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WO2020049829A1 - Composition adhésive sensible à la pression et feuille adhésive sensible à la pression - Google Patents

Composition adhésive sensible à la pression et feuille adhésive sensible à la pression Download PDF

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Publication number
WO2020049829A1
WO2020049829A1 PCT/JP2019/023913 JP2019023913W WO2020049829A1 WO 2020049829 A1 WO2020049829 A1 WO 2020049829A1 JP 2019023913 W JP2019023913 W JP 2019023913W WO 2020049829 A1 WO2020049829 A1 WO 2020049829A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
resin
meth
adhesive composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/023913
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English (en)
Japanese (ja)
Inventor
一博 佐々木
達宏 池谷
中西　健一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to KR1020217003048A priority Critical patent/KR102408062B1/ko
Priority to CN201980052256.8A priority patent/CN112534015B/zh
Priority to JP2020541026A priority patent/JP7363791B2/ja
Publication of WO2020049829A1 publication Critical patent/WO2020049829A1/fr
Anticipated expiration legal-status Critical
Priority to JP2023166256A priority patent/JP7568024B2/ja
Priority to JP2023166260A priority patent/JP7687370B2/ja
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F8/14—Esterification
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • 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 invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet.
  • various adhesive sheets have been used in a semiconductor manufacturing process and the like. Specifically, there are a protective sheet for protecting the wafer in the back grinding process of the semiconductor wafer and a fixing sheet used in the dicing process for cutting the semiconductor wafer into element pieces. These pressure-sensitive adhesive sheets are re-peelable pressure-sensitive adhesive sheets that are adhered to a semiconductor wafer as an adherend and peeled off from the adherend after a predetermined processing step is completed.
  • a pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer of the removable pressure-sensitive adhesive sheet a pressure-sensitive adhesive composition having an ethylenically unsaturated group in a molecule and containing a UV-curable resin is known.
  • Patent Literature 1 discloses that a (meth) acrylic polymer having two or more hydroxyl groups in a side chain is reacted with a compound having an isocyanato group in the presence of a first catalyst to form a (meth) acrylic polymer having a urethane bond. Forming a polymer, and reacting the (meth) acrylic polymer having a urethane bond with a compound having two or more isocyanato groups in one molecule in the presence of a second catalyst to form a pressure-sensitive adhesive layer.
  • a method for producing a pressure-sensitive adhesive sheet is disclosed, which includes a forming step, wherein the first catalyst is a complex of at least one metal selected from zirconium, titanium, and aluminum, and the second catalyst is an amine-based catalyst.
  • the re-peelable pressure-sensitive adhesive sheet has sufficient adhesive strength to the adherend when performing the predetermined processing step, and can be easily peeled from the adherend after the predetermined processing step is completed (easy to be performed). It is required that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is not transferred to the adherend after peeling (no adhesive residue).
  • the conventional pressure-sensitive adhesive sheet has not satisfied all of the above conditions. In particular, when the pressure-sensitive adhesive sheet is stuck to the adherend, the adherend is processed at a high temperature of about 200 ° C., and then the adhesive sheet is peeled off by UV irradiation, it has been a problem that adhesive residue easily occurs. .
  • the present invention has been made in view of the above circumstances, and has a sufficient adhesive strength to an adherend by using it as a material for forming an adhesive layer of an adhesive sheet.
  • a pressure-sensitive adhesive composition capable of obtaining a pressure-sensitive adhesive sheet that can obtain excellent easy-peeling property and hardly generate adhesive residue even when the body is returned to room temperature, returned to room temperature, and peeled after UV irradiation.
  • Another object of the present invention is to provide a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition.
  • a carboxy group-containing resin (b) obtained by polymerizing the carboxy group-containing ethylenically unsaturated monomer (a) as an essential monomer component, and an alicyclic epoxy group-containing ethylenically unsaturated compound (c) It has been found that a pressure-sensitive adhesive composition containing, as essential components, a resin (A) obtained by an addition reaction with a photopolymerization initiator (B) may be used.
  • the pressure-sensitive adhesive composition containing the resin (A) and the photopolymerization initiator (B) has good heat resistance because the resin (A) has a structure derived from an alicyclic compound. Further, in the above-mentioned pressure-sensitive adhesive composition, the unsaturated bond in the resin (A) forms a three-dimensional crosslinked structure by irradiation with ultraviolet rays (UV), and is cured, so that the adhesive strength is changed. Specifically, before the adhesive composition is irradiated with UV, a sufficient adhesive force is obtained on the adherend, and after the UV irradiation, the adhesive force is reduced to obtain excellent easy peelability. And adhesive residue on the adherend after peeling can be sufficiently prevented.
  • UV ultraviolet rays
  • a pressure-sensitive adhesive composition comprising a resin (A) represented by the following general formula (1-1) and a photopolymerization initiator (B).
  • K is more than 0 to 92 or less.
  • L is 0 to 50. is greater than 0 to 90 or less is .k, l, .R 1 ⁇ R 4 the sum of m is 65 ⁇ 95 .n is 5-35 is -H or -CH 3 .
  • R 6 is an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • R 7 is —H or — (CH 2 ) J —COOH (where j is 1 or 2)
  • R 8 is the above general formula (1-2) or (1-3).
  • p and q are any one selected from 0, 1, and 2.
  • s is 0 when p is 0, and 1 when p is 1 or 2.
  • .R 9 is -H or -CH 3.
  • a pressure-sensitive adhesive sheet comprising:
  • the pressure-sensitive adhesive sheet By using the pressure-sensitive adhesive composition of the present invention as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet has a sufficient adhesive strength to the adherend, and the adherend to which the pressure-sensitive adhesive sheet is attached is brought to a high temperature state. Even when the temperature is returned to room temperature and peeled after UV irradiation, excellent peelability is obtained, and a pressure-sensitive adhesive sheet with less adhesive residue is obtained.
