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WO2016002974A2 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2016002974A2
WO2016002974A2 PCT/JP2015/075045 JP2015075045W WO2016002974A2 WO 2016002974 A2 WO2016002974 A2 WO 2016002974A2 JP 2015075045 W JP2015075045 W JP 2015075045W WO 2016002974 A2 WO2016002974 A2 WO 2016002974A2
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WO
WIPO (PCT)
Prior art keywords
protective film
surface protective
acrylate
meth
acrylic copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/075045
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English (en)
Japanese (ja)
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WO2016002974A3 (fr
WO2016002974A8 (fr
Inventor
克彦 堀米
知親 富永
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Lintec Corp
Original Assignee
Lintec Corp
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Publication date
Priority claimed from JP2014137994A external-priority patent/JP6092161B2/ja
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of WO2016002974A2 publication Critical patent/WO2016002974A2/fr
Publication of WO2016002974A3 publication Critical patent/WO2016002974A3/fr
Publication of WO2016002974A8 publication Critical patent/WO2016002974A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to a surface protective film in which a pressure-sensitive adhesive is laminated on one surface of a substrate, and in particular, a surface that is used to protect the surface by being affixed to the surface of various optical members and electronic members. It relates to a protective film.
  • camera lens units communication / sensor modules, motor units such as vibrators, imaging modules, etc., such as unitized optical and electronic components, prevent surface damage during processing, assembly, inspection, transportation, etc.
  • a surface protective film may be stuck on the exposed surface. The surface protective film is peeled off from the optical member or the electronic member when the surface protection is no longer necessary.
  • the optical member and the electronic member may be attached to other members such as a substrate with the surface protective film attached, but a thermosetting adhesive may be used for the attachment.
  • a thermosetting adhesive may be used for the attachment.
  • the surface protective film has a large adhesion performance and peeling performance even when heated. What does not change is required.
  • an adhesive containing a nitrogen-containing monomer with an acrylic copolymer as a main component in the adhesive layer (see Patent Document 1).
  • the surface protective film may be peeled off unexpectedly due to an impact or the like in the process, it is required to adhere to an optical member or an electronic member with a high adhesive force in order to appropriately protect the adherend. ing.
  • the optical member and the electronic member as described above have been reduced in size, and the size of the surface protective film has been reduced accordingly, so that the surface protective film is easily peeled off unexpectedly, The demand is growing.
  • the attachment and peeling of the surface protective film is usually performed manually, but it is required to improve the workability even with a small-sized film. Specifically, it is required to improve the peeling performance when peeling the surface protective film.
  • the film is small in size, misalignment is likely to occur at the time of attachment, the frequency of reattachment is increased, and the ease of reattachment, which is called reworkability, has been required.
  • optical members and electronic members have been improved in performance, it is required to reduce contamination caused by adhesive such as adhesive residue.
  • adhesive such as adhesive residue.
  • the performance of lens portions such as imaging modules is remarkably deteriorated even when a small amount of adhesive remains, it is further required to improve the peeling performance.
  • the surface protective film using the pressure-sensitive adhesive disclosed in Patent Document 1 cannot have excellent adhesiveness, peelability, and reworkability, and the surface protective film is required to be further improved. It has been.
  • This invention is made
  • the subject of this invention is providing the surface protection film for optical members or electronic members excellent in adhesiveness, peelability, and rework property. It is.
  • the inventors have used the energy ray curable type as the adhesive for the surface protective film, and the above-mentioned problem by making the configuration of the acrylic copolymer as the adhesive component a predetermined one. The inventors have found that this can be solved, and have completed the following present invention.
  • the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive composition containing an acrylic copolymer (A),
  • the acrylic copolymer (A) contains 5 to 50% by mass of an alkyl (meth) acrylate having at least 1 or 2 carbon atoms in the alkyl group and does not contain a carboxyl group-containing monomer or less than 5% by mass.
  • a surface protective film obtained by copolymerizing monomer components.
  • the acrylic copolymer (A) is obtained by copolymerizing a monomer component further containing 0.2 to 40 parts by mass of a hydroxyl group-containing (meth) acrylate.
  • the surface protective film in any one.
  • the pressure-sensitive adhesive layer has an adhesive strength before irradiation with energy rays of 1000 to 20000 mN / 25 mm and an adhesive strength after irradiation of energy rays of 0.1 to 100 mN / 25 mm. ).
  • the surface protective film according to any one of (1) to (9), wherein the pressure-sensitive adhesive layer has an initial pressure-sensitive adhesive strength before irradiation with energy rays of less than 10,000 mN / 25 mm.
  • a surface protective film comprising a member selected from either an optical member or an electronic member, and the surface protective film according to any one of (1) to (12) attached to the surface of the member Element.
  • a method for protecting the surface of the optical member or electronic member by applying the surface protective film according to any one of (1) to (12) above to the surface.
