WO2023282007A1 - 両面粘着シート - Google Patents
両面粘着シート Download PDFInfo
- Publication number
- WO2023282007A1 WO2023282007A1 PCT/JP2022/024101 JP2022024101W WO2023282007A1 WO 2023282007 A1 WO2023282007 A1 WO 2023282007A1 JP 2022024101 W JP2022024101 W JP 2022024101W WO 2023282007 A1 WO2023282007 A1 WO 2023282007A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- acrylic
- mass
- double
- adhesive sheet
- 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.)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
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- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to a double-sided adhesive sheet.
- a mobile phone which is a typical mobile device, tends to have thinned main components.
- the display part of a portable device is mainly composed of an LCD module and a backlight unit, and various sheet-like parts are laminated in order to exhibit functions such as light emission, reflection, light blocking, and light guiding. Therefore, a double-sided adhesive sheet (double-sided adhesive tape) is used for assembling (bonding) these parts.
- portable electronic devices are often exposed to the risk of falling due to their usage patterns.
- double-sided pressure-sensitive adhesive sheets used in portable electronic devices are required to have impact resistance so that they are less likely to be damaged or peeled off from parts due to the impact of dropping the portable electronic device.
- Patent Documents 1 to 3 disclose, for example, known double-sided pressure-sensitive adhesive sheets that are used in mobile electronic devices and have excellent impact resistance.
- Patent Documents 1 to 3 do not mention that both impact resistance and reworkability are excellent.
- the present invention was conceived under such circumstances, and its object is to provide a double-sided pressure-sensitive adhesive sheet that has excellent impact resistance and excellent reworkability.
- the present inventors have found that a double-sided pressure-sensitive adhesive sheet having no substrate, wherein the pressure-sensitive adhesive layer constituting the double-sided pressure-sensitive adhesive sheet is a base polymer containing a specific monomer component as a constituent component It has been found that excellent impact resistance and excellent reworkability are achieved by including and having specific properties. The present invention has been completed based on these findings.
- the present invention is a double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer
- the double-sided pressure-sensitive adhesive sheet has a thickness of 500 ⁇ m or less
- the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer,
- the acrylic polymer contains structural units derived from an acrylic monomer (A) having two or more non-aromatic rings
- the pressure-sensitive adhesive layer has a tan ⁇ peak top between ⁇ 20° C. and 0° C., and the peak top value is 0.8 or more to provide a double-sided pressure-sensitive adhesive sheet.
- the acrylic polymer preferably contains structural units derived from a (meth)acrylic acid alkyl ester (B) having a linear or branched alkyl group with 2 to 7 carbon atoms.
- the (meth)acrylic acid alkyl ester (B) is preferably butyl (meth)acrylate.
- the proportion of structural units derived from the (meth)acrylic acid alkyl ester (B) in the acrylic polymer is preferably 50% by mass or more.
- the above acrylic polymer preferably has a structural part derived from an acrylic oligomer.
- the acrylic oligomer preferably contains a structural unit derived from the acrylic monomer (A).
- the content of the acrylic oligomer is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the total acrylic partial polymer.
- the acrylic monomer (A) preferably contains one or more groups selected from the group consisting of a dicyclopentanyl group, a dicyclopentenyl group, and an isobornyl group.
- the adhesive layer preferably further contains a tackifying resin.
- the breaking stress is preferably 0.9 MPa or more.
- the storage elastic modulus G' of the pressure-sensitive adhesive layer at 23°C is preferably 0.09 MPa or more.
- the double-sided pressure-sensitive adhesive sheet is preferably for fixing members to each other in electrical and electronic equipment.
- the present invention also provides an electrical and electronic device comprising the double-sided pressure-sensitive adhesive sheet, wherein both pressure-sensitive adhesive surfaces of the double-sided pressure-sensitive adhesive sheet fix members to each other.
- the double-sided pressure-sensitive adhesive sheet of the present invention has excellent impact resistance and excellent reworkability. Therefore, when used in portable electronic devices, for example, it is difficult to peel off when subjected to a drop impact, and when the double-sided pressure-sensitive adhesive sheet is intentionally peeled off, the pressure-sensitive adhesive sheet is easily peeled off without being broken.
- the double-sided pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer, and is a so-called "substrate-less" double-sided pressure-sensitive adhesive sheet that does not have a substrate.
- the above pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer.
- the acrylic polymer contains structural units derived from an acrylic monomer having two or more non-aromatic rings (sometimes referred to as "acrylic monomer (A)").
- the pressure-sensitive adhesive layer may be referred to as "the pressure-sensitive adhesive layer of the present invention”.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the double-sided pressure-sensitive adhesive sheet of the present invention.
- a double-sided pressure-sensitive adhesive sheet 1 is composed of a single pressure-sensitive adhesive layer 2 of the present invention. Release liners 3 and 4 are attached to the adhesive surfaces of the adhesive layer 2, respectively.
- the pressure-sensitive adhesive layer of the present invention is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer exhibiting adhesiveness.
- the base polymer refers to a main component among the polymer components in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, for example, a polymer component contained in an amount exceeding 50% by mass.
- the above acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth)acryloyl group in the molecule) as a monomer component that constitutes the polymer. That is, the acrylic polymer contains structural units derived from acrylic monomers. In addition, acrylic polymer may use only 1 type, and may use 2 or more types. Moreover, the said acrylic polymer may contain only 1 type of acrylic monomers as a monomer component, and may contain 2 or more types. In the present specification, "(meth)acrylic” means “acrylic” and/or “methacrylic” (one or both of "acrylic” and “methacrylic”), and the same applies to others. .
- the bicyclic or more non-aromatic ring includes a bicyclic or more non-aromatic hydrocarbon ring and a bicyclic or more non-aromatic heterocyclic ring.
- the non-aromatic ring may be either saturated or unsaturated.
- Examples of the non-aromatic hydrocarbon ring having two or more rings include bridged hydrocarbon rings such as bicyclic aliphatic hydrocarbon rings and tricyclic or more aliphatic hydrocarbon rings.
- Bicyclic hydrocarbon rings include pinane ring, pinene ring, bornane ring, norbornane ring, norbornene ring and the like.
- the number of atoms constituting the non-aromatic ring is preferably 6-12, more preferably 7-10. Further, in the acrylic monomer (A), the non-aromatic ring is directly bonded to the (meth)acryloyl group, or bonded to the (meth)acryloyl group via an oxygen atom or an oxyalkylene group. preferably.
- the bicyclic or higher non-aromatic ring is preferably a bicyclic or higher non-aromatic hydrocarbon ring, more preferably a bicyclic or tricyclic non-aromatic hydrocarbon ring, and more preferably bornane.
- ring, norbornane ring, norbornene ring, dicyclopentane ring, and dicyclopentene ring are preferable as the group having two or more non-aromatic rings, which the acrylic monomer (A) has.
- the Tg of the homopolymer of the acrylic monomer (A) is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 60°C or higher. When the Tg is 0°C or higher, the impact resistance is more excellent.
- the above Tg is, for example, 200° C. or less.
- the homopolymer solution is then cast onto a release liner and dried to form a test sample (sheet homopolymer) having a thickness of about 2 mm. Then, this test sample was punched out into a disk shape with a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to shear strain at a frequency of 1 Hz using a viscoelasticity tester (trade name “ARES”, manufactured by Rheometrics Co., Ltd.). The viscoelasticity is measured in the shear mode at a heating rate of 5°C/min in the region of -70 to 150°C, and the peak top temperature of tan ⁇ is defined as the Tg of the homopolymer.
- ARES viscoelasticity tester
- acrylic monomer (A) examples include (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate; , dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl -2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like (meth)acrylic acid esters having a tricyclic or higher aliphatic hydrocarbon ring.
- (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate; ,
- the proportion of the acrylic monomer (A) in the total amount of 100% by mass of all monomer components constituting the acrylic polymer is preferably 1 to 30% by mass, more preferably 2 to 13% by mass.
- the proportion of the acrylic monomer (A) in the total amount of 100% by mass of all monomer components constituting the acrylic polymer is preferably 1 to 30% by mass, more preferably 2 to 13% by mass.
- the above ratio is 1% by mass or more, reworkability is improved.
- the above proportion is 30% by mass or less, the tan ⁇ peak top value of the pressure-sensitive adhesive layer is high, and the impact resistance and reworkability are excellent.
- the acrylic polymer is composed (formed) of an acrylic monomer (A) and a (meth)acrylic acid alkyl ester (sometimes referred to as "(meth)acrylic acid alkyl ester (B)") as a monomer component. Polymers are preferred.
- the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ( meth)isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate isopentyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylate ) isononyl acrylate, decyl (me
- the (meth)acrylic acid alkyl ester having a linear or branched alkyl group has a linear or branched alkyl group having 2 to 7 carbon atoms from the viewpoint of further improving impact resistance.
- a (meth)acrylic acid alkyl ester having such a compound is preferable, and butyl (meth)acrylate is more preferable. It may also contain methyl (meth)acrylate.
