Classifications

• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
• • 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
• • 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
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • 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
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
• • 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
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• • 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
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
  • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/132—Phenols containing keto groups, e.g. benzophenones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5397—Phosphine oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

• the present invention relates to a composition used for temporary fixation.
• inorganic materials such as silicon are used as substrates, and the thickness is obtained by forming an insulating film on the surface, forming a circuit, thinning it by grinding, etc.
• a wafer-type substrate of about 100 ⁇ m is often used.
• this measure has been taken by applying a temporary fixing protective tape to the surface opposite to the surface to be ground (also called the back surface), which can be peeled off after the processing process is completed.
• This tape uses an organic resin film as a base material, and although it is flexible, it has insufficient strength and heat resistance, making it unsuitable for use in processes that involve high temperatures.
• a system has been proposed in which a substrate for an electronic device is bonded to a support such as silicon or glass via an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes.
• a support such as silicon or glass
• an adhesive to provide sufficient durability against the conditions of back grinding and back electrode formation processes.
• the adhesive layer used to bond the substrate to the support This requires that the substrate can be bonded to the support without any gaps, has sufficient durability to withstand subsequent processes, and finally that the thinned wafer can be easily peeled off from the support, in other words, it must be temporarily fixed. It is.
• Processing of such wafers mainly includes a spin coating process, a vacuum bonding and photocuring process, a thinning process by grinding and polishing, a high temperature treatment process, a laser peeling process, and a temporary fixing agent removal process.
• the temporary fixing agent In the spin coating process, in order to uniformly form a film of the temporary fixing agent on the wafer, the temporary fixing agent must have an appropriate viscosity and be a Newtonian fluid (or shear rate independent of shear viscosity). ) is required.
• the temporary fixing agent is required to be able to be cured by irradiation with light such as ultraviolet (UV) light on a support such as glass in a short time, and to generate little outgas (low outgas property).
• light such as ultraviolet (UV) light
• UV ultraviolet
• the load is distributed in the in-plane direction and the planarity is maintained by preventing local subsidence of the substrate.
• Temporary fixatives are required to have appropriate hardness.
• adhesive strength with the support, a moderately high elastic modulus to protect edges, and chemical resistance are also required.
• the temporary fixing agent is required to have heat resistance that can withstand long-term high-temperature treatment in vacuum (for example, at 300° C. or more for one hour or more).
• the temporary fixing agent is required to be capable of high-speed peeling using a laser such as a UV laser.
• Patent Document 1 a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer Tg is -100°C to 60°C; -2) Discloses a temporary fixing composition containing a polyfunctional (meth)acrylate, (B) a polyisobutene homopolymer and/or a polyisobutene copolymer, and (C) a photoradical polymerization initiator, which has high heat resistance and low heat resistance. It is said to have excellent outgassing properties and peelability.
• the laser beam is swept through the glass support to decompose the temporary fixing agent at the irradiated area. form.
• the gas vaporized inside the hole expands at high temperatures, pushing the glass support upward and making it easier to peel off.
• the present invention can provide the following aspects.
• A a polymerizable component that does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton and has a (meth)acryloyl group;
• B a photopolymerization initiator;
• C A non-polymerizable material having one or more selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton, and containing an ultraviolet absorber having a polymerizable functional group.
• the cured product was A light characterized in that the long axis of a recess having a substantially circular footprint formed so as to pierce the surface is 20% or more of the spot diameter, and the depth is 2.3 ⁇ m or more. Curable resin composition.
• Aspect 2 The photocurable resin composition according to aspect 1, wherein the polymerizable component includes a compound having two or more (meth)acryloyl groups.
• Aspect 3 The photocurable resin composition according to aspect 2, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate.
• Aspect 4 The photocurable resin composition according to aspect 2 or 3, wherein the polymerizable component includes a combination of a polyfunctional (meth)acrylate and a polymerizable polymer.
• Aspect 5 The photocurable resin composition according to any one of aspects 1 to 4, wherein the amount of the compound having a (meth)acryloyl group is in the range of 20 to 100% by mass with respect to the mass of the entire polymerizable component. .
• Aspect 6 The photocurable resin composition according to any one of aspects 1 to 5, wherein the polymerizable functional group of the ultraviolet absorber is a (meth)acryloyl group.
• a temporary fixing adhesive comprising the photocurable resin composition according to any one of aspects 1 to 6.