  • weight average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in the examples. .
  • GPC gel permeation chromatography
  • (meth) acrylate is used as a word indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms.
  • the surface protective film of the present invention is used for affixing to an optical member or an electronic member and protecting the surface thereof, and includes a base material and an adhesive layer provided on one surface of the base material. Is provided. Hereinafter, each member of the adhesive sheet will be described.
  • the pressure-sensitive adhesive layer of the present invention is composed of an energy ray-curable pressure-sensitive adhesive composition containing an acrylic copolymer (A).
  • the energy ray curable pressure-sensitive adhesive composition is cured by being irradiated with energy rays and has a reduced adhesive force.
  • Specific examples of energy rays include ultraviolet rays and electron beams, but it is preferable to use ultraviolet rays.
  • the acrylic copolymer (A) is usually a compound that imparts tackiness to the pressure-sensitive adhesive layer.
  • the acrylic copolymer (A) is obtained by copolymerizing a monomer component (hereinafter also referred to as “copolymer component”) containing an alkyl (meth) acrylate as a main monomer.
  • a monomer component hereinafter also referred to as “copolymer component”
  • alkyl (meth) acrylate include those having 1 to 18 carbon atoms in the alkyl group, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, and butyl.
  • an alkyl (meth) acrylate as a copolymer component is usually 50% by mass or more, preferably 50 to 95% by mass, and more preferably 60 to 95% by mass with respect to the total amount of the copolymer component. 90% by mass is contained.
  • the acrylic copolymer (A) contains, as a copolymer component, an alkyl (meth) acrylate having an alkyl group having 1 or 2 carbon atoms out of the alkyl (meth) acrylate, based on the total amount of the copolymer component.
  • the content is 5 to 50% by mass.
  • the adhesive strength particularly the adhesive strength after irradiation with energy rays, becomes too high, and the peeling performance may be deteriorated.
  • the initial adhesive strength becomes too high, and sufficient reworkability may not be obtained.
  • the acrylic copolymer (A) contains, as a copolymer component, an alkyl (meth) acrylate having an alkyl group having 1 or 2 carbon atoms in an amount of 10 to
  • the content is preferably 40% by mass, and more preferably 15 to 35% by mass.
  • alkyl (meth) acrylate having 1 or 2 carbon atoms in the alkyl group examples include methyl (meth) acrylate and ethyl (meth) acrylate. Among these, methyl acrylate and methyl methacrylate are preferable.
  • the acrylic copolymer (A) contains, as a copolymer component, an alkyl (meth) acrylate having an alkyl group with 3 or more carbon atoms in the alkyl (meth) acrylate, based on the total amount of the copolymer component.
  • the content is preferably 30 to 85% by mass.
  • the alkyl (meth) acrylate having 3 or more carbon atoms in the alkyl group is preferably an alkyl (meth) acrylate in which the alkyl group has 3 to 8 carbon atoms, and the alkyl group has 4 to 8 carbon atoms.
  • Alkyl (meth) acrylates are more preferred, and alkyl acrylates having an alkyl group with 4 to 8 carbon atoms are more preferred.
  • n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, and the like are preferable.
  • the acrylic copolymer (A) preferably contains a polymerizable monomer other than alkyl (meth) acrylate as the copolymer component, and specifically contains a functional group-containing monomer.
  • the functional group-containing monomer provides a functional group necessary for allowing the acrylic copolymer (A) to contain an unsaturated group-containing compound, which will be described later, or for a reaction with a crosslinking agent, which will be described later.
  • the functional group-containing monomer is a monomer having a polymerizable double bond and a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group in the molecule.
  • the acrylic copolymer (A) of the present invention does not contain a carboxyl group-containing monomer or contains a carboxyl group-containing monomer as a copolymer component. It is less than 5% by mass with respect to the total amount of components.
  • the carboxyl group-containing monomer is contained in an amount of 5% by mass or more, the pressure-sensitive adhesive layer has an excessively high adhesive strength after irradiation with energy rays, and the peelability of the surface protective film may be deteriorated. In addition, the initial adhesive force may become too high, and the reworkability may be reduced.
  • the content of the carboxyl group-containing monomer in the copolymer component is preferably less than 3% by mass, more preferably less than 1% by mass, and further, no carboxyl group-containing monomer is contained as the copolymer component. Is most preferred.
  • the carboxyl group-containing monomer include acrylic acid, methacrylic acid, itaconic acid and the like.
  • a hydroxyl group-containing compound is preferably used, and more preferably, a hydroxyl group-containing (meth) acrylate is used.
  • the acrylic copolymer (A) is preferably obtained by copolymerizing a copolymer component containing 0.2 to 40% by mass of hydroxyl group-containing (meth) acrylate with respect to the total amount of the copolymer component. .
  • the acrylic copolymer (A) can be appropriately crosslinked with a crosslinking agent described later.