- the above acrylic polymer may contain a copolymerizable monomer together with the acrylic monomer (A) and the (meth)acrylic acid alkyl ester (B) as monomer components constituting the polymer. That is, the acrylic polymer may contain a copolymerizable monomer as a structural unit.
- the above copolymerizable monomers may be used alone or in combination of two or more.
- a carboxy group-containing monomer and/or an acid anhydride monomer are preferable from the viewpoint of being able to form a pressure-sensitive adhesive layer having good adhesiveness even if it is thin.
- the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
- the acid anhydride monomer include maleic anhydride and itaconic anhydride.
- the copolymerizable monomer may further contain a functional group-containing monomer for the purpose of introducing a cross-linking point into the acrylic polymer or increasing the cohesion of the acrylic polymer.
- a functional group-containing monomer examples include hydroxyl group-containing monomers, nitrogen atom-containing monomers (excluding acrylic monomers (A)), keto group-containing monomers, alkoxysilyl group-containing monomers, and sulfonic acid group-containing monomers. , phosphate group-containing monomers, and the like. Only one kind of the functional group-containing monomer may be used, or two or more kinds thereof may be used.
- hydroxy group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) ) hydroxyalkyl (meth)acrylates such as acrylates; unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono(meth)acrylates;
- Examples of the nitrogen atom-containing monomers include amide group-containing monomers, amino group-containing monomers, and cyano group-containing monomers.
- Examples of the amide group-containing monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N -Methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide and the like.
- amino group-containing monomer examples include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate and the like.
- cyano group-containing monomer examples include acrylonitrile and methacrylonitrile.
- keto group-containing monomer examples include diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, and vinyl acetoacetate.
- alkoxysilyl group-containing monomer examples include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-( meth)acryloxypropylmethyldiethoxysilane and the like.
- sulfonic acid group-containing monomer examples include styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth) ) acryloyloxynaphthalenesulfonic acid and the like.
- Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate.
- the ratio of the functional group-containing monomer in the total amount of 100% by mass of all the monomer components constituting the acrylic polymer is, for example, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 5% by mass. % or more, or 10% by mass or more.
- the above ratio may be, for example, 40% by mass or less, 20% by mass or less, or may be substantially absent.
- substantially not included refers to unintentional inclusion, such as unavoidable mixing, rather than active blending. It is 0.01% by mass or less.
- the copolymerizable monomer may further contain other monomers.
- the other monomers include vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), and vinyl toluene; ethylene, propylene.
- the proportion of the other monomers in the total amount of 100% by mass of all monomer components constituting the acrylic polymer may be, for example, 0.05% by mass or more, or 0.5% by mass or more.
- the above ratio may be, for example, 20% by mass or less, 10% by mass or less, 5% by mass or less, or may be substantially absent.
- the acrylic polymer may contain, as a monomer component constituting the polymer, a polyfunctional monomer copolymerizable with the monomer component forming the acrylic polymer, in order to form a crosslinked structure in the polymer skeleton.
- the polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, penta Polyfunctional (meth)acrylates such as erythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates (e.g., poly glycidyl (meth)acrylate), polyester (meth)acrylate, urethane
- the acrylic polymer may have a structure derived from an acrylic oligomer.
- examples of such an acrylic polymer include a polymer containing an acrylic polymer (sometimes referred to as "acrylic polymer (C)") and a polymerization reaction product of a composition containing the acrylic oligomer. Having a structural part derived from an acrylic oligomer results in higher breaking strain and better reworkability.
- the composition containing the acrylic oligomer may further contain a monomer component (sometimes referred to as "monomer component (D)").
- a monomer component sometimes referred to as "monomer component (D)"
- Each of the acrylic polymer (C), the acrylic oligomer, and the monomer component (D) may be used alone or in combination of two or more.
- the acrylic polymer may be a polymerization reaction product obtained by polymerizing a composition containing one or more selected from the group consisting of an acrylic partial polymer, an acrylic oligomer, and a monomer component (D). good.
- the monomer component (D) contains at least an acrylic monomer.
- a polymerization reaction product of a composition containing an acrylic partial polymer is preferred.
- the above-mentioned "partially polymerized product” may also be referred to as "prepolymer", "syrup", and the like.
- Each of the acrylic partial polymer, acrylic oligomer, and monomer component (D) may be used alone or in combination of two or more.
- the acrylic polymer (C), the acrylic partial polymer, and the acrylic oligomer are all compounds composed of an acrylic monomer as an essential monomer component.
- the acrylic monomer and the monomer component (D), which are monomer components constituting the acrylic polymer (C), the acrylic partial polymer, and the acrylic oligomer, are exemplified as the monomer components constituting the acrylic polymer. and those described.
- the acrylic polymer (C) may be a polymer that forms the base polymer alone, or may be a polymer that forms the base polymer together with the polymerization reaction product of the composition containing the acrylic oligomer.
- the acrylic polymer (C) contains an acrylic monomer as a structural unit.
- the acrylic polymer (C) preferably contains a (meth)acrylic acid alkyl ester (B) as a structural unit.
- the (meth)acrylic acid alkyl ester (B) is preferably a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 2 to 7 carbon atoms, more preferably butyl (meth)acrylate. is.
- the acrylic monomer contained as the structural unit may be of one type or two or more types.
- the proportion of the (meth)acrylic acid alkyl ester (B) in 100% by mass of the total amount of all monomer components constituting the acrylic polymer (C) is preferably 50% by mass or more, more preferably 60% by mass. above, more preferably at least 65% by mass.
- the ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
- the acrylic polymer (C) may contain the above copolymerizable monomer as a structural unit.
- a carboxy group-containing monomer and/or acid Anhydride monomers are preferred.
- the acrylic polymer (C) may contain the acrylic monomer (A) as a structural unit.
- the ratio of the carboxy group-containing monomer and/or the acid anhydride monomer in the total amount of 100% by mass of all monomer components constituting the acrylic polymer (C) is not particularly limited, but is preferably 0.2% by mass or more. It is preferably 1% by mass or more, more preferably 1% by mass or more. The proportion is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
- a pressure-sensitive adhesive layer is formed that has a good quantitative balance with the (meth)acrylic acid alkyl ester (B), has excellent impact resistance, and has good adhesion even if it is thin. It becomes possible.
- the acrylic partial polymer is obtained by polymerizing the monomer components at a polymerization conversion rate of 95% by mass or less, for example.
- the polymerization conversion rate is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
- the polymerization conversion rate is preferably 1% by mass or more, more preferably 5% by mass or more.
- the above acrylic partial polymer contains an acrylic monomer as a structural unit.
- the above acrylic partial polymer preferably contains a (meth)acrylic acid alkyl ester (B) as a structural unit.
- the (meth)acrylic acid alkyl ester (B) is preferably a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 2 to 7 carbon atoms, more preferably butyl (meth)acrylate. is.
- the acrylic monomer contained as the structural unit may be of one type or two or more types.
- the proportion of the (meth)acrylic acid alkyl ester (B) in 100% by mass of the total amount of all monomer components constituting the acrylic partial polymer is preferably 50% by mass or more, more preferably 60% by mass. above, more preferably at least 65% by mass.
- the ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
- the acrylic partial polymer may contain the copolymerizable monomer as a structural unit.
- copolymerizable monomers a carboxy group-containing monomer and/or acid Anhydride monomers are preferred.
- the ratio of the carboxy group-containing monomer and/or the acid anhydride monomer in the total amount of 100% by mass of all the monomer components constituting the acrylic partial polymer is not particularly limited, but is preferably 0.2% by mass or more. It is preferably 1% by mass or more, more preferably 1% by mass or more. The proportion is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
- the above ratio is within the above range, the quantitative balance between the acrylic monomer (A) and the (meth)acrylic acid alkyl ester (B) is good, the impact resistance is excellent, and the adhesion is good even if the film is thin. It becomes possible to form a pressure-sensitive adhesive layer having
- the acrylic partial polymer may contain an acrylic monomer (A) as a structural unit.
- the proportion of the acrylic monomer (A) in the total amount of 100% by mass of all the monomer components constituting the partially polymerized product is not particularly limited, but is preferably 3% by mass or more, more preferably 10% by mass. % by mass or more.
- the ratio is preferably 40% by mass or less, more preferably 30% by mass or less.
- the acrylic oligomer preferably has a weight average molecular weight of 2,500 to 10,000, more preferably 3,000 to 8,000.
- the said weight average molecular weight can be calculated
- the above acrylic oligomer contains an acrylic monomer as a structural unit.
- the acrylic oligomer preferably contains an acrylic monomer (A) as a structural unit.
- the acrylic monomer contained as the structural unit may be of one type or two or more types.
- the acrylic monomer (A) accounts for preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass in the total amount of 100% by mass of all monomer components constituting the acrylic oligomer. % by mass or more.
- the ratio is preferably 90% by mass or less, more preferably 80% by mass or less.
- the acrylic oligomer preferably contains a (meth)acrylic acid alkyl ester (B) as a structural unit.