• Aspect 8 An adhesive body comprising the temporary fixing adhesive according to aspect 7 and a base material to be bonded with the temporary fixing adhesive.
• Aspect 10 A cured product obtained by curing the photocurable resin composition according to any one of Aspects 1 to 6.
• monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule.
• Polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in one molecule.
• the n-functional (meth)acrylate refers to a compound having n (meth)acryloyl groups in one molecule.
• the polymerizable functional group in the polyfunctional (meth)acrylate may have only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group.
• composition (hereinafter also simply referred to as "composition” or "temporary fixing agent”) is provided.
• the composition may contain a non-polymerizable component, but the amount of the non-polymerizable component is less than 15% by mass based on the total of 100 parts by mass of the non-polymerizable component and component (A).
• the term "non-polymerizable component” is defined as a component other than component (B), that is, a component that is not used as a photopolymerization initiator in the technical field. More preferably, the composition does not contain non-polymerizable components. If the amount of the non-polymerizable component is 15% by mass or more, a problem will occur in heat resistance.
• the composition becomes a cured product by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds.
• Directional energy with a wavelength of 355 nm, a spot diameter of 40 to 300 ⁇ m, a pulse energy of 50 to 250 ⁇ J, and an energy density of 248 to 11,500 mJ/cm 2 , preferably 360 to 11,500 mJ/cm 2 is applied to the cured body as the cumulative energy per unit area.
• a concave portion having a substantially circular footprint is formed so as to pierce the surface of the cured product when sweeping irradiation is applied through a glass having a thickness of 0.7 mm so that the irradiation amount is 150 to 1000 mJ/cm 2 .
• the long axis is 20% or more of the spot diameter, and the depth is 2.3 ⁇ m or more.
• the (A) component contained in the present composition a polymerizable component having a (meth)acryloyl group, plays a role in forming a (meth)acrylic polymer skeleton.
• a polymerizable organic compound component is preferred.
• Component (A) may preferably include a compound having two or more (meth)acryloyl groups.
• Component (A) may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, a trifunctional or more polyfunctional (meth)acrylate, or a mixture thereof.
• component (A) is a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate (more preferably a combination of a bifunctional (meth)acrylate and a monofunctional (meth)acrylate), a polyfunctional (meth)acrylate, and a polyfunctional (meth)acrylate.
• a combination of an acrylate and a polymerizable polymer (more preferably a combination of a bifunctional (meth)acrylate and a polymerizable polymer), or a combination of a polyfunctional (meth)acrylate, a monofunctional (meth)acrylate, and a polymerizable polymer (more preferably a combination of a difunctional (meth)acrylate and a polymerizable polymer) combinations of functional (meth)acrylates, monofunctional (meth)acrylates, and polymerizable polymers).
• Component (A) does not have a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, or a phenol skeleton (that is, it does not contain the component (C) described below).
• Component (A) preferably does not have a nitrogen atom in its molecule.
• the phenol skeleton refers to a structure in which a hydroxyl group is directly bonded to an aromatic ring. In other words, a structure in which an oxygen atom other than a hydroxyl group is bonded to an aromatic ring is not included in the phenol skeleton according to the definition herein, even if it is a structure derived from phenols. shall be taken as a thing.
• component (A) may contain, aromatic bifunctional (meth)acrylates, alicyclic bifunctional (meth)acrylates, or mixtures thereof are preferred from the viewpoint of providing a rigid structure. Can be mentioned.
• Component (A) may contain an acyclic polyfunctional (meth)acrylate.
• the polyfunctional (meth)acrylate may be a monomer, a polymer, or a mixture thereof. That is, the above-mentioned polymerizable polymer may be a polyfunctional (meth)acrylate polymer.
• the molecular weight of the polyfunctional (meth)acrylate monomer is preferably 900 or less, more preferably 700 or less, most preferably 500 or less, and even more preferably 400 or less.
• aromatic difunctional (meth)acrylates include 9,9-bis[4-(2-hydroxyC 1 -C 20 alkoxy)phenyl]fluorene di(meth)acrylate, C 1 -C 20 alkoxylated bisphenol A Di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxyC 1 -C 20 alkyl)benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl) ) propane, or structural isomers thereof.
• di(meth)acrylates having a fused ring skeleton such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton, may be included.