  • the content of the hydroxyl group-containing (meth) acrylate is more preferably 1 to 30% by mass, and further preferably 5 to 30% by mass.
  • an unsaturated group-containing compound to be described later can be appropriately introduced into the side chain while ensuring appropriate adhesive performance. It becomes possible to appropriately crosslink the polymer (A).
  • Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. Can be mentioned.
  • the above functional group-containing monomers may be used alone or in combination of two or more.
  • the acrylic copolymer (A) includes (meth) acrylic acid esters, dialkyl (meth) acrylamides, vinyl formate, vinyl acetate, styrene other than alkyl (meth) acrylate and functional group-containing monomers. , Vinyl acetate or the like may be included as a copolymer component.
  • (meth) acrylic acid esters other than (meth) acrylic acid alkyl esters and functional group-containing monomers (meth) acrylic acid alkoxyalkyl esters, (meth) acrylic acid alkyleneoxyalkyl esters, (meth) acrylic acid nonylphenoxy polyethylene Glycol, tetrahydrofuran furfuryl acrylate, diacrylates which are esters of polyether and acrylic acid, and the like may also be used.
  • dialkyl (meth) acrylamide dimethyl (meth) acrylamide, diethyl (meth) acrylamide and the like are used.
  • Dialkyl (meth) acrylamide is preferably used when the energy ray-curable pressure-sensitive adhesive composition is an XY type described later.
  • dialkyl (meth) acrylamide as a constituent monomer, the compatibility of the energy beam curable acrylic copolymer with the energy beam polymerizable compound (B) such as a highly polar urethane acrylate is improved.
  • the weight average molecular weight of the acrylic copolymer is preferably 100,000 or more, more preferably 100,000 to 1,500,000, and further preferably 150,000 to 1,000,000.
  • the weight average molecular weight of the acrylic polymer here refers to the reaction of the unsaturated group-containing compound when an unsaturated group-containing compound described later is reacted to form an energy ray-curable acrylic polymer. It means the previous acrylic copolymer.
  • the energy ray-curable pressure-sensitive adhesive composition is not particularly limited as long as it has energy ray curability, but an X-type one is used as a preferred embodiment.
  • the X-type energy ray-curable pressure-sensitive adhesive composition is one in which the acrylic copolymer (A) itself has energy ray curability, and specifically, at least one of the acrylic copolymer (A).
  • the part is an energy ray curable acrylic copolymer having an unsaturated group in the side chain.
  • the energy ray curable acrylic copolymer is obtained by reacting an unsaturated group-containing compound with an acrylic copolymer obtained by copolymerizing the above copolymer components.
  • the unsaturated group-containing compound has a substituent capable of reacting with the functional group of the functional group-containing monomer constituting the acrylic copolymer.
  • This substituent varies depending on the type of functional group possessed by the functional group monomer.
  • the functional group is a hydroxyl group or a carboxyl group
  • the substituent is preferably an isocyanate group or an epoxy group.
  • the functional group is a carboxyl group
  • the substituent is preferably an isocyanate group or an epoxy group
  • the functional group is In the case of an amino group or a substituted amino group, an isocyanate group or the like is preferable as the substituent.
  • the functional group is an epoxy group, a carboxyl group is preferable as the substituent, and among these, an isocyanate group is preferable.
  • One such substituent is contained in each molecule of the unsaturated group-containing compound.
  • the unsaturated group-containing compound contains 1 to 5, preferably 1 to 2, energy beam polymerizable carbon-carbon double bonds per molecule.
  • the energy beam polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group.
  • Specific examples of such unsaturated group-containing compounds include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, Examples include (meth) acrylic acid.
  • an acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; obtained by reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound and hydroxyethyl (meth) acrylate.
  • acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate.
  • a polymerizable group-containing polyalkyleneoxy compound represented by the following formula (1) can also be used.
  • R 1 is hydrogen or a methyl group, preferably a methyl group
  • R 2 to R 5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen
  • n is 2 It is an integer above, preferably 2-4.
  • a plurality of R 2 to R 5 may be the same as or different from each other. That is, since n is 2 or more, the polymerizable group-containing polyalkyleneoxy group represented by the formula (1) contains 2 or more R 2 . In this case, two or more R 2 s may be the same or different. The same applies to R 3 to R 5 .
  • NCO represents an isocyanate group.
  • the unsaturated group-containing compound is usually about 10 to 100 equivalents with respect to 100 equivalents of the functional group possessed by the acrylic copolymer.
  • the ratio is preferably 15 to 95 equivalents, more preferably about 20 to 90 equivalents.
  • a compound having a (meth) acryloyl group and an isocyanate group is preferably used, and specifically, (meth) acryloyloxyethyl isocyanate is preferable.
  • a Y-type energy beam curable pressure-sensitive adhesive composition is used as another preferred embodiment.
