WO2016052424A1 - 粘着シート - Google Patents
粘着シート Download PDFInfo
- Publication number
- WO2016052424A1 WO2016052424A1 PCT/JP2015/077351 JP2015077351W WO2016052424A1 WO 2016052424 A1 WO2016052424 A1 WO 2016052424A1 JP 2015077351 W JP2015077351 W JP 2015077351W WO 2016052424 A1 WO2016052424 A1 WO 2016052424A1
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- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- pressure
- acrylic
- adhesive layer
- adhesive sheet
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Classifications
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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
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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
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet (pressure-sensitive adhesive sheet) in which both force transmission and adhesiveness are compatible.
- the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) of the pressure-sensitive adhesive sheet is a layer composed of a pressure-sensitive adhesive (pressure-sensitive adhesive).
- This pressure-sensitive adhesive is generally a viscoelastic body. For this reason, in general, the pressure-sensitive adhesive has a property of relaxing the force when an external force is applied.
- a pressure-sensitive adhesive sheet (a shock-absorbing pressure-sensitive adhesive sheet) that can reduce impact force transmission by absorbing the shock when an external shock is applied is known (Patent Document 1, Patent Document 2).
- the pressure-sensitive adhesive sheet when an external force is applied, it may be required to transmit the force without reducing the force or suppressing relaxation or attenuation of the force.
- the force acting on one part / member is efficiently transmitted to the other parts / members via the adhesive sheet. May be required.
- An adhesive sheet for protecting the surface of a touch panel may be required to efficiently transmit force to the panel from the viewpoint of response sensitivity to a touch operation on the panel.
- An adhesive sheet used for an electronic device such as a sensor may be required to efficiently transmit the force acting on the adhesive sheet to an adherend from the viewpoint of not hindering sensor sensing.
- the adhesive sheet is required to have a certain adhesive strength (adhesive strength) so that unintentional peeling does not occur from the adherend.
- the present inventors have found that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet can be cured by irradiation, contains an acrylic polymer and a polyfunctional acrylic oligomer, and is cured at 23 ° C.
- an acrylic pressure-sensitive adhesive layer having a Young's modulus of 500 kPa or more and an adhesive strength after curing of 3.0 N / 20 mm or more is used, the force is applied when an external force is applied while ensuring sufficient adhesion.
- the present invention has been completed by finding that the relaxation or attenuation of the material can be suppressed and the force can be transmitted efficiently.
- the pressure-sensitive adhesive sheet provided by the present invention has an acrylic pressure-sensitive adhesive layer that is cured by radiation irradiation, and the acrylic pressure-sensitive adhesive layer contains an acrylic polymer and a polyfunctional acrylic oligomer, and the acrylic pressure-sensitive adhesive after curing.
- the Young's modulus at 23 ° C. of the agent layer is 500 kPa or more and 10,000 kPa or less, and the adhesive strength of the acrylic adhesive layer after curing is 3.0 N / 20 mm or more.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer before curing is preferably 3.0 N / 20 mm or more.
- the Young's modulus at 23 ° C. of the acrylic pressure-sensitive adhesive layer before curing is 30 kPa or more and 200 kPa or less.
- the gel fraction of the acrylic pressure-sensitive adhesive layer after curing is 70% by mass or more.
- the acrylic polymer in the acrylic pressure-sensitive adhesive layer contains 0.5 to 30% by mass of a nitrogen atom-containing monomer as a constituent monomer component.
- the acrylic polymer in the acrylic pressure-sensitive adhesive layer contains 1 to 30% by mass of a hydroxyl group-containing monomer as a constituent monomer component.
- the acrylic polymer in the acrylic pressure-sensitive adhesive layer does not substantially contain an acidic group-containing monomer as a constituent monomer component.
- the weight average molecular weight of the acrylic polymer in the acrylic pressure-sensitive adhesive layer is 400,000 to 2 million.
- the polyfunctional acrylic oligomer in the acrylic pressure-sensitive adhesive layer has two or more (meth) acryloyl groups in the molecule.
- the polyfunctional acrylic oligomer in the acrylic adhesive layer is selected from the group consisting of polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and EO adduct diacrylate of bisphenol A. At least one kind.
- the weight average molecular weight of the polyfunctional acrylic oligomer in the acrylic pressure-sensitive adhesive layer is 400 to 10,000.
- the polyfunctional acrylic oligomer in the acrylic pressure-sensitive adhesive layer has a hardness measured according to JIS K5600-5-4 of the homopolymer thereof of 4B or more.
- the acrylic pressure-sensitive adhesive layer further contains a photopolymerization initiator.
- the content of the polyfunctional acrylic oligomer is 0.05 to 40 parts by mass with respect to 100 parts by mass of the acrylic polymer
- the content of the photopolymerization initiator is The amount is 0.05 to 5 parts by mass with respect to 100 parts by mass of the acrylic polymer.
- the acrylic pressure-sensitive adhesive layer further contains 0.05 to 5 parts by mass of a crosslinking agent with respect to 100 parts by mass of the acrylic polymer.
- the acrylic pressure-sensitive adhesive layer further contains 0.01 to 1 part by mass of a silane coupling agent with respect to 100 parts by mass of the acrylic polymer.
- the pressure-sensitive adhesive sheet (double-sided pressure-sensitive adhesive sheet) of the present invention is suitable for efficiently transmitting the force to an adherend when an external force is applied while having a good adhesive force.
- the pressure-sensitive adhesive sheet of the present invention has an acrylic pressure-sensitive adhesive layer that contains an acrylic polymer and a polyfunctional acrylic oligomer and is cured by irradiation with radiation.
- the Young's modulus at 23 ° C. of the cured acrylic pressure-sensitive adhesive layer is 500 kPa or more and 10,000 kPa or less
- the pressure-sensitive adhesive strength of the cured acrylic pressure-sensitive adhesive layer is 3.0 N / 20 mm or more. is there.
- the pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive tape in the form of a tape.
- an acrylic pressure-sensitive adhesive layer satisfying the following (a) to (d) may be referred to as “acrylic pressure-sensitive adhesive layer A”.
- A It is cured by irradiation.
- B An acrylic polymer and a polyfunctional acrylic oligomer are included.
- C Young's modulus at 23 ° C. after curing by radiation irradiation is 500 kPa or more and 10,000 kPa or less.
- D The adhesive strength after curing by irradiation with radiation is 3.0 N / 20 mm or more.
- the form of the pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it has a pressure-sensitive adhesive surface formed by the surface of the acrylic pressure-sensitive adhesive layer A.
- the pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive sheet having only one side that is a pressure-sensitive adhesive surface, or may be a double-sided pressure-sensitive adhesive sheet in which both sides are pressure-sensitive adhesive surfaces.
- the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet
- the pressure-sensitive adhesive sheet may have a form in which both pressure-sensitive adhesive surfaces are provided by the acrylic pressure-sensitive adhesive layer A, or one pressure-sensitive adhesive surface is acrylic.
- the other pressure-sensitive adhesive surface may have a form provided by a pressure-sensitive adhesive layer other than the acrylic pressure-sensitive adhesive layer A (other pressure-sensitive adhesive layers). From the viewpoint of bonding adherends together, a double-sided PSA sheet is preferred.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having no base material (base material layer), that is, a so-called “base-less type” pressure-sensitive adhesive sheet (sometimes referred to as “base-material-less pressure-sensitive adhesive sheet”).
- base material layer a so-called “base-less type” pressure-sensitive adhesive sheet
- it may be a pressure-sensitive adhesive sheet having a base material (sometimes referred to as a “pressure-sensitive adhesive sheet with a base material”).
- Examples of the base material-less pressure-sensitive adhesive sheet in the present invention include a double-sided pressure-sensitive adhesive sheet consisting only of an acrylic pressure-sensitive adhesive layer A, and an acrylic pressure-sensitive adhesive layer A and other pressure-sensitive adhesive layers (adhesives other than the acrylic pressure-sensitive adhesive layer A).
- a double-sided pressure-sensitive adhesive sheet made of an agent layer).
- the pressure-sensitive adhesive sheet with a substrate in the present invention for example, a single-sided pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer A on one side of the substrate, a double-sided pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer A on both sides of the substrate, and And a double-sided pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer A on one surface side of the substrate and another pressure-sensitive adhesive layer on the other surface side.
- the “base material (base material layer)” means a support, and is a part attached to the adherend together with the pressure-sensitive adhesive layer when the pressure-sensitive adhesive sheet is attached to the adherend and used.
- the separator (release liner) that is peeled off when the adhesive sheet is used (attached) is not included in the base material.
- the pressure-sensitive adhesive sheet of the present invention may have a separator (release liner) for the purpose of protecting the pressure-sensitive adhesive surface.
- this adhesive sheet may have another layer (for example, intermediate
- the pressure-sensitive adhesive sheet of the present invention may have a form wound in a roll shape, or may have a form in which a plurality of sheets are laminated.
- the present pressure-sensitive adhesive sheet may have a form wound in a roll shape with the pressure-sensitive adhesive surface protected by a separator, and has a laminated structure of a base material and a pressure-sensitive adhesive layer. You may have the form wound by the roll shape in the state protected by the peeling process layer (back process layer) formed in the back surface of the base material.
- the release treatment agent (release agent) used when forming the release treatment layer (back treatment layer) on the back surface of the substrate include a silicone release agent and a long-chain alkyl release agent.
- the acrylic pressure-sensitive adhesive layer A is cured by irradiation with radiation.
- the acrylic pressure-sensitive adhesive layer A is cured when the pressure-sensitive adhesive sheet is applied to the adherend and then irradiated with radiation.
- the pressure-sensitive adhesive sheet can transmit the force to the adherend satisfactorily.
- the acrylic pressure-sensitive adhesive layer A contains at least an acrylic polymer and a polyfunctional acrylic oligomer that is a reactive oligomer component. Since the polyfunctional acrylic oligomer undergoes radical reaction and polymerizes by irradiation, the acrylic pressure-sensitive adhesive layer A is cured by irradiation.
- Examples of the radiation for curing include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, X rays, neutron rays, and electron beams, and ultraviolet rays. From the viewpoint of cost, ultraviolet rays are preferable. More preferred is ultraviolet light having a wavelength of 200 to 400 nm.