• Examples of alicyclic difunctional (meth)acrylates include C 1 -C 20 alkoxylated hydrogenated bisphenol A di(meth)acrylate, 1,3-di(meth)acryloyloxyadamantane, tricycloC 10 -C 20 alkoxy
• Examples include candimethanol di(meth)acrylate, dicycloC 5 -C 20 di(meth)acrylate, and structural isomers thereof.
• Examples of acyclic difunctional (meth)acrylates include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, stearic acid modified pentaacrylate Examples include erythrol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and caprolactone-modified neopentyl hydroxypivalate glycol di(meth)acrylate.
• component (A) may contain a trifunctional or more polyfunctional (meth)acrylate.
• trifunctional (meth)acrylates include isocyanuric acid ethylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, etc. Can be mentioned.
• Examples of (meth)acrylates having four or more functional groups include ditrimethylolpropane tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, and dipentaerythritol pentaacrylate.
• Examples include (meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
• component (A) a monofunctional (meth)acrylate having a molecular weight of 550 or less is preferable, and a monofunctional alkyl (meth)acrylate having an alkyl group is more preferable.
• the alkyl group is preferably one or more selected from a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group, and one selected from a linear alkyl group and a branched alkyl group.
• component (A) preferably has a long chain and branched or cyclic alkyl group, for example, a carbon number of 18 to 40, more preferably 18 to 32.
• a branched alkyl group such as an isostearyl group, an isotetracosanyl group (2-decyl-1-tetradecanyl group, etc.), an isotriacontanyl group (2-tetradecyl-1-octadecanyl group, etc.), or a cycloalkyl group. It is preferable to have a group.
• a branched alkyl group such as an isostearyl group, an isotetracosanyl group (2-decyl-1-tetradecanyl group, etc.), an isotriacontanyl group (2-tetradecyl-1-octadecanyl group, etc.), or a cycloalkyl group. It is preferable to have a group.
• the low volatility required for temporary fixing compositions can be achieved. properties, chemical resistance, and heat resistance.
• Component (A) includes stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecanyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, One or more selected from the group consisting of 2-tetradecyl-1-octadecanyl (meth)acrylate is preferred.
• component (A)acrylate of the following formula 1 is preferable.
• R 1 is a hydrogen atom or a methyl group, and a hydrogen atom is more preferable.
• R 2 is an alkyl group, and preferably has 18 to 32 carbon atoms. One or more of these (meth)acrylates can be used.
• Examples of monofunctional alkyl (meth)acrylates in which R 2 is an alkyl group having 18 to 32 carbon atoms include stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicodecyl (meth)acrylate, and behenyl ( Preferred are (meth)acrylates having a linear or branched alkyl group, such as meth)acrylate, 2-decyl-1-tetradecanyl(meth)acrylate, 2-tetradecyl-1-octadecanyl(meth)acrylate, and the like.
• the polymerizable polymer refers to a polymerizable component having a (meth)acryloyl group other than a monofunctional (meth)acrylate monomer or a polyfunctional (meth)acrylate monomer.
• a polyfunctional (meth)acrylate polymer is preferred.
• Examples of polyfunctional (meth)acrylate polymers include "ART CURE RA-341" and "APB-001” manufactured by Negami Kogyo Co., Ltd.
• the amount of the compound having a (meth)acryloyl group contained in component (A) may be in the range of 20 to 100% by mass, more preferably 40% by mass based on the total mass of component (A). ⁇ 100% by mass, and may range from 60 to 100% by mass.
• the amount of polyfunctional (meth)acrylate may range from 20 to 100% by weight, more preferably from 50 to 100% by weight, based on the total weight of component (A).
• the mass ratio of the polyfunctional (meth)acrylate monomer (more preferably bifunctional (meth)acrylate monomer), monofunctional (meth)acrylate monomer, and polymerizable polymer contained in component (A) is as follows: It may range from 40 to 80:10 to 50:10 to 25.
• component (A) does not contain a polyfunctional (meth)acrylate monomer, but contains a monofunctional (meth)acrylate monomer and a polymerizable polymer in a mass ratio of 50 to 80:20 to 50. It's okay to stay.
• the amount of the non-polymerizable component contained in the present composition may be 0% by mass or more and less than 10% by mass, or 0% by mass or more and less than 5% by mass. More preferably, the composition does not contain any non-polymerizable components except for component (B).