  • the Y-type energy beam curable pressure-sensitive adhesive composition is provided with energy beam curability by blending the energy beam polymerizable compound (B) separately from the acrylic copolymer (A). .
  • energy ray polymerizable compound (B) energy ray polymerizable oligomers such as epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate, and energy ray polymerizable monomers are used.
  • energy ray polymerizable monomer a low molecular weight compound having two or more functional groups having at least two photopolymerizable carbon-carbon double bonds in the molecule is used. Specifically, trimethylolpropane tri (meth) is used.
  • Acrylate tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate or 1,4 -Butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and the like are used.
  • urethane acrylate oligomers are preferably used.
  • the urethane acrylate oligomer is a compound including an isocyanate unit and a polyol unit and having a (meth) acryloyl group at the terminal.
  • terminal isocyanate urethane oligomers are produced by reaction of polyols having hydroxyl groups at the ends, such as polyether-type polyols and polyester-type polyols, with polyisocyanates. ) And the like obtained by reacting a compound having an acryloyl group.
  • Such urethane acrylate oligomers have energy ray curability due to the action of the (meth) acryloyl group.
  • Examples of the polyisocyanate used in the urethane acrylate oligomer include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate.
  • Examples of the compound having a (meth) acryloyl group include (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol (meth) acrylate.
  • Examples of the (meth) acrylate having a hydroxyl group include polyhydric alcohols such as pentaerythritol and partial esters of (meth) acrylic acid.
  • the urethane acrylate oligomer is preferably a bifunctional or higher functional group having two or more (meth) acryloyl groups in one molecule, but if not used in combination with the X type, a trifunctional or higher functional group is preferred. More than the group is more preferable. By using one having three or more functional groups, it is easy to lower the adhesive strength after irradiation with energy rays, and the peel performance of the surface protective film tends to be good.
  • the urethane acrylate oligomer usually has 12 functional groups or less.
  • the urethane acrylate oligomer preferably has a weight average molecular weight of 1000 to 15000, more preferably 1500 to 8500.
  • the energy beam polymerizable compound (B) is usually blended in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). 70 to 150 parts by mass is more preferable.
  • the X type and the Y type are used in combination, that is, in addition to the acrylic polymer (A), the energy ray polymerizable compound (B) is contained, and the acrylic copolymer ( A material in which at least a part of A) is an energy ray-curable acrylic copolymer having an unsaturated group in the side chain (hereinafter referred to as XY type) can also be used as a preferred embodiment.
  • XY type an energy ray-curable acrylic copolymer having an unsaturated group in the side chain
  • the energy ray curable acrylic copolymer used in the case of the XY type is the same as that used in the X type described above.
  • the energy ray polymerizable compound (B) is the same as that used in the Y type described above, and a urethane acrylate oligomer is preferable.
  • the polyisocyanate at that time is isophorone diisocyanate. More preferably, 1,3-bis- (isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, or the like is used.
  • polystyrene resin As a polyol which forms the polyol unit in urethane acrylate, it is preferable to use polypropylene glycol (PPG), polyethylene glycol (PEG), polytetramethylene glycol, polycarbonate diol, etc., and the number average molecular weight of these polyols Is preferably 300 to 2000, particularly preferably 500 to 1000.
  • the polyol preferably contains two or more kinds of polyols in order to improve the breaking stress and breaking elongation of the pressure-sensitive adhesive layer, and the polyol contains PPG and PEG. It is particularly preferred that it consists only of PPG and PEG.
  • the molar ratio of PPG to PEG is preferably 9: 1 to 1: 9, more preferably 9: 1 to 1: 4, and further preferably 4: 1 to 3: 2. Most preferably, the ratio is from 5: 2.5 to 6.5: 3.5.
  • the urethane acrylate oligomer in the XY type is preferably a bifunctional group having two (meth) acryloyl groups in one molecule. By using a bifunctional group, it becomes easy to increase the breaking strength and breaking elongation while improving the peeling performance and the adhesiveness.
  • the energy ray polymerizable compound (B) is preferably 1 to 50 parts by mass, and 5 to 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). It is more preferable.
  • the pressure-sensitive adhesive layer may have a crosslinked structure in which the acrylic copolymer (A) is crosslinked.
  • the crosslinking agent (C) contained in the energy ray-curable pressure-sensitive adhesive composition for crosslinking include organic polyvalent isocyanate compounds, organic polyvalent epoxy compounds, and organic polyvalent imine compounds. Among these, Organic polyisocyanate compounds (isocyanate-based crosslinking agents) are preferred.
  • organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds.
  • examples thereof include terminal isocyanate urethane prepolymers obtained by reacting with a polyol compound.
  • organic polyvalent isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4.
  • organic polyvalent epoxy compound examples include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, Examples include ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, and diglycidyl amine.
  • organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetra Mention may be made of methylolmethane-tri- ⁇ -aziridinylpropionate and N, N′-toluene-2,4-bis (1-aziridinecarboxyamide) triethylenemelamine.
  • the content of the crosslinking agent (C) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0 with respect to 100 parts by mass of the acrylic copolymer (A). Used in a ratio of 5 to 8 parts by mass.
  • the content of the crosslinking agent (C) is not more than the above upper limit, the pressure-sensitive adhesive layer is prevented from being excessively crosslinked, and appropriate adhesive force is easily obtained.
  • by making the usage-amount of a crosslinking agent more than the said lower limit it is prevented that an adhesive adheres to an electronic member or an optical member.
  • the energy ray curable pressure-sensitive adhesive composition preferably contains a photopolymerization initiator (D).
  • photopolymerization initiators include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones.
  • 1-hydroxycyclohexyl phenyl ketone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • blending a photoinitiator (D) the irradiation time and irradiation amount of the energy beam for hardening can be decreased.
  • the content of the photopolymerization initiator (D) is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). It is.
  • the pressure-sensitive adhesive layer may be colored so that the light transmittance of the surface protective film is less than 50%. Since the visibility of the surface protective film is improved by coloring the pressure-sensitive adhesive layer, for example, the surface protective film is easily peeled from a release sheet described later by hand.
  • the light transmittance of the surface protective film is measured with a spectrophotometer UV-3600 manufactured by Shimadzu Corporation at a wavelength of 600 nm. The light transmittance is preferably about 10 to 40%.
  • the energy ray-curable pressure-sensitive adhesive composition usually contains a dye and a pigment, and among them, a blue dye and a blue pigment are preferably contained.
  • the energy ray-curable pressure-sensitive adhesive composition may appropriately contain components other than the above components such as a deterioration inhibitor, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent.
  • the pressure-sensitive adhesive layer has an adhesive strength before irradiation with energy rays of preferably 1000 to 20000 mN / 25 mm, and more preferably 4000 to 16000 mN / 25 m.
  • the adhesive strength before energy beam irradiation is 1000 mN / 25 m or more, the adhesive strength of the surface protective film to the optical member and the electronic member is increased, and the protective performance is improved.
  • the adhesive strength before energy beam irradiation can be adjusted by the type and blending ratio of alkyl (meth) acrylate, the amount of crosslinking agent used, and the like.
  • the pressure-sensitive adhesive layer preferably has an adhesive strength after irradiation with energy rays of 0.1 to 100 mN / 25 mm, more preferably 20 to 90 mN / 25 mm.
  • the adhesive strength after energy beam irradiation can be controlled by the type and amount of the energy beam polymerizable compound (B) and the amount of unsaturated groups introduced into the acrylic copolymer.
  • the initial stage adhesive force before energy beam irradiation of an adhesive layer is less than 10000 mN / 25mm.
  • the lower limit value of the initial adhesive strength is not particularly limited, but is usually 500 mN / 25 mm or more.
  • the initial adhesive strength is more preferably 3000 to 9500 mN / 25 mm.
  • the initial adhesive strength can be adjusted by the kind and blending ratio of the alkyl (meth) acrylate, the kind and blending ratio of the functional group-containing monomer, the amount of the crosslinking agent used, and the like.
  • the measuring method of an above-described adhesive force and initial stage adhesive force is the value measured based on the method described in the Example.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 3 to 50 ⁇ m, more preferably 5 to 30 ⁇ m. It becomes easy to improve the adhesiveness with respect to a to-be-adhered body because the thickness of an adhesive layer exists in the said range.
  • ⁇ Base material> There is no particular limitation on the material of the substrate, polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Polyurethane films, ethylene vinyl acetate films, ionomer resin films, ethylene / (meth) acrylic acid copolymer films, polystyrene films, polycarbonate films, fluororesin films, and the like can be used. These crosslinked films and laminated films may also be used.
  • the base material needs to have transparency with respect to the wavelength of the energy ray to be used. That is, when ultraviolet rays are used as the energy rays, a light transmissive film is used as the substrate. Moreover, when using an electron beam as an energy beam, the base material does not need to be light-transmitting, and a colored film may be used.
  • the thickness of the substrate is adjusted according to the performance required for the surface protective film, and is preferably 10 to 300 ⁇ m, particularly preferably 30 to 150 ⁇ m.
  • the film area of the surface protective film is preferably 100 mm 2 or less, more preferably about 10 to 80 mm 2 .
  • the surface protective film is reduced in size depending on the optical member and the electronic member. However, since the release performance is good as described above, the surface protective film is easily peeled off manually even when the size is reduced.
  • the shape of the surface protective film is not limited, but is processed into, for example, a circular shape, an annular shape, a square shape, a rectangular shape, or the like.
  • the pressure-sensitive adhesive layer side of the surface protective film may be protected with a release sheet by attaching a release sheet.
