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WO2024247470A1 - Résine (méth)acrylique modifiée, composition adhésive et feuille adhésive - Google Patents

Résine (méth)acrylique modifiée, composition adhésive et feuille adhésive Download PDF

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Publication number
WO2024247470A1
WO2024247470A1 PCT/JP2024/013418 JP2024013418W WO2024247470A1 WO 2024247470 A1 WO2024247470 A1 WO 2024247470A1 JP 2024013418 W JP2024013418 W JP 2024013418W WO 2024247470 A1 WO2024247470 A1 WO 2024247470A1
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Prior art keywords
meth
group
modified
acrylic resin
acrylate
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Japanese (ja)
Inventor
佑哉 今井
一博 佐々木
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Resonac Corp
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Resonac Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present disclosure relates to a modified (meth)acrylic resin that has a large weight-average molecular weight and a narrow molecular weight distribution. It also relates to an adhesive composition that contains the modified (meth)acrylic resin, and an adhesive sheet, a dicing tape, and an integrated dicing and die bonding film that have an adhesive layer made of a cured product of the adhesive composition.
  • (meth)acrylic resins have been used in a variety of fields, including various coatings, printing, paints, adhesives, color filters, and the manufacture of electronic components such as semiconductors.
  • various coatings, printing, paints, adhesives, color filters, and the manufacture of electronic components such as semiconductors.
  • materials with an optimal molecular weight and narrow molecular weight distribution are required to improve various material properties, such as improving material performance, precision, and quality stability.
  • Living radical polymerization is often used as a manufacturing method for (meth)acrylic resins that meet such needs.
  • Patent Document 1 describes a coloring composition having a block copolymer with a weight average molecular weight (Mw) of 3,000 to 40,000 and a molecular weight distribution (Mw/Mn) of 2.5 or less.
  • Patent Document 2 describes a method for producing a polymer using a microreactor as a method for obtaining a polymer with a narrow molecular weight distribution.
  • the present disclosure provides a modified (meth)acrylic resin that has a high molecular weight and a narrow molecular weight distribution. Furthermore, the present disclosure provides an adhesive composition containing the modified (meth)acrylic resin, as well as an adhesive sheet, a dicing tape, and an integrated dicing and die bonding film that have a cured product of the adhesive composition as an adhesive layer. More specifically, the present disclosure provides an adhesive sheet that has sufficient adhesion to an adherend, has excellent peelability after UV irradiation, and is less likely to cause DAF skipping. The present disclosure also provides a dicing tape and an integrated dicing and die bonding film that have good dicing properties and provide excellent pick-up properties after UV irradiation.
  • the weight average molecular weight (Mw) is 30 ⁇ 10 4 to 150 ⁇ 10 4
  • [5] The modified (meth)acrylic resin according to any one of [1] to [4], wherein the ratio of the isocyanato group-containing ethylenically unsaturated compound (a) is 0.5 to 49 moles relative to 100 moles of the constituent units of the copolymer (A-0), and the number of moles of the isocyanato group-containing ethylenically unsaturated compound (a) relative to the number of moles of the constituent units derived from the hydroxyl group-containing (meth)acrylate (m-1) is 30 to 99%.
  • [6] The modified (meth)acrylic resin according to any one of [1] to [5], having a molecular weight distribution (Mw/Mn) of 1.1 to 2.0.
  • [7] The modified (meth)acrylic resin according to any one of [1] to [6], having a weight average molecular weight (Mw) of 65 ⁇ 10 4 to 150 ⁇ 10 4 .
  • Mw weight average molecular weight
  • [8] The modified (meth)acrylic resin according to any one of [1] to [7], wherein the hydroxyl group-containing (meth)acrylate (m-1) is a hydroxyalkyl (meth)acrylate.
  • [9] The modified (meth)acrylic resin according to any one of [1] to [8], wherein the alkyl (meth)acrylate (m-2) is a (meth)acrylate having a linear alkyl group having 1 to 20 carbon atoms.
  • the pressure-sensitive adhesive composition comprising: [11] A base layer; A pressure-sensitive adhesive layer comprising a heat-cured or photo-cured product of the pressure-sensitive adhesive composition according to [10]; An adhesive sheet having the above structure.
  • the dicing tape has [13] A base layer; A pressure-sensitive adhesive layer comprising a heat-cured or photo-cured product of the pressure-sensitive adhesive composition according to [10];
  • a modified (meth)acrylic resin that has a high molecular weight and a narrow molecular weight distribution. Furthermore, according to the present disclosure, it is possible to provide an adhesive composition containing the modified (meth)acrylic resin, as well as an adhesive sheet, a dicing tape, and an integrated dicing and die bonding film that have a cured product of the adhesive composition as an adhesive layer. According to the present disclosure, it is possible to provide an adhesive sheet that has sufficient adhesion to an adherend, has excellent peelability after UV irradiation, and is less likely to cause DAF skipping. It is also possible to provide a dicing tape and an integrated dicing and die bonding film that have good dicing properties and excellent pick-up properties after UV irradiation.
  • (meth)acrylic means methacrylic or acrylic
  • (meth)acrylate means acrylate or methacrylate
  • (meth)acryloyloxy means acryloyloxy or methacryloyloxy.
  • photocrosslinkable adhesive refers to a thermoset of an adhesive composition that has photocrosslinkability in the thermoset state. Photocrosslinkable adhesives can be crosslinked by exposure to ultraviolet light.
  • photothermally cured product refers to the above-mentioned photocrosslinkable adhesive crosslinked by ultraviolet light irradiation.
  • weight average molecular weight and “number average molecular weight” refer to values measured at room temperature (23° C.) under the following conditions using gel permeation chromatography (GPC) and determined using a standard polystyrene calibration curve.
  • Apparatus Shodex (trademark) GPC-101 (Resonac Co., Ltd.) Column: Shodex (trademark) LF-804 (Resonac Inc.) Column temperature: 40°C Sample: 0.2% by mass solution of sample in tetrahydrofuran Flow rate: 1 mL/min Eluent: tetrahydrofuran Detector: Shodex (trademark) RI-71S (Resonac Corporation)
  • glass transition temperature refers to the onset temperature of heat absorption due to glass transition observed when a 10 mg sample is taken and subjected to differential scanning calorimetry using a differential scanning calorimeter (DSC) while changing the temperature of the sample from -100°C to 200°C at a heating rate of 10°C/min.
  • DSC differential scanning calorimeter
  • the modified (meth)acrylic resin is a resin in which an isocyanato group-containing ethylenically unsaturated compound (a) is added to a portion of the side chain hydroxyl groups of a copolymer (A-0) having a structural unit derived from a hydroxyl group-containing (meth)acrylate (m-1) and a structural unit derived from an alkyl (meth)acrylate (m-2).
  • the weight average molecular weight (Mw) of the modified (meth)acrylic resin is 30 ⁇ 10 4 to 150 ⁇ 10 4 , and the molecular weight distribution (Mw/Mn) is 1.1 to 3.0.
  • the weight average molecular weight (Mw) of the modified (meth)acrylic resin is 30 ⁇ 10 4 or more, preferably 50 ⁇ 10 4 or more, more preferably 65 ⁇ 10 4 or more, and even more preferably 70 ⁇ 10 4 or more.
  • the weight average molecular weight (Mw) of the modified (meth)acrylic resin is 150 ⁇ 10 4 or less, preferably 140 ⁇ 10 4 or less, more preferably 130 ⁇ 10 4 or less, and even more preferably 120 ⁇ 10 4 or less. Any combination of these lower limit values and upper limit values may be used.
  • the weight average molecular weight (Mw) is 30 ⁇ 10 4 or more
  • the adhesive sheet obtained by curing the adhesive composition has sufficient adhesive strength, and when the adhesive sheet is used as a dicing tape or a dicing/die bonding integrated film, good dicing properties are obtained.
  • the weight average molecular weight (Mw) is 30 ⁇ 10 4 or more, sufficient peelability after UV irradiation of the adhesive layer is obtained, and when the adhesive sheet is used as a dicing tape or a die bonding-die bonding integrated film, the pick-up property is sufficient.