• the photopolymerization initiator which is component (B) contained in the present composition, is a substance that can initiate polymerization of component (A) when irradiated with light.
• component (B) may be a radical photopolymerization initiator.
• a photoradical polymerization initiator is, for example, a compound whose molecules are cleaved and split into two or more radicals by irradiation with ultraviolet rays or visible light (for example, wavelength 350 to 700 nm, preferably 365 to 500 nm, more preferably 385 to 450 nm). say.
• photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis( ⁇ 5 -2,4-cyclopentadiene).
• Component (B) may include one or more types or a combination of two or more types of these.
• component (B) may include an acylphosphine oxide compound.
• Preferred acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• As a photo-radical polymerization initiator it is highly sensitive, has photofading properties, and has excellent deep curing properties, and the absorption wavelength range for generating radicals extends to a relatively long wavelength range. It is preferable. In the preferred compound described above, the absorption wavelength range is up to about 440 nm, which is significantly different from the absorption wavelength range of the UV absorber used in the UV laser peeling process described below.
• the degree of inhibition of UV curing by the UV absorber is small, and radical polymerization can be initiated with light of a longer wavelength. Therefore, even in the coexistence of a UV absorber, radical polymerization can be initiated and cured efficiently at a relatively high rate.
• the photoradical polymerization initiator can be selected based on absorbance. Specifically, when dissolved at a concentration of 0.1% by mass in a solvent that does not have maximum absorption in the wavelength region of 300 to 500 nm (for example, acetonitrile or toluene), the absorbance at a wavelength of 365 nm is 0. 5 or more, the absorbance is 0.5 or more at a wavelength of 385 nm, and the absorbance is 0.5 or more at a wavelength of 405 nm. , a photoradical polymerization initiator can be selected.
• An example of a compound that satisfies such conditions is 1-[9-ethyl, which has an absorbance of 0.5 or more at a wavelength of 365 nm when dissolved at a concentration of 0.1% by mass in acetonitrile as a solvent.
• bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis having an absorption wavelength range of 400 to 500 nm is recommended.
• (2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium can also be used as a photoradical polymerization initiator.
• temporary fixing is not a layer compatible with the UV laser peeling process, and is used for temporary fixation to prevent damage from bonding the substrate to the support substrate to the heating process.
• oxime ester compounds can also be selected as photoradical polymerization initiators for resin compositions.
• acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.
• titanocene compounds include bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
• ⁇ -aminoalkylphenone compounds examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-ylphenyl)-butan-1-one and the like.
• oxime ester compounds examples include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethanone 1-(O-acetyloxime) and the like. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.
• the amount of the radical photopolymerization initiator (B) used is preferably 0.01 to 5 parts by mass based on 100 parts by mass of component (A) in terms of reaction rate, heat resistance after curing, and low outgas properties. More preferably 0.1 to 1 part by mass.
• component (B) is 0.01 parts by mass or more, sufficient curability can be obtained, and when it is 5 parts by mass or less, low outgas properties and heat resistance are less likely to be impaired.
• the ultraviolet absorber (UV absorber) having a polymerizable functional group which is the component (C) contained in this composition, has molecules that are cut and decomposed and vaporized by irradiation with ultraviolet or visible light laser. is generated at the interface between the support substrate (or substrate) and the temporary fixing agent, thereby causing a loss of the adhesive force between the temporary fixation agent and the support substrate (or substrate) that was maintained until just before the peeling process.
• Component (C) is a compound having one or more types selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton (preferably a hindered phenol skeleton).
• the purpose of having these skeletons is to obtain a degree of overlap between the UV absorption wavelength region and the UV laser wavelength, UV absorption characteristics at the same wavelength, low outgassing properties, and heat resistance.
• the polymerizable functional group contained in component (C) is preferably a (meth)acryloyl group.
• component (C) examples include 2-[2-hydroxy-5-[2-((meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 2-[1-(2-hydroxy-3, 5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl (meth)acrylate, 2-(2-(meth)acryloyloxy,5-methyl)phenyl-2H-benzotriazole, 1 ,1-bis-[2-(meth)acryloyloxy,3-(2H-benzotriazol-2-yl),5-tert-octyl]methane, 2,2'-dihydroxy-4,4'-di(meth) )
• One or more members of the group consisting of acryloyloxybenzophenone are particularly preferred from the viewpoint of compatibility with the resin component, UV absorption properties, low outgassing properties, and heat resistance.
