WO2016006719A1 - Film de protection de surface - Google Patents

Film de protection de surface Download PDF

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Publication number
WO2016006719A1
WO2016006719A1 PCT/JP2015/075156 JP2015075156W WO2016006719A1 WO 2016006719 A1 WO2016006719 A1 WO 2016006719A1 JP 2015075156 W JP2015075156 W JP 2015075156W WO 2016006719 A1 WO2016006719 A1 WO 2016006719A1
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WO
WIPO (PCT)
Prior art keywords
protective film
surface protective
sensitive adhesive
pressure
energy ray
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PCT/JP2015/075156
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English (en)
Japanese (ja)
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WO2016006719A8 (fr
Inventor
克彦 堀米
知親 富永
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リンテック株式会社
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Priority claimed from JP2014139704A external-priority patent/JP6613516B2/ja
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Publication of WO2016006719A1 publication Critical patent/WO2016006719A1/fr
Publication of WO2016006719A8 publication Critical patent/WO2016006719A8/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
    • 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
    • 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 provided on one surface of a substrate, and in particular, a surface that is used to protect the surface of a surface that is 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 electronic member are usually a combination of a plurality of parts, and depending on the nature of some parts, the function may be remarkably deteriorated if there is glue transfer from the surface protective film.
  • the function may be remarkably deteriorated if there is glue transfer from the surface protective film.
  • an image sensor if there is a glue transfer in a light receiving unit for receiving light, the image quality may be significantly deteriorated.
  • Patent Document 1 for the purpose of eliminating such problems, an uncoated portion where no adhesive is applied is provided at a position corresponding to the light receiving portion of the image sensor, and glue is not contacted with the light receiving portion.
  • a surface protective film is disclosed.
  • the present invention has been made in view of the above problems, and the problem of the present invention is that it can be manufactured by a simple method, and the optical member or the electronic member can be specified without greatly reducing the adhesiveness of the film. It is an object of the present invention to provide a surface protective film in which contamination due to glue transfer does not easily occur at a site.
  • a surface protective film that is applied to an optical member or an electronic member and used to protect the surface thereof, Surface protection provided with a base material and a pressure-sensitive adhesive layer provided on one surface of the base material and made of an energy ray-curable pressure-sensitive adhesive composition, wherein a part of the pressure-sensitive adhesive layer is cured with energy rays the film.
  • the surface protection film according to (1) wherein the part cured with the energy rays is surrounded by a part not cured with the energy rays.
  • 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.
  • [Surface protection film] 1 and 2 show a surface protective film according to an embodiment of the present invention.
  • the surface protective film 10 is attached to an optical member or an electronic member and used to protect the surface.
  • a pressure-sensitive adhesive layer 12 made of an energy ray-curable pressure-sensitive adhesive composition.
  • the adhesive layer 12 is partially cured by irradiation with energy rays, and includes a cured portion 12A cured by the energy rays and an uncured portion 12B not cured by the energy rays.
  • the cured portion 12A has a lower adhesive force than the uncured portion 12B due to curing by energy beam irradiation. Accordingly, since the cured portion 12A is adhered to the adherend with a relatively weak adhesive force or is not adhered to the adherend, glue transfer occurs at a position aligned with the cured portion 12A of the adherend. It becomes difficult.
  • the uncured portion 12B is adhered to the adherend while maintaining high adhesive strength, the adhesion as the surface protective film 10 as a whole is good, and the surface protective property of the surface protective film 10 is excellent. It becomes. Furthermore, the surface protective film 10 is likely to have good reworkability due to the presence of a cured portion 12A having a partially weak adhesive force.
  • the cured portion 12A preferably has a smaller area than the uncured portion 12B. Further, the cured portion 12A is preferably surrounded by the uncured portion 12B over the entire circumference. With these configurations, the surface protective film 10 adheres to the adherend (optical member or electronic member) with a wide adhesion area around the cured portion 12A, and thus the surface of the adherend can be appropriately protected. Further, the cured portion 12A is prevented from being unexpectedly peeled off from the adherend.