  • a release sheet a film such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, etc., which has been subjected to a release treatment with a release agent such as a silicone resin can be used, but is not limited thereto.
  • a plurality of surface protective films may be provided on one release sheet having a size sufficiently larger than the surface protective film.
  • the method for forming the pressure-sensitive adhesive layer is not particularly limited, but an energy ray-curable pressure-sensitive adhesive composition diluted with an appropriate solvent as necessary is applied on the release sheet so as to have a predetermined dry film thickness, and thereafter After drying to form the pressure-sensitive adhesive layer, the substrate may be bonded to the pressure-sensitive adhesive layer. Moreover, the energy ray-curable pressure-sensitive adhesive composition diluted with a suitable solvent as required may be directly applied to a substrate and then dried to form a pressure-sensitive adhesive layer. Moreover, a surface protection film may provide an adhesive layer partially on a base material, and may form a non-adhesion part with an adhesion part on a base material.
  • a non-adhesive part can be formed together with an adhesive part by performing screen printing or inkjet printing.
  • At least one of the adhesive part and the non-adhesive part, and the adhesive part are selected from a stripe shape, a lattice shape, a dot shape, a shape in which a plurality of wavy lines are arranged, a checkered pattern, and a shape in which a plurality of various patterns are arranged It is preferable that it is the pattern of this, and other shapes may be sufficient.
  • the pattern pitch (that is, the interval between adjacent adhesive portions or the interval between adjacent non-adhesive portions) is preferably 10 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, particularly
  • the thickness is preferably 10 to 250 ⁇ m. That is, the width of each stripe, the width of each wavy line and the interval between wavy lines, the width of each line forming a lattice, the interval between adjacent lines constituting the lattice, the interval between dots, and the width of dots
  • the height, or the height and width of each square constituting the checkered pattern is preferably 10 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and particularly preferably 10 to 250 ⁇ m.
  • the punching process may be performed before or after the pressure-sensitive adhesive layer is formed.
  • the punching process may be performed on a laminate of the base material and the pressure-sensitive adhesive layer provided on the release sheet, and by this punching process, the shape of the surface protection film is made circular as described above.
  • corrugation suitably in a surface protection film by stamping etc. at arbitrary timings.
  • an imaging module in which one or more lenses and an imaging sensor such as a CCD or CMOS are housed in a casing or a package; a plurality of lenses is a lens mirror Examples include a lens unit held in a tube and housed in a housing or a package as necessary; a light emitting element unit having a light emitting element such as an LED; a motor unit such as a vibrator; a communication module, a sensor module, and the like.
  • These optical members and electronic members are preferably members that are used by being attached to other members such as a substrate.
  • the optical member refers to an optical component that receives or emits light, or includes an optical component that transmits light.
  • an imaging module, a lens unit, a light emitting element unit, a communication module that transmits or receives an optical signal An example of the optical member is an optical sensor module.
  • the electronic member usually includes at least a part of an electric circuit and includes an electronic component that transmits or receives an electric signal, an electronic component that processes an electric signal, an electronic component that operates by an electric signal or electric power, and the like.
  • a motor unit such as an imaging module, a light emitting element unit, and a vibrator, a communication module that transmits or receives an electrical signal, various sensor modules, and the like are specific examples of the electronic member.
  • a communication module, an optical sensor module, an imaging module, a light emitting element unit, and the like that transmit or receive optical signals are members that are both electronic members and optical members.
  • the optical member or the electronic member is, for example, one in which the electronic component or the optical component is housed in a package or a housing or supported by a support member.
  • a part of electronic component or optical component is exposed on the surface, and the surface protection film is used, for example, to protect the exposed component.
  • the surface protective film of this invention is used in order to stick on the surface of an optical member or an electronic member, and to protect the surface.
  • an optical member or an electronic member hereinafter also simply referred to as a member with a surface protective film
  • the surface protective film protects the surface of the optical member or the electronic member in these steps.
  • the surface protective film is peeled off from the optical member or the electronic member after being irradiated with energy rays and reducing the adhesive force when these steps are finished and the surface protection is no longer necessary.
  • the member with a surface protective film may be heated in steps such as the above-described processing, attachment, inspection, or conveyance.
  • the heating temperature at that time is not particularly limited, but is about 60 to 200 ° C., preferably about 70 to 150 ° C.
  • the pressure-sensitive adhesive layer may become more adhesive when heated, but the pressure-sensitive adhesive layer of the surface protective film of the present invention may be irradiated with energy rays thereafter even if the pressure-sensitive adhesive layer becomes higher due to heating. Since it is possible to reduce the adhesive strength, it is difficult for peeling failure and adhesive residue to occur when the surface protective film is peeled off.
  • the optical member or the electronic member (the member with the surface protective film) to which the surface protective film is attached is attached to another member such as a substrate with an adhesive, for example.