  • the pressure-sensitive adhesive composition of the present embodiment contains a resin (A) and a photopolymerization initiator (B).
  • Resin (A) The resin (A) contained in the pressure-sensitive adhesive composition of the present embodiment is a compound represented by the following general formula (1-1).
  • K is more than 0 to 92 or less.
  • L is 0 to 50. is greater than 0 to 90 or less is .k, l, .R 1 ⁇ R 4 the sum of m is 65 ⁇ 95 .n is 5-35 is -H or -CH 3 .
  • R 6 is an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • R 7 is —H or — (CH 2 ) J —COOH (where j is 1 or 2)
  • R 8 is the above general formula (1-2) or (1-3).
  • p and q are any one selected from 0, 1, and 2.
  • s is 0 when p is 0, and 1 when p is 1 or 2.
  • .R 9 is -H or -CH 3.
  • k is more than 0 to 92 or less.
  • 1 is 0 to 50.
  • m is more than 0 to 90 or less.
  • the sum of k, l and m is 65-95.
  • the pressure-sensitive adhesive composition will have sufficient adhesion to an adherend before UV irradiation.
  • the total of k, l, and m is preferably from 70 to 94, and more preferably from 80 to 90.
  • repeating unit k the repeating unit enclosed by k ( ⁇ ⁇ ⁇ ⁇ ) (hereinafter referred to as “repeating unit k”) is an essential repeating unit.
  • the repeating unit k contributes to the adhesive strength of the adhesive composition before UV irradiation.
  • the number of repetitions k of the repeating unit k is more than 0 to 92 or less, preferably 45 to 90, and more preferably 60 to 88.
  • repeating unit l there may be no repeating unit (hereinafter, referred to as “repeating unit l”) enclosed in parentheses (). In other words, the number of repetitions of the repeating unit 1 may be zero.
  • the repeating unit l contributes to the heat resistance of the pressure-sensitive adhesive composition.
  • the number of repetitions 1 of the repeating unit 1 is from 0 to 50, preferably from 4 to 40, and more preferably from 5 to 30.
  • the repeating unit enclosed by m () (hereinafter referred to as “repeating unit m”) is an essential repeating unit.
  • the repeating unit m contributes to the adhesive strength and heat resistance of the adhesive composition before UV irradiation.
  • the repeating unit m reacts with the cross-linking agent to improve the cohesive strength of the pressure-sensitive adhesive composition.
  • the repeating number m of the repeating unit m is more than 0 to 90 or less, preferably 1 to 15, and more preferably 1 to 5.
  • the repeating unit (hereinafter referred to as “repeating unit n”) enclosed in () by n is an essential repeating unit.
  • the repeating unit n contributes to the heat resistance of the pressure-sensitive adhesive composition.
  • the number of repetitions n of the repeating unit n is 5 to 35, preferably 10 to 33, more preferably 10 to 20.
  • an unsaturated bond in the resin (A) forms a three-dimensional cross-linked structure by UV irradiation, and is cured, and the adhesive strength is reduced to an appropriate range.
  • n is 5 or more, an effect of improving heat resistance due to the structure derived from the alicyclic compound can be obtained.
  • the pressure-sensitive adhesive composition containing the resin (A) can achieve a better balance between the adhesive strength before ultraviolet (UV) irradiation and the adhesive strength after UV irradiation. Become. As a result, a sufficient pressure-sensitive adhesive force is obtained on the adherend before the UV irradiation, and the pressure-sensitive adhesive force is reduced after the UV irradiation, so that a more excellent peelability is obtained. In addition, the pressure-sensitive adhesive composition does not have an excessively high adhesive strength even when the temperature is returned to room temperature after being brought to a high temperature state before the UV irradiation. Glue residue on the body is less likely to occur.
  • R 1 is —H or —CH 3 , preferably —H.
  • R 5 is an alkyl group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 2, 4 or 8 carbon atoms.
  • the repeating unit k may be a plurality of types of repeating units having different R 1 and R 5 .
  • the molar composition ratio k of the repeating unit k indicates the total of the molar compositions of the plurality of types of repeating units. For example, when the repeating unit k includes repeating units A and B having different R 1 and / or R 5 , the molar composition of the repeating unit A is 2 mol%, and the molar composition of the repeating unit B is 3 mol%.
  • the molar composition ratio k of the number of repetitions k is “5” by summing the molar composition ratios of the repeating unit A and the repeating unit B.
  • R 2 is —H or —CH 3 , preferably —H.
  • R 6 is an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group having 6 to 20 carbon atoms or an aromatic group having 6 to 10 carbon atoms. Group hydrocarbon groups are preferred.
  • the repeating unit 1 may be a plurality of types of repeating units having different R 2 and R 6 . When the repeating unit 1 includes a plurality of types of repeating units, the molar composition ratio 1 of the repeating unit 1 indicates the total of the molar compositions of the plurality of types of repeating units.
  • R 3 is —H or —CH 3 , preferably —H.
  • R 7 is —H or — (CH 2 ) j —COOH (where j is 1 or 2), preferably —H.
  • the repeating unit m may be a plurality of types of repeating units having different R 3 and R 7 .
  • the molar composition ratio m of the repeating unit m indicates the sum of the molar composition ratios of a plurality of types of repeating units.
  • R 4 is —H or —CH 3 , preferably —H.
  • R 8 is the formula (1-2) or (1-3).
  • Each of the groups represented by the formulas (1-2) and (1-3) includes a structure derived from an alicyclic compound and has a function of improving the heat resistance of the pressure-sensitive adhesive composition.
  • p and q are any one selected from 0, 1, and 2.
  • s is 0 when p is 0, and 1 when p is 1 or 2.
  • R 9 is —H or —CH 3 .
  • the repeating unit n may be a plurality of types of repeating units having different R 4 and R 8 . In this case, the molar composition ratio n of the repeating unit n indicates the sum of the molar composition ratios of a plurality of types of repeating units.