  • the surface protective film 10 preferably has an entire periphery of the outer edge portion 10 ⁇ / b> A as an uncured portion 12 ⁇ / b> B from the viewpoint of improving the adhesion to the adherend. A part of 10A may be a cured portion 12A. When a part of the outer edge portion 10A becomes the cured portion 12A, the surface protection film 10 can be easily peeled off from the adherend by grasping that portion as a peeling start portion.
  • the surface protective film 10 more preferably has a cured portion 12A at the center in the surface direction of the pressure-sensitive adhesive layer and the other portion becomes an uncured portion 12B.
  • the shape of the hardened portion 12A is not particularly limited, but is preferably made according to the shape of a specific part of an adherend (optical member or electronic member) described later, and has a circular shape as shown in FIG. It may be a rectangle, a rectangle, or the like, or any other shape.
  • the size of the cured portion 12A may be the same as the size of the specific portion, may be slightly smaller, or may be slightly larger.
  • the size is the same as the specific portion or a size that is slightly larger.
  • the specific part of the adherend is a part where, when the adhesive is transferred, the function of the optical member or the electronic member is reduced, the malfunction occurs, or the life is shortened.
  • a light transmitting portion that constitutes a part of the optical path is exemplified.
  • the electrical component etc. which were exposed outside are mentioned. More specifically, when the optical member or electronic member is an electronic component or optical component housed in a package or casing, the electronic component or optical component exposed on a part of one surface of the package or casing is It becomes a specific part.
  • the pressure-sensitive adhesive layer 12 of the present invention is made of an energy ray-curable pressure-sensitive adhesive composition.
  • the energy ray-curable pressure-sensitive adhesive composition is cured by being irradiated with energy rays as described above, and the adhesive force is reduced.
  • energy rays include ultraviolet rays and electron beams, but it is preferable to use ultraviolet rays.
  • Examples of the pressure-sensitive adhesive constituting the energy ray-curable pressure-sensitive adhesive composition include acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives.
  • the energy ray-curable pressure-sensitive adhesive composition is preferably used as an X-type specific example.
  • the X-type energy ray-curable pressure-sensitive adhesive composition is one in which the main polymer itself constituting the pressure-sensitive adhesive component of the pressure-sensitive adhesive has energy ray-curing properties, for example, has an unsaturated group in the side chain of the polymer. .
  • a Y-type energy-beam curable adhesive composition is mentioned as another preferable specific example.
  • the Y-type energy beam curable pressure-sensitive adhesive composition is provided with energy beam curability by blending an energy beam polymerizable compound separately from the main polymer constituting the pressure-sensitive adhesive component.
  • the energy ray-curable pressure-sensitive adhesive composition the X-type and Y-type are used in combination, that is, the energy ray-curable polymer and the pressure-sensitive adhesive component are combined with another energy ray-polymerizable compound.
  • XY type can also be mentioned as a preferred specific example.
  • an acrylic adhesive is used as an adhesive
  • an energy beam-curable pressure-sensitive adhesive composition containing an acrylic copolymer (A) is used as the energy beam-curable pressure-sensitive adhesive composition.
  • the acrylic copolymer (A) is usually a main polymer that constitutes an adhesive component.
  • 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 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 95% 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) has an alkyl group having 1 or 2 carbon atoms in the alkyl group ( It may contain (meth) acrylate.
  • the alkyl (meth) acrylate having 1 or 2 carbon atoms in the alkyl group is preferably contained in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of the copolymer component.
  • the content is preferably 15 to 35% by mass.
  • the adhesive force after energy ray hardening of the adhesive layer 12 is easy to become low, it becomes easier to prevent the glue transfer in the cured portion 12A. Moreover, the peeling performance and reworkability of the surface protective film 10 are likely to be good. On the other hand, when the content is 50% by mass or less, the adhesive strength becomes an appropriate value, the surface protective film 10 is prevented from being unexpectedly peeled off from the adherend, and the protective performance is improved.
  • the alkyl (meth) acrylate having 1 or 2 carbon atoms in the alkyl group include methyl (meth) acrylate and ethyl (meth) acrylate. Among these, methyl acrylate and methyl methacrylate 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 bonding an unsaturated group-containing compound, which will be described later, to the acrylic copolymer (A) and for 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.
