WO2009139357A1 - Method for protection of surface of material to be processed, and temporary fixing method - Google Patents

Method for protection of surface of material to be processed, and temporary fixing method Download PDF

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Publication number
WO2009139357A1
WO2009139357A1 PCT/JP2009/058783 JP2009058783W WO2009139357A1 WO 2009139357 A1 WO2009139357 A1 WO 2009139357A1 JP 2009058783 W JP2009058783 W JP 2009058783W WO 2009139357 A1 WO2009139357 A1 WO 2009139357A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
workpiece
protective film
mass
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Application number
PCT/JP2009/058783
Other languages
French (fr)
Japanese (ja)
Inventor
剛介 中島
貴之 南雲
和宏 大島
Original Assignee
電気化学工業株式会社
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Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2010511972A priority Critical patent/JP5507451B2/en
Priority to CN200980117146.1A priority patent/CN102026807B/en
Publication of WO2009139357A1 publication Critical patent/WO2009139357A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/0017—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor characterised by the choice of the material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/0065—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

Definitions

  • the present invention relates to a surface protection method and a temporary fixing method of the workpiece when processing various materials. More specifically, the present invention provides a protective film made of a curable composition (hereinafter sometimes referred to as a cured body) on the surface of a workpiece when processing an optical member, a semiconductor wafer, or the like.
  • a method for protecting the surface of a workpiece which is intended to protect a portion not to be processed from foreign matter adhesion or scratches during processing, is presented.
  • the present invention is to collect the workpiece by bonding the workpiece to the base material, processing the workpiece, immersing the bonded portion in warm water, and removing the protective film.
  • a characteristic method of temporarily fixing the workpiece is also presented.
  • a surface protective film that temporarily protects components is widely used.
  • a pressure-sensitive adhesive sheet is mainly used.
  • the back surface grinding method protects the circuit surface of the wafer and the non-processed surface of the optical component with the surface protection sheet, and temporarily fixes the substrate to the substrate via the surface protection sheet, and grinds the back surface opposite to the circuit surface. It is a method to do.
  • the pressure-sensitive adhesive surface protection sheet currently in use has a limit in the ability to follow the irregularities of the circuit of the semiconductor wafer. For this reason, contamination due to the ingress of the grinding liquid between the wafer and the surface protective layer often becomes a problem.
  • a typical semiconductor surface protection sheet cannot follow protrusions of 100 ⁇ m or more typified by bumps, causing a problem of contamination and chip jumping. there were.
  • Conventional surface protective sheets are generally sheets having a pressure-sensitive adhesive layer as a surface protective layer on a polymer film material, and the pressure-sensitive adhesive is designed to have a low elastic modulus so as to follow the irregularities of the circuit surface. .
  • the elastic modulus is too low, a large stress is applied to the wafer when the sheet is peeled off from the wafer, leading to damage of the wafer.
  • an energy ray easily peelable protective sheet that cures the pressure-sensitive adhesive by irradiating energy rays such as ultraviolet rays before peeling the sheet, and reduces the adhesive force between the wafer and the protective sheet.
  • the pressure-sensitive adhesive layer is in an uncured state during grinding, and there is a problem that the wafer is damaged during grinding because it is too soft.
  • Patent Document 1 discloses a wafer grinding method in which the energy ray easy-peelable protective sheet as described above is attached to a wafer on which a circuit is formed, and the adhesive layer is cured with energy rays, and then the back surface of the wafer is ground. ing.
  • the pressure-sensitive adhesive is not a fluid, the followability to the unevenness of the wafer circuit surface is not sufficient.
  • Patent Document 2 discloses a hot-melt type semiconductor surface protective sheet.
  • a hot-melt type sheet that melts and exhibits fluidity when heated to 60 to 100 ° C. can follow the unevenness of the circuit surface and exhibit excellent grindability.
  • this sheet has the property of melting whenever the temperature exceeds the melting point.
  • the present inventor has specified a specific material as a composition that has sufficient followability to the unevenness of the circuit surface of a wafer or optical component and has sufficient rigidity as a support during grinding.
  • the resin composition which consists of resin containing a (meth) acryl monomer is proposed (refer patent document 3 and 4).
  • the resin composition is effective for surface protection during back grinding.
  • a resin composition whose surface is completely cured during surface protection. This is because the surface may not be completely cured if it is subjected to polymerization inhibition by oxygen during surface protection during surface grinding / cutting.
  • Patent Document 5 does not describe provision of a heating process in which a protective film is provided on the surface of a workpiece using the resin composition and heat treatment is performed at 80 to 150 ° C. Further, when a heating step is provided, there is no description that the protective film does not fall off during processing even if dicing is performed.
  • the present inventor conducted a heat treatment of the protective film after providing a protective film made of the curable composition on the surface of the processed material, and then processed the workpiece.
  • the inventors have obtained knowledge that the surface of the workpiece can be protected without dropping the protective film during processing, and have completed the present invention.
  • the present invention provides a method for protecting a surface of a workpiece by providing a protective film made of a curable composition on the surface of the workpiece, and after the protective film is laminated on the surface of the workpiece, the protective film is heat-treated.
  • a protective film made of a curable composition is provided on the surface of the workpiece, and after the heat treatment, the workpiece is processed, and then immersed in warm water of 90 ° C. or less.
  • a method for temporarily fixing a workpiece comprising removing a protective film made of a curable composition from the workpiece.
  • the present invention includes a laminating step of laminating a protective film formed of a curable composition containing the following (A), (B) and (C) on the surface of a workpiece, and 80 after the laminating step.
  • a method for protecting a surface of a workpiece by laminating a protective film on the surface of the workpiece, comprising: a heating step of heat-treating to 150 ° C; and a processing step of processing the workpiece after the heating step. is there.
  • the said protective film contains resin which has (D) cyclopentadiene frame
  • the (D) resin containing a cyclopentadiene skeleton is a method for protecting the surface of the workpiece, wherein the molecule contains an ester group or a hydroxyl group.
  • the (A) polyfunctional (meth) acrylate and the (B) monofunctional (meth) acrylate are both hydrophobic methods for protecting the surface of the workpiece.
  • the curable composition comprises 5 to 50 parts by mass of (A) polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate in 100 parts by mass of the total amount of (A) and (B). And (C) 0.1-20 parts by weight of a photopolymerization initiator and (D) cyclopentadiene with respect to 100 parts by weight of the total amount of (A) and (B).
  • a method for protecting a surface of a workpiece comprising 0.1 to 50 parts by mass of a resin having a skeleton.
  • a laminating step of laminating a protective film made of a cured product formed from a curable composition containing the following (A), (B) and (C) on the surface of the workpiece, and 80 to 150 after the laminating step A heating step in which heat treatment is performed at a temperature of C; a processing step in which the workpiece is processed after the heating step; and a removal in which the workpiece is immersed in warm water of 90 ° C. or less after the processing step to remove the protective film from the workpiece A temporary fixing method for a workpiece, wherein a protective film is laminated on the surface of the workpiece.
  • B) Monofunctional (meth) acrylate C) Photopolymerization initiator
  • the method for protecting the surface of a workpiece according to the present invention is effective in that the protective film does not fall off even if processing such as dicing is performed, and scratches or foreign matter on the processed surface, circuit, sensor site, etc. of the workpiece Adhesion can be prevented.
  • a protective film formed from a curable composition is provided on the surface of a workpiece, and then the protective film is heated to 80 to 150 ° C., and then the workpiece is processed.
  • This is a method for protecting the surface of a workpiece, characterized in that the protective film is prevented from falling off.
  • the temperature of the heat treatment is preferably 80 to 150 ° C., more preferably 90 to 120 ° C. from the viewpoint of maintaining the peelability of the protective film. If it is 80 degreeC or more, the effect by heat processing will be acquired, and if it is 150 degrees C or less, peelability is favorable.
  • the curable composition used as a protective film in the present invention includes (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C) photopolymerization initiator, and (D) cyclohexane. It is preferable to contain a resin containing a pentadiene skeleton in order to obtain the effects of the present invention.
  • the polyfunctional (meth) acrylate oligomer / polymer / monomer having two or more (meth) acryloyl groups can be used as the (A) polyfunctional (meth) acrylate used in the curable composition.
  • the polyfunctional (meth) acrylate oligomer / polymer 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, “TE-2000”, “TEA-1000” manufactured by Nippon Soda Co., Ltd.), the hydrogenated product ( For example, Nippon Soda Co., Ltd., “TEAI-1000”), 1,4-polybutadiene terminated urethane (meth) acrylate (for example, “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene terminated (meth) acrylate, polyurethane Acrylate (for example, “UV-7000B” manufactured by Nippon Gosei Co., Ltd.), polyester
  • 1,2-polybutadiene-terminated urethane (meth) acrylate one or two or more selected from the group consisting of 1,2-polybutadiene-terminated urethane (meth) acrylate, polyurethane acrylate oligomer, and polyester-based urethane acrylate oligomer is preferable in that the effect of peelability is great.
  • 1,2-polybutadiene terminated urethane (meth) acrylate is more preferred.
  • bifunctional (meth) acrylate monomers include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (meth) a Lilo propoxy
  • Examples of the tetra- or higher functional (meth) acrylate monomer include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerystol penta (meth) acrylate, and dipenta Examples include erythritol hexa (meth) acrylate.
  • dicyclopentanyl di (meth) acrylate and / or 1,6-hexanediol di (meth) acrylate is preferable and dicyclopentanyl di (meth) acrylate is preferable in that the effect of peelability is large. More preferred.
  • polyfunctional (meth) acrylates polyfunctional (meth) acrylate oligomers / polymers having two or more (meth) acryloyl groups and bifunctional (meth) acrylates in terms of a large effect of peelability It is preferable to use a monomer together.
  • the mixing ratio (mass ratio) of the polyfunctional (meth) acrylate oligomer / polymer having two or more (meth) acryloyl groups and the bifunctional (meth) acrylate monomer is 30 to 30 100: 70 to 0 is preferable, and 50 to 65:50 to 35 is more preferable.
  • the hydrophobic (A) polyfunctional (meth) acrylate used in the present invention is more preferable.
  • hydrophobicity it is possible to prevent a phenomenon that tends to occur when it is water-soluble, that is, a phenomenon in which the cured product of the curable composition swells during processing to cause displacement and poor processing accuracy.
  • the hydrophobic polyfunctional (meth) acrylate refers to (meth) acrylate having no hydroxyl group.
  • the above-mentioned polyfunctional (meth) acrylates can be mentioned.
  • one or more selected from the group consisting of 1,2-polybutadiene-terminated urethane (meth) acrylate, 1,6-hexadiol di (meth) acrylate and dicyclopentanyl di (meth) acrylate Is preferred. Even if it is hydrophilic, it can be used as long as the cured product of the curable composition is not greatly swollen or partially dissolved by water.
  • the amount of (A) polyfunctional (meth) acrylate used is preferably 5 to 50 parts by mass, preferably 20 to 40 parts by mass in 100 parts by mass of the total amount of (A) and the later-described (B) monofunctional (meth) acrylate component. Part is more preferred. If it is 5 parts by mass or more, it is possible to prevent the peelability from decreasing or the cured product of the curable composition from becoming a film, and if it is 50 parts by mass or more, the shrinkage of curing increases and the initial adhesiveness. There is no fear that it will fall.
  • Examples of the (B) monofunctional (meth) acrylate monomer used in the curable composition include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth)
  • -(1,2-cyclohexanedicarboximido) ethyl (meth) acrylate and / or phenol ethylene oxide 2 molar modified (meth) acrylate is more preferred.
  • the mixing ratio (mass ratio) of phenol ethylene oxide 2 mol-modified (meth) acrylate and 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate is 20 to 20 70:80 to 30 is preferable, and 30 to 45:70 to 55 is more preferable.
  • the monofunctional (meth) acrylate is preferably hydrophobic as in the case of the component (A).
  • hydrophobic means (meth) acrylate having no hydroxyl group.
  • hydrophobicity it is possible to prevent a phenomenon that tends to occur when water-soluble, that is, a phenomenon in which the cured product of the curable composition swells during processing to cause displacement and poor processing accuracy. Even if it is hydrophilic, it may be used as long as the cured product of the curable composition does not swell or partially dissolve with water.
  • the amount of the (B) monofunctional (meth) acrylate used is preferably 50 to 95 parts by mass, more preferably 60 to 80 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). If it is 50 parts by mass or more, the initial adhesiveness is not likely to be lowered, and if it is 95 parts by mass or less, the peelability is not lowered, and a cured product of the curable composition is obtained in a film form.
  • the (A) component and the (B) component of the above composition are further added to (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate
  • phosphate ester having vinyl group or (meth) acryloyl group such as
  • the (C) photopolymerization initiator used in the curable composition is used for sensitizing with actinic rays of visible light or ultraviolet rays to promote photocuring of the curable composition, and is known in the art. Various photopolymerization initiators can be used.
  • the amount of the photopolymerization initiator used is preferably 0.1 to 20 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). If it is 0.1 part by mass or more, the effect of promoting curing can be reliably obtained, and if it is 20 parts by mass or less, a sufficient curing rate can be achieved. As a more preferable form, it can harden
  • the resin having a cyclopentadiene skeleton used in the present invention may be any resin having a cyclopentadiene skeleton, but the softening point is preferably 50 to 200 ° C., and the number average molecular weight (Mn) Is preferably from 300 to 600 in terms of solubility in the component (A) and the component (B).
  • the softening point was measured according to JIS K 2207 ring and ball system.
  • the number average molecular weight was measured according to GPC (gel permeation chromatography) polystyrene conversion value.
  • Examples of (D) include petroleum resins produced using cyclopentadiene extracted from the C5 fraction as a main raw material.
  • the amount of the resin having a cyclopentadiene skeleton is preferably 0.5 to 50 parts by mass and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). preferable. If the amount is 0.5 parts by mass or more, no adhesive remains without forming a film, and if it is 50 parts by mass or less, the adhesiveness does not decrease.
  • polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl Hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole, and Examples include 2,6-ditertiary butyl-p-cresol.
  • one or more of the group consisting of 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), hydroquinone monomethyl ether and p-benzoquinone are preferred, More preferred is methylene-bis (4-methyl-6-tertiary butylphenol).
  • the amount of these polymerization inhibitors used is preferably 0.001 to 3 parts by mass, and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). If it is 0.001 part by mass or more, the storage stability is sufficient, and if it is 3 parts by mass or less, reliable adhesiveness is obtained and there is no possibility of becoming uncured.
  • the curable composition used in the present invention includes various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, extenders, Additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
  • elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, extenders, Additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
  • the present invention provides a protective film made of the above curable composition on the surface of the workpiece, heat-treats the protective film, and then processes the workpiece to prevent the protective film from falling off during processing.
  • a protective film is provided by applying a curable composition having a thickness of 20 to 200 ⁇ m, preferably 50 to 150 ⁇ m, on the surface of the workpiece, and the wavelength is 365 nm. integrated quantity of light 1000 ⁇ 4000mJ / cm 2, preferably preferred curing under the conditions of 1500 ⁇ 3000mJ / cm 2.
  • a step of heat-treating the protective film at 80 to 150 ° C., preferably 80 to 120 ° C., for 5 to 30 minutes is preferable.
  • the processing step for processing the workpiece after the heating step includes a rotational speed of 5000 to 40000 rpm, preferably 10,000 to 35000 rpm, a feed rate of 0.2 to 50 mm / sec, preferably 0.5 to 30 mm / sec, a chip size of 0.
  • a step of dicing under conditions of 5 to 15 mm square is preferable.
  • a protective film made of a curable composition is provided on the surface of the work material, and after heat treatment, the work material is processed, and then hot water of 70 to 90 ° C. or less, preferably 75.
  • a method for temporarily fixing a workpiece comprising a step of removing the protective film made of the curable composition from the workpiece by immersing in warm water at ⁇ 85 ° C.
  • Experimental Examples I-1 to I-15 are examples of the present invention
  • Experimental Examples II-1 to II-5 are comparative examples.
  • (Experimental Example I-1) As polyfunctional (meth) acrylate, “TE-2000” (1,2-polybutadiene-terminated urethane methacrylate, hereinafter abbreviated as “TE-2000”) manufactured by Nippon Soda Co., Ltd., dicyclopentanyl di 15 parts by mass of acrylate (manufactured by Nippon Kayaku Co., Ltd., “KAYARAD R-684”, hereinafter abbreviated as “R-684”), (B) 2- (1,2-cyclohexanedicarboxy as monofunctional (meth) acrylate 40 parts by mass of imido) ethyl acrylate (Toa Gosei Co., Ltd., “Aronix M-140
  • Adhesive strength (tensile shear adhesive strength): The bond strength (tensile shear bond strength) was measured according to JIS K 6850. Specifically, heat-resistant Pyrex (registered trademark) glass (25 mm ⁇ 25 mm ⁇ 2.0 mm (length ⁇ width ⁇ thickness)) was used as the adherend.
  • the adhesion site is a circle with a diameter of 8 mm and a thickness of 100 ⁇ m, and two heat-resistant Pyrex (registered trademark) glasses are bonded together with the prepared curable composition, and a fusion device manufactured by Fusion, using an electrodeless discharge lamp, Curing was performed under the condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm to prepare a tensile shear bond strength test piece.
  • the prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
  • adhesion test Status of holding protective film after dicing (adhesion test): The adhesion test was performed in an environment of a temperature of 23 ° C. and a humidity of 50%. A curable composition is applied to a silicon wafer with a thickness of 100 ⁇ m, and the curable composition is cured under a condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm by a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp. Thus, a protective film was produced. Then, after heat-treating the protective film at 100 ° C.
  • dicing is performed under the conditions of a rotation speed of 30000 rpm, a feed rate of 1.0 mm / sec, and a chip size of 1 mm square, and observation is made whether the protective film is retained after dicing. did. Of the 25 chips, the number of chips holding the protective film was measured.
  • peeling test About the test body in which the protective film was hold
  • QM Dicyclopentenyloxyethyl methacrylate (Rohm & Haas, “QM-657”)
  • BZ benzyl methacrylate (manufactured by Kyoeisha Chemical Co., “Light Ester BZ”)
  • UV-7000B Polyurethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., “UV-7000B”)
  • UV-3000B Polyester urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., “UV-3000B”)
  • 1,6-HX-A 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “Light acrylate 1,6-HX-A”)
  • M-5300 ⁇ -carboxy-polycaprolactone monoacrylate (manufactured by Toa Gosei Co., Ltd., “
  • Example II-1 and II-2 A curable composition was prepared in the same manner as in Experimental Example I-1, except that the heat treatment was performed at the temperature shown in Table 2. The obtained curable composition was evaluated in the same manner as in Experimental Example I-1. The results are shown in Table 2. In addition, “ ⁇ ” of the heat treatment temperature in Experimental Example II-1 means that the heat treatment was not performed.
  • the protective film is provided on the surface of the workpiece, the protective film is heat-treated, and then the workpiece is processed to prevent the protective film from falling off during processing. It is possible to protect the surface of the workpiece from contamination and contamination. Moreover, since the curable composition of the present invention has sufficient followability to irregularities on the surface such as a circuit surface, the surface is protected not only from smooth surfaces but also from irregularities to scratches and contamination. It is possible.
  • the protective film of the present invention can be recovered from the workpiece in the form of a film by immersing it in warm water of 90 ° C. or less after the workpiece is processed, an effect of excellent workability can be obtained. Furthermore, it is not necessary to use an organic solvent that is indispensable for conventional adhesives, and the effect of reducing the environmental load can be obtained.
  • a protective film is provided on the surface of a workpiece using the curable composition. In the present invention, for example, even if dicing is performed under a condition where the feed rate is 2 mm / sec or less, an effect that the protective film does not fall off during processing can be obtained.
  • the surface protection method of the present invention has a protective film made of a curable composition that has photocurability because of its composition, and is cured by visible light or ultraviolet light. Therefore, it saves labor and energy compared to conventional hot melt adhesives. A remarkable effect can be obtained in terms of speed and work shortening.
  • a heat treatment process is performed to reduce internal strain of the protective film, and the protective film is prevented from falling off in the subsequent machining process of the workpiece. Can do.
  • the protective film can exhibit high adhesive strength without affecting the cutting fluid used at the time of processing, and the work material can be removed from the entrance of the cutting fluid, scratches due to cutting waste, etc. The surface can be protected. Since the effects as described above are obtained, the present invention is useful in industries such as engineering parts, processing of electronic parts such as sensors, and electrical parts, particularly precision processing such as cutting, grinding, and polishing.