  • the resin (A) represented by the formula (1-1) includes a random copolymer, a block copolymer, and an alternating copolymer composed of a repeating unit k, a repeating unit 1, a repeating unit m, and a repeating unit n. Any of these may be used.
  • the resin (A) represented by the formula (1-1) may not contain the repeating unit 1 and may be a random copolymer or a block copolymer composed of the repeating unit k, the repeating unit m, and the repeating unit n. Or an alternating copolymer.
  • the weight average molecular weight of the resin (A) is preferably from 200,000 to 1,000,000, more preferably from 300,000 to 800,000.
  • the weight average molecular weight of the resin (A) is 200,000 or more, when the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition is peeled off after being adhered to the adherend, the pressure-sensitive adhesive layer is not adhered. Makes it more difficult to remain.
  • the weight average molecular weight of the resin (A) is 1,000,000 or less, the effect that the viscosity of the resin (A) does not become too high and the workability is good can be obtained.
  • the weight average molecular weight of the resin (A) is a value measured by the method described in Examples.
  • the glass transition temperature (Tg) of the resin (A) is preferably from -80 to 0 ° C, more preferably from -60 to -10 ° C, and still more preferably from -50 to -10 ° C.
  • the Tg of the resin (A) is a value measured by the method described in Examples.
  • the acid value of the resin (A) is preferably more than 0 to 20 mgKOH / g, and more preferably 3 to 10 mgKOH / g.
  • the adherend after heating is excellent and good.
  • the pressure-sensitive adhesive composition contains a crosslinking agent
  • the acid value of the resin (A) is a value measured by the method described in Examples.
  • the resin (A) contained in the pressure-sensitive adhesive composition of the present embodiment can be produced, for example, by the following method.
  • a raw material monomer containing a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d) is polymerized to produce a carboxy group-containing resin (b).
  • the ethylenically unsaturated monomer (d) may include a monomer that forms a repeating unit k after polymerization and a monomer that forms a skeleton of the repeating unit 1 after polymerization.
  • a resin (A) is produced by an addition reaction between the carboxy group-containing resin (b) and the specific alicyclic epoxy group-containing ethylenically unsaturated compound (c).
  • the carboxy group-containing ethylenically unsaturated monomer (a) used when producing the carboxy group-containing resin (b) is a monomer that forms a skeleton of a repeating unit m by polymerization.
  • the carboxy group-containing ethylenically unsaturated monomer (a) has one carboxy group.
  • Examples of the carboxy group-containing ethylenically unsaturated monomer (a) include (meth) acrylic acid, ⁇ -carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
  • (meth) acrylic acid and / or ⁇ -carboxyethyl (meth) acrylate are preferably used as the carboxy group-containing ethylenically unsaturated monomer (a) from the viewpoint of reactivity.
  • Method acryl in this specification means “acryl” or “methacryl”.
  • (Meth) acrylate means “acrylate” or “methacrylate”.
  • the carboxy group-containing resin (b) comprises a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) ( and d) is obtained by copolymerizing a raw material monomer containing at least
  • the carboxy group-containing resin (b) is a component serving as a skeleton of the resin (A) represented by the formula (1-1).
  • the repeating unit k, the repeating unit 1 and the repeating unit m are all repeating units derived from the carboxy group-containing resin (b).
  • ethylenically unsaturated monomer (d) one or more monomers that form a skeleton of the repeating unit k by polymerization are used.
  • ethylenically unsaturated monomer (d) one or more monomers that form a skeleton of the repeating unit 1 by polymerization together with a monomer that forms a skeleton of the repeating unit k by polymerization are used. Is also good.
  • the ethylenically unsaturated monomer (d), which forms a skeleton of the repeating unit k by polymerization, is an alkyl (meth) acrylate having 1 to 16 carbon atoms, and from the viewpoint of adjusting the peel strength of the pressure-sensitive adhesive composition. It preferably contains an alkyl (meth) acrylate having 2 to 16 carbon atoms, and more preferably contains an alkyl (meth) acrylate having 4 to 12 carbon atoms.
  • methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate are preferred.
  • Examples of the ethylenically unsaturated monomer (d) which forms a skeleton of a repeating unit 1 by polymerization include a (meth) acrylate having a cyclic alkyl group having 3 to 30 carbon atoms and an aromatic monomer having 6 to 20 carbon atoms.
  • Group-containing (meth) acrylates and the like are examples of the ethylenically unsaturated monomer (d) which forms a skeleton of a repeating unit 1 by polymerization.
  • Examples of the cyclic alkyl group-containing (meth) acrylate having 3 to 30 carbon atoms used as the ethylenically unsaturated monomer (d) which forms a skeleton of the repeating unit 1 by polymerization include cyclohexyl (meth) acrylate, Norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxy Ethyl (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate and the like can be mentioned.
  • isobornyl (meth) acrylate When the cyclic alkyl (meth) acrylate is contained in the raw material monomer of the carboxy group-containing resin (b), the pressure-sensitive adhesive composition containing the resin (A) produced using the carboxy group-containing resin (b) Good heat resistance.
  • Examples of the (meth) acrylate containing an aromatic group having 6 to 20 carbon atoms, which is used as the ethylenically unsaturated monomer (d) which forms a skeleton of a repeating unit 1 by polymerization, include benzyl (meth) acrylate and phenoxyethyl.
  • the raw material monomers of the carboxy group-containing resin (b) include not only the above-mentioned carboxy group-containing ethylenically unsaturated monomer (a) and the above-mentioned ethylenically unsaturated monomer (d), but also A monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) may be contained.
  • the ethylenically unsaturated monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) includes alkoxyalkyl (meth) acrylate, Alkoxy (poly) alkylene glycol (meth) acrylate, hydroxy group-containing (meth) acrylate, fluorinated alkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acrylamide and the like.