  • the weight average molecular weight (Mw) is 30 ⁇ 10 4 or more, the desired adhesive strength can be obtained by maintaining a good cohesive force when attached to the adherend, and when peeled off from the adherend, the adherend contamination such as adhesive residue can be reduced.
  • the weight average molecular weight (Mw) is 150 ⁇ 10 4 or less, the viscosity when used as an adhesive composition can be appropriately suppressed, so that the workability such as the coatability on the substrate can be improved, and the film thickness can be easily controlled.
  • the molecular weight distribution (Mw/Mn) of the modified (meth)acrylic resin is 1.1 or more.
  • the molecular weight distribution (Mw/Mn) of the modified (meth)acrylic resin may be 1.2 or more, or may be 1.3 or more.
  • the molecular weight distribution (Mw/Mn) of the modified (meth)acrylic resin is 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less. Any combination of these lower limit values and upper limit values may be used. From the viewpoint of ease of control of the manufacturing conditions, the molecular weight distribution is preferably 1.1 or more.
  • the molecular weight distribution is 3.0 or less, a remarkable effect can be obtained compared to the case where the molecular weight distribution is not controlled and the resin is synthesized by free radical polymerization. That is, by making the molecular weight distribution narrow, on the one hand, the adverse effect of the modified (meth)acrylic resin in the low molecular weight range on the dicing property, pick-up property, and adherend contamination of the adhesive tape can be sufficiently reduced. On the other hand, the adverse effect of the modified (meth)acrylic resin in the high molecular weight range on the viscosity control of the adhesive composition can be reduced.
  • the hydroxyl value of the modified (meth)acrylic resin is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and even more preferably 15 mgKOH/g or more.
  • the hydroxyl value of the modified (meth)acrylic resin is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less, and even more preferably 50 mgKOH/g or less. Any combination of these lower and upper limits may be used.
  • the hydroxyl value of the modified (meth)acrylic resin is 5 mgKOH/g or more, the adhesive strength of the adhesive sheet is good.
  • the hydroxyl value of the modified (meth)acrylic resin is 200 mgKOH/g or less, contamination of the adherend surface when the adhesive sheet is peeled off from the adherend can be suppressed.
  • the hydroxyl value of modified (meth)acrylic resin is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K0070:1992.
  • the hydroxyl value of a resin refers to the mass (mg) of potassium hydroxide required to neutralize the acetic acid that is bonded to the hydroxyl group when 1 g of the resin is acetylated.
  • the ethylenically unsaturated group equivalent of the modified (meth)acrylic resin is preferably 100 g/mol or more, more preferably 250 g/mol or more, and even more preferably 500 g/mol or more.
  • the ethylenically unsaturated group equivalent of the modified (meth)acrylic resin is preferably 5000 g/mol or less, more preferably 3500 g/mol or less, and even more preferably 2500 g/mol or less. Any combination of these lower and upper limits may be used.
  • the ethylenically unsaturated group equivalent of the modified (meth)acrylic resin is 100 to 5000 g/mol, the amount of crosslinking after UV irradiation is sufficient, and sufficient peelability and pick-up properties after UV irradiation are obtained.
  • the ethylenically unsaturated group equivalent of the modified (meth)acrylic resin is the mass of the modified (meth)acrylic resin per mole of ethylenically unsaturated bond.
  • the ethylenically unsaturated group equivalent of the modified (meth)acrylic resin is a calculated value calculated from the charged amounts, assuming that each raw material used in the production of the modified (meth)acrylic resin reacts 100%.
  • the ethylenically unsaturated group equivalent of the modified (meth)acrylic resin may be calculated from the amount of halogen bonded to the modified (meth)acrylic resin.
  • the amount of halogen bonded to the modified (meth)acrylic resin can be evaluated in accordance with JIS K 0070:1992.
  • the glass transition temperature (Tg) of the modified (meth)acrylic resin is preferably -80°C to 0°C, more preferably -70°C to -10°C, and even more preferably -60°C to -30°C. If the glass transition temperature (Tg) is -80°C or higher, the cohesive strength of the adhesive layer is increased. This provides sufficient strength for the cured product and suppresses adhesive residue when peeled off after UV irradiation. If the glass transition temperature (Tg) is 0°C or lower, sufficient adhesive strength to the adherend and sufficient fixation when processing the adherend are obtained.
  • hydroxyl group-containing (meth)acrylate (m-1) is not particularly limited as long as it has a hydroxyl group and one (meth)acryloyloxy group.
  • hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and (meth)acrylates having an aromatic ring and a hydroxyl group such as hydroxyphenyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate.
  • hydroxyalkyl (meth)acrylates are preferred, hydroxyalkyl (meth)acrylates in which the hydroxyalkyl group has 1 to 6 carbon atoms are more preferred, hydroxyalkyl (meth)acrylates having a hydroxy group at the end of a linear alkyl group are even more preferred, and 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are particularly preferred.
  • the content of the hydroxyl group-containing (meth)acrylate (m-1) in the constituent units of the copolymer (A-0) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more.
  • the content of the hydroxyl group-containing (meth)acrylate (m-1) in the constituent units of the copolymer (A-0) is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 35 mol% or less. Any combination of these lower limit values and upper limit values may be used.
  • the modified (meth)acrylic resin When the content of the hydroxyl group-containing (meth)acrylate (m-1) is 5 mol% or more, the modified (meth)acrylic resin has sufficient hydroxyl groups, and when used in combination with the crosslinking agent (C), sufficient curing properties can be obtained, and an adhesive layer having sufficient cohesive strength can be obtained.
  • the crosslink density can be further improved after UV irradiation. This allows for better peelability when peeling the adhesive sheet from the adherend.
  • the content of the hydroxyl group-containing (meth)acrylate (m-1) is 50 mol% or less, the progression of unintended reactions in the adhesive composition can be suppressed, and the storage stability is good.
  • alkyl (meth)acrylate (m-2) is not particularly limited as long as it does not have a hydroxy group and has an alkyl group and one (meth)acryloyloxy group.
  • alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, and dodecyl (meth)acrylate; and alicyclic alkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
  • alkyl (meth)acrylates and alicyclic alkyl (meth)acrylates in which the alkyl group has 1 to 20 carbon atoms are preferred, and (meth)acrylates having a linear alkyl group in which the alkyl group has 1 to 20 carbon atoms are more preferred.
  • the modified (meth)acrylic resin is used as a pressure-sensitive adhesive
  • Tg glass transition temperature of the modified (meth)acrylic resin
  • one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate are preferred.
  • the content of alkyl (meth)acrylate (m-2) in the constituent units of copolymer (A-0) is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 65 mol% or more.
  • the content of alkyl (meth)acrylate (m-2) in the constituent units of copolymer (A-0) is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less. Any combination of these lower and upper limits may be used.
  • the content of alkyl (meth)acrylate (m-2) is 50 mol% or more, good coatability is obtained when the modified (meth)acrylic resin is used in an adhesive composition, and desired adhesive properties according to the application are obtained.
  • the content of alkyl (meth)acrylate (m-2) is 95 mol% or less, the content of hydroxyl groups and ethylenically unsaturated groups in the modified (meth)acrylic resin can be sufficiently ensured, so that an adhesive composition having balanced physical properties can be obtained from the viewpoints of curability and improved crosslink density after UV irradiation.
  • an adhesive layer having balanced physical properties can be obtained from the viewpoints of the cohesive strength of the adhesive layer and the peelability of the adhesive sheet after UV irradiation.
  • the copolymer (A-0) may contain a structural unit derived from another copolymerizable monomer (m-3) other than (m-1) and (m-2).
  • the other monomer (m-3) include carboxy group-containing monomers, dienes such as butadiene and dicyclopentadiene, styrenes, unsaturated dicarboxylic acid diesters, other vinyl compounds, etc.
  • carboxyl group-containing monomers examples include unsaturated monobasic acids such as (meth)acrylic acid, crotonic acid, vinylbenzoic acid, alpha-position haloalkyl, alkoxyl, halogen, nitro, or cyano-substituted acrylic acid, and unsaturated dibasic acids such as itaconic acid.