Abstract

Disclosed is a surface protection method which can prevent the detachment of a protective film even when a processing such as dicing is carried out. Specifically disclosed is a method for protecting the surface of a material to be processes by laminating a protective film on the surface of the material.  The method is characterized by comprising: a lamination step of laminating the protective film on the surface of the material, wherein the protective film is composed of a cured material formed from a curable composition comprising (A) a polyfunctional (meth)acrylate (B), a monofunctional (meth)acrylate and (C) a photopolymerization initiator; subsequent to the lamination step, a heating step of heating the laminated product to 80 to 150°C; and, subsequent to the heating step, a processing step of processing the material.  Preferably, the protective film additionally contains (D) a resin having a cyclopentadiene skeleton.

Description

被加工材の表面保護方法および仮固定方法Surface protection method and temporary fixing method of work material
　本発明は、いろいろな材料を加工するに際しての当該被加工材の表面保護方法と仮固定方法に関する。より詳細には、本発明は、光学用部材や半導体ウエハ等を加工するに際し、被加工材の表面に硬化性組成物からなる保護膜（以下、硬化体ということもある）を設けることで、加工しない部分を加工時の異物付着や傷等から保護することを目的とする被加工材の表面保護方法を提示する。さらに、本発明は、基材に当該被加工材を接着し、被加工材を加工した後、接着部分を温水に浸漬して、前記保護膜を取り外すことで、被加工材を回収することを特徴とする被加工材の仮固定方法も提示するものである。 The present invention relates to a surface protection method and a temporary fixing method of the workpiece when processing various materials. More specifically, the present invention provides a protective film made of a curable composition (hereinafter sometimes referred to as a cured body) on the surface of a workpiece when processing an optical member, a semiconductor wafer, or the like. A method for protecting the surface of a workpiece, which is intended to protect a portion not to be processed from foreign matter adhesion or scratches during processing, is presented. Furthermore, the present invention is to collect the workpiece by bonding the workpiece to the base material, processing the workpiece, immersing the bonded portion in warm water, and removing the protective film. A characteristic method of temporarily fixing the workpiece is also presented.
　金属板、金型、アルミサッシ、プラスチック板、半導体ウエハ、回路基板、セラミック、ガラス、石英等の工学部品、およびセンサー等の電子、電気部品の加工、特に切断、研削、研磨等の精密加工等に際して、その被加工材の既加工面や回路、センサー部位等への傷や異物付着を防止するために、一時的に部品を保護する表面保護膜が広く使用されている。その表面保護膜としては、感圧接着性シートが主に用いられている。 Metal plates, molds, aluminum sashes, plastic plates, semiconductor wafers, circuit boards, engineering parts such as ceramics, glass and quartz, and electronic and electrical parts such as sensors, especially precision machining such as cutting, grinding and polishing At the time, in order to prevent scratches and foreign matter adhesion to the already processed surface, circuit, sensor site, etc. of the workpiece, a surface protective film that temporarily protects components is widely used. As the surface protective film, a pressure-sensitive adhesive sheet is mainly used.
　例えば、半導体ウエハ、光学部品等の薄型化を行う場合、いわゆる裏面研削方法で加工される。裏面研削方法とは、表面保護シートでウエハの回路面や光学部品の非加工面を保護すると共に、前記表面保護シートを介して基材に仮固定し、回路面とは反対側の裏面を研削する方法である。 For example, when thinning a semiconductor wafer, an optical component, etc., it is processed by a so-called back grinding method. The back surface grinding method protects the circuit surface of the wafer and the non-processed surface of the optical component with the surface protection sheet, and temporarily fixes the substrate to the substrate via the surface protection sheet, and grinds the back surface opposite to the circuit surface. It is a method to do.
　しかし、現在使用されている感圧接着性の表面保護シートは半導体ウエハの回路の凹凸に対する追従性に限界がある。このため、ウエハと表面保護層との間への研削液の進入等によるコンタミネーションがしばしば問題となる。また、半導体ウエハをダイシング（Dicing）する際にも、典型的な半導体表面保護シートでは、バンプに代表される１００μｍ以上の突起に追従することができず、コンタミネーションやチップ飛びを起こすという問題があった。 However, the pressure-sensitive adhesive surface protection sheet currently in use has a limit in the ability to follow the irregularities of the circuit of the semiconductor wafer. For this reason, contamination due to the ingress of the grinding liquid between the wafer and the surface protective layer often becomes a problem. In addition, when a semiconductor wafer is diced, a typical semiconductor surface protection sheet cannot follow protrusions of 100 μm or more typified by bumps, causing a problem of contamination and chip jumping. there were.
　従来の表面保護シートは、一般に、ポリマーフィルム材料上に表面保護層として粘着剤層を有するシートであり、粘着剤は回路面の凹凸に追従するように低弾性率を有するように設計されている。しかしながら、弾性率が低すぎると、シートをウエハから剥離除去する際に大きな応力がウエハに掛かり、ウエハの破損につながる。 Conventional surface protective sheets are generally sheets having a pressure-sensitive adhesive layer as a surface protective layer on a polymer film material, and the pressure-sensitive adhesive is designed to have a low elastic modulus so as to follow the irregularities of the circuit surface. . However, if the elastic modulus is too low, a large stress is applied to the wafer when the sheet is peeled off from the wafer, leading to damage of the wafer.
　そこで、シートを剥離する前に紫外線等のエネルギー線を照射することにより粘着剤を硬化し、ウエハ・保護シート間の接着力を低下させるエネルギー線易剥離型保護シートが開発されている。しかしながら、研削の間は粘着剤層が未硬化の状態であり、柔軟すぎて研削中にウエハが破損するという問題がある。 Therefore, an energy ray easily peelable protective sheet has been developed that cures the pressure-sensitive adhesive by irradiating energy rays such as ultraviolet rays before peeling the sheet, and reduces the adhesive force between the wafer and the protective sheet. However, the pressure-sensitive adhesive layer is in an uncured state during grinding, and there is a problem that the wafer is damaged during grinding because it is too soft.
　特許文献１は、上記のようなエネルギー線易剥離型保護シートを回路が形成されたウエハに貼り付け、エネルギー線で粘着剤層を硬化した後に、ウエハの裏面研削を行うウエハ研削方法を開示している。しかしながら、粘着剤は流動体ではないため、ウエハ回路面の凹凸に対する追従性が十分ではない。 Patent Document 1 discloses a wafer grinding method in which the energy ray easy-peelable protective sheet as described above is attached to a wafer on which a circuit is formed, and the adhesive layer is cured with energy rays, and then the back surface of the wafer is ground. ing. However, since the pressure-sensitive adhesive is not a fluid, the followability to the unevenness of the wafer circuit surface is not sufficient.
　一方、特許文献２には、ホットメルト型の半導体表面保護シートが開示されている。６０～１００℃に加熱することにより溶融し流動性を示すホットメルト型シートは、回路面の凹凸に追従し、優れた研削性を示すことができる。しかしながら、このシートは温度が融点を上回る度に溶融する性質がある。 On the other hand, Patent Document 2 discloses a hot-melt type semiconductor surface protective sheet. A hot-melt type sheet that melts and exhibits fluidity when heated to 60 to 100 ° C. can follow the unevenness of the circuit surface and exhibit excellent grindability. However, this sheet has the property of melting whenever the temperature exceeds the melting point.
　上記問題を解決するため、本発明者はウエハ、光学部品の回路面の凹凸に対する追従性が十分にある材料であって、かつ研削時の支持体として十分な剛性を有する組成物として、特定の（メタ）アクリルモノマーを含有する樹脂からなる樹脂組成物を提案している（特許文献３、および４参照）。上記樹脂組成物は裏面研削時の表面保護には有効である。しかしながら、表面保護の際に、表面が完全に硬化する樹脂組成物が要求されている。表面研削・切断時の表面保護の際に酸素による重合阻害を受けると、表面が完全に硬化しない場合がありうるからである。 In order to solve the above-mentioned problems, the present inventor has specified a specific material as a composition that has sufficient followability to the unevenness of the circuit surface of a wafer or optical component and has sufficient rigidity as a support during grinding. The resin composition which consists of resin containing a (meth) acryl monomer is proposed (refer patent document 3 and 4). The resin composition is effective for surface protection during back grinding. However, there is a demand for a resin composition whose surface is completely cured during surface protection. This is because the surface may not be completely cured if it is subjected to polymerization inhibition by oxygen during surface protection during surface grinding / cutting.
　一方、表面保護シートとは別に、特定の有機溶剤に溶解する紫外線硬化型接着剤を加工物表面に塗布し、紫外線硬化させることで被覆し、加工時の切削屑等から表面を保護する方法が検討されている。しかしながら、有機溶剤を用いるため洗浄処理工程が煩雑で作業環境的に問題があり、また微細な凹凸の場合、有機溶剤が充分に浸透できず保護膜を完全に除去できないため、該被加工物の外観上の問題が発生している。 On the other hand, apart from the surface protection sheet, there is a method of applying a UV curable adhesive that dissolves in a specific organic solvent to the surface of the workpiece and coating it by UV curing to protect the surface from cutting chips etc. during processing. It is being considered. However, since the organic solvent is used, the cleaning process is complicated and there are problems in the working environment. In the case of fine irregularities, the organic solvent cannot sufficiently penetrate and the protective film cannot be completely removed. An appearance problem has occurred.
　ウエハ、光学部品などの回路面の凹凸に対する追従性が十分であり、かつ研削時の支持体として十分な剛性を有する組成物として、（メタ）アクリルモノマーとシクロペンタジエン骨格を含有する樹脂とを成分とする、樹脂組成物が提案されている（特許文献５参照）。 As a composition that has sufficient followability to irregularities on the circuit surface of wafers, optical components, etc., and has sufficient rigidity as a support during grinding, a (meth) acrylic monomer and a resin containing a cyclopentadiene skeleton are used as components. A resin composition has been proposed (see Patent Document 5).
特開平１１－０２６４０６号公報Japanese Patent Laid-Open No. 11-026406 特開２０００－０３８５５６号公報Japanese Unexamined Patent Publication No. 2000-038556 国際公開ＷＯ２００７／００４６２０パンフレットInternational Publication WO2007 / 004620 Pamphlet 国際公開ＷＯ２００６／１００７８８パンフレットInternational Publication WO2006 / 100788 Pamphlet 特開２００７－１８６５８７号公報Japanese Patent Laid-Open No. 2007-186587
　しかしながら、前記特許文献５には、前記樹脂組成物を用いて被加工材の表面に保護膜を設け、かつ、８０～１５０℃に加熱処理する加熱工程を設けることについて記載はない。さらに、加熱工程を設けた場合、ダイシングを行っても加工時に保護膜が脱落しないことについての記載もない。 However, Patent Document 5 does not describe provision of a heating process in which a protective film is provided on the surface of a workpiece using the resin composition and heat treatment is performed at 80 to 150 ° C. Further, when a heating step is provided, there is no description that the protective film does not fall off during processing even if dicing is performed.
　本発明者は前記問題点を解決するために鋭意検討した結果、被加工材の表面に前記硬化性組成物からなる保護膜を設けた後に、保護膜の加熱処理を行い、その後被加工材の加工を行うことで、加工時に保護膜が脱落することなく、前記被加工材の表面を保護することができるとの知見を得て、本発明を完成するに至ったものである。 As a result of intensive studies to solve the above problems, the present inventor conducted a heat treatment of the protective film after providing a protective film made of the curable composition on the surface of the processed material, and then processed the workpiece. By performing the processing, the inventors have obtained knowledge that the surface of the workpiece can be protected without dropping the protective film during processing, and have completed the present invention.