  • alkoxyalkyl (meth) acrylate examples include ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, and 2-ethoxyethoxyethyl (meth). Acrylate and the like.
  • ⁇ Alkoxy (poly) alkylene glycol (meth) acrylates include, for example, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and methoxydipropylene glycol (meth) acrylate.
  • Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, Examples thereof include 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, and 3-methylpentanediol (meth) acrylate.
  • fluorinated alkyl (meth) acrylate examples include octafluoropentyl (meth) acrylate.
  • dialkylaminoalkyl (meth) acrylate examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and the like.
  • Examples of (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropylacrylamide, and N-hexyl (meth) acrylamide , N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, diacetoneacrylamide and the like.
  • Specific examples other than the above of the monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) include acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinyl pyridine, N-vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol , Hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol monovinyl ether or diethylene glycol monovinyl ether, methyl vinyl ketone, allyl Trimethyl ammonium chloride, dimethyl allyl vinyl ketone.
  • the method for producing the carboxy group-containing resin (b) is not particularly limited.
  • a raw material monomer containing a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d), which are constituents of the carboxy group-containing resin (b), is polymerized by known polymerization. It is obtained by copolymerizing according to the method.
  • a polymerization method a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, an alternating copolymerization method, or the like can be used.
  • a radical polymerization initiator and / or a solvent are used as necessary.
  • the radical polymerization initiator is not particularly limited, and can be appropriately selected from known ones.
  • examples of the radical polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2′-azobis (2 , 4-Dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4 Azo-based polymerization initiators such as -trimethylpentane) and dimethyl-2,2'-azobis (2-methylpropionate); benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t- Butylperoxybenzoate, dicum
  • radical polymerization initiators may be used alone or in combination of two or more.
  • the amount of the radical polymerization initiator to be used is preferably 0.01 to 5 parts by mass, and preferably 0.02 to 4 parts by mass, based on 100 parts by mass of the raw material monomer of the carboxy group-containing resin (b). Is more preferable, and the content is more preferably 0.03 to 3 parts by mass.
  • solvent for polymerization used when producing the carboxy group-containing resin (b)
  • various general solvents can be used.
  • the solvent include esters such as ethyl acetate, n-propyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene, xylene and benzene; and aliphatic hydrocarbons such as n-hexane and n-heptane.
  • Cyclohexane alicyclic hydrocarbons such as methylcyclohexane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycols such as ethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, propylene glycol monomethyl ether, dipropylene glycol monomethyl Glycol ethers such as ether, and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate. These solvents may be used alone or in combination of two or more.
  • the carboxy group-containing resin (b) When producing the carboxy group-containing resin (b), the carboxy group-containing ethylenically unsaturated monomer (a), the ethylenically unsaturated monomer (d), and other
  • the content of the carboxy group-containing ethylenically unsaturated monomer (a) in the raw material monomer containing the monomer is preferably 5 to 40% by mass, more preferably 7 to 30% by mass, 10 to 25% by mass is more preferred.
  • the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound By setting the content of the carboxy group-containing ethylenically unsaturated monomer (a) in the raw material monomer in the above range, the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (The adhesive strength before the UV irradiation of the adhesive layer obtained from the adhesive composition containing the resin (A) produced by the addition reaction with c) is improved.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) is an ethylenically unsaturated group-containing compound having an alicyclic epoxy group and represented by the general formula (1-2) or the general formula (1-3).
  • the alicyclic epoxy group in the present embodiment refers to an epoxy group formed by bonding one oxygen to two adjacent carbon atoms on the ring of the alicyclic hydrocarbon compound.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) is represented by the following partial structural formula (1-2 ′) or (1- ′) in the repeating unit n of the photosensitive resin (A) represented by the formula (1-1). 3 ').
  • the partial structural formula (1-2 ′) or (1-3 ′) in the repeating unit n in the formula (1-1) is a group derived from the alicyclic epoxy group-containing ethylenically unsaturated compound (c). .
  • q is any one selected from 0, 1, and 2.
  • R 9 is —H or —CH 3.
  • Examples of the alicyclic epoxy group-containing ethylenically unsaturated compound (c) include compounds represented by the following formula (1) or (2).
  • R 9 is —H or —CH 3.
  • Q is any one selected from 0, 1, and 2.
  • R 9 is —H or —CH 3.
  • Q is any one selected from 0, 1, and 2.
  • R 9 is —H or —CH 3 . q is any one selected from 0, 1, and 2, and q is preferably 1. In the formula (2), R 9 is —H or —CH 3 . q is any one selected from 0, 1, and 2, and q is preferably 1.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) is preferably a compound represented by the formula (1), particularly preferably 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) may be used alone or in combination of two or more.
  • the resin (A) of the present embodiment is obtained by adding an alicyclic epoxy group of the alicyclic epoxy group-containing ethylenically unsaturated monomer (c) to the carboxy group of the carboxy group-containing resin (b). Can be manufactured.
  • the resin (A) is preferably 0.2 to 0.99 mol, more preferably 0.3 to 0.95 mol, and still more preferably 0.6 to 0.9 mol, per 1 mol of the carboxy group of the carboxy group-containing resin (b). It is preferable to produce the compound by subjecting 95 mol of an alicyclic epoxy group-containing ethylenically unsaturated compound (c) to an addition reaction.
  • the pressure-sensitive adhesive composition has a low adhesive strength even when the temperature is returned to room temperature after being brought to a high temperature state before UV irradiation, and excellent peelability after UV irradiation is obtained, and the adherend after peeling is obtained. Glue residue can be more effectively prevented.
  • the temperature of the addition reaction in producing the resin (A) is preferably from 80 to 130 ° C, particularly preferably from 90 to 120 ° C.
  • the temperature of the addition reaction is 80 ° C. or higher, a sufficient reaction rate can be obtained.
  • the temperature of the addition reaction is 130 ° C. or lower, it is possible to prevent a double bond portion from being crosslinked by heat-induced radical polymerization, thereby preventing the formation of a gel.