  • unsaturated monobasic acids such as (meth)acrylic acid, crotonic acid, vinylbenzoic acid, alpha-position haloalkyl, alkoxyl, halogen, nitro, or cyano-substituted acrylic acid
  • unsaturated dibasic acids such as itaconic acid.
  • (meth)acrylic acid is preferred because of the ease of manufacturing the adhesive layer.
  • styrenes include styrene and ⁇ -, o-, m-, or p-alkyl derivatives of styrene.
  • unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.
  • vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .
  • the isocyanato group-containing ethylenically unsaturated compound (a) is not particularly limited as long as it does not have a hydroxy group or a carboxy group, but has one isocyanato group and an ethylenically unsaturated group.
  • (meth)acryloyloxyalkyl isocyanates such as 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, and 4-isocyanatocyclohexyl (meth)acrylate; 2-(2-isocyanatoethyloxy)ethyl (meth)acrylate; and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate.
  • (meth)acryloyloxyalkyl isocyanate is preferred, and 2-(meth)acryloyloxyethyl isocyanate is more preferred.
  • the amount of the isocyanato group-containing ethylenically unsaturated compound (a) is preferably 0.5 mol or more, more preferably 1.0 mol or more, and even more preferably 5.0 mol or more, relative to 100 mol of the constituent units of the copolymer (A-0).
  • the amount of the isocyanato group-containing ethylenically unsaturated compound (a) is preferably 49 mol or less, more preferably 40 mol or less, and even more preferably 30 mol or less, relative to 100 mol of the constituent units of the copolymer (A-0). Any combination of these lower limit values and upper limit values may be used.
  • the amount of the isocyanato group-containing ethylenically unsaturated compound (a) is 0.5 mol or more, a sufficient amount of ethylenically unsaturated groups is introduced into the modified (meth)acrylic resin, improving the crosslinking efficiency after UV irradiation.
  • the modified (meth)acrylic resin is used in the adhesive layer, better releasability can be obtained when peeling the adhesive sheet from the adherend after UV irradiation.
  • the amount of the isocyanato group-containing ethylenically unsaturated compound (a) is 49 moles or less, the content of hydroxyl groups in the modified (meth)acrylic resin can be sufficiently ensured, and the curing property during thermal curing can be improved.
  • the modified (meth)acrylic resin is used in the adhesive layer, the adhesive layer can obtain excellent cohesive strength.
  • the amount of unreacted isocyanato group-containing ethylenically unsaturated compound (a) can be reduced. Therefore, when the modified (meth)acrylic resin is used in the adhesive layer, an adhesive sheet with little adhesive residue can be obtained.
  • the number of moles of the isocyanato group-containing ethylenically unsaturated compound (a) relative to the number of moles of the structural units derived from the hydroxyl group-containing (meth)acrylate (m-1) is preferably 30% or more, more preferably 50% or more, and even more preferably 65% or more.
  • the number of moles of the isocyanato group-containing ethylenically unsaturated compound (a) relative to the number of moles of the structural units derived from the hydroxyl group-containing (meth)acrylate (m-1) is preferably 99% or less, more preferably 90% or less, and even more preferably 85% or less. Any combination of these lower and upper limits may be used.
  • the modified (meth)acrylic resin can be produced by a method including, for example, a step (i) of polymerizing a raw material monomer group (M) containing a hydroxyl group-containing (meth)acrylate (m-1) and an alkyl (meth)acrylate (m-2) by reversible addition-fragmentation chain transfer (RAFT) while irradiating with UV light to obtain a copolymer (A-0), and a step (ii) of adding an isocyanato group-containing ethylenically unsaturated compound (a) to a part of the side chain hydroxyl group of the copolymer (A-0) to obtain a modified (meth)acrylic resin having an ethylenically unsaturated group.
  • the raw material monomer group (M) may contain another monomer (m-3). Exemplary aspects of steps (i) and (ii) are described below.
  • Step (i) is a step of obtaining a copolymer (A-0) by RAFT polymerization of a raw material monomer group (M) containing a hydroxyl group-containing (meth)acrylate (m-1), an alkyl (meth)acrylate (m-2), and optionally other monomers (m-3) in the presence of a reversible addition-fragmentation chain transfer agent (RAFT agent) while irradiating them with UV light.
  • RAFT polymerization means radical polymerization carried out in the presence of a RAFT agent.
  • RAFT polymerization is a type of living radical polymerization.
  • Living radical polymerization is generally known as a polymerization method capable of obtaining a polymer with a small molecular weight distribution, and specific examples thereof include atom transfer radical polymerization, organotellurium-mediated radical polymerization, RAFT polymerization, and the like. Of these, RAFT polymerization is suitable for adhesive applications because it does not use halogens or heavy metals.
  • the RAFT polymerization in step (i) is performed while irradiating with UV light.
  • the start and end of the RAFT polymerization can be controlled by UV irradiation, so the weight-average molecular weight and molecular weight distribution of the copolymer (A-0) can be strictly controlled.
  • the weight-average molecular weight of the copolymer (A-0) can be controlled, for example, by adjusting the amount of the radical polymerization initiator and the RAFT agent used.
  • the modified (meth)acrylic resin obtained in the subsequent step (ii) can also have a strictly controlled weight-average molecular weight and molecular weight distribution.
  • the start and end of the RAFT polymerization can be controlled by UV irradiation, so the generation of radicals can be minimized when heating in the subsequent reaction in step (ii). This makes it possible to suppress gelation and the by-production of low molecular weight polymers due to unintended reactions in step (ii).
  • the UV irradiance is preferably 1 to 50 mW/cm 2 , more preferably 1 to 30 mW/cm 2 , and even more preferably 1 to 10 mW/cm 2.
  • the UV irradiance is 1 mW/cm 2 or more, radicals are sufficiently generated, and RAFT polymerization proceeds well.
  • the UV irradiance is 50 mW/cm 2 or less, the generated radicals and the RAFT agent react sufficiently, and living radical polymerization can proceed preferentially over free radical polymerization.
  • runaway reaction caused by reaction heat accompanying polymerization can be suppressed.
  • the irradiation time depends on the target weight-average molecular weight of copolymer (A-0), but is preferably 1 to 50 hours, more preferably 1 to 40 hours, and even more preferably 1 to 25 hours. By setting the irradiation time within the above range, it is possible to control the weight-average molecular weight of copolymer (A-0) to approach the target value and suppress the progress of free radical polymerization. Irradiation may be performed intermittently or continuously, but continuous irradiation is preferable.
  • continuous irradiation is preferable from the viewpoint of efficiency after 1 hour has elapsed from the start of irradiation, and continuous irradiation from the start of irradiation is preferable from the viewpoint of controlling the molecular weight distribution more narrowly.
  • the reaction temperature can be set appropriately depending on the type of radical polymerization initiator used, etc.
  • the reaction temperature is preferably 10 to 40°C, more preferably 15 to 30°C.
  • the RAFT polymerization in step (i) can be carried out at room temperature without the need for heating, since the reaction proceeds by UV irradiation. Therefore, the progress of free radical polymerization can be suppressed to a high level, and it is possible to obtain a copolymer (A-0) with a narrow molecular weight distribution.
  • solution polymerization As the polymerization method, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, alternating copolymerization, etc. can be used. Among these polymerization methods, in consideration of the addition reaction in step (ii), it is preferable to use the solution polymerization method from the viewpoint of ease of reaction.
  • the total concentration of the components excluding the solvent in the solution polymerization is preferably 30 to 90% by mass, and more preferably 50 to 80% by mass, from the viewpoint of the polymerization rate of the raw material monomer group (M). Since step (i) is a RAFT polymerization, the polymerization proceeds by an equilibrium reaction. Therefore, the polymerization proceeds very gently, and the polymerization can be carried out at a high concentration.
  • RAFT Agents Reversible Addition-Fragmentation Chain Transfer Agents
  • known ones can be used without any particular limitation.
  • the RAFT agent include trithiocarbonate, dithioester, dithiocarbonate, and dithiocarbamate.
  • trithiocarbonate is preferred because the reaction rate and reaction rate of polymerization are increased due to the large transfer constant, and the molecular weight distribution is likely to be narrow.