　即ち、本発明は、被加工材の表面に硬化性組成物からなる保護膜を設ける、被加工材の表面保護方法において、被加工材の表面に保護膜を積層後、保護膜を加熱処理する工程を経て、その後被加工材の加工を行うことを特徴とする、被加工材の表面保護方法である。 That is, the present invention provides a method for protecting a surface of a workpiece by providing a protective film made of a curable composition on the surface of the workpiece, and after the protective film is laminated on the surface of the workpiece, the protective film is heat-treated. A method for protecting a surface of a workpiece, wherein the workpiece is processed through a process.
　また、本発明は、被加工材の表面に硬化性組成物からなる保護膜を設けて加熱処理を行った後、被加工材の加工を行い、その後、９０℃以下の温水に浸漬して前記硬化性組成物からなる保護膜を前記被加工材から取り外すことを特徴とする、被加工材の仮固定方法である。 In the present invention, a protective film made of a curable composition is provided on the surface of the workpiece, and after the heat treatment, the workpiece is processed, and then immersed in warm water of 90 ° C. or less. A method for temporarily fixing a workpiece, comprising removing a protective film made of a curable composition from the workpiece.
　具体的には、本発明は、以下の通りである。
　本発明は、下記（Ａ）、（Ｂ）及び（Ｃ）を含有する硬化性組成物から形成される硬化体からなる保護膜を被加工材の表面に積層する積層工程と、積層工程後に８０～１５０℃に加熱処理する加熱工程と、加熱工程後に被加工材を加工する加工工程とを有することを特徴とする、被加工材の表面に保護膜を積層する被加工材の表面保護方法である。
　（Ａ）多官能（メタ）アクリレート
　（Ｂ）単官能（メタ）アクリレート
　（Ｃ）光重合開始剤
　さらに、前記保護膜が、（Ｄ）シクロペンタジエン骨格を有する樹脂を含有する請求項１に記載の被加工材の表面保護方法である。
　また、前記（Ｄ）シクロペンタジエン骨格を含有する樹脂が、分子内にエステル基又は水酸基を含有する該被加工材の表面保護方法である。
　また、前記（Ａ）多官能（メタ）アクリレートと、前記（Ｂ）単官能（メタ）アクリレートとが、いずれも疎水性である該被加工材の表面保護方法である。 Specifically, the present invention is as follows.
The present invention includes a laminating step of laminating a protective film formed of a curable composition containing the following (A), (B) and (C) on the surface of a workpiece, and 80 after the laminating step. A method for protecting a surface of a workpiece by laminating a protective film on the surface of the workpiece, comprising: a heating step of heat-treating to 150 ° C; and a processing step of processing the workpiece after the heating step. is there.
(A) Polyfunctional (meth) acrylate (B) Monofunctional (meth) acrylate (C) Photoinitiator Furthermore, the said protective film contains resin which has (D) cyclopentadiene frame | skeleton. This is a method for protecting the surface of a workpiece.
The (D) resin containing a cyclopentadiene skeleton is a method for protecting the surface of the workpiece, wherein the molecule contains an ester group or a hydroxyl group.
Moreover, the (A) polyfunctional (meth) acrylate and the (B) monofunctional (meth) acrylate are both hydrophobic methods for protecting the surface of the workpiece.
　また、前記硬化性組成物が、（Ａ）と（Ｂ）との合計量１００質量部中、（Ａ）多官能（メタ）アクリレートを５～５０質量部と（Ｂ）単官能（メタ）アクリレートを５０～９５質量部とを含有し、（Ａ）と（Ｂ）との合計量１００質量部に対して、（Ｃ）光重合開始剤を０．１～２０質量部と（Ｄ）シクロペンタジエン骨格を有する樹脂を０．１～５０質量部とを含有する該被加工材の表面保護方法である。 The curable composition comprises 5 to 50 parts by mass of (A) polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate in 100 parts by mass of the total amount of (A) and (B). And (C) 0.1-20 parts by weight of a photopolymerization initiator and (D) cyclopentadiene with respect to 100 parts by weight of the total amount of (A) and (B). A method for protecting a surface of a workpiece, comprising 0.1 to 50 parts by mass of a resin having a skeleton.
　また、下記（Ａ）、（Ｂ）及び（Ｃ）を含有する硬化性組成物から形成される硬化体からなる保護膜を被加工材の表面に積層する積層工程と、積層工程後に８０～１５０℃に加熱処理する加熱工程と、加熱工程後に被加工材の加工を行う加工工程と、加工工程後に被加工材を９０℃以下の温水に浸漬して前記保護膜を前記被加工材から取り外す取り外し工程とを有することを特徴とする、被加工材の表面に保護膜を積層する被加工材の仮固定方法である。
　（Ａ）多官能（メタ）アクリレート
　（Ｂ）単官能（メタ）アクリレート
　（Ｃ）光重合開始剤 Further, a laminating step of laminating a protective film made of a cured product formed from a curable composition containing the following (A), (B) and (C) on the surface of the workpiece, and 80 to 150 after the laminating step A heating step in which heat treatment is performed at a temperature of C; a processing step in which the workpiece is processed after the heating step; and a removal in which the workpiece is immersed in warm water of 90 ° C. or less after the processing step to remove the protective film from the workpiece A temporary fixing method for a workpiece, wherein a protective film is laminated on the surface of the workpiece.
(A) Multifunctional (meth) acrylate (B) Monofunctional (meth) acrylate (C) Photopolymerization initiator
　本発明の被加工材の表面保護方法は、ダイシング等の加工を行っても、保護膜が脱落しないという効果が得られ、被加工材の既加工面や回路、センサー部位等への傷や異物付着を防止することができる。 The method for protecting the surface of a workpiece according to the present invention is effective in that the protective film does not fall off even if processing such as dicing is performed, and scratches or foreign matter on the processed surface, circuit, sensor site, etc. of the workpiece Adhesion can be prevented.
　本発明は、被加工材の表面に硬化性組成物から形成される保護膜を設けた後、保護膜を８０～１５０℃に加熱処理し、その後、被加工材の加工を行うことで、加工時における保護膜の脱落を防止することを特徴とする被加工材の表面保護方法である。
　加熱処理の温度は、保護膜の剥離性を保持するという観点から８０～１５０℃が好ましく、９０～１２０℃がより好ましい。８０℃以上ならば加熱処理による効果が得られ、１５０℃以下ならば剥離性が良好である。 In the present invention, a protective film formed from a curable composition is provided on the surface of a workpiece, and then the protective film is heated to 80 to 150 ° C., and then the workpiece is processed. This is a method for protecting the surface of a workpiece, characterized in that the protective film is prevented from falling off.
The temperature of the heat treatment is preferably 80 to 150 ° C., more preferably 90 to 120 ° C. from the viewpoint of maintaining the peelability of the protective film. If it is 80 degreeC or more, the effect by heat processing will be acquired, and if it is 150 degrees C or less, peelability is favorable.
　本発明で保護膜として使用される硬化性組成物は、（Ａ）多官能（メタ）アクリレートと、（Ｂ）単官能（メタ）アクリレートと、（Ｃ）光重合開始剤と、（Ｄ）シクロペンタジエン骨格を含有する樹脂と、を含有することが上記発明の効果を得る上で好ましい。 The curable composition used as a protective film in the present invention includes (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C) photopolymerization initiator, and (D) cyclohexane. It is preferable to contain a resin containing a pentadiene skeleton in order to obtain the effects of the present invention.
　上記硬化性組成物で使用される（Ａ）多官能（メタ）アクリレートとしては、２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレートオリゴマー／ポリマー／モノマーを使用することができる。例えば、多官能（メタ）アクリレートオリゴマー／ポリマーとしては１，２-ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、日本曹達社製、「ＴＥ－２０００」、「ＴＥＡ－１０００」）、前記水素添加物（例えば、日本曹達社製、「ＴＥＡＩ－１０００」）、１，４－ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、大阪有機化学社製、「ＢＡＣ－４５」）、ポリイソプレン末端（メタ）アクリレート、ポリウレタンアクリレート（例えば、日本合成社製「ＵＶ－７０００Ｂ」）、ポリエステル系ウレタン（メタ）アクリート（例えば、日本合成社製、「ＵＶ－３０００Ｂ」）、ポリエーテル系ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、ビスフェノールＡ型エポキシ（メタ）アクリレート（例えば、大阪有機化学社製、「ビスコート＃５４０」、昭和高分子社製、「ビスコートＶＲ－７７」）等が挙げられる。これらの中では、剥離性の効果が大きい点で、１，２-ポリブタジエン末端ウレタン（メタ）アクリレート、ポリウレタンアクリレートオリゴマー、及びポリエステル系ウレタンアクリレートオリゴマーからなる群より選ばれる１種又は２種以上が好ましく、１，２-ポリブタジエン末端ウレタン（メタ）アクリレートがより好ましい。 The polyfunctional (meth) acrylate oligomer / polymer / monomer having two or more (meth) acryloyl groups can be used as the (A) polyfunctional (meth) acrylate used in the curable composition. For example, as the polyfunctional (meth) acrylate oligomer / polymer, 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, “TE-2000”, “TEA-1000” manufactured by Nippon Soda Co., Ltd.), the hydrogenated product ( For example, Nippon Soda Co., Ltd., “TEAI-1000”), 1,4-polybutadiene terminated urethane (meth) acrylate (for example, “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene terminated (meth) acrylate, polyurethane Acrylate (for example, “UV-7000B” manufactured by Nippon Gosei Co., Ltd.), polyester urethane (meth) acrylate (for example, “UV-3000B” manufactured by Nihon Gosei Co., Ltd.), polyether urethane (meth) acrylate, polyester (meth) Acrylate, bisphenol A type epoxy (meth) acrylate (For example, “Biscoat # 540” manufactured by Osaka Organic Chemical Co., Ltd., “Biscoat VR-77” manufactured by Showa Polymer Co., Ltd.) and the like. Among these, one or two or more selected from the group consisting of 1,2-polybutadiene-terminated urethane (meth) acrylate, polyurethane acrylate oligomer, and polyester-based urethane acrylate oligomer is preferable in that the effect of peelability is great. 1,2-polybutadiene terminated urethane (meth) acrylate is more preferred.
　さらに２官能（メタ）アクリレートモノマーとしては、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、２－エチル－２－ブチル－プロパンジオール（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、ステアリン酸変性ペンタエリスリトールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、２，２－ビス（４－（メタ）アクリロキシジエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシプロポキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシテトラエトキシフェニル）プロパン等が挙げられる。
３官能（メタ）アクリレートモノマーとしては、トリメチロールプロパントリ（メタ）アクリレート、トリス［（メタ）アクリロイキシエチル］イソシアヌレート等が挙げられる。 Further, bifunctional (meth) acrylate monomers include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis ( 4- (meth) a Lilo propoxy phenyl) propane, 2,2-bis (4- (meth) acryloxy-tetra-ethoxyphenyl) propane.
Examples of the trifunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate and tris [(meth) acryloxyethyl] isocyanurate.
　４官能以上の（メタ）アクリレートモノマーとしては、ジメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールエトキシテトラ（メタ）アクリレート、ジペンタエリストールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
　これらの中では、剥離性の効果が大きい点で、ジシクロペンタニルジ（メタ）アクリレート及び／又は１，６－ヘキサンジオールジ（メタ）アクリレートが好ましく、ジシクロペンタニルジ（メタ）アクリレートがより好ましい。
　（Ａ）多官能（メタ）アクリレートの中では、剥離性の効果が大きい点で、２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレートオリゴマー／ポリマーと、２官能（メタ）アクリレートモノマーとを併用することが好ましい。２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレートオリゴマー／ポリマーと、２官能（メタ）アクリレートモノマーとの混合割合（質量比）は、剥離性の効果が大きい点で、３０～１００：７０～０が好ましく、５０～６５：５０～３５がより好ましい。 Examples of the tetra- or higher functional (meth) acrylate monomer include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerystol penta (meth) acrylate, and dipenta Examples include erythritol hexa (meth) acrylate.
Among these, dicyclopentanyl di (meth) acrylate and / or 1,6-hexanediol di (meth) acrylate is preferable and dicyclopentanyl di (meth) acrylate is preferable in that the effect of peelability is large. More preferred.
(A) Among polyfunctional (meth) acrylates, polyfunctional (meth) acrylate oligomers / polymers having two or more (meth) acryloyl groups and bifunctional (meth) acrylates in terms of a large effect of peelability It is preferable to use a monomer together. The mixing ratio (mass ratio) of the polyfunctional (meth) acrylate oligomer / polymer having two or more (meth) acryloyl groups and the bifunctional (meth) acrylate monomer is 30 to 30 100: 70 to 0 is preferable, and 50 to 65:50 to 35 is more preferable.