- a (meth)acrylic acid alkyl ester (B) methyl methacrylate (MMA) is preferable.
- the proportion of the (meth)acrylic acid alkyl ester (B) in all monomer components constituting the acrylic oligomer is preferably 10% by mass or more, more preferably 20% by mass or more.
- the proportion is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.
- the acrylic oligomer may contain the copolymerizable monomer as a structural unit.
- the content of the acrylic oligomer is preferably 0.5 to 35 parts by mass, more preferably 2 parts by mass, with respect to the total amount of 100 parts by mass of the acrylic polymer (C) and/or the acrylic partial polymer. to 20 parts by mass, more preferably 4 to 10 parts by mass.
- the storage elastic modulus G' tends to be high and the breaking stress tends to be high, resulting in better reworkability.
- the acrylic polymer and the acrylic polymer (C) are obtained by polymerizing a composition containing one or more selected from the group consisting of the acrylic partial polymer, the acrylic oligomer, and the monomer component (D). be done.
- These polymerization methods are not particularly limited, but include, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a thermal polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
- the bulk polymerization method, the thermal polymerization method, and the active energy ray polymerization method are preferable from the viewpoints of the transparency of the pressure-sensitive adhesive layer and the cost.
- various general solvents may be used in the polymerization of the above-mentioned monomer components.
- the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane, methylcyclohexane and the like. alicyclic hydrocarbons; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- a solvent may use only 1 type, and may use 2 or more types.
- a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction.
- a polymerization initiator may use only 1 type, and may use 2 or more types.
- the thermal polymerization initiator is not particularly limited. , benzoyl peroxide, hydrogen peroxide, etc.), substituted ethane-based initiators such as phenyl-substituted ethane, aromatic carbonyl compounds, redox-based polymerization initiators, and the like.
- the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable.
- the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis(2-methylpropionate)dimethyl, 4,4'-azobis-4-cyanovaleric acid and the like.
- the amount of the thermal polymerization initiator to be used may be a normal amount, for example, 0.005 to 1 part by mass, preferably 0.01 to 1 part by mass based on 100 parts by mass of the monomer component. can do.
- the photopolymerization initiator is not particularly limited. Examples include active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators. Other examples include acylphosphine oxide photopolymerization initiators and titanocene photopolymerization initiators.
- benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, anisole methyl ether and the like.
- acetophenone-based photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) and dichloroacetophenone.
- Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. be done.
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(O-ethoxycarbonyl)-oxime.
- Examples of the benzoin-based photopolymerization initiator include benzoin.
- Examples of the benzyl-based photopolymerization initiator include benzyl.
- benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone, and the like.
- ketal photopolymerization initiator examples include benzyl dimethyl ketal.
- Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
- Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
- titanocene photopolymerization initiator examples include bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl ) and titanium.
- the amount of the photopolymerization initiator used may be a normal amount, for example, 0.01 to 3 parts by mass, preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the monomer component. You can choose from
- the above acrylic polymer may be crosslinked with a crosslinking agent.
- a cross-linking agent By using a cross-linking agent, it is possible to form a cross-linked structure in the acrylic polymer in the acrylic pressure-sensitive adhesive layer and control the gel fraction.
- the cross-linking agent is appropriately selected according to the functional groups in the side chains of the acrylic partial polymer, for example.
- the above-mentioned cross-linking agent only one kind of the above-mentioned cross-linking agent may be used, or two or more kinds thereof may be used.
- the cross-linking agent is not particularly limited. cross-linking agent, metal salt cross-linking agent, carbodiimide cross-linking agent, oxazoline cross-linking agent, aziridine cross-linking agent, amine cross-linking agent, hydrazine cross-linking agent, silicone cross-linking agent, silane cross-linking agent (silane coupling agent), etc. mentioned.
- the above isocyanate-based cross-linking agent is a compound (polyfunctional isocyanate compound) having an average of two or more isocyanate groups per molecule.
- examples of the isocyanate-based cross-linking agent include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
- aliphatic polyisocyanates examples include 1,2-ethylene diisocyanate; tetramethylene diisocyanates such as 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate and 1,4-tetramethylene diisocyanate; - hexamethylene diisocyanates such as hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate; 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate and the like.
- alicyclic polyisocyanates examples include isophorone diisocyanate; cyclohexyl diisocyanates such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate and 1,4-cyclohexyl diisocyanate; 1,2-cyclopentyl diisocyanate, 1,3 - cyclopentyl diisocyanate such as cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like.
- isocyanate-based cross-linking agent examples include trimethylolpropane/tolylene diisocyanate adduct (trade name “Coronate L”, manufactured by Tosoh Corporation), trimethylolpropane/hexamethylene diisocyanate adduct (trade name “Coronate HL ”, manufactured by Tosoh Corporation), trimethylolpropane/xylylene diisocyanate adduct (trade name “Takenate D-110N”, manufactured by Mitsui Chemicals, Inc.).
- the content of the isocyanate-based cross-linking agent when using the isocyanate-based cross-linking agent as the cross-linking agent is not particularly limited, but is 0.5 parts by mass with respect to 100 parts by mass of the total amount of the monomer components constituting the acrylic polymer.
- the above is preferable, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass or more.
- the content is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.
- epoxy-based cross-linking agent examples include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl aminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether , glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
- the content of the epoxy-based cross-linking agent when using the epoxy-based cross-linking agent as the cross-linking agent is not particularly limited, it exceeds 0 parts by mass with respect to the total amount of 100 parts by mass of the monomer components constituting the acrylic polymer. is preferably 1 part by mass or less, more preferably 0.001 to 0.5 parts by mass, still more preferably 0.002 to 0.2 parts by mass, still more preferably 0.005 to 0.1 parts by mass, particularly preferably It is 0.008 to 0.05 parts by mass.
- any one that generates radical active species by heat and promotes cross-linking of the base polymer can be used as appropriate. It is preferred to use a peroxide with a temperature of 80-160°C, more preferably a peroxide with a temperature of 90-140°C.
- peroxide-based crosslinking agent examples include di(2-ethylhexyl) peroxydicarbonate (1-minute half-life temperature: 90.6° C.), di(4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 .5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4° C.), 1,1,3,3-tetramethylbut
- the half-life of the peroxide-based cross-linking agent is an index that represents the decomposition rate of the peroxide, and refers to the time it takes for the residual amount of the peroxide to halve.
- the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer's catalog etc. For example, NOF Corporation's "Organic Peroxide Catalog 9th Edition ( May 2003)”.
- HPLC high performance liquid chromatography
- the content of the cross-linking agent when a peroxide-based cross-linking agent is used as the cross-linking agent is not particularly limited. preferably 0.02 to 2 parts by mass, more preferably 0.05 to 1 part by mass.
- an organic cross-linking agent or a polyfunctional metal chelate may be used in combination.
- Polyfunctional metal chelates are those in which polyvalent metals are covalently or coordinately bonded to organic compounds.
- Polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. mentioned.
- Atoms in the organic compounds that are covalently or coordinately bonded include oxygen atoms, and the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.
- the above-mentioned cross-linking agent includes an isocyanate-based cross-linking agent. Further, it is more preferable to contain another cross-linking agent together with the isocyanate-based cross-linking agent.
- an epoxy-based cross-linking agent is preferable.
- the adhesive layer of the present invention preferably further contains a tackifying resin.
- a tackifying resin With a tackifying resin, the adhesive layer tends to have better adhesion even though it is thinner.
- the pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer and a tackifying resin, it has excellent adhesion to the adherend and is more difficult to peel off.
- the tackifying resin examples include phenol-based tackifying resins, terpene-based tackifying resins, rosin-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, and elastomer-based tackifying resins. resins, ketone-based tackifying resins, and the like.
- Other examples of the tackifier resin include low polymers of (meth)acrylic acid alkyl esters such as low polymers of dicyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA). Only one type of the tackifying resin may be used, or two or more types may be used.
- phenol-based tackifier resin examples include terpene phenol resins, hydrogenated terpene phenol resins, alkylphenol resins, and rosin phenol resins.
- the terpene phenol resin is a polymer containing a terpene residue and a phenol residue, and is a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin), a homopolymer or a copolymer of a terpene.
- Phenol-modified ones phenol-modified terpene resins
- terpenes constituting the terpene phenol resin include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (d-form, l-form, d/l-form (dipentene), etc.).
- the above hydrogenated terpene phenol resin is a resin having a structure obtained by hydrogenating the above terpene phenol resin.
- the above alkylphenol resin is a resin (oily phenolic resin) obtained from alkylphenol and formaldehyde. Examples of the alkylphenol resin include novolac type and resol type.
- the rosin phenol resin is a phenol-modified rosin or various rosin derivatives described later.
- the rosin phenol resin can be obtained, for example, by adding phenol to rosins or various rosin derivatives described later with an acid catalyst and thermally polymerizing them.
- the terpene-based tackifying resin examples include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene and dipentene.