- a high pressure mercury lamp, a low pressure mercury lamp, a microwave excitation lamp, a metal halide lamp, a chemical lamp, a black light, or an LED can be used.
- the irradiation energy, irradiation time, and irradiation method of the curing radiation can be appropriately set as long as the acrylic pressure-sensitive adhesive layer A can be cured and does not adversely affect the adherend.
- the amount of irradiation is preferably 1000mJ / cm 2 ⁇ 10000mJ / cm 2, more preferably 2000mJ / cm 2 ⁇ 4000mJ / cm 2.
- the acrylic pressure-sensitive adhesive layer A is formed from a pressure-sensitive adhesive composition.
- the “pressure-sensitive adhesive composition” means the composition used for forming the pressure-sensitive adhesive layer, and includes the meaning of the composition used for forming the pressure-sensitive adhesive.
- the pressure-sensitive adhesive composition for forming the acrylic pressure-sensitive adhesive layer A may be any type of pressure-sensitive adhesive composition. Examples of the pressure-sensitive adhesive composition include emulsion type and solvent type (solution type). ), Active energy ray curable type, and hot melt type (hot melt type). Among these, a solvent-type pressure-sensitive adhesive composition is preferable.
- the acrylic pressure-sensitive adhesive layer A contains at least an acrylic polymer and a polyfunctional acrylic oligomer, and contains an acrylic polymer as a main component.
- the content of the acrylic polymer in the acrylic pressure-sensitive adhesive layer A is not particularly limited, but from the viewpoint of obtaining sufficient adhesion reliability in the acrylic pressure-sensitive adhesive layer A, the total amount (total weight) of the acrylic pressure-sensitive adhesive layer A , 100% by mass), preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.
- the acrylic polymer is preferably a polymer composed of (meth) acrylic acid alkyl ester having a linear or branched alkyl group as an essential monomer component.
- the acrylic polymer is preferably a polymer including a structural unit or a monomer unit derived from a (meth) acrylic acid alkyl ester having a linear or branched alkyl group.
- the acrylic polymer may further contain a copolymerizable monomer such as a nitrogen atom-containing monomer or a hydroxyl group-containing monomer as a constituent monomer component. That is, the acrylic polymer may be an acrylic copolymer including a structural unit derived from a copolymerizable monomer such as a nitrogen atom-containing monomer or a hydroxyl group-containing monomer.
- a copolymerizable monomer such as a nitrogen atom-containing monomer or a hydroxyl group-containing monomer.
- (meth) acryl represents “acryl” and / or “methacryl”, that is, “acryl”, “methacryl”, or both “acryl” and “methacryl”.
- the above (meth) acrylic acid alkyl ester is a main monomer component for constituting an acrylic polymer, and plays a role of developing basic characteristics as a pressure-sensitive adhesive (or pressure-sensitive adhesive layer) such as adhesiveness.
- the alkyl acrylate ester tends to impart flexibility to the acrylic polymer serving as the base polymer, and thus tends to exhibit the effect of developing the adhesion and tackiness in the acrylic pressure-sensitive adhesive layer A.
- the methacrylic acid alkyl ester tends to give hardness to the acrylic polymer as the base polymer, and therefore tends to exhibit the effect of developing removability and force transmission in the acrylic pressure-sensitive adhesive layer A. .
- (meth) acrylic acid alkyl ester having a linear or branched alkyl group examples include, for example, methyl (meth) acrylate, ( (Meth) ethyl acrylate, (meth) propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, (meth) acrylic acid t-butyl, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Isooctyl acrylate, non
- the (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms, and more preferably n-butyl acrylate (BA). Selected from the group consisting of 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), methyl acrylate (MA), ethyl acrylate (EA), isooctyl acrylate, and isononyl acrylate.
- One kind of (meth) acrylic acid alkyl ester may be used for the acrylic polymer of the present embodiment, or two or more kinds of (meth) acrylic acid alkyl ester may be used.
- the content of the (meth) acrylic acid alkyl ester in the total amount (100% by mass) of the monomer component for constituting the acrylic polymer is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more. It is.
- the same content of the (meth) acrylic acid alkyl ester is preferably 100% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.
- the acrylic polymer may contain a copolymerizable monomer as a constituent monomer component together with the (meth) acrylic acid alkyl ester.
- One type of copolymerizable monomer may be used for the acrylic polymer of the present embodiment, or two or more types of copolymerizable monomers may be used.
- Such a copolymerizable monomer is not particularly limited, but is preferably a hydroxyl group-containing monomer (hydroxyl group-containing monomer).
- a hydroxyl group-containing monomer is a monomer having at least one hydroxyl group in the molecule.
- the acrylic polymer contains a monomer unit derived from a hydroxyl group-containing monomer and the acrylic pressure-sensitive adhesive layer A contains a crosslinking agent (curing agent) such as an isocyanate crosslinking agent
- a hydroxyl group-containing monomer is used with the crosslinking agent. Since the unit can be cross-linked, it is easy to obtain hardness and good adhesion reliability in the acrylic pressure-sensitive adhesive layer A.
- the hardness of the acrylic pressure-sensitive adhesive layer A contributes to an improvement in workability of the acrylic pressure-sensitive adhesive layer A before radiation curing and an improvement in force transmission in the acrylic pressure-sensitive adhesive layer A after radiation curing.
- one type of hydroxyl group-containing monomer may be used, or two or more types of hydroxyl group-containing monomers may be used.
- Examples of the hydroxyl group-containing monomer include a hydroxyl group-containing (meth) acrylic acid ester, vinyl alcohol, and allyl alcohol.
- Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid 6- Examples include hydroxyhexyl, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, and (meth) acrylic acid (4-hydroxymethylcyclohexyl).
- the hydroxyl group-containing (meth) acrylic acid ester is preferably selected from a hydroxyl group-containing (meth) acrylic acid ester, and more preferably selected from the group consisting of 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate.
- the content of the hydroxyl group-containing monomer in the total amount (100% by mass) of the monomer component for constituting the acrylic polymer is not particularly limited, but the acrylic pressure-sensitive adhesive layer A has sufficient adhesiveness and appropriate cohesive strength. From the viewpoint of obtaining, and when the acrylic pressure-sensitive adhesive layer A contains a crosslinking agent such as an isocyanate-based crosslinking agent, it is preferably 1% by mass from the viewpoint of obtaining hardness and good adhesion reliability in the pressure-sensitive adhesive layer. As mentioned above, More preferably, it is 2 mass% or more, More preferably, it is 5 mass% or more.
- the same content of the hydroxyl group-containing monomer is preferably 30% by mass from the viewpoint of suppressing the acrylic pressure-sensitive adhesive layer A from becoming too hard and obtaining good adhesive reliability in the pressure-sensitive adhesive layer.
- it is more preferably 25% by mass or less, and further preferably 20% by mass or less.
- Preferred examples of the copolymerizable monomer also include nitrogen atom-containing monomers.
- the nitrogen atom-containing monomer is a monomer having at least one nitrogen atom in the molecule.
- such a nitrogen atom-containing monomer is not included in the hydroxyl group-containing monomer. That is, in this specification, a monomer having both a hydroxyl group and a nitrogen atom in the molecule is not a hydroxyl group-containing monomer but a nitrogen atom-containing monomer.
- the monomer component for constituting the acrylic polymer contains a nitrogen atom-containing monomer, that is, when the acrylic polymer contains a monomer unit derived from the nitrogen atom-containing monomer, in the acrylic pressure-sensitive adhesive layer A, the hardness or transparency , Moderate cohesive strength, adhesion, and excellent adhesion reliability.
- the hardness of the acrylic pressure-sensitive adhesive layer A contributes to an improvement in force transmission in the acrylic pressure-sensitive adhesive layer A after radiation curing. Further, the transparency of the acrylic pressure-sensitive adhesive layer A tends to be improved when the acrylic polymer does not contain a nitrogen atom-containing monomer unit.
- the acrylic polymer contains a nitrogen atom-containing monomer unit, the compatibility between the polymer and the polyfunctional acrylic oligomer is improved.
- one type of nitrogen atom-containing monomer may be used, or two or more types of nitrogen atom-containing monomers may be used.
- nitrogen atom-containing monomers examples include N-vinyl cyclic amides and (meth) acrylamides.
- N-vinyl cyclic amide examples include N-vinyl cyclic amide represented by the following formula (1).
- R 1 represents a divalent organic group
- R 1 in the above formula (1) is a divalent organic group, preferably a divalent saturated hydrocarbon group or an unsaturated hydrocarbon group, more preferably an alkylene group having 3 to 5 carbon atoms. .
- N-vinyl cyclic amide represented by the above formula (1) examples include N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, and N-vinyl-2-caprolactam. , N-vinyl-1,3-oxazin-2-one, and N-vinyl-3,5-morpholinedione.
- Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, and N, N-dialkyl (meth) acrylamide.
- Examples of the N-alkyl (meth) acrylamide include N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, and N-octyl (meth) acrylamide. .
- the N-alkyl (meth) acrylamide includes (meth) acrylamide having an amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide.
- Examples of the N, N-dialkyl (meth) acrylamide include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, and N, N-diisopropyl. Examples include (meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, and N, N-di (t-butyl) (meth) acrylamide.
- the (meth) acrylamides include, for example, various N-hydroxyalkyl (meth) acrylamides.
- N-hydroxyalkyl (meth) acrylamide include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- ( 1-hydroxypropyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, N -(4-hydroxybutyl) (meth) acrylamide and N-methyl-N-2-hydroxyethyl (meth) acrylamide.
- the (meth) acrylamides include, for example, various N-alkoxyalkyl (meth) acrylamides.
- N-alkoxyalkyl (meth) acrylamide include N-methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide.
- nitrogen atom-containing monomers other than the N-vinyl cyclic amide and the (meth) acrylamides include amino group-containing monomers, cyano group-containing monomers, heterocyclic-containing monomers, imide group-containing monomers, and isocyanate group-containing monomers.
- the amino group-containing monomer include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate.
- the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- heterocycle-containing monomer examples include (meth) acryloylmorpholine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, N-vinylpyrazine, N-vinylmorpholine, N-vinylpyrazole, vinylpyridine, and vinylpyrimidine.