　本発明で使用する（Ａ）多官能（メタ）アクリレートは、疎水性のものがより好ましい。疎水性の場合には、水溶性の場合に発生しがちの現象、即ち、加工時に硬化性組成物の硬化体が膨潤することにより位置ずれを起こし加工精度が劣る現象を防止できる。ここで、疎水性の多官能（メタ）アクリレートとは、水酸基を有さない（メタ）アクリレートをいう。例えば、上記の多官能（メタ）アクリレート等が挙げられる。これらの中では、１，２-ポリブタジエン末端ウレタン（メタ）アクリレート、１，６－ヘキサジオールジ（メタ）アクリレート及びジシクロペンタニルジ（メタ）アクリレートからなる群より選ばれる１種又は２種以上が好ましい。親水性であっても、その硬化性組成物の硬化体が水によって大きく膨潤もしくは一部溶解することがなければ、使用しても差し支えない。 The hydrophobic (A) polyfunctional (meth) acrylate used in the present invention is more preferable. In the case of hydrophobicity, it is possible to prevent a phenomenon that tends to occur when it is water-soluble, that is, a phenomenon in which the cured product of the curable composition swells during processing to cause displacement and poor processing accuracy. Here, the hydrophobic polyfunctional (meth) acrylate refers to (meth) acrylate having no hydroxyl group. For example, the above-mentioned polyfunctional (meth) acrylates can be mentioned. Among these, one or more selected from the group consisting of 1,2-polybutadiene-terminated urethane (meth) acrylate, 1,6-hexadiol di (meth) acrylate and dicyclopentanyl di (meth) acrylate Is preferred. Even if it is hydrophilic, it can be used as long as the cured product of the curable composition is not greatly swollen or partially dissolved by water.
　（Ａ）多官能（メタ）アクリレートの使用量は、（Ａ）及び後述する（Ｂ）単官能（メタ）アクリレート成分の合計量１００質量部中、５～５０質量部が好ましく、２０～４０質量部がより好ましい。５質量部以上ならば、剥離性が低下したり、硬化性組成物の硬化体がフィルム状とならなかったりすることを防止でき、５０質量部以上ならば、硬化収縮が大きくなり初期の接着性が低下する恐れもない。 The amount of (A) polyfunctional (meth) acrylate used is preferably 5 to 50 parts by mass, preferably 20 to 40 parts by mass in 100 parts by mass of the total amount of (A) and the later-described (B) monofunctional (meth) acrylate component. Part is more preferred. If it is 5 parts by mass or more, it is possible to prevent the peelability from decreasing or the cured product of the curable composition from becoming a film, and if it is 50 parts by mass or more, the shrinkage of curing increases and the initial adhesiveness. There is no fear that it will fall.
　上記硬化性組成物で使用される（Ｂ）単官能（メタ）アクリレートモノマーとしては、　メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メトキシ化シクロデカトリエン（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、ｔ－ブチルアミノエチル（メタ）アクリレート、エトキシカルボニルメチル（メタ）アクリレート、フェノールエチレンオキサイド変性（メタ）アクリレート、フェノール（エチレンオキサイド２モル変性）（メタ）アクリレート、フェノール（エチレンオキサイド４モル変性）（メタ）アクリレート、パラクミルフェノールエチレンオキサイド変性（メタ）アクリレート、ノニルフェノールエチレンオキサイド変性（メタ）アクリレート、ノニルフェノール（エチレンオキサイド４モル変性）（メタ）アクリレート、ノニルフェノール（エチレンオキサイド８モル変性）（メタ）アクリレート、ノニルフェノール（プロピレンオキサイド２．５モル変性）（メタ）アクリレート、２－エチルヘキシルカルビトール（メタ）アクリレート、エチレンオキサイド変性フタル酸（メタ）アクリレ－ト、エチレンオキサイド変性コハク酸（メタ）アクリレート、トリフロロエチル（メタ）アクリレート、アクリル酸、メタクリル酸、マレイン酸、フマル酸、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸ダイマー、β－（メタ）アクリロイルオキシエチルハイドロジェンサクシネート、ｎ－（メタ）アクリロイルオキシアルキルヘキサヒドロフタルイミド、２－（１，２－シクロヘキサンジカルボキシイミド）エチル（メタ）アクリレート等が挙げられる。 Examples of the (B) monofunctional (meth) acrylate monomer used in the curable composition include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy- 3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, ω-carboxy-polycaprolactone mono (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) ) Acrylate, phenol ethylene oxide modified (meth) acrylate, phenol (ethylene oxide 2 mol modified) (meth) acrylate, phenol (ethylene oxide 4 mol modified) (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, Nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 8 mol modified) (meth) acrylate, nonylphenol (2.5 mol modified propylene oxide) (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified Succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, ( (Meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) acryloyloxyalkylhexahydrophthalimide, 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate, etc. Can be mentioned.
　これらの中では、剥離性の効果が大きい点で、２－（１，２－シクロヘキサンジカルボキシイミド）エチル（メタ）アクリレート、フェノールエチレンオキサイド２モル変性（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート、および２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレートからなる群より選ばれる１種又は２種以上が好ましく、２－（１，２－シクロヘキサンジカルボキシイミド）エチル（メタ）アクリレート及び／又はフェノールエチレンオキサイド２モル変性（メタ）アクリレートがより好ましい。フェノールエチレンオキサイド２モル変性（メタ）アクリレートと、２－（１，２－シクロヘキサンジカルボキシイミド）エチル（メタ）アクリレートとの混合割合（質量比）は、剥離性の効果が大きい点で、２０～７０：８０～３０が好ましく、３０～４５：７０～５５がより好ましい。 Among these, 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate, phenol ethylene oxide 2 molar modified (meth) acrylate, dicyclopentenyloxyethyl (meta ) Acrylate, benzyl (meth) acrylate, ω-carboxy-polycaprolactone mono (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate are preferably used. -(1,2-cyclohexanedicarboximido) ethyl (meth) acrylate and / or phenol ethylene oxide 2 molar modified (meth) acrylate is more preferred. The mixing ratio (mass ratio) of phenol ethylene oxide 2 mol-modified (meth) acrylate and 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate is 20 to 20 70:80 to 30 is preferable, and 30 to 45:70 to 55 is more preferable.
　（Ｂ）単官能（メタ）アクリレートは、（Ａ）成分と同様に疎水性のものが好ましい。 (B) The monofunctional (meth) acrylate is preferably hydrophobic as in the case of the component (A).
　ここで、疎水性とは、水酸基を有さない（メタ）アクリレートをいう。疎水性の場合には、水溶性の場合に発生しがちの現象、即ち、加工時に硬化性組成物の硬化体が膨潤することにより位置ずれを起こし、加工精度が劣る現象を防止できる。また、親水性であっても、その硬化性組成物の硬化体が水によって膨潤もしくは一部溶解することがなければ、使用しても差し支えない。 Here, hydrophobic means (meth) acrylate having no hydroxyl group. In the case of hydrophobicity, it is possible to prevent a phenomenon that tends to occur when water-soluble, that is, a phenomenon in which the cured product of the curable composition swells during processing to cause displacement and poor processing accuracy. Even if it is hydrophilic, it may be used as long as the cured product of the curable composition does not swell or partially dissolve with water.
　（Ｂ）単官能（メタ）アクリレートの使用量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部中、５０～９５質量部が好ましく、６０～８０質量部がより好ましい。５０質量部以上ならば初期の接着性が低下する恐れもなく、９５質量部以下ならば、剥離性が低下することもなく、硬化性組成物の硬化体がフィルム状で得られる。 The amount of the (B) monofunctional (meth) acrylate used is preferably 50 to 95 parts by mass, more preferably 60 to 80 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). If it is 50 parts by mass or more, the initial adhesiveness is not likely to be lowered, and if it is 95 parts by mass or less, the peelability is not lowered, and a cured product of the curable composition is obtained in a film form.
　また、前記組成の（Ａ）成分及び（Ｂ）成分に、さらに（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジブチル２－（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジオクチル２－（メタ）アクリロイルオキシエチルフォスフェート、ジフェニル２－（メタ）アクリロイルオキシエチルフォスフェート、（メタ）アクリロイルオキシエチルポリエチレングリコールアシッドフォスフェート等のビニル基又は（メタ）アクリロイル基を有するリン酸エステルを併用することで、金属面への密着性をさらに向上させることができる。 In addition, the (A) component and the (B) component of the above composition are further added to (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate By using together with phosphate ester having vinyl group or (meth) acryloyl group such as fete, diphenyl 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethylene glycol acid phosphate, Adhesion can be further improved.
　上記硬化性組成物で使用される（Ｃ）光重合開始剤は、可視光線や紫外線の活性光線により増感させて硬化性組成物の光硬化を促進するために使用するものであり、公知の各種光重合開始剤が使用可能である。具体的には、ベンゾフェノン及びその誘導体、ベンジル及びその誘導体、アントラキノン及びその誘導体、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン誘導体、ジエトキシアセトフェノン、４－ｔ－ブチルトリクロロアセトフェノン等のアセトフェノン誘導体、２－ジメチルアミノエチルベンゾエート、ｐ－ジメチルアミノエチルベンゾエート、ジフェニルジスルフィド、チオキサントン及びその誘導体、カンファーキノン、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボン酸、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボキシ－２－ブロモエチルエステル、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボキシ－２－メチルエステル、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボン酸クロライド等のカンファーキノン誘導体、２－メチル－１－［４-（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１等のα－アミノアルキルフェノン誘導体、ベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾイルジエトキシホスフィンオキサイド、２，４，６－トリメチルベンゾイルジメトキシフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジエトキシフェニルホスフィンオキサイド等のアシルホスフィンオキサイド誘導体等が挙げられる。（Ｃ）光重合開始剤は１種又は２種以上を組み合わせて用いることができる。 The (C) photopolymerization initiator used in the curable composition is used for sensitizing with actinic rays of visible light or ultraviolet rays to promote photocuring of the curable composition, and is known in the art. Various photopolymerization initiators can be used. Specifically, benzophenone and derivatives thereof, benzyl and derivatives thereof, anthraquinone and derivatives thereof, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin derivatives such as benzyl dimethyl ketal, diethoxyacetophenone, Acetophenone derivatives such as 4-t-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy- -Bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [ 2.2.1] Camphorquinone derivatives such as heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Α-aminoalkylphenone derivatives such as dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, , Etc. acylphosphine oxide derivatives such as 4,6-trimethylbenzoyl dichloride ethoxyphenyl phosphine oxide. (C) A photoinitiator can be used 1 type or in combination of 2 or more types.
　（Ｃ）光重合開始剤の使用量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対して、０．１～２０質量部が好ましく、３～１０質量部がより好ましい。０．１質量部以上ならば、硬化促進の効果が確実に得られ、２０質量部以下ならば充分な硬化速度が達成できる。より好ましい形態としては、（Ｃ）成分を３質量部以上使用することで、光照射量に依存なく硬化することができる。 (C) The amount of the photopolymerization initiator used is preferably 0.1 to 20 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). If it is 0.1 part by mass or more, the effect of promoting curing can be reliably obtained, and if it is 20 parts by mass or less, a sufficient curing rate can be achieved. As a more preferable form, it can harden | cure irrespective of light irradiation amount by using 3 mass parts or more of (C) component.
　本発明で使用する（Ｄ）シクロペンタジエン骨格を有する樹脂は、シクロペンタジエン骨格を有する樹脂ならばどのようなものでも構わないが、軟化点は５０～２００℃が好ましく、さらに数平均分子量（Ｍｎ）が３００～６００のものが（Ａ）成分や（Ｂ）成分への溶解性の面で望ましい。軟化点の測定はＪＩＳ　Ｋ　２２０７環球式に従った。数平均分子量の測定はＧＰＣ（ゲルパーミエーションクロマトグラフィー法）ポリスチレン換算値に従った。（Ｄ）としては、Ｃ５留分から抽出されたシクロペンタジエンを主原料に製造された石油樹脂が挙げられ、具体的には日本ゼオン社製の「クイントン１７００」、「クイントン１５００」、「クイントン１３２５」等が挙げられる。これらの中では、接着性の面で、水酸基を含有するものが好ましい。水酸基を含有するものとしては、「クイントン１７００」等が挙げられる。 The resin having a cyclopentadiene skeleton used in the present invention may be any resin having a cyclopentadiene skeleton, but the softening point is preferably 50 to 200 ° C., and the number average molecular weight (Mn) Is preferably from 300 to 600 in terms of solubility in the component (A) and the component (B). The softening point was measured according to JIS K 2207 ring and ball system. The number average molecular weight was measured according to GPC (gel permeation chromatography) polystyrene conversion value. Examples of (D) include petroleum resins produced using cyclopentadiene extracted from the C5 fraction as a main raw material. Specifically, “Quinton 1700”, “Quinton 1500”, “Quinton 1325” manufactured by Nippon Zeon Co., Ltd. Etc. Among these, those containing a hydroxyl group are preferable in terms of adhesiveness. Examples of those containing a hydroxyl group include “Quinton 1700”.