- the terpene polymer may be a single terpene homopolymer or a copolymer of two or more terpenes. Examples of homopolymers of terpenes include ⁇ -pinene polymer, ⁇ -pinene polymer, and dipentene polymer.
- the modified terpene-based tackifying resin is a modified terpene resin (modified terpene resin). Examples of the modified terpene resins include styrene-modified terpene resins and hydrogenated terpene resins.
- the rosin-based tackifying resins include rosins and rosin derivative resins.
- the rosins include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin; disproportionated rosin, polymerized rosin, other chemically modified rosins, etc.).
- the rosin derivative resin include derivatives of the above rosins.
- rosin derivative resin examples include rosin esters such as an unmodified rosin ester that is an ester of an unmodified rosin and an alcohol, and a modified rosin ester that is an ester of a modified rosin and an alcohol; Unsaturated fatty acid-modified rosins modified with fatty acids; Unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; Rosins or rosin alcohols obtained by reducing the carboxy groups of the above rosin derivatives; Rosins Alternatively, metal salts of the various rosin derivatives described above may be used. Specific examples of the rosin esters include unmodified rosin or modified rosin methyl ester, triethylene glycol ester, glycerin ester, pentaerythritol ester, and the like.
- hydrocarbon-based tackifying resin examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, and aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc.). , aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone-indene-based resins.
- the adhesive layer of the present invention may contain fillers. Addition of a filler tends to further improve impact resistance. Only one type of the filler may be used, or two or more types may be used.
- the shape of the filler is not particularly limited, and a particulate or fibrous filler can be used. Among them, a particulate form is preferable.
- the filler may be either an organic substance or an inorganic substance.
- Examples of materials constituting the above inorganic substances include metals such as copper, silver, gold, platinum, nickel, aluminum, chromium, iron, and stainless steel; aluminum oxide, silicon oxide (silicon dioxide), titanium oxide, zirconium oxide, and zinc oxide. , tin oxide, copper oxide, nickel oxide and other metal oxides; aluminum hydroxide, boehmite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, silicic acid, iron hydroxide, copper hydroxide, barium hydroxide, zirconium oxide water hydrates, tin oxide hydrates, basic magnesium carbonate, hydrotalcite, dawsonite, borax, zinc borate and other metal hydroxides and hydrated metal compounds; silicon carbide, boron carbide, nitrogen carbide, calcium carbide, etc.
- metals such as copper, silver, gold, platinum, nickel, aluminum, chromium, iron, and stainless steel
- aluminum oxide silicon oxide (silicon dioxide), titanium oxide, zirconium oxide, and zinc oxide.
- nitrides such as aluminum nitride, silicon nitride, boron nitride, gallium nitride
- carbonates such as calcium carbonate
- titanates such as barium titanate and potassium titanate
- carbon black, carbon tube (carbon nanotube), carbon fiber carbonaceous materials such as diamond
- inorganic materials such as glass
- natural raw material particles such as volcanic shirasu, clay, sand, and the like.
- the filler may have a hollow body structure.
- the hollow portion (internal space of the hollow particles) of the filler having the hollow body structure may be in a vacuum state or may be filled with a medium.
- the medium include inert gases such as nitrogen and argon, air, and volatile solvents.
- a filler whose surface is composed of an organic or inorganic substance other than an acrylic resin and a filler having a hollow body structure are preferable. These fillers have little interaction with the acrylic component in the acrylic pressure-sensitive adhesive layer or have a hollow body structure, so that the pressure-sensitive adhesive layer is less likely to break when stretched, and is more excellent in reworkability.
- the average particle diameter of the particulate filler is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 40 ⁇ m or less.
- the average particle size is preferably 0.5 ⁇ m or more, more preferably 1.5 ⁇ m or more, and still more preferably 10 ⁇ m or more.
- the pressure-sensitive adhesive layer can have an appropriate hardness. As a result, the apparent cohesive strength of the pressure-sensitive adhesive layer is increased, the breaking stress and breaking strain are within appropriate ranges, and the impact resistance and reworkability can be further improved.
- the said average particle diameter is a median diameter (D50) measured by a dynamic light-scattering method.
- the content of the filler in the pressure-sensitive adhesive layer of the present invention is preferably more than 0 parts by mass and 30 parts by mass or less, more preferably 0.008 to 10 parts by mass, with respect to 100 parts by mass as the total amount of the base polymer. More preferably, it is 0.4 to 6 parts by mass.
- the breaking stress and breaking strain are within appropriate ranges, and both impact resistance and reworkability are excellent.
- the proportion of the filler in the adhesive layer of the present invention is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, relative to 100% by mass of the total amount of the adhesive layer.
- the hardness of the pressure-sensitive adhesive layer can be made appropriate. Moreover, it is excellent in reworkability.
- the adhesive layer of the present invention may contain a coloring agent.
- the pressure-sensitive adhesive layer is colored by containing a coloring agent, and the double-sided pressure-sensitive adhesive sheet of the present invention is excellent in visibility and design.
- the coloring agent may be a pigment or a dye. Examples of coloring agents include black coloring agents, cyan coloring agents, magenta coloring agents, and yellow coloring agents. A black colorant is preferable from the viewpoint of better visibility and light-shielding properties.
- the coloring agent may contain only one kind, or may contain two or more kinds.
- the proportion of the coloring agent in the pressure-sensitive adhesive layer of the present invention is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight, based on 100% by weight of the total amount of the pressure-sensitive adhesive layer.
- black colorants include carbon black, carbon nanotubes, graphite (graphite), copper oxide, manganese dioxide, azo pigments such as azomethine azo black, aniline black, perylene black, titanium black, cyanine black, activated carbon, and ferrite. , magnetite, chromium oxide, iron oxide, molybdenum disulfide, complex oxide-based black dyes, anthraquinone-based organic black dyes, and azo-based organic black dyes.
- carbon black include furnace black, channel black, acetylene black, thermal black and lamp black.
- a black colorant C.I. I. Solvent Black 3, 7, 22, 27, 29, 34, 43, 70; C.I. I.
- cyan colorant for example, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95; C.I. I. Acid Blue 6, 45; C.I. I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17, 17:1, 18, 22, 25, 56, 60, 63, 65, 66; C.I. I. Bat Blue 4; 60, C.I. I. Pigment Green 7 and the like.
- magenta colorant for example, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122; C.I. I. disperse thread 9;C. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Disperse Violet 1; C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28 and the like.
- magenta colorants include C.I. I.
- yellow colorants examples include C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162; I. Pigment Orange 31, 43; C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 24, 34, 35, 37, 42, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 116, 117, 120, 128, 129, 133, 138, 139 , 147, 150, 151, 153, 154, 155, 156, 167, 172, 173, 180, 185, 195; I. Bat Yellow 1, 3, 20 and the like.
- the pressure-sensitive adhesive layer of the present invention may optionally further contain a cross-linking accelerator, an anti-aging agent, an antioxidant, a plasticizer, a softening agent, a surfactant, an antistatic agent, a surface lubricant, a leveling agent, and a light stabilizer.
- Additives such as agents, ultraviolet absorbers, polymerization inhibitors, foil-like materials, and rust preventives may be contained within a range that does not impair the effects of the present invention. Only one kind of the above additives may be used, or two or more kinds thereof may be used.
- the pressure-sensitive adhesive layer of the present invention has a tan ⁇ peak top between -20 and 0°C, as described above.
- the peak top value is 0.8 or more, preferably 1.2 or more, and more preferably 1.5 or more. Having a peak top of tan ⁇ between ⁇ 20 and 0° C. provides excellent impact resistance when, for example, a member to which a double-sided pressure-sensitive adhesive sheet is applied is dropped at high speed. When the peak top value is 0.8 or more, the impact resistance and reworkability are further improved.
- the adhesive layer of the present invention preferably has a storage modulus G' at 23°C of 0.09 MPa or more, more preferably 0.10 MPa or more, and still more preferably 0.15 MPa or more.
- a storage modulus G' at 23°C of 0.09 MPa or more, more preferably 0.10 MPa or more, and still more preferably 0.15 MPa or more.
- the storage elastic modulus G' is 0.09 MPa or more, it has an appropriate hardness at room temperature and is more excellent in reworkability.
- the storage elastic modulus G' is preferably 0.25 MPa or less.
- the storage modulus G' can be calculated using a dynamic viscoelasticity measurement (DMA) device.
- DMA dynamic viscoelasticity measurement
- the pressure-sensitive adhesive layer of the present invention may be in any form, such as an emulsion type, a solvent type (solution type), an active energy ray-curable type, or a heat-melting type (hot-melt type).
- solvent-type and active-energy-ray-curable adhesive compositions are preferred because they facilitate the formation of an adhesive layer with excellent productivity.