  • RAFT agents include sulfur-based compounds (trithiocarbonates, dithioesters, dithiocarbonates, and dithiocarbamates) represented by the following formula (1), (2), (3), or (4).
  • R 1a and R 1b each independently represent a hydrogen atom, a hydrocarbon group, a carboxy group, or a cyano group
  • R 1c represents a cyano group, a saturated or unsaturated aliphatic hydrocarbon group which may be substituted with a cyano group or a carboxy group, or a phenyl group which may be substituted
  • R 2 represents a saturated or unsaturated aliphatic hydrocarbon group some of the hydrogen atoms of which may be substituted with a carboxy group, or a benzyl group some of the hydrogen atoms of which may be substituted with a substituted carbamoyl group, an alkoxycarbonyl group having 2 to 5 carbon atoms which may be substituted with a hydroxy group, or an alkenyloxycarbonyl group having 3 to 5 carbon atoms.
  • R3a and R3b each independently represent a hydrogen atom, a hydrocarbon group, or a cyano group;
  • R3c represents a carboxy group, an acetoxymethyl group, or a hydrocarbon group which may be substituted with a cyano group or a carboxy group; and
  • R4 represents a hydrocarbon group.
  • R5a and R5b each independently represent a hydrogen atom, a hydrocarbon group, a carboxy group which may be substituted with a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a cyano group; R5c represents a hydrocarbon group which may be substituted with an alkoxy group; and R6 represents a hydrocarbon group.
  • R 7a and R 7b each independently represent a hydrogen atom or a hydrocarbon group
  • R 7c represents a cyano group
  • R 8 and R 9 each independently represent a hydrocarbon group, or R 8 and R 9 may combine with each other to form a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms or a pyrazole ring which may be substituted with a chlorine atom.
  • examples of the hydrocarbon group represented by R 1a and R 1b include linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, and among these, linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms are preferred.
  • hydrocarbon group examples include linear, branched or cyclic saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, dodecyl group, and octadecyl group; aryl groups having 6 to 12 carbon atoms, such as phenyl group; and arylalkyl groups having 7 to 10 carbon atoms, such as benzyl group and phenethyl group.
  • examples of the saturated or unsaturated aliphatic hydrocarbon group represented by R 1c include linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and among these, linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms are preferred.
  • aliphatic hydrocarbon group examples include linear, branched or cyclic, saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a dodecyl group, and an octadecyl group.
  • 1 to 3 hydrogen atoms of the saturated or unsaturated aliphatic hydrocarbon group represented by R 1c may be substituted with a carboxy group or a cyano group, and the carboxy group may be further substituted with a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms.
  • substituent of the phenyl group represented by R 1c which may be substituted include a substituted carbamoyl group, an alkoxycarbonyl group having 2 to 5 carbon atoms which may be substituted with a hydroxy group, and an alkenyloxycarbonyl group having 3 to 5 carbon atoms.
  • Examples of the substituent of the substituted carbamoyl group include a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a hydroxy group or an acetyloxy group.
  • examples of the saturated or unsaturated aliphatic hydrocarbon group represented by R 2 include linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and among these, an aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferred.
  • Examples of the aliphatic hydrocarbon group include linear, branched or cyclic saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, dodecyl and octadecyl groups.
  • 1 to 3 hydrogen atoms of the saturated or unsaturated aliphatic hydrocarbon group represented by R 2 may be substituted with a carboxy group.
  • examples of the substituent of the substituted carbamoyl group of the optionally substituted benzyl group represented by R 2 include saturated aliphatic hydrocarbon groups having 1 to 3 carbon atoms which may be substituted with a hydroxy group or an acetyloxy group.
  • R 1a and R 1b are each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a carboxy group, or a cyano group
  • R 1c is a hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a carboxy group, or a phenyl group which may be substituted
  • R 2 is a linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a benzyl group which may be substituted
  • R 1a and R 1b are a hydrogen atom, a combination of a methyl group or an ethyl group and a carboxy group, or a hydrogen atom
  • R 1c is a methyl group, an ethyl group, or a phenyl group which may be substituted
  • R More preferred is a compound represented by formula (1), in which 2 is a linear saturated aliphatic hydro
  • examples of the hydrocarbon group represented by R 3a , R 3b , R 3c and R 4 include linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, and among these, linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms are preferred.
  • hydrocarbon group examples include linear, branched or cyclic saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, dodecyl and octadecyl groups; aryl groups having 6 to 12 carbon atoms, such as phenyl; and arylalkyl groups having 7 to 10 carbon atoms, such as benzyl and phenethyl groups.
  • examples of the hydrocarbon group which may be substituted with a cyano group or a carboxy group, represented by R 3c include the above-mentioned hydrocarbon group in which 1 to 3 hydrogen atoms have been substituted with a cyano group or a carboxy group, etc.
  • a compound represented by formula (2) in which R 3a and R 3b are each independently a linear saturated hydrocarbon group having 1 to 4 carbon atoms, R 3c is an aryl group, and R 4 is an aryl group or a benzyl group is preferred, and a compound represented by formula (2) in which R 3a and R 3b are each independently a methyl group or an ethyl group, R 3c is a phenyl group, and R 4 is a phenyl group or a benzyl group is more preferred.
  • examples of the hydrocarbon group represented by R 5a , R 5b , R 5c and R 6 include linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, and among these, linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms are preferred.
  • hydrocarbon group examples include linear, branched or cyclic saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, dodecyl and octadecyl groups; aryl groups having 6 to 12 carbon atoms, such as phenyl; and arylalkyl groups having 7 to 10 carbon atoms, such as benzyl and phenethyl groups.
  • examples of the hydrocarbon group which may be substituted with an alkoxy group, represented by R 5c include the above-mentioned hydrocarbon groups in which 1 to 3 hydrogen atoms have been substituted with an alkoxy group.
  • examples of the hydrocarbon group represented by R 7a , R 7b , R 8 and R 9 include linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, and among these, linear, branched or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms are preferred.
  • hydrocarbon group examples include linear, branched or cyclic saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, dodecyl group, and octadecyl group; aryl groups having 6 to 12 carbon atoms, such as phenyl group; and arylalkyl groups having 7 to 10 carbon atoms, such as benzyl group and phenethyl group.
  • R 8 and R 9 may form a pyrazole ring together with the nitrogen atom of formula (4).
  • the pyrazole ring may be substituted with a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms or a chlorine atom.
  • RAFT agents are commercially available. Those that are not commercially available can be easily synthesized by known or conventional methods.
  • RAFT agents include S-cyanomethyl-S-dodecyl trithiocarbonate, 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 2- ⁇ [(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl ⁇ propanoic acid, bis ⁇ 4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl ⁇ trithiocarbonate, 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid, and 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl] Pentanoic acid, S,S-dibenzyl trithiocarbonate, methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]p
  • trithiocarbonates and dithioesters are preferred, and 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2- ⁇ [(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl ⁇ propanoic acid, 2-phenyl-2-propyldithiobenzoic acid, S,S-dibenzyltrithiocarbonate, and bis ⁇ 4-[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl ⁇ trithiocarbonate are more preferred.
  • RAFT agents may be used alone or in combination of two or more.
  • the amount of the RAFT agent used is preferably 0.0005 to 1 part by mass, more preferably 0.001 to 0.5 parts by mass, and even more preferably 0.001 to 0.01 parts by mass, relative to 100 parts by mass of the total amount of the raw material monomer group (M). If it is 0.0005 parts by mass or more, polymerization can be performed in an efficient reaction time. If it is 1 part by mass or less, a copolymer (A-0) with a sufficiently high molecular weight can be obtained.
  • the RAFT polymerization is preferably carried out in the presence of a radical polymerization initiator. Since the RAFT polymerization in step (i) is carried out under UV irradiation, a photopolymerization initiator is used as the radical polymerization initiator. Examples of the photopolymerization initiator include carbonyl-based photopolymerization initiators, sulfide-based photopolymerization initiators, quinone-based photopolymerization initiators, sulfochloride-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators.