　（Ｄ）シクロペンタジエン骨格を有する樹脂の使用量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対して、０．５～５０質量部が好ましく、５～３０質量部がより好ましい。０．５質量部以上ならば、フィルムを形成せずに糊残りすることもなく、５０質量部以下ならば接着性が低下することもない。 (D) The amount of the resin having a cyclopentadiene skeleton is preferably 0.5 to 50 parts by mass and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). preferable. If the amount is 0.5 parts by mass or more, no adhesive remains without forming a film, and if it is 50 parts by mass or less, the adhesiveness does not decrease.
　本発明の硬化性組成物は、その貯蔵安定性向上のため少量の重合禁止剤を使用することができる。例えば重合禁止剤としては、メチルハイドロキノン、ハイドロキノン、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、２，５－ジターシャリーブチルハイドロキノン、ｐ－ベンゾキノン、２，５－ジフェニル－ｐ－ベンゾキノン、２，５－ジターシャリーブチル－ｐ－ベンゾキノン、ピクリン酸、クエン酸、フェノチアジン、ターシャリーブチルカテコール、２－ブチル－４－ヒドロキシアニソール及び２，６－ジターシャリーブチル－ｐ－クレゾール等が挙げられる。 In the curable composition of the present invention, a small amount of a polymerization inhibitor can be used for improving the storage stability. For example, polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl Hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole, and Examples include 2,6-ditertiary butyl-p-cresol.
　これらの中では、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）、ハイドロキノンモノメチルエーテル及びｐ－ベンゾキノンからなる群のうちの１種又は２種以上が好ましく、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）がより好ましい。 Of these, one or more of the group consisting of 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), hydroquinone monomethyl ether and p-benzoquinone are preferred, More preferred is methylene-bis (4-methyl-6-tertiary butylphenol).
　これらの重合禁止剤の使用量は、（Ａ）成分及び（Ｂ）成分の合計量１００質量部に対し、０．００１～３質量部が好ましく、０．０１～２質量部がより好ましい。０．００１質量部以上であれば貯蔵安定性が充分であり、３質量部以下で確実な接着性が得られ、未硬化になるおそれもない。 The amount of these polymerization inhibitors used is preferably 0.001 to 3 parts by mass, and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). If it is 0.001 part by mass or more, the storage stability is sufficient, and if it is 3 parts by mass or less, reliable adhesiveness is obtained and there is no possibility of becoming uncured.
　本発明で用いる硬化性組成物は、本発明の目的を損なわない範囲で、一般に使用されているアクリルゴム、ウレタンゴム、アクリロニトリル－ブタジエン－スチレンゴム等の各種エラストマー、無機フィラー、溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤、シランカップリング剤及び界面活性剤等の添加剤を使用してもよい。 The curable composition used in the present invention includes various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, extenders, Additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
　本発明は、被加工材の表面に上記硬化性組成物からなる保護膜を設け、保護膜を加熱処理した後、被加工材の加工を行うことで、加工時の保護膜の脱落を防止し、被加工材の表面を保護することを特徴とする被加工材の表面保護方法である。 The present invention provides a protective film made of the above curable composition on the surface of the workpiece, heat-treats the protective film, and then processes the workpiece to prevent the protective film from falling off during processing. A method for protecting a surface of a workpiece, comprising protecting the surface of the workpiece.
　保護膜を被加工材の表面に積層する積層工程としては、被加工材の表面に厚さ２０～２００μｍ、好ましくは５０～１５０μｍの硬化性組成物を塗布して保護膜を設け、波長３６５ｎｍ、積算光量１０００～４０００ｍＪ／ｃｍ２、好ましくは１５００～３０００ｍＪ／ｃｍ２の条件下で硬化する工程が好ましい。
　積層工程後に加熱処理する加熱工程としては、保護膜を８０～１５０℃、好ましくは８０～１２０℃で、５～３０分間加熱処理する工程が好ましい。
　加熱工程後に被加工材を加工する加工工程としては、回転数５０００～４００００ｒｐｍ、好ましくは１００００～３５０００ｒｐｍ、送り速度０．２～５０ｍｍ／ｓｅｃ、好ましくは０．５～３０ｍｍ／ｓｅｃ、チップサイズ０．５～１５ｍｍ角の条件下でダイシングを行う工程が好ましい。 In the laminating step of laminating the protective film on the surface of the workpiece, a protective film is provided by applying a curable composition having a thickness of 20 to 200 μm, preferably 50 to 150 μm, on the surface of the workpiece, and the wavelength is 365 nm. integrated quantity of light 1000 ~ 4000mJ / cm 2, preferably preferred curing under the conditions of 1500 ~ 3000mJ / cm 2.
As the heating step of performing the heat treatment after the lamination step, a step of heat-treating the protective film at 80 to 150 ° C., preferably 80 to 120 ° C., for 5 to 30 minutes is preferable.
The processing step for processing the workpiece after the heating step includes a rotational speed of 5000 to 40000 rpm, preferably 10,000 to 35000 rpm, a feed rate of 0.2 to 50 mm / sec, preferably 0.5 to 30 mm / sec, a chip size of 0. A step of dicing under conditions of 5 to 15 mm square is preferable.
　また、本発明は被加工材の表面に硬化性組成物からなる保護膜を設け、加熱処理を行ったのち、被加工材の加工を行い、その後、７０～９０℃以下の温水、好ましくは７５～８５℃の温水に浸漬して前記硬化性組成物からなる保護膜を前記被加工材から取り外す取り外し工程を有することを特徴とする、被加工材の仮固定方法である。 Further, in the present invention, a protective film made of a curable composition is provided on the surface of the work material, and after heat treatment, the work material is processed, and then hot water of 70 to 90 ° C. or less, preferably 75. A method for temporarily fixing a workpiece, comprising a step of removing the protective film made of the curable composition from the workpiece by immersing in warm water at ˜85 ° C.
　前記硬化性組成物の硬化体を取り外すときは、フィルム状に部材から回収できるため、作業性に優れるという効果が得られる。尚、硬化体と温水との接触の方法については、温水中に被加工材ごと浸漬する方法が簡便であり、推奨される。 When removing the cured body of the curable composition, since it can be recovered from the member in the form of a film, an effect of excellent workability can be obtained. In addition, about the method of contact with a hardening body and warm water, the method of immersing the whole to-be-processed material in warm water is simple and recommended.
　以下に実験例を挙げて本発明を更に詳細に説明するが、本発明はこれら実験例に限定されて解釈されるものではない。
　なお、実験例Ｉ－１～Ｉ－１５は本発明の実施例であり、実験例II－１～II－５は比較例である。
（実験例Ｉ－１）
　（Ａ）多官能（メタ）アクリレートとして、日本曹達社製、「ＴＥ-２０００」（１，２-ポリブタジエン末端ウレタンメタクリレート、以下「ＴＥ－２０００」と略す。）２０質量部、ジシクロペンタニルジアクリレート（日本化薬社製、「ＫＡＹＡＲＡＤ　Ｒ－６８４」、以下「Ｒ－６８４」と略す。）１５質量部、（Ｂ）単官能（メタ）アクリレートとして、２－（１，２－シクロヘキサンジカルボキシイミド）エチルアクリレート（東亜合成社製、「アロニックスＭ－１４０」、以下「Ｍ－１４０」と略す。）４０質量部、およびフェノールエチレンオキサイド２モル変性アクリレート（東亜合成社製、「アロニックスＭ－１０１Ａ」、以下「Ｍ－１０１Ａ」と略す。）２５質量部からなる組成物の１００質量部に、（Ｃ）光重合開始剤として、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン（チバ・スペシャルティ・ケミカルズ社製、「ＩＲＧＡＣＵＲＥ９０７」、以下「Ｉ－９０７」と略す。）６質量部と、（Ｄ）シクロペンタジエン骨格を含有する樹脂として、シクロペンタジエン骨格樹脂（日本ゼオン社製、「Ｑｕｉｎｔｏｎｅ１７００」、水酸基を含有し、軟化点が１００℃であり、数平均分子量は３８０である。以下「Ｑｕｉｎｔｏｎｅ１７００」と略す。）１０質量部と、重合禁止剤として２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）（以下、「ＭＤＰ」と略す。）０．１質量部と、を配合して硬化性組成物を作製した。得られた硬化性組成物を使用して、以下に示す評価方法にて引張せん断接着強さの測定、密着性試験及び剥離試験を行った。結果を表１に示した。 The present invention will be described in more detail below with reference to experimental examples, but the present invention is not construed as being limited to these experimental examples.
Experimental Examples I-1 to I-15 are examples of the present invention, and Experimental Examples II-1 to II-5 are comparative examples.
(Experimental Example I-1)
(A) As polyfunctional (meth) acrylate, “TE-2000” (1,2-polybutadiene-terminated urethane methacrylate, hereinafter abbreviated as “TE-2000”) manufactured by Nippon Soda Co., Ltd., dicyclopentanyl di 15 parts by mass of acrylate (manufactured by Nippon Kayaku Co., Ltd., “KAYARAD R-684”, hereinafter abbreviated as “R-684”), (B) 2- (1,2-cyclohexanedicarboxy as monofunctional (meth) acrylate 40 parts by mass of imido) ethyl acrylate (Toa Gosei Co., Ltd., “Aronix M-140”, hereinafter abbreviated as “M-140”), and phenol ethylene oxide 2 mol modified acrylate (Toa Gosei Co., Ltd., “Aronix M-101A”) ”, Hereinafter abbreviated as“ M-101A ”.) (C) Photopolymerization initiator was added to 100 parts by mass of a composition comprising 25 parts by mass. 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, “IRGACURE907”, hereinafter abbreviated as “I-907”) As a resin containing 6 parts by mass and (D) cyclopentadiene skeleton, cyclopentadiene skeleton resin (manufactured by Nippon Zeon Co., Ltd., “Quintone 1700”, containing hydroxyl group, softening point is 100 ° C., number average molecular weight is 380 10 parts by mass and 2,2-methylene-bis (4-methyl-6-tert-butylphenol) (hereinafter abbreviated as “MDP”) 0.1 as a polymerization inhibitor A curable composition was prepared by blending with parts by mass. Using the obtained curable composition, the measurement of the tensile shear bond strength, the adhesion test, and the peel test were performed by the following evaluation methods. The results are shown in Table 1.
（評価方法）
接着強さ（引張せん断接着強さ）：
　接着強さ（引張せん断接着強さ）は、ＪＩＳ　Ｋ　６８５０に従い測定した。具体的には、被着材として耐熱パイレックス（登録商標）ガラス（２５ｍｍ×２５ｍｍ×２．０ｍｍ（縦×横×厚さ））を用いた。接着部位は直径８ｍｍの円形で、厚さ１００μｍとして、作製した硬化性組成物にて２枚の耐熱パイレックス（登録商標）ガラスを貼り合わせ、無電極放電ランプを使用したフュージョン社製硬化装置により、３６５ｎｍの波長の積算光量２０００ｍＪ／ｃｍ２の条件にて硬化させ、引張せん断接着強さ試験片を作製した。作製した試験片は、万能試験機を使用して、温度２３℃、湿度５０％の環境下、引張速度１０ｍｍ／ｍｉｎで引張せん断接着強さを測定した。
ダイシング後の保護膜の保持状況（密着性試験）：
　温度２３℃、湿度５０％の環境下で密着性の試験を行なった。シリコンウエハ上に硬化性組成物を厚さ１００μｍとして塗布し、無電極放電ランプを使用したフュージョン社製硬化装置により、３６５ｎｍの波長の積算光量２０００ｍＪ／ｃｍ２の条件にて硬化性組成物を硬化させ、保護膜を作製した。その後、保護膜を１００℃で１０分間加熱処理した後、回転数３００００ｒｐｍ、送り速度１．０ｍｍ／ｓｅｃ、チップサイズ１ｍｍ角の条件にてダイシングを行い、ダイシング後も保護膜が保持されているか観察した。２５枚のチップのうち保護膜が保持されているチップの枚数を計測した。 (Evaluation methods)
Adhesive strength (tensile shear adhesive strength):
The bond strength (tensile shear bond strength) was measured according to JIS K 6850. Specifically, heat-resistant Pyrex (registered trademark) glass (25 mm × 25 mm × 2.0 mm (length × width × thickness)) was used as the adherend. The adhesion site is a circle with a diameter of 8 mm and a thickness of 100 μm, and two heat-resistant Pyrex (registered trademark) glasses are bonded together with the prepared curable composition, and a fusion device manufactured by Fusion, using an electrodeless discharge lamp, Curing was performed under the condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm to prepare a tensile shear bond strength test piece. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
Status of holding protective film after dicing (adhesion test):
The adhesion test was performed in an environment of a temperature of 23 ° C. and a humidity of 50%. A curable composition is applied to a silicon wafer with a thickness of 100 μm, and the curable composition is cured under a condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm by a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp. Thus, a protective film was produced. Then, after heat-treating the protective film at 100 ° C. for 10 minutes, dicing is performed under the conditions of a rotation speed of 30000 rpm, a feed rate of 1.0 mm / sec, and a chip size of 1 mm square, and observation is made whether the protective film is retained after dicing. did. Of the 25 chips, the number of chips holding the protective film was measured.
　８０℃温水剥離時間（剥離試験）：
上記のダイシング後も保護膜が保持されていた試験体について、温水（８０℃）に浸漬してから、シリコンウエハから保護膜が剥離するまでの時間を測定した。
剥離状態の観察（剥離試験）：