- imide group-containing monomer examples include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide, N-methylitaconimide, N-ethylitaconimide, and N-butyl.
- maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide, N-methylitaconimide, N-ethylitaconimide, and N-butyl.
- Itaconic imide monomers such as itaconic imide, N-octyl itaconic imide, N-2-ethylhexylitaconimide, N-lauryl itaconic imide, and N-cyclohexyl leuconconimide, and N- (meth) acryloyloxymethylene succinimide, N- ( And succinimide monomers such as (meth) acryloyl-6-oxyhexamethylenesuccinimide and N- (meth) acryloyl-8-oxyoctamethylenesuccinimide.
- Examples of the isocyanate group-containing monomer include 2- (meth) acryloyloxyethyl isocyanate.
- the nitrogen atom-containing monomer is, for example, an N-vinyl cyclic amide or (meth) acrylamide represented by the above formula (1), preferably N-vinyl-2-pyrrolidone, N-vinyl-2-caprolactam, It is selected from the group consisting of N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide, more preferably N-vinyl-2-pyrrolidone.
- the content of the nitrogen atom-containing monomer in the total amount (100% by mass) of monomer components for constituting the acrylic polymer is not particularly limited, but sufficient hardness and sufficient adhesion in the acrylic pressure-sensitive adhesive layer A, From the viewpoint of obtaining sufficient transparency, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more.
- the same content of the nitrogen atom-containing monomer is preferable from the viewpoint of obtaining good adhesion reliability by suppressing being too hard in the acrylic pressure-sensitive adhesive layer A and achieving high transparency. Is 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.
- copolymerizable monomers include, for example, carboxyl group-containing monomers, epoxy group-containing monomers, sulfonic acid group-containing monomers such as sodium vinyl sulfonate, phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate, and And isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate.
- carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, maleic anhydride and itaconic anhydride). It is done.
- the epoxy group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate.
- (meth) acrylic acid alkoxyalkyl ester [alkoxyalkyl (meth) acrylate], (meth) acrylic acid ester having an alicyclic hydrocarbon group, and aromatic hydrocarbon group (meta Also included are acrylic esters, vinyl esters, and aromatic vinyl compounds.
- Examples of (meth) acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and (meth) acrylic acid 3- Mention may be made of methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
- Examples of the (meth) acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
- Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate.
- Vinyl esters include vinyl acetate and vinyl propionate.
- Examples of the aromatic vinyl compound include styrene and vinyl toluene.
- Examples of the copolymerizable monomer further include olefins or dienes such as ethylene, butadiene, isoprene, and isobutylene, vinyl ethers such as vinyl alkyl ether, and vinyl chloride.
- the acrylic polymer in the acrylic pressure-sensitive adhesive layer A does not contain an acidic group-containing monomer as a constituent monomer component or substantially from the viewpoint of realizing the acrylic pressure-sensitive adhesive layer A having an excellent corrosion prevention effect.
- the acrylic pressure-sensitive adhesive layer A chemically acts on the adherend while the pressure-sensitive adhesive sheet of the present invention is adhered to the adherend, thereby impairing the appearance and function of the adherend.
- the acidic group-containing monomer examples include a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, and a phosphoric acid group-containing monomer.
- the proportion of the acidic group-containing monomer in the total amount (100% by mass) of the monomer components for constituting the acrylic polymer is 0.05% by mass or less (preferably 0.01% by mass or less), the acrylic polymer is It can be said that it contains substantially no acidic group-containing monomer.
- the acrylic polymer as described above can be obtained by polymerizing the above monomer components.
- the polymerization technique include solution polymerization, emulsion polymerization, bulk polymerization, and polymerization by active energy ray irradiation (active energy ray polymerization).
- solution polymerization is preferred. That is, the acrylic polymer in the acrylic pressure-sensitive adhesive layer A is preferably obtained by polymerizing the above monomer components by a solution polymerization method.
- organic solvents can be used as a solvent.
- organic solvents 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 and Examples include alicyclic hydrocarbons such as methylcyclohexane, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- one type of solvent may be used, or two or more types of solvents may be used.
- the weight average molecular weight (Mw) of the acrylic polymer is not particularly limited, but is preferably 400,000 or more from the viewpoint of the adhesive properties of the acrylic adhesive layer A before radiation curing and the processability of the adhesive sheet of the present invention. More preferably, it is 600,000 or more. From the viewpoint of adhesiveness of the acrylic pressure-sensitive adhesive layer A, the weight average molecular weight of the acrylic polymer is preferably 2 million or less, more preferably 1.5 million or less.
- the weight average molecular weight of the acrylic polymer can be controlled by the type and amount of the polymerization initiator, the temperature and time during polymerization, the monomer concentration, the monomer dropping rate, and the like.
- a weight average molecular weight shall mean the value calculated by polystyrene conversion in the measurement by GPC (gel permeation chromatography). Specifically, the weight average molecular weight can be measured by the method described later with respect to the examples.
- a polymerization initiator can be used when the monomer component is polymerized in order to obtain the acrylic polymer.
- a thermal polymerization initiator can be preferably used.
- one type of polymerization initiator may be used, or two or more types of polymerization initiators may be used.
- the polymerization initiator used in the solution polymerization is not particularly limited, and examples thereof include an azo initiator, a peroxide polymerization initiator, and a redox polymerization initiator.
- an azo initiator disclosed in JP-A-2002-69411 can be preferably used.
- the azo-based initiator is preferable for suppressing the decomposition product derived from the polymerization initiator from remaining in the acrylic polymer, for example, as a heat-generating gas (outgas) -causing component.
- Such azo initiators include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile (AMBN), 2,2′-azobis (2 -Methylpropionate) dimethyl, and 4,4'-azobis-4-cyanovaleric acid.
- the peroxide-based polymerization initiator include dibenzoyl peroxide and tert-butyl permaleate.
- the usage-amount of a polymerization initiator is not specifically limited, What is necessary is just the range which can be utilized as a polymerization initiator with which desired polymer molecular weight and reactivity are obtained.
- the acrylic pressure-sensitive adhesive layer A of the pressure-sensitive adhesive sheet of the present invention contains a polyfunctional acrylic oligomer together with an acrylic polymer.
- the polyfunctional acrylic oligomer is a compound containing two or more repeating units and having two or more (meth) acryloyl groups. That is, the polyfunctional acrylic oligomer is a polymer having two or more (meth) acryloyl groups in the molecule.
- “(meth) acryloyl group” means “acryloyl group” and / or “methacryloyl group”, that is, “acryloyl group”, “methacryloyl group”, or “acryloyl group” and “methacryloyl group”. Means both.
- one type of polyfunctional acrylic oligomer may be used, or two or more types of polyfunctional acrylic oligomers may be used.
- Polyester (meth) acrylate is obtained, for example, by reacting (meth) acrylic acid with a terminal hydroxyl group of polyester obtained by polymerizing polyhydric alcohol and polycarboxylic acid.
- Specific examples of the polyester (meth) acrylate include Aronix M-6000, Aronix M-7000, Aronix M-8000, and Aronix M-9000 manufactured by Toa Gosei Co., Ltd.
- Epoxy (meth) acrylate is obtained, for example, by reacting (meth) acrylic acid with an epoxy resin.
- Specific examples of the epoxy (meth) acrylate include Lipoxy SP and Lipoxy VR manufactured by Showa Polymer Co., Ltd., and Epoxy ester series manufactured by Kyoeisha Chemical Co., Ltd.
- Urethane (meth) acrylate is obtained, for example, by reacting polyol, isocyanate, and hydroxy (meth) acrylate.
- isocyanate include aromatic isocyanate and aliphatic isocyanate, and specifically include toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
- urethane (meth) acrylate include Art Resin UN series manufactured by Negami Kogyo Co., Ltd., NK Oligo U series manufactured by Shin-Nakamura Chemical Co., Ltd., and Purple Light UV Series manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- the number of (meth) acryloyl groups in the molecule (number of functional groups) in the polyfunctional acrylic oligomer is not particularly limited as long as it is 2 or more, but the adhesive reliability of the acrylic pressure-sensitive adhesive layer A and the acrylic pressure-sensitive adhesive layer after curing From the viewpoint of coexistence with the hardness of A, it is preferably 3 or more, more preferably 5 or more. From the viewpoint of obtaining good adhesion to the adherend in the acrylic pressure-sensitive adhesive layer A, the number of (meth) acryloyl groups in the molecule in the polyfunctional acrylic oligomer is preferably 15 or less, more preferably 12 or less. is there.
- the weight average molecular weight of the polyfunctional acrylic oligomer is not particularly limited, but the viewpoint of ensuring workability in the pressure-sensitive adhesive sheet before curing the acrylic pressure-sensitive adhesive layer A and the decrease in the adhesion reliability of the acrylic pressure-sensitive adhesive layer A From the viewpoint of suppressing the disadvantage that sufficient hardness cannot be obtained in the acrylic pressure-sensitive adhesive layer A even by irradiation, preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more, particularly preferably 700 or more.
- the weight average molecular weight of the polyfunctional acrylic oligomer is preferably 10,000 or less, more preferably 7000 or less, and still more preferably from the viewpoint of obtaining sufficient hardness in the acrylic pressure-sensitive adhesive layer A cured by irradiation.
- the weight average molecular weight of the polyfunctional oligomer can be determined by, for example, high performance liquid chromatography (HPLC).
- HPLC high performance liquid chromatography
- an HPLC 8020 manufactured by Tosoh Corporation is used as an apparatus, two TSKgelGMH-H (20) connected in series are used as a column, tetrahydrofuran is used as a solvent, and the flow rate is 0.5 mL / min.
- a weight average molecular weight can be measured.
- the hardness of the homopolymer of the polyfunctional acrylic oligomer is not particularly limited, but from the viewpoint of improving the hardness of the acrylic pressure-sensitive adhesive layer A, it is preferably 4B or more, more preferably HB or more, and still more preferably H or more. is there. In order to obtain sufficient force transmission in the acrylic pressure-sensitive adhesive layer A, it is preferable that the acrylic pressure-sensitive adhesive layer A has sufficient hardness.