- the active energy rays include ionizing radiation such as ⁇ -rays, ⁇ -rays, ⁇ -rays, neutron beams and electron beams, and ultraviolet rays, with ultraviolet rays being particularly preferred. That is, the active energy ray-curable pressure-sensitive adhesive layer is preferably an ultraviolet-curable pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer of the present invention can be formed, for example, by applying (coating) a pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer onto a release liner and drying and curing the resulting pressure-sensitive adhesive composition layer, or It can be produced by applying (coating) the pressure-sensitive adhesive composition onto a release liner and irradiating the resulting pressure-sensitive adhesive composition layer with active energy rays to cure it. Moreover, you may heat-dry further as needed.
- the pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive composition) forming the pressure-sensitive adhesive layer of the present invention includes, for example, an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as an essential component, or the acrylic partial polymer, An acrylic pressure-sensitive adhesive composition containing, as an essential component, the above-mentioned acrylic oligomer or a monomer mixture containing the above-mentioned acrylic monomer can be used.
- the former includes, for example, a so-called solvent-type acrylic pressure-sensitive adhesive composition. Also. Examples of the latter include so-called active energy ray-curable acrylic pressure-sensitive adhesive compositions.
- the pressure-sensitive adhesive composition preferably contains an acrylic polymer (C) and/or an acrylic partial polymer, and may further contain the acrylic oligomer.
- the pressure-sensitive adhesive composition further contains a cross-linking agent.
- it may contain a tackifying resin, a filler, a coloring agent, and the like.
- the double-sided pressure-sensitive adhesive sheet of the invention is composed of the pressure-sensitive adhesive layer of the invention.
- the thickness of the double-sided pressure-sensitive adhesive sheet is 500 ⁇ m or less, preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less. When the thickness is 500 ⁇ m or less, the thickness of the double-sided pressure-sensitive adhesive sheet can be reduced.
- the thickness of the double-sided pressure-sensitive adhesive sheet is preferably over 10 ⁇ m, more preferably 30 ⁇ m or more, and even more preferably 50 ⁇ m or more. When the thickness is more than 10 ⁇ m, the impact resistance and reworkability are more excellent.
- the thickness of the double-sided pressure-sensitive adhesive sheet refers to the thickness from one pressure-sensitive adhesive surface to the other pressure-sensitive adhesive surface, that is, the thickness of the pressure-sensitive adhesive body, and does not include the release liner.
- the breaking stress of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 0.9 MPa or more, more preferably 1.0 MPa or more.
- the breaking stress is preferably 3.0 MPa or less, more preferably 2.0 MPa or less.
- the above breaking stress is a value measured under the conditions of a sample size of 40 mm ⁇ 40 mm, a thickness of about 0.2 mm, a distance between chucks of 10 mm, and a tensile speed of 50 mm/min under an environment of 23° C. and 50% RH.
- the breaking strain of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 60% or more, more preferably 700% or more, and even more preferably 1000% or more.
- the breaking strain is a value measured under the conditions of a sample size of 40 mm ⁇ 40 mm, a thickness of about 0.2 mm, a distance between chucks of 10 mm, and a tensile speed of 50 mm/min, under an environment of 23° C. and 50% RH.
- the double-sided pressure-sensitive adhesive sheet of the present invention preferably has an energy (load x height) before one of the stainless steel plates is peeled off, as measured by the following DuPont impact test, and is preferably 0.1 or more. It is preferably 0.2 or more, more preferably 0.3 or more.
- ⁇ Shock resistance test> A frame-shaped double-sided adhesive sheet with an outer diameter of 24.5 mm square and a width of 2 mm was placed on a stainless steel plate with a hole in the center of a square with an outer diameter of 2 mm and an outer diameter of 50 mm, and a stainless steel plate with a square with an outer diameter of 3 mm and an outer diameter of 25 mm.
- the weight and height of the drop weight on the above evaluation sample were changed by 50 mm from 50 to 500 mm at 100 g, changed by 50 mm from 350 to 500 mm at 150 g, and 400 to 500 mm at 200 g.
- the energy is changed by 50 mm from 350 to 500 mm, and the energy is increased until peeling occurs.
- the energy that has already been evaluated is not tested, and the load and height are set so that the amount of energy does not overlap. After that, the energy until at least one of the stainless steel plates peels off is calculated by multiplying the load by the height.
- the double-sided pressure-sensitive adhesive sheet may have a release liner attached to the surface (adhesive surface) of the pressure-sensitive adhesive layer until use.
- the adhesive surfaces on both sides of the double-sided pressure-sensitive adhesive sheet may be protected by two release liners, respectively, or one release liner having release surfaces on both sides is wound into a roll. It may be protected in a form (wound body).
- a release liner is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when applied to an adherend. Note that the release liner may not necessarily be provided.
- a conventional release paper or the like can be used, and is not particularly limited. etc.
- the base material having the release treatment layer include plastic films and paper surface-treated with release agents such as silicone, long-chain alkyl, fluorine, and molybdenum sulfide.
- the fluorine-based polymer in the low-adhesive substrate made of the fluorine polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro fluoroethylene-vinylidene fluoride copolymer and the like.
- the non-polar polymer include olefin resins (eg, polyethylene, polypropylene, etc.).
- the release liner can be formed by a known or commonly used method. Also, the thickness of the release liner is not particularly limited.
- the double-sided pressure-sensitive adhesive sheet is preferably for attaching to electrical and electronic members, which is used by being attached to members provided in electrical and electronic equipment.
- the above-mentioned double-sided pressure-sensitive adhesive sheet is particularly preferably used for bonding parts provided in electrical and electronic equipment to both adhesive surfaces of the double-sided pressure-sensitive adhesive sheet, i.e., for fixing members to each other in electrical and electronic equipment.
- the double-sided pressure-sensitive adhesive sheet may be used for fixing the members together or temporarily fixing them. For example, when a double-sided adhesive sheet is used for fixing or temporarily fixing parts provided in electrical and electronic equipment, there are cases in which it is necessary to peel off the double-sided adhesive sheet and rework due to a problem in attaching the double-sided adhesive sheet.
- the double-sided pressure-sensitive adhesive sheet must be peeled off in order to repair, replace, inspect, recycle, or the like a member having an adherend to which the double-sided pressure-sensitive adhesive sheet is attached.
- the double-sided pressure-sensitive adhesive sheet is used, for example, for fixing or temporarily fixing parts (members) provided in electrical and electronic equipment, the frequency of removing the double-sided pressure-sensitive adhesive sheet is particularly high.
- the above-mentioned double-sided pressure-sensitive adhesive sheet is preferably used by pasting the outer frames of optical members (especially electrical and electronic devices) together. Therefore, the double-sided pressure-sensitive adhesive sheet can be preferably used even if it has a width of 5 mm or less, preferably 3 mm or less.
- Electric and electronic equipment refers to equipment that corresponds to at least either electrical equipment or electronic equipment.
- Examples of the electric/electronic devices include image display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, and mobile electronic devices.
- Examples of the portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, and various wearable devices (for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body) Modular type to be worn, eyewear type including eyeglass type (monocular type and binocular type, including head-mounted type), clothing type that can be attached to shirts, socks, hats, etc.
- wearable devices for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body
- Modular type to be worn for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body
- eyewear type including eyeglass type (monocular type and binocular type, including head-mounted type)
- clothing type that can be attached to shirts, socks, hats, etc.
- the term “portable” means not only being able to be carried but also having a level of portability that allows individuals (standard adults) to relatively easily carry it. shall mean.
- the double-sided pressure-sensitive adhesive sheet is used, for example, so that the pressure-sensitive adhesive layer adheres to the member of the portable electronic device.
- Example 1 A reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 68 parts by weight of toluene, 95 parts by weight of butyl acrylate (BA), and 5 parts by weight of acrylic acid (AA). Nitrogen substitution was performed for more than one hour. Add azobisisobutyronitrile as an initiator, then raise the temperature of the inner bath to 62°C, maintain the same temperature, and continue until the reaction is almost complete, then cool to complete the polymerization reaction.
- azobisisobutyronitrile as an initiator
- the pressure-sensitive adhesive composition is coated on a release-treated layer of a 38 ⁇ m-thick polyethylene terephthalate film (product name “MRF #38”, manufactured by Mitsubishi Chemical Corporation) whose one side has been release-treated with silicone, and dried.
- a double-sided pressure-sensitive adhesive sheet of Example 1 was produced by forming a pressure-sensitive adhesive layer of 200 ⁇ m.
- Example 2 The polymer prepared in Example 1: 100 parts by mass, the acrylic oligomer (1) obtained in Production Example 1: 2.5 parts by mass, an isocyanate cross-linking agent (trade name “Coronate L", Tosoh Corporation ): 5 parts by mass, and an epoxy cross-linking agent (trade name “Tetrad C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.): 0.02 parts by mass, and a terpene phenol-based tackifying resin (trade name “YS Polyster T115", manufactured by Yasuhara Chemical Co., Ltd.): 20 parts by mass, polyethylene powder as a filler (trade name "Frick UF-80", manufactured by Sumitomo Seika Co., Ltd.): 2 parts by mass, and a black pigment containing carbon black (trade name "Multilac A903", manufactured by Toyocolor Co., Ltd.): 6 parts by mass were added to obtain an adhesive composition.