　上記８０℃温水による剥離時間（剥離試験）の試験後に、剥離した保護膜を観察した。 80 ° C. hot water peeling time (peeling test):
About the test body in which the protective film was hold | maintained after said dicing, the time until a protective film peels from a silicon wafer after being immersed in warm water (80 degreeC) was measured.
Observation of peeled state (peeling test):
After the test of the peeling time (peeling test) with 80 ° C. warm water, the peeled protective film was observed.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（実験例Ｉ－２、Ｉ－３、Ｉ－１１、およびＩ－１２）
　加熱処理を表１に示す温度で行ったこと以外は実験例Ｉ－１と同様にして硬化性組成物を作製した。得られた硬化性組成物に関して、実験例Ｉ－１と同様に評価を行った。それらの結果を表１に示す。 (Experimental Examples I-2, I-3, I-11, and I-12)
A curable composition was prepared in the same manner as in Experimental Example I-1, except that the heat treatment was performed at the temperature shown in Table 1. The obtained curable composition was evaluated in the same manner as in Experimental Example I-1. The results are shown in Table 1.
（実験例Ｉ－４～Ｉ－１０、およびＩ－１３～Ｉ－１５）
　表１に示す種類の原材料を表１に示す組成で使用したこと以外は実験例Ｉ－１と同様にして硬化性組成物を作製した。得られた硬化性組成物に関して、実験例Ｉ－１と同様に評価を行った。それらの結果を表１に示す。
（使用材料）
ＱＭ：ジシクロペンテニルオキシエチルメタクリレート（ローム＆ハース社製、「ＱＭ－６５７」）
ＢＺ：ベンジルメタクリレート（共栄社化学社製、「ライトエステルＢＺ」）
ＵＶ－７０００Ｂ：ポリウレタンアクリレートオリゴマー（日本合成化学社製、「ＵＶ－７０００Ｂ」）
ＵＶ－３０００Ｂ：ポリエステル系ウレタンアクリレートオリゴマー（日本合成化学社製、「ＵＶ－３０００Ｂ」）
１，６－ＨＸ－Ａ：１，６－ヘキサンジオールジアクリレート（共栄社化学社製、「ライトアクリレート　１，６－ＨＸ－Ａ」）
Ｍ－５３００：ω－カルボキシ－ポリカプロラクトンモノアクリレート（東亜合成社製、「アロニックスＭ－５３００」）
Ｍ－５７１０：２－ヒドロキシ－３－フェノキシプロピルアクリレート（東亜合成社製、「アロニックスＭ－５７１０」）
Ｑｕｉｎｔｏｎｅ１５００：シクロペンタジエン骨格樹脂（日本ゼオン社製、「Ｑｕｉｎｔｏｎｅ１５００」、エステル基を含有し、軟化点が１２５℃であり、数平均分子量が４７０である。）
ＢＤＫ：ベンジルジメチルケタール（チバ・スペシャルティ・ジャパン社製、「ＩＲＧＡＣＵＲＥ６５１」） (Experimental Examples I-4 to I-10 and I-13 to I-15)
A curable composition was prepared in the same manner as in Experimental Example I-1, except that the raw materials of the type shown in Table 1 were used in the composition shown in Table 1. The obtained curable composition was evaluated in the same manner as in Experimental Example I-1. The results are shown in Table 1.
(Materials used)
QM: Dicyclopentenyloxyethyl methacrylate (Rohm & Haas, “QM-657”)
BZ: benzyl methacrylate (manufactured by Kyoeisha Chemical Co., “Light Ester BZ”)
UV-7000B: Polyurethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., “UV-7000B”)
UV-3000B: Polyester urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., “UV-3000B”)
1,6-HX-A: 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “Light acrylate 1,6-HX-A”)
M-5300: ω-carboxy-polycaprolactone monoacrylate (manufactured by Toa Gosei Co., Ltd., “Aronix M-5300”)
M-5710: 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Toa Gosei Co., Ltd., “Aronix M-5710”)
Quintone 1500: Cyclopentadiene skeleton resin (manufactured by Nippon Zeon Co., Ltd., “Quintone 1500”, containing an ester group, having a softening point of 125 ° C. and a number average molecular weight of 470)
BDK: benzyl dimethyl ketal (Ciba Specialty Japan, “IRGACURE651”)
（実験例ＩＩ－１、およびＩＩ－２）
　加熱処理を表２に示す温度で行ったこと以外は実験例Ｉ－１と同様にして硬化性組成物を作製した。得られた硬化性組成物に関して、実験例Ｉ－１と同様に評価を行った。それらの結果を表２に示す。なお、実験例ＩＩ－１の加熱処理温度の「－」は、加熱処理を行わなかったことを意味する。 (Experimental examples II-1 and II-2)
A curable composition was prepared in the same manner as in Experimental Example I-1, except that the heat treatment was performed at the temperature shown in Table 2. The obtained curable composition was evaluated in the same manner as in Experimental Example I-1. The results are shown in Table 2. In addition, “−” of the heat treatment temperature in Experimental Example II-1 means that the heat treatment was not performed.
（実験例ＩＩ－３～ＩＩ－５）
　表２に示す種類の原材料を表２に示す組成で行ったこと以外は実験例Ｉ－１と同様にして硬化性組成物を作製した。得られた硬化性組成物に関して、実験例Ｉ－１と同様に評価を行った。それらの結果を表２に示す。 (Experimental Examples II-3 to II-5)
A curable composition was prepared in the same manner as in Experimental Example I-1, except that the raw materials of the types shown in Table 2 were used in the composition shown in Table 2. The obtained curable composition was evaluated in the same manner as in Experimental Example I-1. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
 （使用材料）
ＩＢＸ：イソボルニルメタクリレート（共栄社化学社製、「ライトエステルＩＢ－Ｘ」）
　その結果、実験例ＩＩ－１は加熱処理せずにダイシングを行ったため、ダイシング時に保護膜が剥離してしまった。また、実験例ＩＩ－２では、ダイシング時は保護膜が剥離せずに保持していたが、加熱処理の温度が高すぎたため、剥離性が低下してしまい、その後温水剥離することができなかった。
Figure JPOXMLDOC01-appb-T000003
 (Materials used)
IBX: Isobornyl methacrylate (manufactured by Kyoeisha Chemical Co., “Light Ester IB-X”)
As a result, in Experimental Example II-1, dicing was performed without heat treatment, and thus the protective film was peeled off during dicing. Further, in Experimental Example II-2, the protective film was held without peeling during dicing, but the temperature of the heat treatment was too high, so that the peelability was lowered, and the hot water could not be peeled thereafter. It was.
　また、実験例ＩＩ－３では、（Ａ）多官能（メタ）アクリレートを配合しなかったため、硬化性組成物の硬化体は熱可塑性となり、加工前の加熱処理によって保護膜が溶解してしまい、表面を保護することができなかった。また、実験例ＩＩ－４では、（Ｃ）光重合開始剤を配合しなかったため、光照射後も硬化しなかった。実験例ＩＩ－５では（Ｂ）単官能（メタ）アクリレートを配合しなかったため、硬化収縮によるひずみが大きく、硬化体の表面にひび割れが見られた。実験例ＩＩ－５では、ウエハから硬化性組成物の硬化体が剥離しなかった。 In Experimental Example II-3, since (A) the polyfunctional (meth) acrylate was not blended, the cured product of the curable composition became thermoplastic, and the protective film was dissolved by the heat treatment before processing, The surface could not be protected. In Experimental Example II-4, since (C) the photopolymerization initiator was not blended, it was not cured after the light irradiation. In Experimental Example II-5, since (B) monofunctional (meth) acrylate was not blended, strain due to curing shrinkage was large, and cracks were observed on the surface of the cured product. In Experimental Example II-5, the cured product of the curable composition did not peel from the wafer.
　これに対して、実験例Ｉ－１～Ｉ－１４では、加熱処理してからダイシングを行ったため、いずれの場合でもダイシング時に保護膜が脱落することなく、表面を保護することができた。また、実験例Ｉ－１～Ｉ－１４では、いずれも（Ａ）多官能（メタ）アクリレート及び（Ｂ）単官能（メタ）アクリレートを光重合開始剤とともにバランスよく配合しているため、光重合後の硬化性組成物の接着強さが充分であり、ダイシング後にシリコンウエハから硬化性組成物の硬化体を剥離する際の剥離状態も良好であった。さらに、ダイシング後のシリコンウエハの表面も良好に保護されていた。また、実験例Ｉ－１５では（Ｄ）シクロペンタジエン骨格樹脂を配合しなかったため、表面が完全に硬化せず、べたつきが見られたものの、接着強さは良好であった。 On the other hand, in Experimental Examples I-1 to I-14, since the dicing was performed after the heat treatment, the surface could be protected without dropping the protective film during dicing in any case. In Experimental Examples I-1 to I-14, since (A) polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate are blended together with a photopolymerization initiator in a balanced manner, The adhesive strength of the subsequent curable composition was sufficient, and the peeled state when peeling the cured body of the curable composition from the silicon wafer after dicing was also good. Furthermore, the surface of the silicon wafer after dicing was well protected. In Experimental Example I-15, since (D) cyclopentadiene skeleton resin was not blended, the surface was not completely cured and stickiness was observed, but the adhesive strength was good.
　本発明は、被加工材の表面に上記保護膜を設け、保護膜を加熱処理した後、被加工材の加工を行うことで、加工時の保護膜の脱落を防止することができるため、傷やコンタミネーションから被加工材の表面を保護することが可能である。また、本発明の硬化性組成物は回路面等の表面の凹凸に対する追従性が十分にあるため、平滑な面だけでなく、凹凸のある面に対しても傷やコンタミネーションから表面を保護することが可能である。 In the present invention, since the protective film is provided on the surface of the workpiece, the protective film is heat-treated, and then the workpiece is processed to prevent the protective film from falling off during processing. It is possible to protect the surface of the workpiece from contamination and contamination. Moreover, since the curable composition of the present invention has sufficient followability to irregularities on the surface such as a circuit surface, the surface is protected not only from smooth surfaces but also from irregularities to scratches and contamination. It is possible.
　本発明の保護膜は、被加工材の加工後に９０℃以下の温水に浸漬することで、フィルム状で前記被加工材から回収することができるので、作業性に優れるという効果が得られる。さらに、従来の接着剤では必要不可欠であった有機溶媒を用いる必要がなく、環境負荷の低減という効果が得られる。
　本発明は、前記硬化性組成物を用いて被加工材の表面に保護膜を設けるものである。本発明は、例えば送り速度が２ｍｍ／ｓｅｃ以下の条件でダイシングを行っても、加工時に保護膜が脱落しないという効果が得られる。 Since the protective film of the present invention can be recovered from the workpiece in the form of a film by immersing it in warm water of 90 ° C. or less after the workpiece is processed, an effect of excellent workability can be obtained. Furthermore, it is not necessary to use an organic solvent that is indispensable for conventional adhesives, and the effect of reducing the environmental load can be obtained.
In the present invention, a protective film is provided on the surface of a workpiece using the curable composition. In the present invention, for example, even if dicing is performed under a condition where the feed rate is 2 mm / sec or less, an effect that the protective film does not fall off during processing can be obtained.
　本発明の表面保護方法は、硬化性組成物からなる保護膜がその組成故に光硬化性を有し、可視光や紫外線によって硬化するために、従来のホットメルト接着剤に比べ、省力化、省エネルギー化、作業短縮の面で著しい効果が得られる。また、前記保護膜を被加工材の表面に積層後、加熱処理工程を経ることで、前記保護膜の内部歪を緩和し、後に続く被加工材の加工工程において保護膜の脱落を抑制することができる。さらに、上記方法を用いることで、前記保護膜は加工時に用いる切削液等に影響せずに高い接着強度を発現でき、切削液の進入や切削屑等による傷や異物の付着から被加工材の表面を保護することができる。
　上記のような効果が得られることから、本発明は、工学部品、センサー等の電子、電気部品の加工、特に切断、研削、研磨等の精密加工等の産業で有用である。 The surface protection method of the present invention has a protective film made of a curable composition that has photocurability because of its composition, and is cured by visible light or ultraviolet light. Therefore, it saves labor and energy compared to conventional hot melt adhesives. A remarkable effect can be obtained in terms of speed and work shortening. In addition, after laminating the protective film on the surface of the workpiece, a heat treatment process is performed to reduce internal strain of the protective film, and the protective film is prevented from falling off in the subsequent machining process of the workpiece. Can do. Furthermore, by using the above method, the protective film can exhibit high adhesive strength without affecting the cutting fluid used at the time of processing, and the work material can be removed from the entrance of the cutting fluid, scratches due to cutting waste, etc. The surface can be protected.
Since the effects as described above are obtained, the present invention is useful in industries such as engineering parts, processing of electronic parts such as sensors, and electrical parts, particularly precision processing such as cutting, grinding, and polishing.
　なお、２００８年５月１２日に出願された日本特許出願２００８－１２５３２１号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2008-125321 filed on May 12, 2008 are incorporated herein by reference. Is.