  • photopolymerization initiators include carbonyl-based photopolymerization
  • radical polymerization initiators carbonyl-based photopolymerization initiators and acylphosphine oxides are preferred from the viewpoint of solubility in solvents, and it is more preferable to use at least one selected from 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • the radical polymerization initiator may be used alone or in combination of two or more types.
  • the amount of radical polymerization initiator used is preferably 0.0001 to 1 part by mass, more preferably 0.0001 to 0.1 parts by mass, and even more preferably 0.0005 to 0.05 parts by mass, relative to 100 parts by mass of the total amount of the raw material monomer group (M). If it is 0.0001 part by mass or more, polymerization can be performed in an efficient reaction time. If it is 1 part by mass or less, a copolymer (A-0) with a sufficiently high molecular weight can be obtained.
  • the molar ratio of the radicals generated from the radical polymerization initiator to the RAFT agent is preferably 1.0:1.0 to 1.0:1.3, from the viewpoint of preferentially progressing living radical polymerization over free radical polymerization.
  • the solvent that may be used in step (i) may be a general solvent.
  • the solvent include esters such as ethyl acetate, propyl acetate, and butyl acetate; aromatic hydrocarbons such as toluene, xylene, and benzene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycols such as ethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers such as methyl cellosolve, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate.
  • the solvent may be used alone or in combination of two or more.
  • Step (ii) is a step of obtaining a modified (meth)acrylic resin by adding an isocyanato group-containing ethylenically unsaturated compound (a) to a part of the side chain hydroxyl groups derived from the hydroxyl group-containing (meth)acrylate (m-1) of the copolymer (A-0). If the isocyanato group-containing ethylenically unsaturated compound (a) is added to all of the side chain hydroxyl groups of the copolymer (A-0), there will be no reaction sites with the crosslinking agent (C) described later, so the addition is limited to a part of the side chain hydroxyl groups.
  • the addition reaction is performed at 30 to 99 mol%.
  • the method of adding the isocyanato group-containing ethylenically unsaturated compound (a) is not particularly limited, and any method known in the technical field of this specification can be used.
  • the modified (meth)acrylic resin has an ethylenically unsaturated group in the side chain, so that the length of the molecular chain between crosslinking points is relatively short compared to a (meth)acrylic copolymer having an ethylenically unsaturated group introduced at the end, and the crosslinking density can be efficiently improved by UV irradiation.
  • the adhesive sheet using the modified (meth)acrylic resin has excellent peelability from the adherend.
  • the adhesive composition produced using the (meth)acrylic resin has excellent adhesion to the adhesive layer. Therefore, the adhesive composition produced using the modified (meth)acrylic resin is preferably used for the adhesive layer of the dicing/die-bonding integrated film.
  • a known catalyst in the addition reaction in step (ii), can be used as necessary, such as a urethanization catalyst such as dibutyltin dilaurate, titanium diisopropoxybis(ethylacetoacetate), tetrakis(2,4-pentanedionato)zirconium, or bismuth tris(2-ethylhexanoate).
  • a urethanization catalyst such as dibutyltin dilaurate, titanium diisopropoxybis(ethylacetoacetate), tetrakis(2,4-pentanedionato)zirconium, or bismuth tris(2-ethylhexanoate).
  • the amount of the catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.03 to 1 part by mass, per 100 parts by mass of the total of the copolymer (A-0) and the isocyanato group-containing ethylenically unsaturated compound (a).
  • a known polymerization inhibitor in the addition reaction in step (ii), a known polymerization inhibitor can be used as necessary.
  • the polymerization inhibitor a known one can be used, and there is no particular limitation, but examples thereof include 4-methoxyphenol, hydroquinone, methoquinone, 2,6-di-t-butylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and phenothiazine.
  • the polymerization inhibitor may be used alone or in combination of two or more kinds.
  • the amount of the polymerization inhibitor used is preferably 0.005 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and even more preferably 0.05 to 1.5 parts by mass, per 100 parts by mass of the total of the copolymer (A-0) and the isocyanato group-containing ethylenically unsaturated compound (a). If the amount of the polymerization inhibitor used is 0.005 parts by mass or more, gelation during the addition reaction can be prevented. On the other hand, if the amount of the polymerization inhibitor used is 5 parts by mass or less, sufficient exposure sensitivity of the modified (meth)acrylic resin during UV irradiation can be obtained.
  • the temperature of the addition reaction is preferably 25° C. to 130° C., and particularly preferably 40° C. to 90° C. When the temperature of the addition reaction is 25° C. or higher, a sufficient reaction rate can be obtained. When the temperature of the addition reaction is 130° C. or lower, crosslinking of the double bonds due to radical polymerization caused by heat and generation of gelled products can be prevented.
  • a gas that inhibits polymerization may be introduced into the reaction system.
  • a gas that inhibits polymerization By introducing a gas that inhibits polymerization into the reaction system, gelation during the addition reaction can be prevented.
  • Gases that have the effect of inhibiting polymerization include gases that contain oxygen to a degree that does not fall within the explosive range of the substances in the system, such as air.
  • the combined use of a gas that has a polymerization inhibitor effect and a polymerization inhibitor is preferable because it reduces the amount of polymerization inhibitor used and increases the polymerization inhibitor effect.
  • the adhesive composition contains a modified (meth)acrylic resin (A), a photopolymerization initiator (B), a crosslinking agent (C), and other components added as necessary.
  • the adhesive composition containing the modified (meth)acrylic resin (A) is suitable for use in removable adhesive sheets, particularly dicing tapes and dicing/die-bond integrated films.
  • Photopolymerization initiator (B) examples include benzophenone, benzil, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, and benzoin isopropyl alcohol.
  • Carbonyl-based photopolymerization initiators such as butyl ether, benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, 4'-dimethylaminoacetophenone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one can be mentioned.
  • Examples of the photopolymerization initiator (B) include sulfide-based photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethyl thiuram disulfide, and tetramethyl ammonium monosulfide; acyl phosphine oxides such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide; quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; sulfochloride-based photopolymerization initiators; and thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.
  • sulfide-based photopolymerization initiators such as diphenyl dis
  • photopolymerization initiators (B) carbonyl-based photopolymerization initiators and acylphosphine oxides are preferred from the viewpoint of solubility in the adhesive composition, and it is more preferred to use at least one selected from 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • the photopolymerization initiator (B) may be used alone or in combination of two or more types.
  • the photopolymerization initiator (B) is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 2.0 parts by mass, relative to 100 parts by mass of the modified (meth)acrylic resin (A).
  • the content of the photopolymerization initiator (B) relative to 100 parts by mass of the modified (meth)acrylic resin (A) is 0.1 parts by mass or more, the crosslinking density of the photocrosslinkable adhesive (thermosetting product of the adhesive composition) can be improved at a sufficiently fast curing speed during UV irradiation. Therefore, when the photocrosslinkable adhesive is used in the adhesive layer, the adhesive strength of the adhesive layer after UV irradiation can be sufficiently reduced.
  • the content of the photopolymerization initiator (B) relative to 100 parts by mass of the modified (meth)acrylic resin (A) is 5.0 parts by mass or less, the effect of the photopolymerization initiator (B) on the properties of the cured product can be suppressed.
  • the adhesive sheet having a photocrosslinkable adhesive as an adhesive layer is attached to an adherend and then peeled off, the adhesive layer is less likely to remain on the adherend.
  • the adhesive composition can be produced economically.
  • the crosslinking agent (C) is a compound that does not have an ethylenically unsaturated bond and has two or more functional groups that react with the hydroxyl group and/or the carboxyl group, which is an optional functional group, contained in the modified (meth)acrylic resin (A).
  • the functional group of the crosslinking agent (C) reacts with the hydroxyl group of the modified (meth)acrylic resin (A) by heating to cure the adhesive composition, thereby obtaining a photocrosslinkable adhesive.
  • an adhesive sheet having a good balance between the adhesive strength before UV irradiation and the adhesive strength after UV irradiation can be obtained.
  • the crosslinking agent (C) is not particularly limited, but a compound having two or more functional groups reactive to a hydroxy group is preferred.