  • a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.
  • the functional group monomer does not include a carboxyl group-containing monomer or the like and is composed of a hydroxyl group-containing monomer, it becomes easier to prevent transfer of the pressure-sensitive adhesive to the adherend.
  • the acrylic copolymer (A) is preferably obtained by copolymerizing a copolymer component containing 0.2 to 40% by mass of a functional 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 functional 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 described later can be appropriately introduced into the side chain while ensuring appropriate adhesive performance. It becomes possible to appropriately crosslink the polymer (A).
  • examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, and itaconic acid.
  • hydroxyl group-containing monomer for example, hydroxyl group-containing (meth) acrylate is used.
  • 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.
  • 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 acrylic copolymer (A) itself has energy-ray curable properties. Specifically, at least a part of the acrylic copolymer (A) 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 substituent is preferably an isocyanate group, an epoxy group or the like.
  • the substituent is preferably an isocyanate group or an epoxy group, and the functional group is an amino group or In the case of a substituted amino group, the substituent is preferably an isocyanate group or the like, and when the functional group is an epoxy group, the substituent is preferably a carboxyl group, but the substituent is preferably an isocyanate group.
  • the said substituent is contained one by one for 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.
  • the energy ray-curable pressure-sensitive adhesive composition forming the acrylic pressure-sensitive adhesive is Y-type
  • the energy ray-curable pressure-sensitive adhesive composition is an energy ray-polymerizable compound separately from the acrylic copolymer (A).
  • Energy beam curability is imparted by blending (B).
  • 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.
  • 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 energy ray-curable pressure-sensitive adhesive composition in the case of the XY type contains the energy ray-polymerizable compound (B) in addition to the acrylic polymer (A), and an acrylic copolymer. At least a part of the polymer (A) is an energy ray curable acrylic copolymer having an unsaturated group in the side chain.
  • the adhesive layer has good breaking strength and breaking elongation, and the adhesive residue on the adherend tends to decrease when the surface protective film is peeled off.
  • 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 preferably 5 to 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). More preferred.
  • the pressure-sensitive adhesive layer may have a crosslinked structure in which a main polymer such as an acrylic copolymer (A) is crosslinked.
  • a main polymer such as an acrylic copolymer (A)
  • 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 25 parts by mass, more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the main polymer such as the acrylic copolymer (A). Particularly preferred is a ratio of 0.5 to 10 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 with respect to 100 parts by mass of the main polymer such as the acrylic copolymer (A). Is 5 parts by mass.
  • the adhesive layer 12 may be colored so that the light transmittance of the surface protective film 10 is less than 50%. Since the visibility of the surface protective film 10 is improved by coloring the pressure-sensitive adhesive layer 12, the surface protective film 10 is easily peeled from a release sheet to be described later, for example, manually.
  • the light transmittance of the surface protective film 10 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 surface protective film 10 preferably has an adhesive strength before energy ray curing (that is, an adhesive strength of the uncured portion 12B) of 1000 to 30000 mN / 25 mm, more preferably 2000 to 25000 mN / 25 m. More preferably, it is 20000 mN / 25 m.
  • an adhesive strength before energy ray curing is 1000 mN / 25 m or more, the adhesive force of the surface protective film 10 to the optical member and the electronic member is increased, and the protection performance is improved. Moreover, it becomes easy to make the adhesive force after energy ray hardening into a desired magnitude
  • the adhesive strength before energy ray curing 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 surface protective film 10 has an adhesive strength after energy ray curing (that is, an adhesive strength of the cured portion 12A) of preferably 10 to 300 mN / 25 mm, more preferably 15 to 200 mN / 25 mm, 20 More preferably, it is ⁇ 100 mN / 25 mm.
  • an adhesive strength of the cured portion 12A is preferably 10 to 300 mN / 25 mm, more preferably 15 to 200 mN / 25 mm, 20 More preferably, it is ⁇ 100 mN / 25 mm.