• the UV transmittance of the cured product in this specification is a value obtained by reflectance measurement spectroscopy. Specifically, the transmittance was measured using a reflectance spectrometer (V-650 manufactured by JASCO Corporation) using a cured film with a thickness of approximately 50 ⁇ m sandwiched between PET resin sheets under the following conditions. ) is obtained using
• the amount of component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, per 100 parts by weight of component (A).
• the amount is 0.01 parts by mass or more, a sufficient UV laser peeling rate can be obtained, and when it is 10 parts by mass or less, the effect of low outgassing property and heat resistance being less likely to be impaired can be obtained.
• the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, the weight average molecular weight is determined by creating a calibration curve with commercially available standard polystyrene using a GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. .
• GPC gel permeation chromatography
• a cured product of the composition described above can also be provided.
• Such curing may be performed using a light source described below.
• the cured product is in the form of a cured film with a thickness of 50 ⁇ m, it is preferable that one or more of the following conditions be satisfied, and more preferably that all of the following conditions are satisfied.
• the following conditions can be met, for example, by using a UV absorber.
• the light transmittance in a wavelength region of 395 nm or more among the wavelengths of the light source used for curing is 70% or more.
• the light transmittance in the wavelength range of 385 nm or more and less than 395 nm among the wavelengths of the light source used for curing is 20% or more.
• the light transmittance at the wavelength (355 nm) of the UV laser used for UV laser peeling is 1% or less.
• a temporary fixing agent having such characteristics can be suitably used in a process including a high-temperature vacuum process such as ion implantation, annealing, and electrode formation by sputtering, especially in the back surface process after thinning.
• the cured product to be subjected to laser irradiation which is a feature of the present invention, is produced by irradiating it with light having a wavelength of 405 nm and an illuminance of 100 mW/cm 2 for 50 seconds.
• the viscosity of the composition of the present invention is preferably 100 mPa ⁇ s or more, more preferably 500 mPa ⁇ s or more, and most preferably 1000 mPa ⁇ s or more at 23° C. (under atmospheric pressure) in terms of coatability and workability.
• the viscosity of the composition of the present invention is preferably 10,000 mPa ⁇ s or less, more preferably 5,000 mPa ⁇ s or less, and most preferably 4,000 mPa ⁇ s or less in terms of applicability and workability.
• the pressure is 100 mPa ⁇ s or more, the coating properties, particularly the coating properties by spin coating, are excellent. Workability is excellent when the pressure is 10,000 mPa ⁇ s or less.
• the viscosity can be measured using a known viscometer.
• Spin coating is a method of applying the composition to the surface of the substrate by, for example, dropping a liquid composition onto the substrate and rotating the substrate at a predetermined number of rotations. Spin coating enables efficient production of high-quality coatings.
• the present composition can be used as a temporary fixing resin composition, a temporary fixing adhesive, a pressure-sensitive adhesive sheet, or a temporary fixing adhesive for manufacturing electronic devices.
• the temporary fixing composition, the temporary fixing resin composition, and the temporary fixing adhesive may be collectively referred to as a temporary fixing agent.
• the amount of energy in visible light or ultraviolet rays is 1 to 20,000 mJ. It is preferable to irradiate so that the amount of radiation becomes /cm 2 .
• the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and when it is 20,000 mJ/cm 2 or less, productivity is excellent, and decomposition products from the photoradical polymerization initiator are difficult to generate, suppressing outgas generation. be done.
• productivity adhesion, low outgas properties, and easy peelability, it is preferably 1000 to 10000 mJ/cm 2 .
• the substrates to be bonded with the present composition it is preferable that at least one of the substrates be a transparent substrate that transmits light.
• the transparent substrate include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic.
• inorganic base materials are preferred because they are versatile and can provide great effects.
• one or more selected from glass and quartz is preferred.
• the laser irradiation conditions that characterize the present invention are those when glass with a thickness of 0.7 mm is selected as the base material.
• the present composition may be photocurable, and the cured product provided thereby has excellent heat resistance and peelability.
• the cured product of the composition of the present invention has a small amount of outgassing even when exposed to high temperatures, and is suitable for joining, sealing, and coating various optical components, optical devices, and electronic components.