- the above-mentioned hardness is so-called pencil hardness and can be measured in accordance with a scratch hardness test (pencil method) described in JIS K5600-5-4.
- the refractive index of the acrylic polymer used in the acrylic pressure-sensitive adhesive layer A and the polyfunctional acrylic oligomer alone It is preferable that the difference from the refractive index of the polymer is small. That is, it is preferable to use a polyfunctional acrylic oligomer whose homopolymer has a refractive index that is the same as or close to the refractive index of the acrylic polymer.
- the refractive index of the homopolymer of the polyfunctional acrylic oligomer is not particularly limited, but is preferably 1.46 to 1.54, more preferably 1.47 to 1.52, and still more preferably 1.47 to 1.51. is there.
- the refractive index can be determined by measurement using an Abbe refractometer and sodium D line (wavelength 589 nm) in accordance with JIS K K0062 (1992).
- the content of the polyfunctional acrylic oligomer in the acrylic pressure-sensitive adhesive layer A is not particularly limited, but from the viewpoint of obtaining sufficient adhesiveness in the acrylic pressure-sensitive adhesive layer A or by irradiation with radiation. From the viewpoint of obtaining sufficient hardness in the acrylic pressure-sensitive adhesive layer A, it is preferably 0.05 parts by weight or more, more preferably 3 parts by weight with respect to 100 parts by weight of the acrylic polymer in the acrylic pressure-sensitive adhesive layer A. Part or more, more preferably 5 parts by weight or more.
- the content of the polyfunctional acrylic oligomer in the acrylic pressure-sensitive adhesive layer A is from the viewpoint of suppressing a decrease in the adhesion reliability of the acrylic pressure-sensitive adhesive layer A and from the viewpoint of the handleability of the pressure-sensitive adhesive sheet of the present invention.
- the amount is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and still more preferably 30 parts by mass or less with respect to 100 parts by mass of the acrylic polymer in the acrylic adhesive layer A.
- the acrylic pressure-sensitive adhesive layer A may contain a basic monomer as a polymerizable monomer.
- This basic monomer means a monomer having basicity, and basic means that the acid dissociation constant pKa value is large or the base dissociation constant pKb value is small. That is, a strongly basic monomer is preferable.
- Such a basic monomer preferably has at least one of an amide group and an amino group in the molecule.
- the above basic monomer is preferably a high-boiling material that does not volatilize at the drying temperature at the time of preparation of the pressure-sensitive adhesive sheet. That is, the boiling point of the basic monomer at normal pressure is preferably 120 ° C. or higher, more preferably 130 ° C. or higher.
- DMAPMA dimethylaminopropylmethacrylamide
- DMAPAA dimethylaminopropylacrylamide
- DMAPMA dimethylaminopropyl methacrylamide
- the content of the basic monomer in the acrylic pressure-sensitive adhesive layer A is not particularly limited.
- acrylic monomer Preferably it is 0.5 mass part or more with respect to 100 mass parts of a system polymer, More preferably, it is 1 mass part or more.
- the content of the basic monomer in the acrylic pressure-sensitive adhesive layer A is preferably 20 with respect to 100 parts by mass of the acrylic polymer from the viewpoint of suppressing a decrease in adhesion reliability of the acrylic pressure-sensitive adhesive layer A. It is 15 parts by mass or less, more preferably 15 parts by mass or less.
- the acrylic pressure-sensitive adhesive layer A may contain a photopolymerization initiator.
- the acrylic pressure-sensitive adhesive layer A contains a photopolymerization initiator, the acrylic pressure-sensitive adhesive layer A can be more easily cured by irradiation with radiation.
- the acrylic pressure-sensitive adhesive layer A can be more easily cured (ie, radiation polymerization) by irradiation with radiation such as an electron beam or ultraviolet light.
- the acrylic pressure-sensitive adhesive layer A contains a photopolymerization initiator, but when it is performed by ultraviolet irradiation, the acrylic pressure-sensitive adhesive layer A has It is preferable to contain a photopolymerization initiator.
- the acrylic pressure-sensitive adhesive layer A one type of photopolymerization initiator may be used, or two or more types of photopolymerization initiators may be used.
- the photopolymerization initiator is not particularly limited, but for example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, and acylphosphine oxide photopolymerization initiator Initiators are mentioned.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-one ( Trade name “Irgacure 651” manufactured by BASF).
- acetophenone photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name “Irgacure 2959”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl- Propan-1-one (trade name “Darocur 1173”, manufactured by BASF) and methoxyacetophenone.
- 1-hydroxycyclohexyl phenyl ketone trade name “Irgacure 184”, manufactured by BASF
- 4-phenoxydichloroacetophenone 4-t-butyl-dichloroacetophenone
- Examples of ⁇ -ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1. -ON.
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.
- examples of the benzoin photopolymerization initiator include benzoin.
- examples of the benzyl photopolymerization initiator include benzyl.
- examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, and ⁇ -hydroxycyclohexyl phenyl ketone.
- examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.
- Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, Examples include 2,4-diisopropylthioxanthone and dodecylthioxanthone.
- examples of the acylphosphine photopolymerization initiator include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, Bis (2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-( 1-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) Octylphosphine oxide, bis (2-methoxy Benzoyl
- the content of the photopolymerization initiator in the acrylic pressure-sensitive adhesive layer A is not particularly limited, but the effect obtained by containing the photopolymerization initiator (acrylic pressure-sensitive adhesive layer by radiation irradiation) From the viewpoint of sufficiently obtaining the effect of facilitating curing of A), it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably, with respect to 100 parts by mass of the acrylic polymer. 0.2 parts by mass or more.
- the content of the photopolymerization initiator in the acrylic pressure-sensitive adhesive layer A is caused by excessive radiation absorption by the photopolymerization initiator at the time of radiation irradiation on the acrylic pressure-sensitive adhesive layer A. From the viewpoint of suppressing the problem that curing does not occur sufficiently, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1.5 parts by mass or less with respect to 100 parts by mass of the acrylic polymer. is there.
- the acrylic pressure-sensitive adhesive layer A of the pressure-sensitive adhesive sheet of the present invention or the pressure-sensitive adhesive composition for forming the same may contain a crosslinking agent.
- the inclusion of the crosslinking agent is suitable for imparting cohesive force to the acrylic pressure-sensitive adhesive layer A before radiation curing, and obtains good processability in the pressure-sensitive adhesive sheet and good adhesiveness in the acrylic pressure-sensitive adhesive layer A.
- one type of crosslinking agent may be used, or two or more types of crosslinking agents may be used.
- crosslinking agent For example, isocyanate type crosslinking agent, epoxy type crosslinking agent, melamine type crosslinking agent, peroxide type crosslinking agent, urea type crosslinking agent, metal alkoxide type crosslinking agent, metal chelate type Examples include a crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and an amine crosslinking agent.
- Examples of the isocyanate crosslinking agent include lower aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
- Examples of the lower aliphatic polyisocyanates include 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate.
- Examples of the alicyclic polyisocyanates include cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate.
- aromatic polyisocyanates examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate.
- isocyanate crosslinking agents include trimethylolpropane / tolylene diisocyanate adduct (trade name “Coronate L”, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate adduct (trade name).
- Core HL manufactured by Nippon Polyurethane Industry Co., Ltd.
- trimethylolpropane / xylylene diisocyanate adduct trade name “Takenate 110N”, manufactured by Mitsui Chemicals
- HDI crosslinking agent hexamethylene diisocyanate crosslinking agent
- epoxy crosslinking agent polyfunctional epoxy compound
- examples of the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, and 1,3-bis (N, N-diglycidylamino).
- the content of the crosslinking agent in the acrylic pressure-sensitive adhesive layer A or the pressure-sensitive adhesive composition for forming the same is not particularly limited, but the gel fraction of the acrylic pressure-sensitive adhesive layer A before being cured by radiation irradiation is 10%. The amount is preferably (mass%) or more. When the gel fraction of the acrylic pressure-sensitive adhesive layer A before curing is 10% or more, the acrylic pressure-sensitive adhesive layer A can obtain sufficient cohesive force to easily obtain good processability in the pressure-sensitive adhesive sheet. It is easy to obtain good adhesiveness with the system pressure-sensitive adhesive layer A.
- the specific content of the crosslinking agent is set according to the molecular weight of the acrylic polymer, the composition of the monomer components for constituting the acrylic polymer, the type of the crosslinking agent, etc. On the other hand, it is, for example, 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass.
- the acrylic pressure-sensitive adhesive layer A may contain a tackifier resin (tackifier).
- tackifier resin tackifier resin
- the configuration in which the acrylic pressure-sensitive adhesive layer A contains a tackifier resin is suitable for realizing good adhesion in the acrylic pressure-sensitive adhesive layer A.
- the tackifying resin is not particularly limited, and examples thereof include rosin derivatives, polyterpene resins, petroleum resins, and oil-soluble phenols.
- one type of tackifying resin may be used, or two or more types of tackifying resins may be used.
- the content of the tackifier resin in the acrylic pressure-sensitive adhesive layer A is not particularly limited. For example, it is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the acrylic copolymer. is there.
- the acrylic pressure-sensitive adhesive layer A may contain a silane coupling agent.
- the structure that the acrylic pressure-sensitive adhesive layer A contains a silane coupling agent is used when the pressure-sensitive adhesive sheet of the present invention is attached to a hydrophilic adherend such as glass, and the adherend and the acrylic pressure-sensitive adhesive layer A. It is suitable for realizing good water resistance at the interface.
- one type of silane coupling agent may be used, or two or more types of silane coupling agents may be used.
- silane coupling agent an epoxy group containing silane coupling agent, an amino group containing silane coupling agent, a (meth) acryl group containing silane coupling agent, and an isocyanate group containing silane coupling agent are mentioned, for example.
- the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4) -Epoxycyclohexyl) ethyltrimethoxysilane.
- amino group-containing silane coupling agents examples include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxysilyl-N- (1,3- Dimethylbutylidene) propylamine, and N-phenyl- ⁇ -aminopropyltrimethoxysilane.
- the (meth) acryl group-containing silane coupling agent examples include 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.