Claims (6)

  1. 　下記（Ａ）、（Ｂ）及び（Ｃ）を含有する硬化性組成物から形成される硬化体からなる保護膜を被加工材の表面に積層する積層工程と、積層工程後に８０～１５０℃に加熱処理する加熱工程と、加熱工程後に被加工材を加工する加工工程とを有することを特徴とする、被加工材の表面に保護膜を積層する被加工材の表面保護方法。
    　（Ａ）多官能（メタ）アクリレート
    　（Ｂ）単官能（メタ）アクリレート
    　（Ｃ）光重合開始剤     A laminating step of laminating a protective film made of a cured product formed from a curable composition containing the following (A), (B) and (C) on the surface of the workpiece, and after the laminating step, the temperature is 80 to 150 ° C. A method for protecting a surface of a workpiece by laminating a protective film on the surface of the workpiece, comprising: a heating step for heat treatment; and a processing step for processing the workpiece after the heating step.
    (A) Multifunctional (meth) acrylate (B) Monofunctional (meth) acrylate (C) Photopolymerization initiator
  2. 　前記保護膜が、（Ｄ）シクロペンタジエン骨格を有する樹脂を含有する請求項１に記載の被加工材の表面保護方法。 The method for protecting a surface of a workpiece according to claim 1, wherein the protective film contains (D) a resin having a cyclopentadiene skeleton.
  3. 　前記（Ｄ）シクロペンタジエン骨格を含有する樹脂が、分子内にエステル基又は水酸基を含有する請求項２に記載の被加工材の表面保護方法。 The method for protecting a surface of a workpiece according to claim 2, wherein the resin containing the (D) cyclopentadiene skeleton contains an ester group or a hydroxyl group in the molecule.
  4. 　前記（Ａ）多官能（メタ）アクリレートと、前記（Ｂ）単官能（メタ）アクリレートとが、いずれも疎水性である請求項１乃至３のいずれか一項に記載の被加工材の表面保護方法。 The surface protection of the workpiece according to any one of claims 1 to 3, wherein both the (A) polyfunctional (meth) acrylate and the (B) monofunctional (meth) acrylate are hydrophobic. Method.
  5. 　前記硬化性組成物が、（Ａ）と（Ｂ）との合計量１００質量部中、（Ａ）多官能（メタ）アクリレートを５～５０質量部と（Ｂ）単官能（メタ）アクリレートを５０～９５質量部とを含有し、（Ａ）と（Ｂ）との合計量１００質量部に対して、（Ｃ）光重合開始剤を０．１～２０質量部と（Ｄ）シクロペンタジエン骨格を有する樹脂を０．１～５０質量部とを含有する請求項２乃至４のいずれか一項に記載の被加工材の表面保護方法。 The curable composition contains 5 to 50 parts by mass of (A) polyfunctional (meth) acrylate and 50 (B) monofunctional (meth) acrylate in 100 parts by mass of the total amount of (A) and (B). To 95 parts by mass, with respect to 100 parts by mass of the total amount of (A) and (B), 0.1 to 20 parts by mass of (C) photopolymerization initiator and (D) cyclopentadiene skeleton The method for protecting a surface of a workpiece according to any one of claims 2 to 4, comprising 0.1 to 50 parts by mass of a resin.
  6. 　下記（Ａ）、（Ｂ）及び（Ｃ）を含有する硬化性組成物から形成される硬化体からなる保護膜を被加工材の表面に積層する積層工程と、積層工程後に８０～１５０℃に加熱処理する加熱工程と、加熱工程後に被加工材の加工を行う加工工程と、加工工程後に被加工材を９０℃以下の温水に浸漬して前記保護膜を前記被加工材から取り外す取り外し工程とを有することを特徴とする、被加工材の表面に保護膜を積層する被加工材の仮固定方法。
    　（Ａ）多官能（メタ）アクリレート
    　（Ｂ）単官能（メタ）アクリレート
    　（Ｃ）光重合開始剤     A laminating step of laminating a protective film made of a cured product formed from a curable composition containing the following (A), (B) and (C) on the surface of the workpiece, and after the laminating step, the temperature is 80 to 150 ° C. A heating step for performing heat treatment, a processing step for processing the workpiece after the heating step, and a detaching step for detaching the protective film from the workpiece by immersing the workpiece in warm water of 90 ° C. or less after the processing step. A method for temporarily fixing a workpiece by laminating a protective film on the surface of the workpiece.
    (A) Multifunctional (meth) acrylate (B) Monofunctional (meth) acrylate (C) Photopolymerization initiator
PCT/JP2009/058783 2008-05-12 2009-05-11 Method for protection of surface of material to be processed, and temporary fixing method WO2009139357A1 (en)