  • the adhesive force after energy ray curing can be controlled by the type and amount of the energy ray polymerizable compound (B) and the amount of unsaturated groups introduced into the acrylic copolymer.
  • the initial stage adhesive force before energy beam hardening of the surface protection film 10 (namely, initial stage adhesive force of the uncured part 12B)
  • 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. Moreover, 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.
  • the method of forming the pressure-sensitive adhesive layer 12 on the substrate 11 is not particularly limited, but the energy ray-curable pressure-sensitive adhesive composition diluted with an appropriate solvent as necessary is formed on the release sheet to a predetermined dry film thickness. Then, after applying to form a 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.
  • the method for forming the cured portion 12A is not particularly limited.
  • a method of irradiating the adhesive layer 12 with energy rays from a known irradiation device through a mask having an opening having a shape matching the cured portion 12A can be mentioned.
  • the energy rays may be applied to the pressure-sensitive adhesive layer 12 from the base material 11 side through the base material 11, or from the opposite side of the base material 11.
  • the energy rays are applied to the pressure-sensitive adhesive layer through the release sheet.
  • 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.
  • the adhesive portion and the non-adhesive portion may be arranged in any pattern 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 various patterns are arranged in a plurality. Other shapes may be preferable.
  • the pattern is normally provided in the whole surface of a base material.
  • one part for example, center part as shown in FIG. 2 is made into a hardening part, and another part is uncured. Part.
  • 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.
  • 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.
  • the material of the substrate 11 is not particularly limited, and a 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 11 has permeability
  • the film area of the surface protective film 10 is preferably 100 mm 2 or less, more preferably about 10 to 80 mm 2 .
  • the surface protective film 10 is reduced in size according to the optical member and the electronic member. However, as described above, the entire film is cured with energy rays to improve the peeling performance. Makes it easier to peel off the deposit.
  • the surface protection film is processed into a circle, a square, a rectangle, etc., for example.
  • the ratio of the area of the cured portion 12A to the film area of the surface protective film 10 is preferably less than 5/10, more preferably 3/10 or less, and even more preferably 1/10 or less. .
  • the lower limit of this area ratio is not particularly limited, but is, for example, 1/1000 or more, preferably 1/100 or more.
  • the pressure-sensitive adhesive layer 12 side of the surface protective film 10 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 the surface protection films 10 may be provided on one release sheet having a size sufficiently larger than the surface protection film 10.
  • 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 cylinder 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 used by being mounted on 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 10 of the present invention is used for affixing to one surface of an optical member or an electronic member to protect the surface.
  • the surface protective film 10 is provided with the cured portion 12A.
  • the cured portion 12A is aligned with a specific portion of the optical member or the electronic member so as to be aligned with the optical member or the electronic member. It is preferable to be affixed to one side of the member. Thereby, it is possible to appropriately protect the specific part of the optical member or the electronic member while preventing the glue transfer from occurring in the specific part.
  • An optical member or an electronic member (hereinafter also simply referred to as a member with a surface protective film) to which a surface protective film is attached is processed, attached to another member, inspected, or transported, etc.
  • the 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 when these steps are finished and the surface protection is no longer necessary.
  • the surface protective film is preferably peeled off from the optical member or the electronic member after being irradiated with the energy rays.
  • the member with a surface protective film may be heated in the process such as processing, attachment, inspection, or conveyance described above.
  • 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 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 the step of curing the adhesive, the member with a surface protective film is usually at a temperature of 60 to 200 ° C. or more, preferably about 70 to 150 ° C. as described above. Heated. Thereafter, when the surface protection becomes unnecessary, the surface protective film is peeled off from the optical member or the electronic member after the surface protective film is irradiated with energy rays and the adhesive force is lowered.
  • 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 image pickup module 20 is usually provided with a light receiving portion 21 for receiving light from the outside on one surface 20A and guiding the light to the image pickup element via a lens inside the module.
  • the light receiving unit 21 is provided on a part (for example, the center) of one surface 20A of the imaging module 20, and is made of glass or transparent resin.