  • a compound having two or more functional groups reactive to a carboxy group may be used.
  • functional groups reactive to a hydroxy group include an isocyanato group, an epoxy group, a carboxy group, an acid anhydride group, and an aziridinyl group, but from the viewpoint of reactivity, an isocyanato group and an epoxy group are preferred, and an isocyanato group is particularly preferred.
  • Examples of functional groups reactive to a carboxy group include an epoxy group, a hydroxy group, and an aziridinyl group, but from the viewpoint of reactivity, an epoxy group and an aziridinyl group are preferred.
  • crosslinking agent (C) examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, isocyanurate of hexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate adduct of trimethylolpropane, xylylene diisocyanate adduct of trimethylolpropane, triphenylmethane triisocyanate, methylene Polyisocyanates such as bis(4-phenylmethane)triisocyanate; 1,3-bis(N-
  • crosslinking agents (C) it is preferable to use at least one selected from the group consisting of polyisocyanates and polyepoxy compounds, because of their good reactivity with the modified (meth)acrylic resin (A), and it is more preferable to use polyisocyanates.
  • the crosslinking agent (C) may be used alone or in combination of two or more types.
  • the crosslinking agent (C) is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the modified (meth)acrylic resin (A).
  • the content of the crosslinking agent (C) per 100 parts by mass of the modified (meth)acrylic resin (A) is 0.1 parts by mass or more, a three-dimensional crosslinked structure is sufficiently formed in the photocrosslinkable adhesive upon UV irradiation. Therefore, when a photocrosslinkable adhesive is used as an adhesive, the adhesive strength of the adhesive after UV irradiation can be sufficiently reduced.
  • the content of the crosslinking agent (C) per 100 parts by mass of the (meth)acrylic resin (A) is 30 parts by mass or less, the balance of the properties of the photocrosslinkable adhesive and the cured product after UV irradiation is good.
  • a photocrosslinkable adhesive is used as an adhesive, the adhesive strength of the adhesive before UV irradiation is good.
  • the pressure-sensitive adhesive composition may contain other components, as necessary, in addition to the modified (meth)acrylic resin (A), the photopolymerization initiator (B), and the crosslinking agent (C).
  • the other components include a tackifier, a solvent, and various additives.
  • the tackifier may be any known tackifier without any particular limitation.
  • the tackifier include terpene-based tackifier resins, phenol-based tackifier resins, rosin-based tackifier resins, aliphatic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins, alicyclic petroleum resins, xylene resins, epoxy-based tackifier resins, polyamide-based tackifier resins, ketone-based tackifier resins, and elastomer-based tackifier resins. These tackifiers may be used alone or in combination of two or more.
  • the amount added is preferably 30 parts by mass or less, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the modified (meth)acrylic resin (A).
  • the solvent can be used to dilute the adhesive composition for the purpose of adjusting the viscosity of the adhesive composition.
  • the solvent can be used to adjust the viscosity of the adhesive composition to an appropriate viscosity.
  • the solvent used in synthesizing the modified (meth)acrylic resin (A) may be used as it is, or a solvent may be added to the solvent.
  • organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, hexane, toluene, xylene, n-propanol, isopropyl alcohol, etc. can be used. These solvents may be used alone or in combination of two or more.
  • additives examples include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antiaging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate ester-based and other flame retardants, surfactants, and antistatic agents.
  • the pressure-sensitive adhesive composition can be produced, for example, by a method including a step (iii) of mixing a modified (meth)acrylic resin (A), a photopolymerization initiator (B), a crosslinking agent (C), and other components added as necessary.
  • the method for mixing the components contained in the adhesive composition is not particularly limited. Mixing can be performed, for example, using a stirring device equipped with stirring blades such as a homodisper or paddle blade.
  • the photocrosslinkable pressure-sensitive adhesive can be produced, for example, by a method including a step (iv) of applying a pressure-sensitive adhesive composition onto a substrate or a release sheet, and thermally curing the composition.
  • the adhesive composition obtained in step (iii) may be used as is, or a solvent may be added to adjust the viscosity.
  • Thermal curing proceeds by heating, drying and curing as necessary during the process of forming the photocrosslinkable adhesive.
  • the adhesive composition is applied onto a substrate, and if a solvent is contained, the composition is heated and dried to remove the solvent, forming an adhesive composition layer. Thereafter, a release sheet is attached to the adhesive composition layer as necessary. Furthermore, the obtained sheet is cured in an oven for a certain period of time as necessary to form a crosslinked structure, thereby obtaining a photocrosslinkable adhesive layer.
  • step (iv) includes step (iv-1) of applying the adhesive composition onto a release sheet to obtain an adhesive composition layer, step (iv-2) of thermally curing the adhesive composition layer to obtain a photocrosslinkable adhesive layer, and step (iv-3) of laminating a substrate on the adhesive composition layer or the photocrosslinkable adhesive layer.
  • Step (iv-3) may be performed between step (iv-1) and step (iv-2), or may be performed after step (iv-2).
  • the adhesive composition is applied onto a release sheet, and if a solvent is contained, the adhesive composition is heated and dried to remove the solvent, thereby forming an adhesive composition layer (step (iv-1)).
  • the release sheet having the adhesive composition layer is placed on a substrate with the surface of the adhesive composition layer facing the substrate, and the adhesive composition layer is transferred (transferred) onto the substrate (step (iv-3)). Furthermore, if necessary, the obtained sheet can be cured in an oven for a certain period of time to form a crosslinked structure, thereby obtaining a photocrosslinkable pressure-sensitive adhesive layer (step (iv-2)).
  • the adhesive composition can be applied to the substrate (or release sheet) by a known method.
  • a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, or direct coater.
  • the conditions for heat-drying the applied adhesive composition are not particularly limited, but are usually 25 to 180°C, preferably 60 to 150°C, and heat-drying is usually performed for 1 to 20 minutes, preferably 1 to 10 minutes. Heat-drying within the above ranges makes it possible to remove the solvent contained in the adhesive composition.
  • the conditions for curing the sheet after heat-drying in an oven for a certain period of time are not particularly limited, but are usually 25 to 100°C, preferably 30 to 80°C, and curing is usually performed for 1 to 30 days, preferably 1 to 14 days. Curing under the above conditions makes it possible to crosslink the modified (meth)acrylic resin (A) with the crosslinking agent (C) and adjust the gel fraction of the photocrosslinkable adhesive to the desired range.
  • the pressure-sensitive adhesive sheet has a base layer and a pressure-sensitive adhesive layer made of a thermosetting or photothermally cured product of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive sheet may have a release sheet on the exposed surface of the pressure-sensitive adhesive layer (the surface opposite to the base layer) as necessary before being attached to the adherend.
  • the pressure-sensitive adhesive sheet can be obtained, for example, by step (iv).
  • the pressure-sensitive adhesive layer is used in the state of a photocrosslinkable pressure-sensitive adhesive layer, and when peeling off from the adherend, the photocrosslinkable pressure-sensitive adhesive layer is crosslinked by UV irradiation to reduce the adhesive force, and is peeled off.
  • the substrate is not particularly limited and can be appropriately selected depending on the application.
  • a resin film is preferred, and examples of the resin material include polyvinyl chloride, polyvinylidene chloride, polyolefin (PO), polyester, polyurethane, polycarbonate, polyether ether ketone, polyimide, polyetherimide, polyamide, wholly aromatic polyamide (aramid), polyphenyl sulfide, fluororesin, cellulose-based resin, and silicone resin.
  • polyolefin examples include polyethylene (PE) such as low-density polyethylene, linear polyethylene, medium-density polyethylene, high-density polyethylene, and very low-density polyethylene; polypropylene (PP) such as random copolymer polypropylene, block copolymer polypropylene, and homopolypropylene; polybutene; polymethylpentene; ethylene-vinyl acetate copolymer; ionomer resin; ethylene-(meth)acrylic acid copolymer; ethylene-(meth)acrylic acid ester copolymer; ethylene-butene copolymer; and ethylene-hexene copolymer.