- isocyanate group-containing silane coupling agent examples include 3-isocyanatopropyltriethoxysilane.
- the content of the silane coupling agent in the acrylic pressure-sensitive adhesive layer A is not particularly limited, but from the viewpoint of suppressing a decrease in durability of the acrylic pressure-sensitive adhesive layer A, with respect to 100 parts by mass of the acrylic polymer, Preferably it is 0.01 mass part or more, More preferably, it is 0.02 mass part or more.
- the content of the silane coupling agent in the acrylic pressure-sensitive adhesive layer A is preferably 1 from the viewpoint of suppressing problems such as the cohesive force of the acrylic pressure-sensitive adhesive layer A becoming too strong and lowering the adhesiveness. It is not more than part by mass, more preferably not more than 0.6 part by mass.
- the acrylic pressure-sensitive adhesive layer A may contain other additives as long as the effects of the present invention are not impaired.
- powders such as colorants, pigments, dyes, surfactants, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, polymerization inhibitors, inorganic or organic
- You may contain a filler, metal powder, a particulate matter, and a foil-like thing.
- About content of these additives when suitably determined in the range which does not impair the effect of this invention, it is 10 mass parts or less with respect to 100 mass parts of acrylic polymers.
- the acrylic pressure-sensitive adhesive layer A is formed from a pressure-sensitive adhesive composition.
- a pressure-sensitive adhesive composition for example, when the acrylic pressure-sensitive adhesive layer A is formed from a solvent-type pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition is applied onto a support such as a base material or a separator (release liner), and a coating layer (pressure-sensitive adhesive composition)
- the acrylic pressure-sensitive adhesive layer A can be formed by forming a physical layer) and heating and drying the coating layer to remove the polymerization solvent and the like.
- one or more solvents other than the polymerization solvent may be added to the composition as appropriate.
- Various methods are used as a method of applying the radiation-curable pressure-sensitive adhesive composition.
- An applicator may also be used. For example, by comma coat, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, and die coater A technique of extrusion coating is mentioned.
- the heat-drying temperature and the heat-drying time are not particularly limited to heat-dry the pressure-sensitive adhesive composition layer.
- the heat drying temperature is preferably selected in the range of 50 to 120 ° C.
- the heat drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and still more preferably 10 seconds to 5 minutes.
- the thickness of the acrylic pressure-sensitive adhesive layer A is not particularly limited, but is preferably 1 to 300 ⁇ m, more preferably 5 to 200 ⁇ m, still more preferably 7 to 100 ⁇ m, and particularly preferably 10 to 80 ⁇ m. is there.
- the cured acrylic pressure-sensitive adhesive layer A has a Young's modulus at 23 ° C. of 500 kPa or more, preferably 700 kPa or more, more preferably 1000 kPa or more.
- a Young's modulus at 23 degrees C of the acrylic adhesive layer A after hardening is 10,000 kPa or less, Preferably it is 7000 kPa or less.
- Such a configuration is suitable for suppressing the problem that the acrylic pressure-sensitive adhesive layer A becomes too hard and its adhesion reliability is lowered.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A after curing is 3.0 N / 20 mm or more, preferably 4.0 N / 20 mm or more, more preferably 6.0 N / 20 mm or more. .
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A after curing is preferably 30 N / 20 mm or less, more preferably 25 N / 20 mm or less.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A after curing refers to the adhesive strength when a stainless steel plate (SUS304) or a PC plate (polycarbonate resin plate) is used as an adherend.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A can be determined in accordance with JISJZ 0237. After the acrylic pressure-sensitive adhesive layer A is applied to the adherend, it is pressure-bonded, and the peel angle (tensile angle) is 180. This is the force required to peel the acrylic pressure-sensitive adhesive layer A from the adherend under the conditions of ° and a tensile speed of 300 mm / min.
- the Young's modulus at 23 ° C. of the acrylic pressure-sensitive adhesive layer A before curing is not particularly limited, but the viewpoint of obtaining a pressure-sensitive adhesive sheet with good handleability and workability, and force transmission From the viewpoint of obtaining a good pressure-sensitive adhesive sheet, it is preferably 30 kPa or more, more preferably 50 kPa or more, and further preferably 70 kPa or more.
- the Young's modulus at 23 ° C. of the acrylic pressure-sensitive adhesive layer A before curing is preferably 200 kPa or less from the viewpoint of suppressing the problem that the acrylic pressure-sensitive adhesive layer A becomes too hard and its adhesion reliability is lowered. More preferably, it is 150 kPa or less.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A before curing is not particularly limited, but from the viewpoint of fixability to the adherend, for example, after bonding the pressure-sensitive adhesive sheet to the adherend. From the viewpoint of obtaining good temporary fixability until the acrylic pressure-sensitive adhesive layer A is cured, it is preferably 3.0 N / 20 mm or more, more preferably 5.0 N / 20 mm or more, and still more preferably 10.0 N. / 20 mm or more.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A before curing is preferably 30 N / 20 mm or less, more preferably 25 N / 20 mm or less.
- the adhesive strength of the acrylic pressure-sensitive adhesive layer A before curing refers to the adhesive strength when a stainless steel plate (SUS304) or a PC plate (polycarbonate resin plate) is used as an adherend.
- the haze (HAZE) of the acrylic pressure-sensitive adhesive layer A is not particularly limited, but is preferably 10% or less, more preferably 5% from the viewpoint of obtaining good transparency in the pressure-sensitive adhesive sheet. It is as follows. That is, the haze of the acrylic pressure-sensitive adhesive layer A before curing is preferably 10% or less, more preferably 5% or less, and the haze of the acrylic pressure-sensitive adhesive layer A after curing is preferably 10% or less, more Preferably it is 5% or less.
- the haze can be obtained according to JIS K 7136 (2000).
- the gel fraction of the acrylic pressure-sensitive adhesive layer A after curing is not particularly limited, but is preferable from the viewpoint of coexistence of adhesiveness and force transmission in the acrylic pressure-sensitive adhesive layer A. Is 70% (mass%) or more, more preferably 75% or more, and still more preferably 80% or more.
- the gel fraction of the acrylic pressure-sensitive adhesive layer A before curing is not particularly limited, but a pressure-sensitive adhesive sheet having good adhesiveness and a viewpoint of obtaining a pressure-sensitive adhesive sheet having good workability From the viewpoint of obtaining, it is preferably 1% or more, more preferably 30% or more, and still more preferably 50% or more.
- the gel fraction of the pressure-sensitive adhesive layer is determined as follows. First, a sample is taken from the pressure-sensitive adhesive layer, the weight of the sample is measured, and this weight is defined as “W1”. Next, the sample is wrapped in a purse-like shape with a porous film made of tetrafluoroethylene resin, and the mouth is tied with a tako thread to obtain a wrap. The packet is then immersed in ethyl acetate and allowed to stand for 7 days at room temperature (typically 23 ° C.). Next, the packet is recovered from the ethyl acetate, and the recovered packet is dried at 130 ° C. for 2 hours.
- the pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet with a substrate. That is, the pressure-sensitive adhesive sheet of the present invention may have a substrate together with the acrylic pressure-sensitive adhesive layer A.
- This base material may have a single layer structure or a laminated structure.
- the substrate is not particularly limited, and examples thereof include a plastic film, a porous material substrate, a net, a rubber sheet, a foamed sheet, and a metal foil. These laminates are also included.
- the plastic film include, but are not limited to, polyolefin film, polyester film, vinyl chloride resin film, vinyl acetate resin film, polyimide resin film, polyamide resin film, fluorine resin film, and cellophane. It is done.
- the polyolefin film is not particularly limited, and examples thereof include a polyethylene film, a polypropylene film, and a film made of an ethylene-propylene copolymer. Although it does not specifically limit as a polyester film, For example, a polyethylene terephthalate film is mentioned.
- the plastic film may be of a non-stretching type or of a stretching type (uniaxial stretching type or biaxial stretching type).
- the porous material constituting the substrate made of the porous material is not particularly limited.
- paper such as Japanese paper, kraft paper, glassine paper, fine paper, synthetic paper, and topcoat paper, and woven fabric And cloths such as nonwoven fabrics.
- Textile materials for fabrics include natural fibers, semi-synthetic fibers, or synthetic fibers such as cotton fibers, sufu, manila hemp, pulp, rayon, acetate fibers, polyester fibers, polyvinyl alcohol fibers, polyamide fibers, and polyolefin fibers. Can be mentioned.
- gum which comprises said rubber sheet For example, natural rubber and butyl rubber are mentioned.
- foam which comprises said foam sheet For example, the foam of a polyurethane and the foam of a polychloroprene rubber are mentioned.
- metal foil For example, aluminum foil and copper foil are mentioned.
- fillers inorganic fillers, organic fillers, etc.
- anti-aging agents antioxidants, UV absorbers, lubricants, plasticizers, colorants (pigments, dyes, etc.), etc.
- Various additives may be blended.
- the surface of the substrate may be subjected to surface treatment. Examples of the surface treatment include physical treatment such as corona treatment and plasma treatment, and chemical treatment such as undercoating treatment and back treatment.
- the thickness of the substrate is not particularly limited, but is, for example, 1 to 200 ⁇ m, preferably 10 to 100 ⁇ m.
- the pressure-sensitive adhesive sheet of the present invention may have other pressure-sensitive adhesive layers (pressure-sensitive adhesive layers other than the acrylic pressure-sensitive adhesive layer A) as long as the effects of the present invention are not impaired.
- a urethane adhesive, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive, an epoxy adhesive A pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive such as a vinyl alkyl ether pressure-sensitive adhesive or a fluorine-based pressure-sensitive adhesive.
- one type of pressure-sensitive adhesive may be used, or a mixture of two or more types of pressure-sensitive adhesives may be used.
- the pressure-sensitive adhesive sheet of the present invention may be provided with a separator (release liner) on the pressure-sensitive adhesive surface until use.
- the separator is a member for protecting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet from being exposed, and is peeled off from the pressure-sensitive adhesive sheet when the pressure-sensitive adhesive sheet is attached to the adherend.