  • a portion corresponding to the light receiving portion 21 of the imaging module (for example, the central portion of the film 10) is cured with energy rays to become a cured portion 12A, and the other portion becomes an uncured portion 12B.
  • . 3 shows an example in which the hardened portion 12 is circular according to the shape of the light receiving unit 21, but is not limited to circular.
  • the surface protective film 10 is attached to the one surface 20A of the imaging module 20 after the cured portion 12A is aligned with the light receiving unit 21.
  • the uncured portion 12B of the surface protective film 10 adheres to the outer periphery (the surface of the casing or the package) of the light receiving portion 21 on the one surface 20A with high adhesive force. Therefore, it is possible to appropriately protect the light receiving unit 21 of the imaging module 20.
  • the adhesive of the surface protection film 10 is difficult to transfer, and contamination of the light-receiving part 21 is prevented.
  • the cured portion 12 ⁇ / b> A may be only in contact with the light receiving portion 21 without being bonded to the light receiving portion 21.
  • the surface protection film 10 will be peeled from the imaging module 20, but the surface protection film 10 is as above mentioned. It is preferable that the energy beam is irradiated and then peeled off from the imaging module 20. Further, as described above, the imaging module 20 to which the surface protective film 10 is attached is preferably heated and attached to another member such as a substrate, and then the energy protective ray is irradiated and the surface protective film is peeled off. It is preferable.
  • the surface protective film may be used similarly.
  • the optical member is usually provided with a light transmission portion made of glass, transparent resin, or the like that forms a part of the optical path on one surface to which the surface protective film is attached.
  • the light transmitting portion is a light receiving portion for receiving light, but in the light emitting element, for example, the light transmitting portion is an emitting portion for emitting light.
  • the surface protective film is hardened with energy rays at a position corresponding to the light transmitting portion in order to make it difficult for adhesive residue to be generated in the light transmitting portion. After being aligned with the part, it is affixed to the optical member. Thereby, the surface of the optical member is appropriately protected while preventing the light transmitting portion from being contaminated by the adhesive.
  • 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 surface protective film before the punching process was cut to a width of 25 mm to prepare a sample, which 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 ray curing.
  • 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 a RAD-2000 m / 12 manufactured by Lintec Corporation). Light quantity 190 mJ / cm 2 ). Thereafter, the adhesive strength when peeled at 180 ° in a tensile rate of 300 mm / min in an environment of 23 ° C.
  • an imaging module 20 having a light receiving portion 21 provided on one surface 20 ⁇ / b> A of the module was prepared.
  • the surface protective film 10 obtained in each example is attached to one surface 20A of the imaging module 20 so that the position of the cured portion 12A matches the position of the light receiving portion 21 when there is a cured portion, and the following evaluation is performed. Evaluated by criteria. ⁇ Reworkability> A: Even after the surface protective film was attached to the imaging module, it was easy to reattach and the reworkability was good. B: Once the surface protective film was affixed to the imaging module, it was difficult to reattach and the reworkability was insufficient.
  • Example 1 90 parts by mass of n-butyl acrylate and 10 parts by mass of acrylic acid were polymerized in an ethyl acetate solvent to obtain an acrylic copolymer having a weight average molecular weight of 550,000.
  • 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.
  • the surface protective film was cut into a 5 mm diameter (area: 19.6 mm 2 ).
  • An iron plate mask with a hole having a diameter of 1 mm is placed on the surface protective film, and a mask is applied to the surface protective film in a nitrogen atmosphere using an ultraviolet irradiation device (RAD-2000m / 12, manufactured by Lintec Corporation).
  • Example 2 80 parts by mass of 2-ethylhexyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate are polymerized in an ethyl acetate solvent to obtain an acrylic copolymer having a weight average molecular weight of 470,000, and further 100 parts by mass of this acrylic copolymer Then, 21 parts by mass of methacryloyloxyethyl isocyanate (MOI), which is an unsaturated group-containing compound, was reacted (80 equivalents with respect to 100 equivalents of 2-hydroxyethyl acrylate) to obtain an energy ray curable acrylic copolymer. .