- an isocyanate cross-linking agent trade name “Coronate L", Toso
- a double-sided PSA sheet of Example 2 was produced in the same manner as in Example 1, except that the PSA composition obtained above was used.
- Examples 3-7 A double-sided pressure-sensitive adhesive sheet of each example was prepared in the same manner as in Example 2 except that the amount of the acrylic oligomer (1) obtained in Production Example 1 or the thickness of the pressure-sensitive adhesive layer was changed as shown in Table 1. made.
- Example 8 As monomer components, butyl acrylate (BA): 70 parts by mass, acrylic acid (AA): 5 parts by mass, and isobornyl acrylate (IBXA, Tg: 97 ° C.): 25 parts by mass were mixed into a liquid monomer mixture ( monomer composition), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “OMNIRAD651”, manufactured by IGM Resins B.V.) as a photopolymerization initiator: 0.05 parts by mass After blending, the viscosity (BH viscometer No. 5 rotor, 10 rpm, measurement temperature: 30 ° C.) was pulsed with ultraviolet light until it reached about 15 Pa s, and a partial polymer (polymerization yield: about 8%) was obtained (partially polymerized product).
- BH viscometer No. 5 rotor, 10 rpm, measurement temperature: 30 ° C. was pulsed with ultraviolet light until it reached about 15 Pa s, and
- Syrup obtained above 100 parts by mass, isocyanate cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation): 5 parts by mass, and epoxy cross-linking agent (trade name "Tetrad C", Mitsubishi Gas Chemical Co., Ltd.): 0.02 parts by mass, and further terpene phenolic tackifier resin (trade name “YS Polyster T115”, manufactured by Yasuhara Chemical Co., Ltd.): 20 parts by mass, polyethylene powder as a filler (trade name “Frick UF-80”, manufactured by Sumitomo Seika Co., Ltd.): 2 parts by mass, and a black pigment containing carbon black (trade name "Multilac A903", manufactured by Toyocolor Co., Ltd.): After adding 6 parts by mass, disper It was mixed uniformly using the above, and then defoamed to obtain an acrylic pressure-sensitive adhesive composition.
- the resulting acrylic pressure-sensitive adhesive composition was coated on a 38- ⁇ m-thick polyethylene terephthalate film (product name “MRF#38”, manufactured by Mitsubishi Chemical Corporation) whose one side was treated with silicone for release, and the pressure-sensitive adhesive layer thickness was 200 ⁇ m. was applied using an applicator to form a coating layer.
- MRF#38 polyethylene terephthalate film
- a 25 ⁇ m-thick polyethylene terephthalate film (product name “MRE #25”, manufactured by Mitsubishi Chemical Corporation) whose one side was release-treated with silicone was coated with the coating layer so that the release-treated surface was on the side of the coating layer. , oxygen was cut off.
- a black light lamp was used to irradiate ultraviolet rays with an illuminance of 4 mW/cm 2 (UV checker "UVR-T1", manufactured by Topcon Corporation, maximum sensitivity at measurement: about 350 nm) for 180 seconds.
- a pressure-sensitive adhesive layer having a thickness of 200 ⁇ m was formed to prepare a double-sided pressure-sensitive adhesive sheet.
- Example 9 The acrylic oligomer (1) obtained in Production Example 1: The same as in Example 2 except that 5 parts by mass of the acrylic oligomer (2) obtained in Production Example 2 was used in place of 2.5 parts by mass. A double-sided pressure-sensitive adhesive sheet of Example 9 was prepared.
- Example 11 Same as Example 2, except that 5 parts by mass of the acrylic oligomer (4) obtained in Production Example 4 was used in place of 2.5 parts by mass of the acrylic oligomer (1) obtained in Production Example 1. A double-sided pressure-sensitive adhesive sheet of Example 11 was prepared.
- Comparative example 1 A double-sided pressure-sensitive adhesive sheet of Comparative Example 1 was produced in the same manner as in Example 2, except that the acrylic oligomer (1) obtained in Production Example 1 was not blended.
- Comparative example 2 A double-sided pressure-sensitive adhesive sheet of Comparative Example 2 was produced in the same manner as in Example 2, except that the amount of the acrylic oligomer (1) obtained in Production Example 1 was changed to 40 parts by mass.
- Comparative example 3 An acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 2, except that the amount of the acrylic oligomer (1) obtained in Production Example 1 was changed to 5 parts by mass.
- the pressure-sensitive adhesive composition is coated on a release-treated layer of a 38 ⁇ m-thick polyethylene terephthalate film (product name “MRF #38”, manufactured by Mitsubishi Chemical Corporation) whose one side has been release-treated with silicone, and dried. A 178 ⁇ m adhesive layer was formed.
- the release liner (trade name “MRE #25”, manufactured by Mitsubishi Chemical Corporation) provided on the surface of the prepared adhesive layer is peeled off to expose the adhesive layer, and the PET film (thickness 12 ⁇ m) was laminated on the exposed surface of the pressure-sensitive adhesive layer.
- Comparative example 4 The acrylic oligomer (1) obtained in Production Example 1: The same as in Example 2 except that 5 parts by mass of the acrylic oligomer (5) obtained in Production Example 5 was used in place of 2.5 parts by mass. Then, a double-sided pressure-sensitive adhesive sheet of Comparative Example 4 was produced.
- a pressure-sensitive adhesive layer having a thickness of about 2 mm was prepared by stacking a plurality of pressure-sensitive adhesive layers prepared in Examples and Comparative Examples. A disk-shaped sample with a diameter of 7.9 mm was punched out of this adhesive layer and fixed by sandwiching it between parallel plates. (manufactured by A Instruments Co., Ltd.), dynamic viscoelasticity was measured under the following conditions, and the peak top value of storage elastic modulus G′ (23° C.) and tan ⁇ was calculated. It was confirmed that all pressure-sensitive adhesive layers had a tan ⁇ peak top within the range of -20 to 0°C. Measurement mode: Shear mode Temperature range: -70°C to 150°C Heating rate: 5°C/min Measurement frequency: 1Hz
- a cylindrical measurement table with a length of 50 mm, an outer diameter of 49 mm, and an inner diameter of 43 mm is installed on the pedestal of a DuPont impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a test piece is placed on it, a square stainless steel plate. (stainless steel plate without holes) was placed on the bottom side.
- a stainless steel striking core with a tip radius of 3.1 mm is placed on the test piece, and the weight and height of the falling weight are changed by 50 mm from 50 to 500 mm at 100 g, by 50 mm from 350 to 500 mm at 150 g, and then to 200 g.
- the energy was changed by 50 mm from 400 to 500 mm, and at 300 g by 50 mm from 350 to 500 mm, the energy was increased until peeling occurred. At this time, no test was performed on the energy that had already been evaluated, and the load and height were set so that the amount of energy would not overlap. After that, the energy until at least one of the stainless steel plates (for Comparative Example 3, the stainless steel plate attached to the adhesive layer) peeled off was calculated by multiplying the load by the height, and the result was obtained.
- the reworkability required for practical use is 2 or more, preferably 3 or more in the following criteria.
- Rank 1 The tape is torn and cannot be peeled.
- Rank 2 The tape is not torn and can be peeled off by pulling at a speed of less than 0.2 m/min.
- Rank 3 The tape is torn by pulling at a speed of 0.2 m/min or more. peelable without
- the double-sided pressure-sensitive adhesive sheet of the present invention is excellent in both impact resistance and reworkability.
- Table 2 when the acrylic polymer contained in the double-sided pressure-sensitive adhesive sheet does not contain the acrylic monomer (A) having two or more non-aromatic rings as a structural unit (Comparative Examples 1 and 4). , was inferior in reworkability.
- the pressure-sensitive adhesive layer had a low tan ⁇ peak top value (Comparative Example 2) and when it had a base layer (Comparative Example 3), the impact resistance was poor and the reworkability was also poor.