• the composition of the present invention is suitable for applications that require a wide variety of durability such as solvent resistance, heat resistance, adhesiveness, etc., particularly for semiconductor manufacturing process applications.
• the cured product of this composition can be used in processes in a wide temperature range from room temperature to high temperatures.
• the heating temperature during the process is preferably 350°C or lower, more preferably 300°C or lower. In a preferred embodiment, the temperature at which the heating mass reduction rate of the cured product is 2% may be 250° C. or higher.
• the bonded body bonded with the present composition has high shear adhesive strength and can withstand thinning processes, etc., and can be easily peeled off after passing through a heating process such as forming an insulating film.
• the cured product of the present composition can be used in a high temperature process, for example, preferably at 200°C or higher, more preferably at 250°C or higher.
• an adhesive body is also provided in which substrates are adhered by using the present composition as an adhesive.
• the adhesive body can be peeled off by applying external force. For example, it can be peeled off by inserting a knife, sheet, or wire into the joint. Alternatively, it is also possible to peel off the adhesive by irradiating the optically transparent base material side of the adhesive body with a UV laser or an IR laser so as to scan the entire surface.
• Curable resin compositions (hereinafter also referred to as liquid resin compositions) having the compositions shown in the table below (unit: parts by mass) were prepared and evaluated. The following compounds were selected as each component.
• A-BPEF-2 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate (“NK ester A-BPEF-2” manufactured by Shin-Nakamura Chemical Co., Ltd.)
• HBPE-4 EO-modified hydrogenated bisphenol A diacrylate (“HBPE-4” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., m+n ⁇ 4)
• HX-620 Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd. "Kayarad HX-620", m+n ⁇ 4)
• HX-220 Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd.
• DDDA 1,10-decanediol diacrylate
• A-DOD-N 1,10-decanediol diacrylate
• DTDA 2-decyl-1-tetradecanyl acrylate
• Light Acrylate DTD-A manufactured by Kyoeisha Chemical Co., Ltd.
• A-DCP Tricyclodecane dimethanol diacrylate (“NK ester A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
• ISTA Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• DCP Tricyclodecane dimethanol dimethacrylate (“NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
• M-111 Nonylphenol EO modified acrylate (“Aronix M-111” manufactured by Toagosei Co., Ltd., n ⁇ 1)
• M-113 Nonylphenol EO modified acrylate
• component (C) 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine (“Tinuvin 460” manufactured by BASF) 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (“Tinuvin 479” manufactured by BASF) 2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (Otsuka Chemical Co., Ltd.
• PIB Polyisobutene (“Oppanol N 50 SF” manufactured by BASF, weight average molecular weight 565,000)
• the removability after irradiation is excellent if there is no stickiness and the glass support can be easily peeled off by hand from the temporary fixing agent, or if the glass support remains sticky but the glass support is not on the temporary fixing agent.
• the evaluation was performed by defining fair if the glass support could be peeled off by hand from above, and NG if the glass support could not be peeled off by hand from the temporary fixing agent.
• the profile of the concave shape formed on the surface of the temporary fixing agent was measured using a hybrid laser microscope "OPTELICS HYBRID" manufactured by Lasertec Corporation. The major axis and depth were determined. The hole is in the shape of a recess and has a generally circular footprint. Profile measurements were performed with an objective lens magnification of 50 times and a resolution of 0.01 ⁇ m. When the concave shape formed on the surface of the temporary fixing agent was not a perfect circle, the diameter of the longest side (major axis) was measured. The height difference from the outermost surface of the temporary fixing agent to the point where the deepest concave shape was formed was measured and determined as the depth of the hole.
• the support glass and silicon wafer were broken and the exposed temporary fixative was measured.
• the ratio was calculated by dividing the hole diameter (major axis) measured by the above method by the spot diameter set during UV laser irradiation.
• the bonded sample produced by the above method was heat-treated in a high temperature and reduced pressure environment of 300° C. and 20 Pa for 1 hour. Thereafter, the glass and Si wafers were mechanically peeled off from the temporary fixing agent using a cutter, and the appearance of the surfaces of both substrates was checked to evaluate the presence or absence of bleed-out.
• Comparative Examples b1 to b5 which did not contain component (C) that met the conditions of the present invention, all had unsuitable heat resistance.
• Comparative Example b6 which contained component (C) but contained many non-polymerizable components, the size of the holes formed was not appropriate even if the energy irradiation amount was increased.

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