  • a known catalyst can be used for the addition reaction in the production of the resin (A), if necessary.
  • the catalyst include triethylamine, tributylamine, dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,5-diazabicyclo [4,3,0] non-5-ene Tertiary amines such as 1,4-diazabicyclo [2,2,2] octane, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, Alkylguanidines such as methylguanidine, triphenylphosphine, dimethylphenylphosphine, tricyclohexylphosphine, tributylphosphine, tris (4-methylphenyl) phosphine, tri
  • the amount of the catalyst used in the addition reaction is 0.01 to 30 parts by mass based on 100 parts by mass of the total of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated monomer (c). Is preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 2 parts by mass.
  • a gas having a polymerization inhibiting effect may be introduced into the reaction system, or a polymerization inhibitor may be added. Gelation during the addition reaction can be prevented by introducing a gas having a polymerization inhibiting effect into the reaction system or adding a polymerization inhibitor.
  • the gas having a polymerization inhibiting effect include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air.
  • polymerization inhibitors can be used, and are not particularly limited.
  • One of these polymerization inhibitors may be used alone, or two or more thereof may be used in combination.
  • the amount of the polymerization inhibitor to be used is 0.005 to 5 parts by mass with respect to 100 parts by mass of the total of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated monomer (c). Is preferably 0.03 to 3 parts by mass, and most preferably 0.05 to 1.5 parts by mass. If the amount of the polymerization inhibitor is too small, the polymerization inhibition effect may not be sufficient. On the other hand, if the amount of the polymerization inhibitor is too large, the exposure sensitivity of the resin (A) may decrease. It is more preferable to use a gas having a polymerization inhibiting effect and a polymerization inhibitor in combination, since the amount of the polymerization inhibitor to be used can be reduced or the polymerization inhibiting effect can be increased.
  • Photopolymerization initiator (B) examples include benzophenone, benzyl, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2.
  • Examples of the photopolymerization initiator (B) include sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Acylphosphine oxides such as 2,6-trimethylbenzoylphenylethoxyphosphine oxide; quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; sulfochloride-based photopolymerization initiators; thioxanthones such as thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone A system photopolymerization initiator or the like may be used.
  • sulfide photopolymerization initiators such as diphenyl disulfide, dibenzy
  • photopolymerization initiators (B) 1-hydroxycyclohexylphenyl ketone and / or 2,4,6-trimethylbenzoyldiphenylphosphine oxide may be used from the viewpoint of solubility in the pressure-sensitive adhesive composition. preferable.
  • the above photopolymerization initiators (B) may be used alone or in combination of two or more.
  • the photopolymerization initiator (B) contained in the pressure-sensitive adhesive composition is preferably 0.1 to 5.0 parts by mass, and more preferably 0.5 to 2.0 parts by mass based on 100 parts by mass of the resin (A). Is more preferable.
  • the content of the photopolymerization initiator (B) is 0.1 parts by mass or more based on 100 parts by mass of the resin (A)
  • the pressure-sensitive adhesive composition is cured at a sufficiently high curing rate by UV irradiation, and the UV irradiation is performed.
  • the adhesive strength of the adhesive composition after irradiation becomes sufficiently small, which is preferable.
  • the content of the photopolymerization initiator (B) is 5.0 parts by mass or less, when the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition is peeled off after being attached to the adherend, the pressure-sensitive adhesive is The agent layer hardly remains on the adherend. Further, even if the content of the photopolymerization initiator (B) exceeds 5.0 parts by mass, no effect corresponding to the content of the photopolymerization initiator (B) is obtained.
  • the pressure-sensitive adhesive composition of the present embodiment may contain not only the resin (A) and the photopolymerization initiator (B) but also a crosslinking agent (C).
  • a crosslinking agent (C) By containing the cross-linking agent (C), a pressure-sensitive adhesive composition having a better balance between the pressure-sensitive adhesive strength before UV irradiation and the pressure-sensitive adhesive strength after UV irradiation is obtained.
  • the crosslinking agent (C) is not particularly limited, but is preferably a compound having two or more functional groups reactive with the hydroxyl group of the repeating unit n or the hydroxyl group of the repeating unit n and the carboxy group of the repeating unit m.
  • 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 (N, N'-diglycidylaminomethyl) cyclohexane, 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 bis (4-
  • Epoxy compound Tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide) , Aziridine compounds such as N, N'-hexamethylene-1,6-bis (1-aziridinecarboxamide); Melamine-based compounds such as hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexaptoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine are exemplified.
  • crosslinking agent (C) it is preferable to use an epoxy compound and / or an isocyanate compound because the reactivity with the resin (A) is good.
  • the above crosslinking agents (C) may be used alone or in combination of two or more.
  • the crosslinking agent (C) contained in the pressure-sensitive adhesive composition is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin (A). More preferably, it is 0.1 to 1.0 part by mass.
  • the content of the crosslinking agent (C) is at least 0.05 part by mass with respect to 100 parts by mass of the resin (A)
  • a three-dimensional crosslinked structure is sufficiently formed in the pressure-sensitive adhesive composition.
  • the adhesive strength of the adhesive composition after UV irradiation is sufficiently reduced, which is preferable.
  • the content of the crosslinking agent (C) is 10 parts by mass or less based on 100 parts by mass of the resin (A)
  • the adhesive force of the pressure-sensitive adhesive composition before UV irradiation becomes good.
  • the pressure-sensitive adhesive composition of the present embodiment may contain components other than the above-mentioned resin (A), photopolymerization initiator (B), and crosslinking agent (C), if necessary.
  • Other components include a tackifier, a solvent, various additives, and the like.
  • Tackifier Conventionally known tackifiers can be used without particular limitation.
  • the tackifier include terpene-based tackifier resins, phenol-based tackifier resins, rosin-based tackifier resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and alicyclic petroleum resins.