  • PE polyethylene
  • PP polypropylene
  • PP random copolymer polypropylene, block copolymer polypropylene, and homopolypropylene
  • polybutene polymethylpentene
  • ethylene-vinyl acetate copolymer ionomer resin
  • polyester examples include polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • the resin material used as the substrate material may be one type or a mixture of two or more types.
  • polyolefin When used as a dicing tape, it is preferable to use polyolefin.
  • the substrate may be made of one type of material or two or more types of materials.
  • the substrate may have a single layer structure or a multilayer structure. Since the photocrosslinkable adhesive on the substrate is of the ultraviolet curing type, it is preferable that the substrate is ultraviolet transparent.
  • the substrate is a resin film, the substrate may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.
  • the substrate may be treated to enhance adhesion.
  • treatments include physical treatments such as corona discharge treatment, plasma treatment, sand matting, ozone exposure, flame exposure, high-voltage shock exposure, and ionizing radiation treatment, chemical treatments such as chromate treatment, and undercoat treatment.
  • a PO film As the substrate, it is preferable to use a PO film.
  • PO film has low heat resistance and is not suitable for the above-mentioned heat drying temperature. Therefore, it is preferable to apply the adhesive composition to a release sheet, heat dry to remove the solvent, and then transfer the adhesive composition layer to the PO film. Specifically, it is preferable to apply the adhesive composition to the release-treated surface of a silicone-based light release PET film, heat dry, and then attach the PO film to the adhesive composition layer using a rubber roller so that the corona-treated surface of the PO film is adhered to the exposed surface of the adhesive composition layer.
  • the release sheet is not particularly limited, and for example, any sheet generally used for adhesive applications can be used without restriction.
  • the same resin film as that used for the above-mentioned substrate is preferable, and from the viewpoint of ease of handling, it is preferable to use a resin film containing one or more selected from PE, PP, and PET.
  • the release sheet may be treated with a release agent to provide easy release.
  • a release agent such as silicone may be used.
  • the thickness of the photocrosslinkable adhesive layer is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 10 to 20 ⁇ m. If the thickness of the photocrosslinkable adhesive layer is 5 ⁇ m or more, sufficient adhesive properties are exhibited and coating is easy. If the thickness of the photocrosslinkable adhesive layer is 100 ⁇ m or less, the generation of air bubbles during heating and drying and residual solvent can be suppressed.
  • the adhesive sheet can be used as a removable adhesive sheet, for example, when manufacturing electronic components.
  • the removable adhesive sheet can be used as a surface protection tape for protecting the surface of the adherend in each step of manufacturing electronic components.
  • the adherend is fixed, subjected to various processing steps, and then irradiated with UV (ultraviolet rays) to be peeled off from the adherend. Therefore, the adhesive sheet can be used as a backgrind tape, dicing tape, dicing/die bonding integrated film, etc. when processing semiconductor wafers.
  • the adhesive sheet can also be used as a support tape for fragile members such as ultrathin glass substrates and members that are prone to warping such as FPC substrates.
  • the adhesive sheet has excellent adhesion to the adhesive layer and excellent peelability after UV irradiation, so it is suitable for a dicing tape used when manufacturing a dicing/die bonding integrated film.
  • the dicing tape has a base layer and an adhesive layer made of a heat-cured or photo-cured adhesive composition.
  • the adhesive sheet is attached to a wafer on which multiple components are formed.
  • the wafer is cut and separated (diced) into individual components to form element pieces (chips).
  • the adhesive sheet attached to each element piece is then irradiated with UV light. This causes UV light to be irradiated to the photocrosslinkable adhesive layer through the base material of the adhesive sheet, and the unsaturated bonds in the photocrosslinkable adhesive form a three-dimensional crosslinked structure and harden. As a result, the adhesive strength of the adhesive layer decreases.
  • the adhesive sheet is then peeled off from each element piece.
  • the dicing tape can be produced, for example, by forming a photocrosslinkable pressure-sensitive adhesive layer on a substrate.
  • the photocrosslinkable pressure-sensitive adhesive layer can be formed, for example, by the same method as in the above step (iv).
  • the substrate is preferably made of a material suitable for the expanding process, and polyolefin film is preferred.
  • the thickness of the photocrosslinkable adhesive layer is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 10 to 20 ⁇ m. If the thickness of the photocrosslinkable adhesive layer is 5 ⁇ m or more, sufficient adhesive properties are exhibited and coating is easy. If the photocrosslinkable adhesive layer is 100 ⁇ m or less, the generation of air bubbles during heating and drying and residual solvent can be suppressed. In particular, if the thickness of the photocrosslinkable adhesive layer is 10 to 20 ⁇ m, sufficient peelability and severability (cuttability) can be obtained.
  • the dicing/die bonding integrated film has, in this order, a base layer, a pressure-sensitive adhesive layer made of a thermoset or photo-cured pressure-sensitive adhesive composition, and an adhesive layer.
  • the dicing and die bonding integrated film can be obtained, for example, by laminating a dicing tape and a die bonding tape.
  • the dicing tape can be produced, for example, by the same method as the above-mentioned production method.
  • An example of a method for producing a dicing/die bonding integrated film includes the following steps.
  • a step (v) of laminating the dicing tape and the die bonding tape The order of the steps may be changed, except that step (iv-1) is carried out first and step (v) is carried out last.
  • Step (iv-3) may be carried out between step (iv-1) and step (iv-2), or after step (iv-2).
  • the thickness of the photocrosslinkable adhesive layer is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 10 to 20 ⁇ m. If the thickness of the photocrosslinkable adhesive layer is 5 ⁇ m or more, sufficient adhesive properties are exhibited and coating is easy. If the thickness of the photocrosslinkable adhesive layer is 100 ⁇ m or less, the generation of air bubbles during heating and drying and residual solvent can be suppressed. In particular, if the thickness of the photocrosslinkable adhesive layer is 10 to 20 ⁇ m, sufficient peelability and severability (cuttability) can be obtained.
  • Step (v) can be carried out, for example, by preparing a die bonding tape and pressing it to a dicing tape.
  • the die bonding tape can be obtained, for example, by applying an adhesive composition onto a release sheet and curing it to form an adhesive layer.
  • the lamination temperature is, for example, 30 to 50°C.
  • the lamination pressure linear pressure is, for example, 0.1 to 20 kgf/cm.
  • the thermal curing of the adhesive composition may be carried out in two separate steps, step (iv-2) and step (v).
  • step (iv-2) the dicing tape and the die bonding tape may be laminated in step (v), and then the resulting product may be cured to further advance the thermal curing (thermal crosslinking) of the photocrosslinkable adhesive layer.
  • the release sheet in step (iv-1) may be replaced with the die-bonding tape in step (v), and the formation of the photocrosslinkable adhesive layer and the lamination of the dicing tape and die-bonding tape may be carried out at the same time.
  • the adhesive composition is applied onto the adhesive layer of the die-bonding tape, thermally cured, and a substrate is laminated before or after thermal curing, thereby obtaining a dicing/die-bonding integrated film.
  • the cured product of the photocrosslinkable pressure-sensitive adhesive (also referred to as a photothermally cured product) can be produced, for example, by a method including a step (vi) of irradiating the photocrosslinkable pressure-sensitive adhesive with UV light to form a crosslinked structure.
  • Light sources used for UV irradiation include, for example, high-pressure mercury lamps, extra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, and black lights.
  • the amount of UV irradiation applied to the photocrosslinkable adhesive is preferably 50 to 3,000 mJ/cm 2 , more preferably 100 to 600 mJ/cm 2.
  • the amount of UV irradiation applied to the photocrosslinkable adhesive is 50 mJ/cm 2 or more, the crosslink density of the photocrosslinkable adhesive can be improved at a sufficiently fast curing speed by UV irradiation. Therefore, when the photocrosslinkable adhesive is used in the adhesive layer, the adhesive strength of the adhesive layer after UV irradiation can be sufficiently reduced. When the photocrosslinkable adhesive is used in the resist, the strength can be improved.
  • This reaction raw material liquid was continuously irradiated with UV having a wavelength of 385 nm and an illuminance of 1.5 mW/cm 2 , and reacted at room temperature (25 ° C) for 10 hours.