  • MOI methacryloyloxyethyl isocyanate
  • Example 3 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 1 100 parts by mass (converted to solid content) of the energy ray-curable acrylic copolymer diluted with ethyl acetate, 10 parts by mass of a bifunctional urethane acrylate oligomer having a weight average molecular weight of 5500, and a photopolymerization initiator Irgacure 184 (manufactured by BASF) of 3.3 parts by mass and an organic polyvalent isocyanate compound (product name “BHS8515”, Toyochem Co., Ltd.) 0.5 parts by mass as a crosslinking agent are mixed and the same as in Example 1 Was diluted to obtain a diluted solution of an energy ray-curable pressure-sensitive adhesive composition (XY type). Then, it implemented similarly to Example 1.
  • Example 3 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. A product obtained by reacting 2 parts by mass of 2-hydroxypropyl acrylate was used.
  • Comparative Example 1 After the punching process, the same procedure as in Example 1 was performed except that the surface protective film was not irradiated with ultraviolet rays. In Comparative Example 1, since no ultraviolet irradiation was performed, no cured portion was formed.
  • Comparative Example 2 After the punching process, the same procedure as in Example 2 was performed except that the surface protective film was not irradiated with ultraviolet rays. In Comparative Example 2, since the ultraviolet irradiation was not performed, a cured portion was not formed.
  • the cured portion of the surface protective film was aligned with the light receiving portion of the imaging module and then attached to the imaging module, so that no glue transfer to the light receiving portion occurred. It was. Further, since the surface protective film was adhered to the surface of the imaging module around the light receiving portion by the uncured portion 12B having a relatively high adhesive force, the protective performance of the surface protective film was improved. On the other hand, in Comparative Examples 1 and 2, the adhesive strength and the initial adhesive strength were the same as in Examples 1 and 2, but the cured portion was not formed, so there was an adhesive residue in the light receiving portion, and the peelability was good. It was difficult to make.

Abstract

Le film de protection de surface (10) selon l'invention est collé à des éléments optiques ou électroniques et est utilisé pour protéger la surface desdits éléments. Le film de protection de surface est pourvu d'un substrat (11) et d'une couche adhésive (12) qui est disposée sur une surface du substrat (11) et comprend une composition adhésive durcissable par un rayonnement d'énergie. Une partie de la couche adhésive (12) est durcie au moyen d'un rayonnement d'énergie, ce qui produit une partie durcie (12A).
PCT/JP2015/075156 2014-07-07 2015-09-04 Film de protection de surface WO2016006719A1 (fr)

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JP2014-139704 2014-07-07
JP2014139704A JP6613516B2 (ja) 2014-07-07 2014-07-07 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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6475580A (en) * 1987-09-18 1989-03-22 Nitto Denko Corp Ultraviolet ray curable tacky tape or sheet
JPH01251737A (ja) * 1988-03-31 1989-10-06 Toyo Ink Mfg Co Ltd 半導体ウェハ固定用粘着シート
JPH0578629A (ja) * 1991-09-18 1993-03-30 Furukawa Electric Co Ltd:The 放射線硬化性粘着テープ
JPH1117158A (ja) * 1997-06-20 1999-01-22 Nec Corp 固体撮像素子の組立方法
JP2004158812A (ja) * 2002-09-13 2004-06-03 Sekisui Chem Co Ltd 半導体チップの製造方法及びダイシング用粘着テープ
JP2004300333A (ja) * 2003-03-31 2004-10-28 Lintec Corp 易剥離性粘着シート、その製造法及び使用方法
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JP2005322695A (ja) * 2004-05-06 2005-11-17 Fujitsu Ltd 撮像用装置とその製造方法とカメラモジュール
JP2007254619A (ja) * 2006-03-24 2007-10-04 Panac Co Ltd 再剥離性着色粘着フィルム
JP2008031226A (ja) * 2006-07-26 2008-02-14 Lintec Corp 光学機能性フィルム貼合用粘着剤、光学機能性フィルム及びその製造方法
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JP2010199541A (ja) * 2009-01-30 2010-09-09 Nitto Denko Corp ダイシングテープ一体型ウエハ裏面保護フィルム

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