  • the content is preferably 30 parts by mass or less, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin (A). More preferred.
  • the solvent can be used for diluting the pressure-sensitive adhesive composition for the purpose of adjusting the viscosity of the pressure-sensitive adhesive composition when applying the pressure-sensitive adhesive composition.
  • an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol can be used. It can.
  • These solvents may be used alone or in combination of two or more.
  • Additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters And other flame retardants, antistatic agents such as surfactants and the like.
  • the pressure-sensitive adhesive composition of the present embodiment can be manufactured by a conventionally known method.
  • the resin (A) and the photopolymerization initiator (B) described above are mixed with a crosslinking agent (C), a tackifier, a solvent, and various additives, which are contained as necessary, using a conventionally known method. Then, it can be produced by stirring.
  • the pressure-sensitive adhesive composition of the present embodiment is suitable as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive composition of the present embodiment is preferable as a material for forming a pressure-sensitive adhesive layer of a removable pressure-sensitive adhesive sheet. Since the pressure-sensitive adhesive composition of this embodiment contains the resin (A) represented by the formula (1-1) and the photopolymerization initiator (B), it is used as a material for forming a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet.
  • the adhesive sheet having a sufficient adhesive strength to the adherend is obtained.
  • the adhesive sheet provides excellent easy peelability after UV irradiation and hardly causes adhesive residue.
  • the pressure-sensitive adhesive sheet of the present invention has a sheet-shaped substrate and a pressure-sensitive adhesive layer formed on the substrate. It is preferable that a release sheet (separator) is provided on the surface of the pressure-sensitive adhesive layer opposite to the substrate. When a release sheet is provided on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be protected by the release sheet until use. When a release sheet is provided on the pressure-sensitive adhesive layer, the operation of peeling the release sheet to expose the pressure-sensitive adhesive layer and pressing the pressure-sensitive adhesive layer (adhering surface) to the adherend can be efficiently performed. .
  • the pressure-sensitive adhesive sheet of this embodiment may be used as a pressure-sensitive adhesive tape formed into a shape according to the shape of the adherend by a punching method or the like. Further, the pressure-sensitive adhesive sheet of the present embodiment may be wound and cut to be used as a pressure-sensitive adhesive tape.
  • a known sheet material can be appropriately selected and used. It is preferable to use a resin sheet made of a transparent resin material as the base material.
  • the resin material include polyolefins such as polyethylene (PE) and polypropylene (PP); polyester sheets such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate; polyvinyl chloride (PVC); polyimide (PI) Polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA); polytetrafluoroethylene (PTFE), and the like.
  • PE polyolefins
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PVC polyvinyl chloride
  • PI polyimide
  • PPS polyphenylene sulfide
  • EVA ethylene vinyl acetate
  • PTFE polytetrafluoroethylene
  • the resin sheet When a resin sheet is used as the base material, the resin sheet may have a single-layer structure or a multilayer structure having two or more layers (for example, a three-layer structure).
  • the resin material constituting each layer may be a resin material containing only one type or a resin material containing two or more types.
  • the thickness of the substrate can be appropriately selected according to the use of the pressure-sensitive adhesive sheet, the material of the substrate, and the like.
  • the base material preferably has a thickness of, for example, 10 to 1000 ⁇ m, More preferably, it is 50 to 300 ⁇ m.
  • the thickness of the base material is 10 ⁇ m or more, the rigidity of the pressure-sensitive adhesive sheet becomes high (stiffness becomes high). Therefore, when the pressure-sensitive adhesive sheet is attached to or adhered to an adherend such as a wafer, the pressure-sensitive adhesive sheet tends to be less likely to wrinkle or float.
  • the thickness of the base material is 10 ⁇ m or more, the pressure-sensitive adhesive sheet attached to the adherend is easily peeled off from the adherend, and workability (handling property, handling) is improved.
  • the thickness of the base material is 1000 ⁇ m or less, it is possible to prevent the rigidity of the pressure-sensitive adhesive sheet from becoming too high (stiffness) and lowering the workability.
  • a resin sheet is used as the substrate
  • a conventionally known general sheet forming method for example, extrusion molding, T-die molding, inflation molding, or uniaxial or biaxial stretching molding
  • T-die molding for example, extrusion molding, T-die molding, inflation molding, or uniaxial or biaxial stretching molding
  • uniaxial or biaxial stretching molding is appropriately adopted to form the substrate.
  • the surface of the substrate on the side in contact with the pressure-sensitive adhesive layer may be subjected to a surface treatment for improving the adhesion between the substrate and the pressure-sensitive adhesive layer.
  • a surface treatment for improving the adhesion between the substrate and the pressure-sensitive adhesive layer.
  • the surface treatment include corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, and application of a primer (primer).
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present embodiment includes the above-described pressure-sensitive adhesive composition.
  • the thickness of the pressure-sensitive adhesive layer is preferably from 1 to 100 ⁇ m, more preferably from 2 to 80 ⁇ m, even more preferably from 5 to 50 ⁇ m. When the thickness of the pressure-sensitive adhesive layer is 1 ⁇ m or more, the uniformity of the thickness of the pressure-sensitive adhesive layer is improved. On the other hand, the thickness of the pressure-sensitive adhesive layer is preferably 100 ⁇ m or less, because the solvent can be easily removed even when the pressure-sensitive adhesive layer is formed using a solvent.
  • a release sheet When a release sheet is provided on the surface of the pressure-sensitive adhesive layer opposite to the base material, a known sheet-like material can be appropriately selected and used as the release sheet.
  • the release sheet the same as the above-described resin sheet used as the base material can be used.
  • the thickness of the release sheet can be appropriately selected according to the use of the pressure-sensitive adhesive sheet, the material of the release sheet, and the like.
  • the thickness of the release sheet is preferably, for example, 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and further preferably 25 to 100 ⁇ m.