  • a thermosetting adhesive is used, and in order to cure the adhesive, the member with a surface protective film is usually at a temperature of 60 to 200 ° C. or higher, preferably about 70 to 150 ° C. as described above. Heating is preferred.
  • the surface protection film is peeled from the optical member or the electronic member after the surface protection film is irradiated with energy rays and the adhesive force is reduced.
  • the surface protective film is particularly preferably used as a surface protective film for an imaging module in the above-described optical member or electronic member.
  • the imaging module is usually provided with a light receiving portion for receiving light from the outside on one surface and guiding the light to the imaging device via a lens inside the module.
  • the light receiving unit is provided on a part (for example, the center) of one surface of the imaging module and is made of glass or transparent resin.
  • the surface protective film is preferably attached to one surface of the imaging module where the light receiving part is provided so as to cover the light receiving part.
  • the surface protective film adheres to the surface of the light receiving unit and the casing or package around the light receiving unit with high adhesive force before irradiation with energy rays, the light receiving unit provided on one surface of the imaging module should be appropriately protected. Is possible. Moreover, since the adhesive strength of the surface protective film is reduced after irradiation with energy rays, the surface protective film can be easily peeled off from the imaging module, and it is possible to prevent adhesive residue from being generated in the light receiving portion and the like. In addition, as above-mentioned, it is preferable that the imaging module with which the surface protective film was stuck is heated for hardening of a thermosetting adhesive, and is attached to other members, such as a board
  • the measurement method and evaluation method in the present invention are as follows. [Weight average molecular weight (Mw)] Using a gel permeation chromatograph, measurement was performed under the following conditions, and values measured in terms of standard polystyrene were used. (Measurement condition) Measuring device: Product name “HLC-8220GPC”, manufactured by Tosoh Corporation) Column: Product name “TSKGel SuperHZM-M” manufactured by Tosoh Corporation) Developing solvent: Tetrahydrofuran Column temperature: 40 ° C Flow rate: 1.0 mL / min [Adhesive force] The pressure-sensitive adhesive sheet was cut to a width of 25 mm to prepare a sample, and was attached to a silicon wafer as an adherend with a 2 kg roller in an environment of 23 ° C.
  • the adhesive strength when peeled at 180 ° at a tensile speed of 300 mm / min was measured and taken as the adhesive strength before energy beam irradiation.
  • the sample attached to the silicon wafer after standing for 20 minutes was irradiated with ultraviolet rays in a nitrogen atmosphere (illuminance 230 mW / cm 2 , using an ultraviolet irradiation device (RAD-2000m / 12, manufactured by Lintec Corporation). Light quantity 190 mJ / cm 2 ). Then, the adhesive force when peeled at 180 ° in a tensile rate of 300 mm / min in an environment of 23 ° C.
  • the pressure-sensitive adhesive sheet was cut to a width of 25 mm to prepare a sample, and was attached to a silicon wafer as an adherend with a 2 kg roller in an environment of 23 ° C. and 50% relative humidity. Immediately after the application (within 1 minute), the adhesive strength when peeled at 180 ° in a tensile rate of 300 mm / min in an environment of 23 ° C. and 50% relative humidity was measured, and the adhesive strength was defined as initial adhesive strength.
  • a surface protection film having a circular shape with a diameter of 5 mm and a film area of 19.6 mm 2 was attached to one surface provided with the light receiving portion of the imaging module and evaluated according to the following evaluation criteria.
  • Example 1 69.5 parts by mass of n-butyl acrylate, 30 parts by mass of methyl acrylate, and 0.5 parts by mass of 2-hydroxyethyl acrylate were polymerized in an ethyl acetate solvent to obtain an acrylic copolymer having a weight average molecular weight of 460,000. Obtained.
  • This diluted solution is applied to a base material made of a polyethylene terephthalate film having a thickness of 50 ⁇ m so that the thickness after drying becomes 20 ⁇ m, and then heated and dried at 100 ° C. for 1 minute, on the base material.
  • a pressure-sensitive adhesive layer was formed to obtain a surface protective film.
  • Example 2 An acrylic copolymer having a weight average molecular weight of 500,000 was obtained by polymerizing 52 parts by mass of n-butyl acrylate, 20 parts by mass of methyl methacrylate and 28 parts by mass of 2-hydroxyethyl acrylate in an ethyl acetate solvent, Then, 100 parts by mass of the acrylic copolymer is reacted with 33.7 parts by mass of methacryloyloxyethyl isocyanate (MOI) which is an unsaturated group-containing compound (90 equivalents with respect to 100 equivalents of 2-hydroxyethyl acrylate), An ethyl acetate dilution of an energy ray curable acrylic copolymer was obtained.