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Abstract
Description
上記両面粘着シートの厚さは500μm以下であり、
上記粘着剤層は、ペースポリマーとしてアクリル系ポリマーを含むアクリル系粘着剤層であり、
上記アクリル系ポリマーは、二環以上の非芳香族性環を有するアクリル系モノマー(A)に由来する構成単位を含み、
上記粘着剤層は、-20~0℃の間にtanδのピークトップを有し、上記ピークトップの値は0.8以上である、両面粘着シートを提供する。
本発明の両面粘着シートは、粘着剤層からなる両面粘着シートであり、基材を有しないいわゆる「基材レス」の両面粘着シートである。
本発明の粘着剤層は、粘着性を発揮するベースポリマーとしてアクリル系ポリマーを含むアクリル系粘着剤層である。なお、本明細書において、ベースポリマーとは、粘着剤層を構成する粘着剤におけるポリマー成分の中の主成分、例えば50質量%を超えて含まれるポリマー成分をいうものとする。
カラム:TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000
溶媒:テトラヒドロフラン
流速:0.6ml/分
本発明の両面粘着シートは、本発明の粘着剤層から構成される。上記両面粘着シートの厚さは、500μm以下であり、好ましくは300μm以下、より好ましくは200μm以下である。上記厚さが500μm以下であることにより、両面粘着シートの厚さを薄くすることができる。上記両面粘着シートの厚さは、10μm超であることが好ましく、より好ましくは30μm以上、さらに好ましくは50μm以上である。上記厚さが10μm超であると、耐衝撃性およびリワーク性により優れる。なお、上記両面粘着シートの厚さは、一方の粘着面から他方の粘着面までの厚さ、すなわち粘着体の厚さをいい、はく離ライナーを含まない。
<耐衝撃試験>
外径24.5mm角、幅2mmの枠状の両面粘着シートを、厚さ2mm、外形50mm角の正方形の中央部に穴の開いたステンレスプレートと、厚さ3mm、外形25mm角の正方形のステンレスプレートの間に挟み込んで圧着し、温度50℃の環境下に2時間静置し、その後常温に戻して評価サンプルとする。デュポン式衝撃試験機を用い、上記評価サンプルに、落下おもり重量と落下高さを、100gにて50~500mmまで50mmずつ変化、150gにて350~500mmまで50mmずつ変化、200gにて400~500mmまで50mmずつ変化、300gにて350~500mmまで50mmずつ変化させ、剥がれが生じるまでエネルギーが増えていくようにする。この際に、評価済みであるエネルギーについては、試験を行わず、エネルギー量が重複しないように荷重と高さを設定する。その後、少なくともいずれか一方のステンレスプレートが剥がれる前までのエネルギーを荷重×高さで算出する。
フラスコに、ジシクロペンタニルメタクリレート(DCPMA、Tg:175℃):60質量部、メチルメタクリレート(MMA):40質量部、α-チオグリセロ-ル:3質量部、2,2’-アゾビスイソブチロニトリル:0.2質量部、および酢酸エチル:65質量部を投入した。フラスコを充分に窒素で充填し、70℃で5時間重合させた後、さらに、2,2’-アゾビスイソブチロニトリル0.1質量部を投入し、80℃で8時間重合させた。その後、反応液から酢酸エチルを留去し、さらに減圧乾燥機により乾燥して、アクリル系オリゴマー(重量平均分子量:5080)を得た。
フラスコに、ジシクロペンテニルアクリレート(Tg:97℃):60質量部、メチルメタクリレート(MMA):40質量部、α-チオグリセロ-ル:3質量部、2,2’-アゾビスイソブチロニトリル:0.2質量部、および酢酸エチル:65質量部を投入した。フラスコを充分に窒素で充填し、70℃で5時間重合させた後、さらに、2,2’-アゾビスイソブチロニトリル0.1質量部を投入し、80℃で8時間重合させた。その後、反応液から酢酸エチルを留去し、さらに減圧乾燥機により乾燥して、アクリル系オリゴマー(重量平均分子量:7600)を得た。
フラスコに、ジシクロペンタニルアクリレート(DCPA、Tg:約100℃):60質量部、メチルメタクリレート(MMA):40質量部、α-チオグリセロ-ル:3質量部、2,2’-アゾビスイソブチロニトリル:0.2質量部、および酢酸エチル:65質量部を投入した。フラスコを充分に窒素で充填し、70℃で5時間重合させた後、さらに、2,2’-アゾビスイソブチロニトリル0.1質量部を投入し、80℃で8時間重合させた。その後、反応液から酢酸エチルを留去し、さらに減圧乾燥機により乾燥して、アクリル系オリゴマー(重量平均分子量:5900)を得た。
フラスコに、ジシクロペンテニルオキシエチルアクリレ-ト(Tg:約100℃):60質量部、メチルメタクリレート(MMA):40質量部、α-チオグリセロ-ル:3質量部、2,2’-アゾビスイソブチロニトリル:0.2質量部、および酢酸エチル:65質量部を投入した。フラスコを充分に窒素で充填し、70℃で5時間重合させた後、さらに、2,2’-アゾビスイソブチロニトリル0.1質量部を投入し、80℃で8時間重合させた。その後、反応液から酢酸エチルを留去し、さらに減圧乾燥機により乾燥して、アクリル系オリゴマー(重量平均分子量:3000)を得た。
フラスコに、シクロヘキシルメタクリレ-ト(Tg:66℃):60質量部、メチルメタクリレート(MMA):40質量部、α-チオグリセロ-ル:3質量部、2,2’-アゾビスイソブチロニトリル:0.2質量部、および酢酸エチル:65質量部を投入した。フラスコを充分に窒素で充填し、70℃で5時間重合させた後、さらに、2,2’-アゾビスイソブチロニトリル0.1質量部を投入し、80℃で8時間重合させた。その後、反応液から酢酸エチルを留去し、さらに減圧乾燥機により乾燥して、アクリル系オリゴマー(重量平均分子量:3600)を得た。
温度計、撹拌機、窒素導入管、および還流冷却機を備えた反応器に、トルエン68質量部、アクリル酸ブチルアクリレート(BA)95質量部、およびアクリル酸(AA)5質量部を仕込み、1時間以上窒素置換をした。開始剤としてアゾビスイソブチロニトリルを投入し、その後内浴温度を62℃まで昇温し、同様の温度を維持し、反応がほぼ終了するまで継続し、その後、冷却して重合反応を終了させた。得られたポリマー:100質量部に対して、製造例1で得られたアクリル系オリゴマー(1):5質量部、イソシアネート化合物(商品名「コロネートL」、東ソー株式会社製):5質量部およびエポキシ化合物(商品名「テトラッドC」、三菱ガス化学株式会社製):0.02質量部を添加し、さらにテルペンフェノール系粘着付与樹脂(商品名「YSポリスターT115」、ヤスハラケミカル株式会社製):20質量部、およびカーボンブラックを含む黒色顔料(商品名「マルチラックA903」、トーヨーカラー株式会社製):6質量部を添加して粘着剤組成物を調製した。
実施例1で作製したポリマー:100質量部に対して、製造例1で得られたアクリル系オリゴマー(1):2.5質量部、イソシアネート系架橋剤(商品名「コロネートL」、東ソー株式会社製):5質量部、およびエポキシ系架橋剤(商品名「テトラッドC」、三菱ガス化学株式会社製):0.02質量部を添加し、さらにテルペンフェノール系粘着付与樹脂(商品名「YSポリスターT115」、ヤスハラケミカル株式会社製):20質量部、フィラーとしてのポリエチレン粉末(商品名「フローセンUF-80」、住友精化株式会社製):2質量部、およびカーボンブラックを含む黒色顔料(商品名「マルチラックA903」、トーヨーカラー株式会社製):6質量部を添加して粘着剤組成物を得た。
製造例1で得られたアクリル系オリゴマー(1)の配合量または粘着剤層の厚さを表1に示すように変更したこと以外は実施例2と同様にして各実施例の両面粘着シートを作製した。
モノマー成分として、ブチルアクリレート(BA):70質量部、アクリル酸(AA):5質量部、およびイソボルニルアクリレート(IBXA、Tg:97℃):25質量部が混合された液状のモノマー混合物(モノマー組成物)に、光重合開始剤としての2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(商品名「OMNIRAD651」、IGM Resins B.V.製):0.05質量部を配合した後、粘度(BH粘度計No.5ローター、10rpm、測定温度:30℃)が約15Pa・sになるまで紫外線をパルス照射して、モノマー成分の一部が重合した部分重合体(重合率:約8%)を含むシロップ(部分重合物)を得た。
製造例1で得られたアクリル系オリゴマー(1):2.5質量部に代えて製造例2で得られたアクリル系オリゴマー(2):5質量部を用いたこと以外は実施例2と同様にして実施例9の両面粘着シートを作製した。
製造例1で得られたアクリル系オリゴマー(1):2.5質量部に代えて製造例3で得られたアクリル系オリゴマー(3):5質量部を用いたこと以外は実施例2と同様にして実施例10の両面粘着シートを作製した。
製造例1で得られたアクリル系オリゴマー(1):2.5質量部に代えて製造例4で得られたアクリル系オリゴマー(4):5質量部を用いたこと以外は実施例2と同様にして実施例11の両面粘着シートを作製した。
製造例1で得られたアクリル系オリゴマー(1)を配合しなかったこと以外は実施例2と同様にして比較例1の両面粘着シートを作製した。
製造例1で得られたアクリル系オリゴマー(1)の配合量を40質量部としたこと以外は実施例2と同様にして比較例2の両面粘着シートを作製した。
製造例1で得られたアクリル系オリゴマー(1)の配合量を5質量部に変更したこと以外は実施例2と同様にしてアクリル系粘着剤組成物を作製した。
上記粘着剤組成物を、片面をシリコーンで剥離処理した厚さ38μmのポリエチレンテレフタレートフィルム(製品名「MRF#38」、三菱ケミカル株式会社製)の剥離処理層上に塗布して乾燥し、厚さ178μmの粘着剤層を形成した。
そして、作製した粘着剤層表面に設けられたはく離ライナー(商品名「MRE#25」、三菱ケミカル株式会社製)を剥離して粘着剤層を露出させ、基材層となるPETフィルム(厚さ12μm)の一方の面を露出した上記粘着剤層の表面にラミネートした。このようにして、基材層上に粘着剤層が形成された比較例3の片面粘着シート(厚さ190μm)を作製した。