  • the release surface of the release sheet (the surface placed in contact with the pressure-sensitive adhesive layer) is subjected to a release treatment using a conventionally known release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent, if necessary. You may.
  • the pressure-sensitive adhesive sheet of the present embodiment can be manufactured, for example, by the following method. First, a pressure-sensitive adhesive solution in which the above-described pressure-sensitive adhesive composition is dissolved or dispersed in a solvent is prepared. The above-mentioned pressure-sensitive adhesive composition may be used as a pressure-sensitive adhesive solution as it is. Next, a pressure-sensitive adhesive solution is applied on the substrate, and dried by heating to form a pressure-sensitive adhesive layer. Thereafter, it is obtained by laminating a release sheet on the pressure-sensitive adhesive layer as necessary.
  • the above-mentioned pressure-sensitive adhesive solution is applied onto a release sheet, and dried by heating to form a pressure-sensitive adhesive layer.
  • a release sheet having an adhesive layer is placed on a substrate with the surface on the adhesive layer side facing the substrate, and the adhesive layer is transferred (transferred) onto the substrate.
  • a known method can be used as a method of applying the above-mentioned pressure-sensitive adhesive solution on a base material (or on a release sheet).
  • a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a method of applying using a direct coater and the like.
  • a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a method of applying using a direct coater and the like.
  • the pressure-sensitive adhesive sheet of the present embodiment can be used as a removable pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet of the present embodiment can be used, for example, when manufacturing an electronic component.
  • the adhesive sheet according to the present embodiment is, specifically, in each step of manufacturing an electronic component, after fixing an adherend, performing various processing steps, and then irradiating an ultraviolet ray (UV) with the adherend. Used for exfoliating and collecting body. Therefore, the pressure-sensitive adhesive sheet of this embodiment can be used as a back grinding tape, a dicing tape, or the like when processing a semiconductor wafer.
  • the pressure-sensitive adhesive sheet of the present embodiment can be suitably used as a support tape for a fragile member such as an ultra-thin glass substrate, a plastic film, or a easily warped member such as a flexible printed circuit board (FPC board).
  • the pressure-sensitive adhesive sheet of the present embodiment is suitable as a dicing tape for protecting a wafer when performing a wafer dicing step.
  • the pressure-sensitive adhesive sheet of the present embodiment is attached to a wafer on which a plurality of components are formed before performing a dicing step.
  • the wafer is cut and cut into individual parts (diced) to obtain element small pieces (chips).
  • UV is irradiated to the adhesive sheet stuck on each element piece.
  • UV is irradiated to the pressure-sensitive adhesive layer through the base material of the pressure-sensitive adhesive sheet, and the unsaturated bond in the pressure-sensitive adhesive forms a three-dimensional crosslinked structure and is cured.
  • the adhesive strength of the adhesive layer decreases.
  • the adhesive sheet is peeled off from each element piece.
  • UV dose to be irradiated to the adhesive sheet is preferably 50 ⁇ 3000mJ / cm 2, more preferably 100 ⁇ 600mJ / cm 2.
  • the pressure-sensitive adhesive layer is cured at a sufficiently high curing speed by UV irradiation, and the adhesive force of the pressure-sensitive adhesive layer after UV irradiation is sufficiently high. It is smaller and preferable. Even if the UV irradiation amount irradiating the pressure-sensitive adhesive sheet is 3000 mJ / cm 2 or more, the effect corresponding thereto cannot be obtained.
  • reaction system was charged with 0.15 g of 4-methoxyphenol as a polymerization inhibitor based on 100 parts by mass of the total of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated monomer (c). Parts by weight were added.
  • the temperature of the reaction system to which 4-methoxyphenol was added was raised to 100 ° C., and the second mixed solution was added dropwise over 0.5 hour. Then, stirring was continued at a temperature of 100 ° C. for 8 hours to obtain resin (A-1).
  • the resin (A-1) was identified by a nuclear magnetic resonance method (NMR method), and as a result, it was a compound represented by the general formula (2-1).
  • the repeating unit k in the formula (1-1) is two kinds of repeating units (k-1, k-2) having different R 5 .
  • the resin (A-1) was examined for weight average molecular weight and glass transition temperature by the following method.
  • the acid value of the resin (A-1) was measured according to JIS K0070. Table 3 shows the results.
  • Tg ⁇ Glass transition temperature
  • Resins (A-2) to (A-8) (A-10) to (A-12) were obtained in the same manner as in Production Example 1 except that the first mixed solution and the second mixed solution were used.
  • the repeating unit k in the formula (1-1) is different from R 5 or 2 in which both R 1 and R 5 are different.
  • the resin (A-2) is a compound represented by the following general formula (2-2).
  • the resin (A-3) is a compound represented by the following general formula (2-3).
  • the resin (A-4) is a compound represented by the following general formula (2-4).
  • the resin (A-5) is a compound represented by the general formula (2-5).
  • the resin (A-6) is a compound represented by the following general formula (2-6).
  • Resin (A-7) is a compound represented by the following general formula (2-7).
  • Resin (A-8) is a compound represented by the following general formula (2-8).
  • Resin (A-10) is a compound represented by the following general formula (2-10).
  • the resin (A-11) is a compound represented by the following general formula (2-11).
  • the resin (A-12) is a compound represented by the following general formula (2-12).
  • k-1 is 32, k-2 is 48, m is 1, and the sum of k-1, k-2, and m is 81. n is 19 Is.
  • k-1 is 70, k-2 is 16, m is 1, and the sum of k-1, k-2, and m is 87. n is 13 Is.
  • k-1 is 52, k-2 is 34, m is 3, and the sum of k-1, k-2, and m is 89.
  • n is 11 Is.
  • k-1 is 11, k-2 is 52, m is 4, the sum of k-1, k-2, and m is 67, and n is 33 Is.
  • k-1 is 37, k-2 is 44, m is 2, and the sum of k-1, k-2, and m is 83.