- the protection form by a separator is not specifically limited,
- the adhesive sheet of this invention is a double-sided adhesive sheet, it may take the form where an adhesive sheet is pinched
- the pressure-sensitive adhesive sheet may take a form wound in a roll shape with a separator.
- the separator is not particularly limited, and examples thereof include a substrate having a release treatment layer, a low adhesive substrate made of a fluoropolymer, and a low adhesive substrate made of a nonpolar polymer.
- the substrate having a release treatment layer include plastic films and paper surface-treated with a release treatment agent such as silicone, long chain alkyl, fluorine, and molybdenum sulfide.
- the plastic film include the same plastic film as described above for the base material.
- fluorine-based polymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene-vinylidene fluoride copolymer. Coalescence is mentioned.
- nonpolar polymer olefin resin, such as polyethylene and a polypropylene, is mentioned, for example.
- the surface of the separator may be subjected to release treatment, antifouling treatment, or antistatic treatment.
- release treatment a silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based release agent, or silica powder can be used.
- Silica powder can be used for the antifouling treatment.
- antistatic treatment a coating type, kneading type, or vapor deposition type antistatic treatment can be employed.
- the thickness of the separator is not particularly limited, but is, for example, 5 to 200 ⁇ m, and preferably 5 to 100 ⁇ m.
- the thickness of the separator is not included in the thickness of the pressure-sensitive adhesive sheet of the present invention.
- the pressure-sensitive adhesive sheet of the present invention has at least an acrylic pressure-sensitive adhesive layer A having the above-described configuration. For this reason, the pressure-sensitive adhesive sheet of the present invention is suitable for efficiently transmitting force while having good adhesive force and capable of suppressing relaxation or attenuation of the force when an external force is applied. The pressure-sensitive adhesive sheet of the present invention is suitable for realizing both adhesiveness and force transmission.
- the pressure-sensitive adhesive sheet of the present invention can be produced, for example, as follows.
- the pressure-sensitive adhesive composition is applied on the separator and then dried to form the acrylic pressure-sensitive adhesive layer A.
- This acrylic pressure-sensitive adhesive layer A separator is provided on A.
- the pressure-sensitive adhesive composition is applied on one side of the substrate and then dried to form an acrylic pressure-sensitive adhesive layer A.
- the acrylic pressure-sensitive adhesive layer A formed on the separator may be transferred onto the base material.
- the thickness of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 5 to 300 ⁇ m, more preferably 8 to 150 ⁇ m, and still more preferably 10 to 100 ⁇ m.
- the haze of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 10% or less, more preferably 5% or less. According to such a configuration, since the pressure-sensitive adhesive sheet is excellent in transparency, the surface of the adherend can be visually recognized through the pressure-sensitive adhesive sheet in a state where the pressure-sensitive adhesive sheet of the present invention is stuck to the body. It is possible.
- the pressure-sensitive adhesive sheet of the present invention has at least the acrylic pressure-sensitive adhesive layer A having the above-described configuration, it can suppress relaxation or attenuation of the force when an external force is applied while having a good adhesive force. It is suitable for transmitting power efficiently.
- a pressure-sensitive adhesive sheet of the present invention can be suitably used as a pressure-sensitive adhesive sheet for connecting parts and members and for fixing purposes. This is because in such an application, it may be required to efficiently transmit the force acting on one component / member to the other component / member via the adhesive sheet.
- the adhesive sheet of this invention can be used suitably as an adhesive sheet for the surface protection use of a touch panel.
- the pressure-sensitive adhesive sheet for surface protection of the touch panel may be required to efficiently transmit force to the panel from the viewpoint of response sensitivity to the touch operation on the panel.
- the pressure-sensitive adhesive sheet of the present invention can be suitably used as a pressure-sensitive adhesive sheet used in electronic devices such as sensors. This is because an adhesive sheet used in an electronic device such as a sensor may be required to efficiently transmit the force acting on the adhesive sheet to the adherend from the viewpoint of not hindering sensor sensing.
- polymer solution (A) The solid content concentration of the polymer in the polymer solution (A) was 36.0% (mass%), and the weight average molecular weight of the polymer was 850,000.
- polymer solution (B) The solid content concentration of the polymer in the polymer solution (B) was 40.0% (mass%), and the weight average molecular weight of the polymer was 500,000.
- polyfunctional urethane acrylate as a polyfunctional acrylic oligomer (trade name “purple UV-7650B”, weight average molecular weight 2300, in a ratio of 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution. 4-5, solid content concentration 99% by mass, manufactured by Nippon Synthetic Chemical Co., Ltd.), and photopolymerization initiator at a ratio of 0.2 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution. (Trade name “Irgacure 184”, manufactured by BASF Japan Ltd.) was added, and the solution was sufficiently stirred until these were dissolved.
- 3-glycidoxypropyltrimethoxysilane (trade name “KBM403”, Shin-Etsu) as a silane coupling agent is added to the solution at a ratio of 0.3 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution.
- Chemical Industry Co., Ltd. and a trimethylolpropane adduct of xylylene diisocyanate as a crosslinking agent (trade name “Takenate” at a ratio of 0.2 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution.
- D-110N solid content concentration 75% by mass, manufactured by Mitsui Chemicals, Inc.
- the adhesive composition (solvent type adhesive composition).
- the adhesive obtained after drying on the release-treated surface of the separator release liner whose surface is silicone-based release treatment, polyethylene terephthalate, thickness 38 ⁇ m, trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.
- the said adhesive composition was apply
- a separator release liner whose surface is treated with a silicone-based release treatment, made of polyethylene terephthalate, thickness 38 ⁇ m, trade name “MRE38”, manufactured by Mitsubishi Plastics, Inc.
- MRF separator
- MRE pressure-sensitive adhesive layer / separator
- Examples 2 to 15 The same operation as in Example 1 except that the type and addition amount of the polyfunctional acrylic oligomer used in Example 1, the compounding amount of the silane coupling agent, and the compounding amount of the crosslinking agent were changed as shown in Table 1.
- the adhesive sheet was produced.
- UV-7650B is urethane acrylate (trade name “UV-7650B”, hard type, number of functional groups: 4 to 5, weight average molecular weight: 2300, hardness: 2H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- UV-1700B is urethane acrylate (trade name “purple light UV-1700B”, hard type, number of functional groups: 10, weight average molecular weight: 2000, hardness: 4H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
- UV-7600B is urethane acrylate (trade name “purple light UV-7600B”, hard type, number of functional groups: 6, weight average molecular weight: 1400, hardness: 3H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) -7605B "is urethane acrylate (trade name” purple light UV-7605B ", hard type, number of functional groups: 6, heavy Average molecular weight: 1100, hardness: 3-4H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “UA-306T” is urethane acrylate (trade name “UA-306T”, urethane polymer (pentaerythritol triacrylate / toluene diisocyanate)
- “DMAPMA” with respect to the basic monomer is N- [3- (dimethylamino) propyl] methacrylamide.
- “Irgacure.184” is a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF Japan Ltd.)
- “Irgacure.819” is a photopolymerization initiator (trade name “Irgacure 819”). , Manufactured by BASF Japan Ltd.).
- Takenate D-110N is a trimethylolpropane adduct of xylylene diisocyanate (trade name “Takenate D-110N”, solid content concentration 75 mass%, manufactured by Mitsui Chemicals, Inc.), “Coronate L”. Is an aromatic polyisocyanate (trade name “Coronate L”, solid content concentration 75% by mass, manufactured by Nippon Polyurethane Industry Co., Ltd.).
- silane coupling agent “KBM403” is 3-glycidoxypropyltrimethoxysilane (trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.).
- polyfunctional urethane acrylate as a polyfunctional acrylic oligomer (trade name “purple UV-7650B”, weight average molecular weight 2300, in a ratio of 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution. 4-5, solid content concentration 99% by mass, manufactured by Nippon Synthetic Chemical Co., Ltd.), and photopolymerization initiator at a ratio of 0.2 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution. (Trade name “Irgacure 184”, manufactured by BASF Japan Ltd.) was added, and the solution was sufficiently stirred until these were dissolved.
- the solution is mixed with N- (3-dimethylaminopropyl) methacrylamide (trade name “DMAPMA”, Evonik, Inc.) as a basic monomer at a ratio of 5 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution. From Japan) was added.
- N- (3-dimethylaminopropyl) methacrylamide trade name “DMAPMA”, Evonik, Inc.
- the adhesive composition solvent type adhesive composition
- Example 17 A baseless double-sided PSA sheet was prepared in the same manner as in Example 16 except that the addition amount of N- (3-dimethylaminopropyl) methacrylamide as a basic monomer was changed to 10 parts by mass instead of 5 parts by mass. .
- polyfunctional urethane acrylate (trade name “UA-306H”, urethane polymer (pentaerythritol triglyceride) as a polyfunctional acrylic oligomer at a ratio of 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution.
- Acrylate / hexamethylene diisocyanate functional group number: 6, weight average molecular weight: 1350, hardness: 6H, manufactured by Kyoeisha Chemical Co., Ltd.
- 0.4 mass with respect to 100 mass parts of the polymer in the polymer solution (A), polyfunctional urethane acrylate (trade name “UA-306H”, urethane polymer (pentaerythritol triglyceride) as a polyfunctional acrylic oligomer at a ratio of 10 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution.
- Acrylate / hexamethylene diisocyanate functional group number: 6
- a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF Japan Ltd.) is added at a ratio of parts by weight, and light is added at a ratio of 0.4 parts by weight with respect to 100 parts by weight of the polymer in the polymer solution.
- Add a polymerization initiator (trade name “Irgacure 819”, manufactured by BASF Japan Ltd.) Et is sufficiently stirred the solution until dissolved.
- the said solution it diluted with ethyl acetate so that solid content concentration might be 30.0 mass%, and was fully stirred, and the adhesive composition (solvent type adhesive composition) was obtained.
- the base material-less double-sided adhesive sheet was obtained like Example 1 except having used this adhesive composition.
- Example 19 The polymer solution (C) was used in place of the polymer solution (A), no silane coupling agent was added, and a trimethylolpropane adduct of xylylene diisocyanate (trade name “Takenate D-110N” was used as a crosslinking agent.