製造例1で得られたアクリル系オリゴマー(1):2.5質量部に代えて製造例5で得られたアクリル系オリゴマー(5):5質量部を用いたこと以外は実施例2と同様にして比較例4の両面粘着シートを作製した。
実施例および比較例で得られた粘着剤層および粘着シートについて、以下の評価を行った。結果を表に示す。なお、表における各成分の配合量は質量部を示す。
実施例および比較例で作製した粘着剤層を複数枚重ね合わせることにより、厚さ約2mmの粘着剤層を作製した。この粘着剤層を直径7.9mmの円盤状に打ち抜いた試料をパラレルプレートで挟み込んで固定し、23℃、50%RHの環境下、粘弾性試験機(商品名「ARESレオメーター」、ティー・エー・インスツルメント社製)を用いて以下の条件で動的粘弾性測定を行い、貯蔵弾性率G’(23℃)およびtanδのピークトップ値を算出した。なお、全ての粘着剤層において、-20~0℃の範囲内においてtanδのピークトップが存在することが確認された。
測定モード:せん断モード
温度範囲 :-70℃~150℃
昇温速度 :5℃/min
測定周波数:1Hz
実施例および比較例で得られた粘着シートを幅40mm、長さ40mmのサイズにカットして試験片を得た。23℃、50%RHの環境下において、全てのはく離ライナーを剥がして粘着シートを露出させ、万能引張圧縮試験機(製品名「TCM-1kNB」、ミネベア社製)を用いてチャック間距離10mm、引張速度50mm/分の条件で上記試験片の引張試験を行ってS-S曲線を求め、試験片破断時の応力(破断応力)およびひずみ(破断ひずみ)を測定した。なお、試験に際しては、チャックする箇所の粘着面にパウダーを塗して、粘着剤のべたつきによる影響を除去しておくことが好ましい。
実施例および比較例で作製した、はく離ライナーに挟まれた状態の両面粘着シート(比較例3についてははく離ライナーが設けられた状態の片面粘着シート)を、外径24.5mm角、幅2mmの枠状に打ち抜いた。その後、粘着シートからはく離ライナーを剥離し、厚さ2mm、外形50mm角の正方形の中央部に穴の開いたステンレスプレートと、厚さ3mm、外形25mm角の正方形のステンレスプレートとの間に挟み込んで圧着し、温度50℃の環境下に2時間静置し、その後常温に戻して評価サンプルとした。デュポン式衝撃試験機(株式会社東洋精機製作所製)の台座の上に、長さ50mm、外径49mm、内径43mmの円柱状の測定台を設置し、その上に試験片を、正方形のステンレスプレート(穴の開いていないステンレスプレート)を下側にして載せた。先端半径3.1mmのステンレス製の撃芯を試験片に載せ、落下おもり重量と落下高さを、100gにて50~500mmまで50mmずつ変化、150gにて350~500mmまで50mmずつ変化、200gにて400~500mmまで50mmずつ変化、300gにて350~500mmまで50mmずつ変化させ、剥がれが生じるまでエネルギーが増えていくようにした。この際に、評価済みであるエネルギーについては、試験を行わず、エネルギー量が重複しないように荷重と高さを設定した。その後、少なくともいずれか一方のステンレスプレート(比較例3については粘着剤層に貼り合わせられたステンレスプレート)が剥がれる前までのエネルギーを荷重×高さで算出して結果とした。
実施例および比較例で得られた粘着シートから10mm×50mmのサイズを切り出して評価用サンプルとした。そして、評価用サンプルからはく離ライナー(両面粘着シートについては軽剥離側のはく離ライナー)を剥離し、ステンレス被着体に粘着シートの粘着面をラミネート(2kgローラー×1往復)し、50℃で24時間、加温保存を行った。その後、両面粘着シートについては重剥離側のはく離ライナーを剥がし、ステンレス板から短辺側の端部を剥がし、そのまま、被着体に対して剥離角度30°で引っ張って粘着シートの剥離を試み、リワーク性を確認した。そして、リワーク性を以下の判断基準で評価した。なお、実使用上必要なリワーク性は以下の判断基準における2以上、好ましくは3以上である。
ランク1:テープがちぎれてしまい、剥離できない
ランク2:0.2m/min未満の速度で引っ張ることでテープがちぎれず剥離可能
ランク3:0.2m/min以上の速度で引っ張ることでテープがちぎれず剥離可能
2 粘着剤層
3,4 はく離ライナー
Claims (15)
- 粘着剤層からなる両面粘着シートであり、
前記両面粘着シートの厚さは500μm以下であり、
前記粘着剤層は、ペースポリマーとしてアクリル系ポリマーを含むアクリル系粘着剤層であり、
前記アクリル系ポリマーは、二環以上の非芳香族性環を有するアクリル系モノマー(A)に由来する構成単位を含み、
前記粘着剤層は、-20~0℃の間にtanδのピークトップを有し、前記ピークトップの値は0.8以上である、両面粘着シート。 - 前記アクリル系ポリマー中の前記アクリル系モノマー(A)に由来する構成単位の割合は1~15質量%である請求項1に記載の両面粘着シート。
- 前記アクリル系ポリマーは、炭素数2~7の直鎖または分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステル(B)に由来する構成単位を含む、請求項1または2に記載の両面粘着シート。
- 前記(メタ)アクリル酸アルキルエステル(B)は(メタ)アクリル酸ブチルである請求項3に記載の両面粘着シート。
- 前記アクリル系ポリマー中の前記(メタ)アクリル酸アルキルエステル(B)に由来する構成単位の割合は50質量%以上である請求項3または4に記載の両面粘着シート。
- 前記アクリル系ポリマーはアクリル系オリゴマーに由来する構造部を有する請求項1~5のいずれか1項に記載の両面粘着シート。
- 前記アクリル系オリゴマーは前記アクリル系モノマー(A)に由来する構成単位を含む、請求項6に記載の両面粘着シート。
- 前記アクリル系オリゴマーの含有量は、アクリル系部分重合物の総量100質量部に対して0.5~30質量部である、請求項7に記載の両面粘着シート。
- 前記アクリル系モノマー(A)は、ジシクロペンタニル基、ジシクロペンテニル基、およびイソボルニル基からなる群より選択される1以上の基を含む、請求項1~8のいずれか1項に記載の両面粘着シート。
- 前記粘着剤層はさらに粘着付与樹脂を含む請求項1~9のいずれか1項に記載の両面粘着シート。
- 破断応力は0.9MPa以上である請求項1~10のいずれか1項に記載の両面粘着シート。
- 破断ひずみは60%以上である請求項1~11のいずれか1項に記載の両面粘着シート。
- 前記粘着剤層の23℃における貯蔵弾性率G’は0.09MPa以上である請求項1~12のいずれか1項に記載の両面粘着シート。
- 電気電子機器における部材同士の固定用である請求項1~13のいずれか1項に記載の両面粘着シート。
- 請求項14に記載の両面粘着シートを備え、
前記両面粘着シートは両方の粘着面で部材同士を固定している、電気電子機器。
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| JP2011074308A (ja) * | 2009-10-01 | 2011-04-14 | Three M Innovative Properties Co | 透明粘着シート及びそれを含む画像表示装置 |
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| JP6975189B2 (ja) | 2019-02-07 | 2021-12-01 | 日東電工株式会社 | 両面粘着テープ |
| JP6705542B1 (ja) * | 2019-10-03 | 2020-06-03 | 王子ホールディングス株式会社 | 粘着シート |
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- 2022-06-16 KR KR1020247003394A patent/KR20240032058A/ko active Pending
- 2022-06-16 WO PCT/JP2022/024101 patent/WO2023282007A1/ja not_active Ceased
- 2022-06-16 CN CN202280044530.9A patent/CN117545816A/zh active Pending
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| US20150315425A1 (en) * | 2014-04-30 | 2015-11-05 | Samsung Sdi Co., Ltd. | Adhesive film and optical display including the same |
| EP3034575A1 (en) * | 2014-12-18 | 2016-06-22 | 3M Innovative Properties Company | Pressure sensitive adhesive for outdoor applications |
| JP2019131678A (ja) * | 2018-01-30 | 2019-08-08 | 日東電工株式会社 | 粘着シートおよびその製造方法、ならびに画像表示装置 |
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| JP2021024907A (ja) * | 2019-08-01 | 2021-02-22 | 日東電工株式会社 | 両面粘着テープ |
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| JP2023008631A (ja) | 2023-01-19 |
| CN117545816A (zh) | 2024-02-09 |
| KR20240032058A (ko) | 2024-03-08 |
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