  • n ' is 17
  • k-1 is 34, k-2 is 47, m is 4, and the sum of k-1, k-2, and m is 85.
  • n is 15 Is.
  • the resin (A-9) was identified in the same manner as in Production Example 1, and as a result, it was a compound represented by the general formula (2-9).
  • the repeating unit k in the formula (1-1) is two kinds of repeating units (k-1, k-2) having different R 5 .
  • the resin (A-9) was examined for weight average molecular weight, glass transition temperature, and acid value in the same manner as for the resin (A-1). Table 3 shows the results.
  • resins (A-1) to (A-12) k-1, k-2, and k (sum of k-1 and k-2) in chemical formulas (2-1) to (2-12) are respectively used. )
  • L, m, n, n ′, and n ′′ are shown in Table 3.
  • Tables 1 and 2 show the carboxy group-containing ethylenically unsaturated monomer (a) used in the production of the resins (A-1) to (A-12), and the ethylene copolymerizable with the above (a).
  • An unsaturated unsaturated monomer (d), a polymerization initiator, an alicyclic epoxy group-containing ethylenically unsaturated compound (c), a catalyst, a polymerization inhibitor and a type and amount of a solvent (parts by mass)
  • the amounts (parts by mass) of glycidyl methacrylate (GMA) and 2-isocyanatoethyl methacrylate (MOI) are shown.
  • Examples 1 to 12 Comparative Examples 1 and 2
  • Ethyl acetate as a solvent was added to the reaction solution of the resins (A-1) to (A-12) synthesized in Production Examples 1 to 12, and the content of each of the resins (A-1) to (A-12) was reduced. It was adjusted to be 30% by mass.
  • a pressure-sensitive adhesive composition was obtained by the following method. .
  • the resin (A), the photopolymerization initiator (B), and the crosslinking agent (C) shown in Tables 4 to 6 are contained in the plastic containers shown in Tables 4 to 6, respectively.
  • the resulting mixture was stirred in an amount (parts by mass) to obtain pressure-sensitive adhesive compositions of Examples 1 to 12 and Comparative Examples 1 and 2.
  • the numerical values of the resins (A-1) to (A-12) in Tables 4 to 6 indicate that the content of the resins (A-1) to (A-12) is 30% by mass. (A-12) The amount (parts by mass) of the solution used.
  • the numerical value of the photopolymerization initiator (B) is the amount (parts by mass) of the photopolymerization initiator (B) used per 100 parts by mass of the resin (A).
  • the numerical value of the crosslinking agent (C) is the amount (parts by mass) of the crosslinking agent (C) used per 100 parts by mass of the resin (A).
  • TTRAD-C 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane
  • TETRAD-C 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane
  • TETRAD-X 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane
  • TETRAD-X N, N '-[1,3-phenylenebis (methylene)] bis [bis (oxiran-2-ylmethyl) amine]
  • TETRAD-X "HX” isocyanurate of hexamethylene diisocyanate
  • Coronate registered trademark
  • HX manufactured by Tosoh Corporation
  • TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • the pressure-sensitive adhesive sheets of Examples 1 to 12 all had a "peel strength before UV irradiation" of 1.0 N / 25 mm or more, and a “peel strength after heat-resistant UV irradiation” of 2. It was less than 5 N / 25 mm, and the evaluation of adhesive residue was ⁇ or ⁇ .
  • the pressure-sensitive adhesive sheets of Comparative Examples 1 and 2 in which the resin (A) did not contain a structure derived from an alicyclic compound had sufficient “peel strength after UV irradiation”. Although it was low, the "peel strength after heat resistant UV irradiation" was high, and the evaluation of adhesive residue was x.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition adhésive sensible à la pression comprenant une résine représentée par la formule (1-1), et un initiateur de photopolymérisation. R1 à R4 représentent chacun -H ou -CH3 ; R5 représente un groupe alkyle en C1-16 ; R6 représente un groupe hydrocarboné alicyclique ou un groupe hydrocarboné aromatique ; R7 représente -H ou –(CH2)j-COOH (où j est 1 ou 2) ; et R8 est un groupe spécifique.
PCT/JP2019/023913 2018-09-03 2019-06-17 Composition adhésive sensible à la pression et feuille adhésive sensible à la pression Ceased WO2020049829A1 (fr)

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KR1020217003048A KR102408062B1 (ko) 2018-09-03 2019-06-17 점착제 조성물 및 점착 시트
CN201980052256.8A CN112534015B (zh) 2018-09-03 2019-06-17 粘着剂组合物及粘着片
JP2020541026A JP7363791B2 (ja) 2018-09-03 2019-06-17 粘着剤組成物および粘着シート
JP2023166256A JP7568024B2 (ja) 2018-09-03 2023-09-27 樹脂
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Publication number Priority date Publication date Assignee Title
WO2023112427A1 (fr) * 2021-12-14 2023-06-22 株式会社レゾナック Procédé de production de dispositif à semi-conducteurs, et dispositif à semi-conducteurs
WO2024228363A1 (fr) * 2023-05-01 2024-11-07 株式会社レゾナック Procédé de nettoyage de puce à semi-conducteur et procédé de fabrication de dispositif à semi-conducteur
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WO2025169708A1 (fr) * 2024-02-06 2025-08-14 株式会社レゾナック Composition adhésive, feuille adhésive et procédé de production d'un dispositif à semi-conducteur

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JP7687370B2 (ja) 2025-06-03
CN112534015A (zh) 2021-03-19
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JP2024014872A (ja) 2024-02-01
JP2023182666A (ja) 2023-12-26
CN112534015B (zh) 2022-02-25
JPWO2020049829A1 (ja) 2021-08-12
JP7568024B2 (ja) 2024-10-16
JP7363791B2 (ja) 2023-10-18
TWI779208B (zh) 2022-10-01
KR20210027424A (ko) 2021-03-10

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