- Example 1 (Comparative Examples 1, 3 to 7) The same operation as in Example 1 was performed except that the type and addition amount of the polyfunctional acrylic oligomer used in Example 1, the compounding amount of the silane coupling agent, and the compounding amount of the crosslinking agent were changed as shown in Table 2. This was done to prepare an adhesive sheet.
- rosin resin (trade name “Pencel D-125”, solid content 100%, manufactured by Arakawa Chemical Industries, Ltd.) is added to the polymer solution (B) at a ratio of 4 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution.
- rosin resin (trade name “Superester A-100”, solid content 100%, manufactured by Arakawa Chemical Industries, Ltd.) is added at a ratio of 4 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution.
- a rosin resin (trade name “Forarin 8020F”, solid content 100%, manufactured by Eastman Chemical Co., Ltd.) is added at a ratio of 2 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution, and the polymer 100 mass in the polymer solution Add terpene phenol resin (trade name “Tamanol 803L”, solid content 100%, manufactured by Arakawa Chemical Co., Ltd.) at a ratio of 6 parts by mass with respect to parts. It was stirred the solution thoroughly until they are dissolved.
- aromatic polyisocyanate (trade name “Coronate L”, solid concentration 75% by mass, as a crosslinking agent at a ratio of 1.1 parts by mass with respect to 100 parts by mass of the polymer in the polymer solution. Nippon Polyurethane Industry Co., Ltd.) was added and sufficiently stirred to obtain a pressure-sensitive adhesive composition (solvent-type pressure-sensitive adhesive composition). And the base material-less double-sided adhesive sheet was obtained like Example 1 except having used this adhesive composition.
- UV-7650B is urethane acrylate (trade name “UV-7650B”, hard type, number of functional groups: 4 to 5, weight average molecular weight: 2300, hardness: 2H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- Light acrylate BP-4EAL is an EO adduct diacrylate of bisphenol A (trade name “Light acrylate BP-4EAL”, number of functional groups: 2, weight average molecular weight: 500, Tg: 75 ° C., Kyoeisha Chemical Co., Ltd.)
- U-306H is urethane acrylate (trade name “UA-306H”, urethane polymer (pentaerythritol triacrylate / hexamethylene diisocyanate), number of functional groups: 6, weight average molecular weight: 1350, hardness: 6H.
- APG- “00” is polypropylene glycol # 400 diacrylate (trade name “APG-400”, functional group number: 2, weight average molecular weight: 536, Tg: ⁇ 8 ° C., manufactured by Shin-Nakamura Chemical Co., Ltd.), “APG-700 Is polypropylene glycol # 700 diacrylate (trade name “APG-700”, number of functional groups: 2, weight molecular weight 808, Tg: ⁇ 32 ° C., manufactured by Shin-Nakamura Chemical Co., Ltd.).
- “Pencel D-125” is rosin resin (trade name “Pencel D-125”, solid content 100%, manufactured by Arakawa Chemical Industries, Ltd.), and “Superester A-100” is rosin resin ( The product name is “Superester A-100”, solid content 100%, manufactured by Arakawa Chemical Co., Ltd., and “Foraline 8020F” is rosin resin (trade name “Foraline 8020F”, solid content 100%, manufactured by Eastman Chemical Co., Ltd.) “Tamanol 803” is a terpene phenol resin (trade name “Tamanol 803L”, solid content 100%, manufactured by Arakawa Chemical Industries, Ltd.).
- “Irgacure.184” is a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF Japan Ltd.).
- “Coronate L” is an aromatic polyisocyanate (trade name “Coronate L”, solid content concentration: 75 mass%, manufactured by Nippon Polyurethane Industry Co., Ltd.), and “Takenate D-110N” is a trixylylene diisocyanate It is a methylolpropane adduct (trade name “Takenate D-110N”, solid concentration 75% by mass, manufactured by Mitsui Chemicals, Inc.).
- “KBM403” is 3-glycidoxypropyltrimethoxysilane (trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.).
- ⁇ Weight average molecular weight> The weight average molecular weight of the obtained polymer was measured by GPC (gel permeation chromatography) according to the specifications listed below.
- GPC gel permeation chromatography
- the gel fraction of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet was determined as follows. About 0.1 g (mass: W 1 mg) of an adhesive sample is taken from the adhesive layer of the adhesive sheet, and is drawn in a tetrafluoroethylene resin porous membrane (mass: W 2 mg) with an average pore diameter of 0.2 ⁇ m. The mouth was tied with silk thread (mass: W 3 mg) to obtain a wrap. This packet was put into a screw tube with a capacity of 50 mL, and the screw tube was filled with ethyl acetate (one screw tube was used for each packet).
- porous membrane made of tetrafluoroethylene resin examples include “Nitoflon (registered trademark) NTF1122” manufactured by Nitto Denko Corporation.
- NTF1122 manufactured by Nitto Denko Corporation.
- the gel fraction measurement an adhesive sheet that was covered with a light-shielding sheet and stored so as not to be exposed to light was used.
- the “gel fraction (before UV irradiation)” was not subjected to UV irradiation (ultraviolet irradiation), that is, covered with a light-shielding sheet so as not to be exposed to light. It was calculated using a thing.
- the “gel fraction (after UV irradiation)” is the surface covered with a separator (MRE) as opposed to being covered with a light shielding sheet so as not to be exposed to light.
- the pressure-sensitive adhesive layer was obtained by irradiating ultraviolet rays from the side of the adhesive.
- a metal halide lamp M3000L / 22, manufactured by Toshiba Corporation
- the illuminance of ultraviolet rays was 300 mW / cm 2
- the integrated irradiation amount was 3000 mJ / cm 2 .
- the Young's modulus (before UV irradiation) of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet was determined as follows. First, a pressure-sensitive adhesive layer was collected from the pressure-sensitive adhesive sheet before ultraviolet irradiation, and the pressure-sensitive adhesive layer was wound into a columnar shape to prepare a columnar measurement sample having a diameter of 3 mm and a length of 30 mm. Next, in a measurement environment with a temperature of 23 ° C.
- the measurement sample was set in a testing machine so that the length of the sample (corresponding to the initial sample length for measurement) was 10 mm, and the measurement sample was pulled under conditions of a tensile speed of 10 mm / min. And Young's modulus was computed from the result of the obtained displacement and stress.
- the measurement sample to be subjected to such measurement was covered and stored with a light shielding sheet so as not to be exposed to light until the measurement.
- the Young's modulus (after UV irradiation) of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet was determined as follows. First, a metal halide lamp (M3000L / 22, Inc.) from the separator (MRE) side to the adhesive sheet (base material-less double-sided adhesive sheet having a laminated structure of separator (MRF) / adhesive layer / separator (MRE)). The pressure-sensitive adhesive layer was cured by irradiating with ultraviolet rays at an illuminance of 300 mW / cm 2 and an integrated dose of 3000 mJ / cm 2 .
- a cured pressure-sensitive adhesive layer was collected from the pressure-sensitive adhesive sheet after irradiation with ultraviolet rays, and the pressure-sensitive adhesive layer was wound into a columnar shape to prepare a columnar measurement sample having a diameter of 3 mm and a length of 30 mm.
- a tensile tester (trade name “Tension / Compression Tester TG-1kN”, manufactured by Minebea Co., Ltd.) in a measurement environment of 23 ° C. and 50% RH, the length between the chucks (measurement)
- the measurement sample was set on a testing machine so that the initial sample length of the sample was 10 mm, and the measurement sample was pulled under the condition of a tensile speed of 10 mm / min.
- Young's modulus was computed from the result of the obtained displacement and stress.
- the measurement sample to be subjected to such measurement was covered and stored with a light shielding sheet so as not to be exposed to light until the measurement.
- the haze (before UV irradiation) of the pressure-sensitive adhesive sheet was determined as follows. First, the separator (MRE) on one side of the pressure-sensitive adhesive sheet is peeled off, and the pressure-sensitive adhesive sheet is bonded to a slide glass (trade name “Slide Glass S1112”, manufactured by Matsunami Glass Industry Co., Ltd.), and then the other separator (MRF). Was peeled off to prepare a measurement sample. With respect to this measurement sample, haze was measured using “HAZE METER HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd. as a measuring instrument. For the measurement, an adhesive sheet that was covered with a light-shielding sheet and stored so as not to be exposed to light was used.
- the haze (after UV irradiation) of the pressure-sensitive adhesive sheet was determined as follows. First, the separator (MRE) on one side of the pressure-sensitive adhesive sheet is peeled off, and the pressure-sensitive adhesive sheet is bonded to a slide glass (trade name “Slide Glass S1112”, manufactured by Matsunami Glass Industrial Co., Ltd.) and covered with the other separator (MRF). From the broken surface side, the pressure-sensitive adhesive layer was cured by irradiating with ultraviolet rays at an illuminance of 300 mW / cm 2 and an integrated irradiation amount of 3000 mJ / cm 2 .
- the separator MRF
- haze was measured using “HAZE METER HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd. as a measuring instrument.
- a pressure-sensitive adhesive sheet that was covered with a light-shielding sheet so as not to be exposed to light until measurement was used.
- the “adhesive strength (before UV irradiation)” of the pressure-sensitive adhesive sheet was determined as follows. First, the separator (MRE) on one surface of the pressure-sensitive adhesive sheet was peeled off, and then the exposed pressure-sensitive adhesive surface was attached to a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m to line the pressure-sensitive adhesive sheet. A test piece (width 20 mm ⁇ length 100 mm) was cut out from the backed adhesive sheet.
- MRE separator
- PET polyethylene terephthalate
- the separator (MRF) on the other side is peeled off from the test piece, the test piece is bonded to the adherend with the adhesive surface exposed thereby, and the test piece and the adherend are moved by reciprocating a 2 kg roller. Was crimped. Thereafter, it was stored for 24 hours. After storage, use a tensile tester (trade name “Tension / Compression Tester TG-1kN”, manufactured by Minebea Co., Ltd.) to remove the test piece from the adherend under conditions of a tensile speed of 300 mm / min and a tensile angle of 180 °. After peeling, the peel strength (N / 20 mm) was measured. The peel strength was defined as the adhesive strength before UV irradiation.