  • MOI methacryloyloxyethyl isocyanate
  • Example 3 10 parts by mass of a bifunctional urethane acrylate oligomer having a weight average molecular weight of 5,500 is added to 100 parts by mass of the energy ray curable acrylic copolymer in the diluted liquid of the energy ray curable pressure-sensitive adhesive composition of Example 2. This was carried out in the same manner as in Example 2 except that the prepared one was used (XY type).
  • the bifunctional urethane acrylate oligomer was obtained by polymerizing 3 parts by mass of isophorone diisocyanate, 1.4 parts by mass of polypropylene glycol, and 0.6 parts by mass of polyethylene glycol, and further adding 2-hydroxypropyl acrylate. Was used by reacting 2 parts by mass.
  • the acrylic copolymer contains a predetermined amount of alkyl (meth) acrylate having 1 or 2 carbon atoms of the alkyl group as a copolymer component, and also contains a carboxyl group-containing monomer. Therefore, the adhesive strength before UV irradiation and the initial adhesive strength were good values, and a surface protective film excellent in reworkability and protective properties could be obtained. Moreover, the adhesive strength after UV irradiation was lowered, and the peeling performance was also improved.
  • the acrylic copolymer does not contain a predetermined amount of alkyl (meth) acrylate having an alkyl group having 1 or 2 carbon atoms as a copolymer component, or a carboxyl group-containing monomer. Since the content was 5% by mass or more, the adhesive strength after UV irradiation was not sufficiently lowered, and the peeling performance was not improved. In Comparative Example 2, the initial adhesive strength was high and the reworkability was good. Furthermore, in Comparative Example 4, since the non-energy ray curable type was used, it was difficult to improve the protection and peelability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Film de protection de surface lié à des éléments optiques ou électroniques, et utilisé pour protéger les surfaces desdits éléments. Ce film de protection de surface est pourvu d'un matériau de base et d'une couche adhésive disposée sur une surface du matériau de base. La couche adhésive comprend une composition d'adhésif durcissable sous l'effet d'un rayonnement énergétique, contenant un copolymère acrylique (A), ce dernier étant formé par copolymérisation de composants monomères comprenant 5 à 50 % en poids d'alkyl(méth)acrylate comportant un groupe alkyle C1-2, et soit comprenant moins de 5 % en poids de monomères contenant du carboxyle soit ne comprenant aucun monomère contenant du carboxyle.
PCT/JP2015/075045 2014-07-03 2015-09-03 Feuille de protection de surface Ceased WO2016002974A2 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2014-137994 2014-07-03
JP2014137994A JP6092161B2 (ja) 2014-07-03 2014-07-03 表面保護フィルム
JP2014191337 2014-09-19
JP2014-191337 2014-09-19
JP2015072975 2015-03-31
JP2015-072975 2015-03-31
JP2015098349 2015-05-13
JP2015-098349 2015-05-13

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WO2016002974A2 true WO2016002974A2 (fr) 2016-01-07
WO2016002974A3 WO2016002974A3 (fr) 2016-02-25
WO2016002974A8 WO2016002974A8 (fr) 2016-04-14

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WO2017126454A1 (fr) * 2016-01-19 2017-07-27 富士フイルム株式会社 Stratifié à film conducteur

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JP2008201899A (ja) * 2007-02-20 2008-09-04 Nitto Denko Corp 固体撮像デバイス用表面保護粘着テープ及び固体撮像デバイスの実装方法
JP6068438B2 (ja) * 2012-03-12 2017-01-25 リンテック株式会社 バックグラインドシート用基材および粘着シート、当該基材およびシートの製造方法、ならびにワークの製造方法
JP5979953B2 (ja) * 2012-04-16 2016-08-31 日本合成化学工業株式会社 透明電極用粘着剤、タッチパネル及び画像表示装置、並びに粘着剤層含有積層体の製造方法
JP2014043546A (ja) * 2012-07-31 2014-03-13 Nitto Denko Corp 放射線硬化型粘着剤層及び放射線硬化型粘着シート
JP6195839B2 (ja) * 2012-10-19 2017-09-13 リンテック株式会社 電子部品加工用粘着シートおよび半導体装置の製造方法
JP6275945B2 (ja) * 2012-12-10 2018-02-07 日東電工株式会社 両面粘着剤付き光学フィルム、およびそれを用いた画像表示装置の製造方法
JP6129541B2 (ja) * 2012-12-17 2017-05-17 リンテック株式会社 ダイシングシート
JP2014025073A (ja) * 2013-10-08 2014-02-06 Mitsubishi Plastics Inc 粘着シート
JP5809685B2 (ja) * 2013-12-12 2015-11-11 リンテック株式会社 粘着シートおよび半導体装置の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017126454A1 (fr) * 2016-01-19 2017-07-27 富士フイルム株式会社 Stratifié à film conducteur
JPWO2017126454A1 (ja) * 2016-01-19 2018-11-29 富士フイルム株式会社 導電フィルム積層体

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