X 〇

INDUSTRIAL APPLICABILITY φ By comparing the examples and the comparative examples, it is understood that the ultraviolet curable re-peelable adhesive composition of the present invention has an excellent appearance of the adhesive layer after application, and the adhesion and retention before ultraviolet irradiation The force is excellent, and a cured film having no paste residue can be obtained after ultraviolet irradiation. -33-

Claims (1)

201014892 X. Patent application scope 1. An ultraviolet curing type re-peelable adhesive composition characterized by (a) acrylic adhesive polymer, (... polyfunctional epoxy acrylate, (c) photopolymerization a starting agent, (d) a curing agent reactive with a hydroxyl group, a carboxyl group or an epoxy group, and (b) a polyfunctional epoxy acrylate comprising any one of the following: a compound represented by the formula (1), [Chemical 1] h5 : CR: -〇+*X士CHi-CH-CH.-OC-CR1 0-R! II ο Wherein R1 is a hydrogen atom or a methyl group which may be the same or different from each other' R2 is a hydrogen atom or a group having an ethylenically unsaturated bond, and X is a compound having at least 2 epoxy groups in the molecule. a group obtained by polymerizing a reopening ring, wherein R2 is a hydrogen atom, X is a group having at least one ethylenically unsaturated bond, and η is an integer) or a compound represented by formula (2) [Chemical 2] -34- 201014892, which may be the same or different from each other: this may be the same or different, the other substituents are substituted, the base of the R5 bond, among R5, at least - m is an integer) (wherein R3 In the case of a hydrogen atom or a methyl group, R4 is a hydrogen atom or a methyl group, and the benzene skeleton bonded to R4 may be a hydrogen atom or a group having an ethylenically unsaturated bond having an ethylenic unsaturation, or a compound represented by the formula (3), [Chemical 3] 0 'They can be the same or different unsaturated bond groups, among R7, [base]. 1 ultraviolet curing type re-peeling adhesive E: (wherein, R6 is a hydrogen atom or a methyl group, R7 is a hydrogen atom or has at least one of having ethylenic unsaturation. 1 item; a composition of the agent, wherein the base of the X system is represented by the formula (4), [Chemical 4] R8 OR9 I -CH2 — CH — CH2~〇 (wherein R8 is a hydrogen atom or a group of a methyl unsaturated bond) 〇- R9 is a hydrogen atom or has a vinyl group or a group of formula (5)-35 - 201014892 [Chem. 5] OR11 I CH2-CH-CH2-〇 (wherein R1G is a hydrogen atom or a methyl group, and R11 is a hydrogen atom or a group having an ethylenically unsaturated bond). 3. The ultraviolet curable re-peelable adhesive composition according to any one of claims 1 to 2, wherein the ruler 2, the ruler 5, the 117, the 119 or the 1^1 A hydrogen atom or a group represented by the formula (6): [Chem. 6] H2C = CR12-c-〇-CH2-CH2-N_C-II I II Ο Η Ο (wherein 'R12 is a hydrogen atom or a methyl group). 4. The ultraviolet curable re-peelable adhesive composition according to any one of the above-mentioned items, wherein the (a) acrylic adhesive polymer contains 100 parts by mass of (b) 20 to 200 parts by mass of the polyfunctional epoxy acrylate. 5. The ultraviolet curable re-peelable adhesive composition according to any one of claims 1, 2, 3 or 4, wherein (a) the acrylic-based adhesive polymer has a weight average molecular weight of 200,000 to 200 The glass transition temperature is -50 ° C to 10 ° C and is composed of a (meth) acrylate copolymer having a hydroxyl group. 6. The ultraviolet curable re-peelable adhesive composition according to any one of claims 1, 2, 3, 4 or 5, wherein (b) a polyfunctional ring -36- 201014892 A reactive product of an oxyacrylate epoxy acrylate and an ethylenically unsaturated monoisocyanate. 7. An adhesive sheet characterized by using the ultraviolet curable re-peelable adhesive composition of any one of claims 1, 2, 3, 4, 5 or 6. -37- 201014892 七明说单单单符表 is the map of the generation of the map and the table of the map: the representative of the map, this table ' ' Generation ZN fixed one or two ^ ((No no eight, if there is a chemical formula in this case, please Reveal the chemical formula that best shows the characteristics of the invention: none -4-