  • the temperature of the reactant was raised to 60 ° C, and a mixture of 16 parts by mass (17.3 mol) of 2-isocyanatoethyl methacrylate and 0.19 parts by mass of dibutyltin dilaurate as a urethanization catalyst was dropped through a dropping funnel. After the dropwise addition was completed, the reaction system was maintained at 70°C for 4 hours to eliminate the isocyanato group.
  • the temperature of the reactants was maintained at 80°C, and the reaction was allowed to proceed for 10 hours.
  • the temperature of the reactants was lowered to 60°C, and a mixture of 16 parts by mass (17.3 mol) of 2-isocyanatoethyl methacrylate and 0.19 parts by mass of dibutyltin dilaurate, a urethanization catalyst, was dropped through a dropping funnel.
  • the reaction system was held at 70°C for 4 hours to eliminate the isocyanato group.
  • ethyl acetate was added so that the solid content became 35% by mass.
  • modified (meth)acrylic resin (A) or (cA), photopolymerization initiator (B) and crosslinking agent (C) shown in Table 2 were added to a plastic container in the amounts (parts by mass) shown in Table 2 and stirred to obtain adhesive compositions (D1) to (D9) and (cD1) to (cD4).
  • the values for modified (meth)acrylic resin (A) and (cA) in Table 2 are the solids content of the solution used, i.e., the amount (parts by mass) of modified (meth)acrylic resin (A) and (cA) used.
  • Example 2-1 Preparation of dicing tape A silicone-based light release PET film (Toyobo Co., Ltd., product name: E7006, thickness 25 ⁇ m) was prepared as a separator, and the adhesive composition (D1) was applied to the release-treated surface using an applicator so that the thickness after heat curing was 20 ⁇ m, and the adhesive composition layer was formed by heating and drying at 100 ° C. for 2 minutes. Next, a PO film having a thickness of 90 ⁇ m was prepared as a sheet-like substrate. The PO film was attached to the adhesive composition layer using a rubber roller so that the corona-treated surface of the PO film was adhered to the exposed surface of the adhesive composition layer. The adhesive composition layer was cured in an oven at 40 ° C. for 3 days, and the adhesive composition layer was crosslinked and cured to obtain a dicing tape of Example 2-1.
  • Example 2-2 to 2-9 and Comparative Examples 2-1 to 2-4 Preparation of dicing tape Dicing tapes of Examples 2-2 to 2-9 and Comparative Examples 2-1 to 2-4 were obtained in the same manner as in Example 2-1, except that the pressure-sensitive adhesive composition shown in Table 2 was used instead of the pressure-sensitive adhesive composition (D1).
  • the adhesive layer was exposed by peeling off the cover film on one side of a die bonding film (FH-D25T-50, Resonac Co., Ltd.) in which both sides of the adhesive layer were protected by cover films.
  • This adhesive layer was bonded with the photocrosslinkable adhesive layer of the dicing tape of Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-4, in which the light release PET film was peeled off to expose the photocrosslinkable adhesive layer, using a rubber roller.
  • the film was left at room temperature for one day to obtain a dicing/die bonding integrated film.
  • the peel strength of the dicing tape to the die bonding film was measured using a tensile tester (VPA-H200, Kyowa Interface Science Co., Ltd.). The measurement conditions were a peel angle of 30° and a tensile speed of 600 mm/min. The storage of the sample and the measurement of the peel strength were performed under an environment of a temperature of 23°C and a relative humidity of 40%. The results are shown in Table 2.
  • Tensile test (elongation, tensile strength)
  • the dicing tape was cut into a dumbbell shape with a width of 5 mm and a length of 50 mm as shown in FIG. 1, and the light release PET film and the PO film were peeled off to expose the adhesive layer.
  • a tensile test was performed on the adhesive layer using a tensile tester (manufactured by Stable MicroSystems) under conditions of a gauge length of 20 mm and a tensile speed of 100 mm/min, and the elongation at break and the breaking strength (tensile strength) were measured.
  • the elongation was calculated according to the following formula.
  • the silicon wafer after stealth dicing was polished to a thickness of 30 ⁇ m.
  • a grinder polisher device (DGP8761, Disco Corporation) was used for polishing.
  • the adhesive layer of the dicing/die bonding integrated film was attached to the polished silicon wafer under the following conditions, with the substrate side of the dicing tape facing the dicing ring. Then, the BG tape was peeled off from the surface of the silicon wafer.
  • DFM2800 Disco Corporation
  • Application temperature 70°C
  • Application speed 10 mm/s -
  • Application tension level Level 6
  • a die separator (DDS2300, Disco Corporation) was used to cool and expand under the following conditions. After that, the base layer (PO film) of the dicing/die bonding integrated film was heat-shrunk under the following conditions. Through these steps, the silicon wafer and adhesive layer were singulated into multiple adhesive chips (size 10 mm x 10 mm).
  • the photocrosslinkable pressure-sensitive adhesive layer was irradiated with ultraviolet light from the surface of the dicing tape facing the substrate under the following conditions, thereby curing the photocrosslinkable pressure-sensitive adhesive layer and reducing its adhesive strength to the adhesive layer.
  • ⁇ Dicing ability (kerf width)> The spacing (kerf width) between the chips with adhesive pieces after individualization was measured using a microscope.
  • the kerf width in the MD/TD direction was measured at two points each on the outer periphery of the silicon wafer (top, bottom, left, right) and one point in the center (18 points in total), and the average value was calculated. Evaluation was based on the following criteria. The results are shown in Table 2.
  • C The average kerf width was 50 ⁇ m or more and less than 70 ⁇ m.
  • a modified (meth)acrylic resin having a high molecular weight and a narrow molecular weight distribution can be obtained.
  • a photocrosslinkable adhesive layer produced using the modified (meth)acrylic resin can be particularly preferably used as an adhesive layer for dicing tapes and integrated dicing and die-bonding films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une résine (méth)acrylique modifiée obtenue par ajout d'un composé éthyléniquement insaturé contenant un groupe isocyanate (a) à une partie d'un groupe hydroxy à chaîne latérale d'un copolymère (A-0) ayant une unité structurale dérivée d'un (méth)acrylate contenant un groupe hydroxy (m-1) et une unité structurale dérivée d'un (méth)acrylate d'alkyle (m-2), le poids moléculaire moyen en poids (Mw) étant de 30 × 104 à 150 × 104, et la distribution de poids moléculaire (Mw/Mn) étant de 1,1 à 3,0.
PCT/JP2024/013418 2023-05-29 2024-04-01 Résine (méth)acrylique modifiée, composition adhésive et feuille adhésive Pending WO2024247470A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012025808A (ja) * 2010-07-21 2012-02-09 Nippon Synthetic Chem Ind Co Ltd:The アクリル系粘着剤、粘着シート、アクリル系樹脂組成物
JP2018138682A (ja) * 2018-06-18 2018-09-06 積水化学工業株式会社 粘着テープ
JP2022023819A (ja) * 2020-07-27 2022-02-08 三菱ケミカル株式会社 活性エネルギー線硬化性剥離型粘着剤組成物、活性エネルギー線硬化性剥離型粘着シートおよび活性エネルギー線硬化性剥離型粘着剤
JP2024000458A (ja) * 2022-06-20 2024-01-05 マクセル株式会社 ダイシングテープおよびダイシングテープを使用する、半導体チップおよび半導体装置の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012025808A (ja) * 2010-07-21 2012-02-09 Nippon Synthetic Chem Ind Co Ltd:The アクリル系粘着剤、粘着シート、アクリル系樹脂組成物
JP2018138682A (ja) * 2018-06-18 2018-09-06 積水化学工業株式会社 粘着テープ
JP2022023819A (ja) * 2020-07-27 2022-02-08 三菱ケミカル株式会社 活性エネルギー線硬化性剥離型粘着剤組成物、活性エネルギー線硬化性剥離型粘着シートおよび活性エネルギー線硬化性剥離型粘着剤
JP2024000458A (ja) * 2022-06-20 2024-01-05 マクセル株式会社 ダイシングテープおよびダイシングテープを使用する、半導体チップおよび半導体装置の製造方法

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