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JP2011155112A (en) * 2010-01-27 2011-08-11 Disco Abrasive Syst Ltd Method of processing wafer
JP2012033788A (en) * 2010-08-02 2012-02-16 Denki Kagaku Kogyo Kk Machining and peeling method of planar article to be ground
WO2018159110A1 (en) * 2017-02-28 2018-09-07 デクセリアルズ株式会社 Manufacturing method for laminated body, and photocurable resin composition

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CN110235222B (en) * 2017-02-02 2023-07-14 株式会社力森诺科 Method for producing electronic component, resin composition for temporary protection, and resin film for temporary protection
KR102236041B1 (en) * 2019-07-23 2021-04-05 주식회사 한솔케미칼 Quantum dot optical film and quantum dot composition included therein

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JP2007186587A (en) * 2006-01-13 2007-07-26 Denki Kagaku Kogyo Kk Resin composition, method for temporarily fixing member to be processed and method for protecting surface by using the same
JP2008069255A (en) * 2006-09-14 2008-03-27 Denki Kagaku Kogyo Kk Method for peeling protective film applied on matter to be processed

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WO2007080936A1 (en) * 2006-01-13 2007-07-19 Denki Kagaku Kogyo Kabushiki Kaisha Curable resin composition, surface protection method, temporary fixation method, and separation method
JP2007186587A (en) * 2006-01-13 2007-07-26 Denki Kagaku Kogyo Kk Resin composition, method for temporarily fixing member to be processed and method for protecting surface by using the same
JP2008069255A (en) * 2006-09-14 2008-03-27 Denki Kagaku Kogyo Kk Method for peeling protective film applied on matter to be processed

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JP2011155112A (en) * 2010-01-27 2011-08-11 Disco Abrasive Syst Ltd Method of processing wafer
JP2012033788A (en) * 2010-08-02 2012-02-16 Denki Kagaku Kogyo Kk Machining and peeling method of planar article to be ground
WO2018159110A1 (en) * 2017-02-28 2018-09-07 デクセリアルズ株式会社 Manufacturing method for laminated body, and photocurable resin composition
JP2018140601A (en) * 2017-02-28 2018-09-13 デクセリアルズ株式会社 Manufacturing method for laminate, and light curable resin composition

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KR20110008180A (en) 2011-01-26
KR101555729B1 (en) 2015-09-25
CN102026807A (en) 2011-04-20
CN102026807B (en) 2014-05-21
JPWO2009139357A1 (en) 2011-09-22

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