- test piece Preparation of the test piece, storage of the test piece, and measurement of peel strength were performed in an environment of 23 ° C. and 50% RH.
- the test piece was produced and stored in a state where it was covered with a light-shielding sheet so as not to be exposed to light.
- the adhesive strength measurement as described above is performed for each example and each comparative example, both when the stainless steel plate (SUS304) is used as the adherend and when the PC plate (polycarbonate resin plate) is used as the adherend. It was.
- the “adhesive strength (after UV irradiation)” of the pressure-sensitive adhesive sheet was determined as follows. First, the separator (MRE) on one surface of the pressure-sensitive adhesive sheet was peeled off, and then the exposed pressure-sensitive adhesive surface was attached to a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m to line the pressure-sensitive adhesive sheet. A test piece (width 20 mm ⁇ length 100 mm) was cut out from the backed adhesive sheet.
- MRE separator
- PET polyethylene terephthalate
- the separator on the other side was peeled off from the test piece, the test piece was bonded to the adherend, and the test piece and the adherend were pressure bonded by reciprocating a 2 kg roller once. Thereafter, it was stored for 12 hours.
- the test piece was irradiated with ultraviolet rays from the PET film side to cure the adhesive layer of the test piece.
- a metal halide lamp M3000L / 22, manufactured by Toshiba Corporation
- the illuminance of the ultraviolet light was 300 mW / cm 2
- the integrated irradiation amount was 3000 mJ / cm 2 .
- a tensile tester (trade name “Tension / Compression Tester TG-1kN”, manufactured by Minebea Co., Ltd.) to remove the test piece from the adherend under conditions of a tensile speed of 300 mm / min and a tensile angle of 180 °. After peeling, the peel strength (N / 20 mm) was measured. The peel strength was defined as the adhesive strength after UV irradiation. Preparation of the test piece, storage of the test piece, irradiation of ultraviolet rays, and measurement of peel strength were performed in an environment of 23 ° C. and 50% RH.
- the test piece was produced and stored in a state where it was covered with a light-shielding sheet so as not to be exposed to light.
- the adhesive strength measurement as described above is performed for each example and each comparative example, both when the stainless steel plate (SUS304) is used as the adherend and when the PC plate (polycarbonate resin plate) is used as the adherend. It was.
- a pressure-sensitive adhesive layer was collected from the pressure-sensitive adhesive sheet before ultraviolet irradiation, and the pressure-sensitive adhesive layer was wound into a columnar shape to prepare a columnar measurement sample having a diameter of 3 mm and a length of 30 mm.
- a tensile tester (trade name “Tension / Compression Tester TG-1kN”, manufactured by Minebea Co., Ltd.) in a measurement environment of 23 ° C.
- the length between the chucks The measurement sample was set on a testing machine so that the initial sample length of the sample was 10 mm, and the measurement sample was pulled under the condition of a tensile speed of 10 mm / min. And the result of the obtained displacement and stress was analyzed, and elongation rate was computed from the following formula from the displacement amount of the measurement sample when a load is 0.5 N / mm ⁇ 2 >.
- the displacement amount of the measurement sample means the amount of change of the measurement sample due to the load, that is, the amount of elongation when the measurement sample is stretched due to the load. For example, when a measurement sample having a length of 10 mm extends 3 mm due to a load acting in the length direction to a length of 13 mm, the amount of displacement at that time is 3 mm.
- ⁇ Elongation to load (after UV irradiation)> a metal halide lamp (M3000L / 22, Ltd.) from the separator (MRE) side to the pressure-sensitive adhesive sheet (base material-less double-sided pressure-sensitive adhesive sheet having a laminated structure of separator (MRF) / adhesive layer / separator (MRE)).
- the pressure-sensitive adhesive layer was cured by irradiating with ultraviolet rays at an illuminance of 300 mW / cm 2 and an integrated dose of 3000 mJ / cm 2 .
- a cured pressure-sensitive adhesive layer was collected from the pressure-sensitive adhesive sheet after irradiation with ultraviolet rays, and the pressure-sensitive adhesive layer was wound into a columnar shape to prepare a columnar measurement sample having a diameter of 3 mm and a length of 30 mm.
- a tensile tester (trade name “Tension / Compression Tester TG-1kN”, manufactured by Minebea Co., Ltd.) in a measurement environment of 23 ° C. and 50% RH, the length between the chucks (measurement) The measurement sample was set on a testing machine so that the initial sample length of the sample was 10 mm, and the measurement sample was pulled under the condition of a tensile speed of 10 mm / min.
- Young's modulus was computed from the result of the obtained displacement and stress.
- the measurement sample to be subjected to such measurement was covered and stored with a light shielding sheet so as not to be exposed to light until the measurement.
- the result of the obtained displacement and stress was analyzed, and elongation rate was computed from the following formula from the displacement amount of the measurement sample when a load is 0.5 N / mm ⁇ 2 >.
- ⁇ Resistance change rate (resistance change rate after ITO corrosion test)> First, on one surface of a glass plate (width 25 mm, length 25 mm, thickness 7 mm), a double-sided pressure-sensitive adhesive tape (double-sided pressure-sensitive adhesive tape with a base material having a laminated structure of separator / adhesive layer / base material / adhesive layer, A double-sided PSA sheet (width 25 mm, length 25 mm) cut out from the trade name “No. 5606” (manufactured by Nitto Denko Corporation) was bonded to obtain a laminate (laminate 1).
- a double-sided pressure-sensitive adhesive tape double-sided pressure-sensitive adhesive tape with a base material having a laminated structure of separator / adhesive layer / base material / adhesive layer
- a double-sided PSA sheet (width 25 mm, length 25 mm) cut out from the trade name “No. 5606” (manufactured by Nitto Denko Corporation) was bonded to obtain a
- an ITO film hard coat treatment (anti-glare treatment) PET film (PET film having a non-deposition surface)
- pressure-sensitive adhesive layer A transparent conductive film having a laminated structure of / PET film / ITO layer, an ITO film (width 15 mm, length 15 mm) cut out from a trade name “ELECRYSTA” (manufactured by Nitto Denko Corporation), its non-deposition surface and the adhesive
- a laminated body (laminated body 2) was obtained by pasting in a form in contact with the surface.
- a separator in a measurement sample (width 8 mm, length 8 mm) cut out from the pressure-sensitive adhesive sheet to be measured base material-less double-sided pressure-sensitive adhesive sheet having a laminated structure of separator (MRF) / adhesive layer / separator (MRE)) ( MRE) was peeled to expose the adhesive surface, and the measurement sample was attached to the center of the ITO layer surface (deposition surface) of the ITO film in the laminate 2 to obtain a laminate (laminate 3).
- a Hall effect measuring device device name “HL5500PC”, manufactured by Accent Optical Technologies
- the electrical resistance value is measured using four corners of the ITO layer surface (deposition surface) of the ITO film of the laminate 3 as measurement points. did.
- This electrical resistance value was “R1”. After measuring the electrical resistance value R1, the laminate 3 was allowed to stand for 500 hours under conditions of 60 ° C. and 95% RH, and was further allowed to stand for 1 hour under conditions of 23 ° C. and 50% RH. About the laminated body 3 after standing, the electrical resistance value was measured in the same manner as described above. The measured electric resistance value was defined as “R2”. And the electrical resistance value change rate was computed from the following formula.
- (Appendix 1) It has an acrylic pressure-sensitive adhesive layer that is cured by irradiation,
- the acrylic pressure-sensitive adhesive layer contains an acrylic polymer and a polyfunctional acrylic oligomer,
- the Young's modulus at 23 ° C. of the acrylic pressure-sensitive adhesive layer after curing is 500 kPa or more and 10,000 kPa or less,
- the pressure-sensitive adhesive sheet wherein the adhesive strength of the acrylic pressure-sensitive adhesive layer after curing is 3.0 N / 20 mm or more.
- (Appendix 2) The pressure-sensitive adhesive sheet according to supplementary note 1, wherein the adhesive strength of the acrylic pressure-sensitive adhesive layer before curing is 3.0 N / 20 mm or more.
- (Appendix 12) The pressure-sensitive adhesive sheet according to any one of appendices 1 to 11, wherein the polyfunctional acrylic oligomer has a hardness measured according to JIS K5600-5-4 for a homopolymer thereof of 4B or more.
- (Appendix 13) The pressure-sensitive adhesive sheet according to any one of appendices 1 to 12, wherein the acrylic pressure-sensitive adhesive layer further contains a photopolymerization initiator.
- the content of the polyfunctional acrylic oligomer is 0.05 to 40 parts by mass with respect to 100 parts by mass of the acrylic polymer, and the content of the photopolymerization initiator is the acrylic polymer.
- the pressure-sensitive adhesive sheet according to supplementary note 13 which is 0.05 to 5 parts by mass with respect to 100 parts by mass of the polymer.
- Appendix 15 The pressure-sensitive adhesive sheet according to any one of supplementary notes 1 to 14, wherein the acrylic pressure-sensitive adhesive layer further comprises 0.05 to 5 parts by mass of a crosslinking agent with respect to 100 parts by mass of the acrylic polymer.
- Appendix 16 The pressure-sensitive adhesive sheet according to any one of supplementary notes 1 to 15, wherein the acrylic pressure-sensitive adhesive layer further comprises 0.01 to 1 part by mass of a silane coupling agent with respect to 100 parts by mass of the acrylic polymer.
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- Chemical & Material Sciences (AREA)
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Abstract
Description
(a)放射線照射により硬化する。
(b)アクリル系ポリマーおよび多官能アクリルオリゴマーを含む。
(c)放射線照射による硬化後の23℃におけるヤング率が500kPa以上10000kPa以下である。
(d)放射線照射による硬化後の粘着力が3.0N/20mm以上である。
アクリル系粘着剤層Aは、放射線の照射により硬化する。例えば、被着体に本発明の粘着シートを貼付した後、当該粘着シートに放射線を照射すると、アクリル系粘着剤層Aは硬化する。硬化したアクリル系粘着剤層Aを伴う粘着シートが貼付された被着体に対し、当該粘着シートを介して力が加わった場合、当該粘着シートは良好にその力を被着体に伝達できる。
上述のように、本発明の粘着シートは、基材付き粘着シートであってもよい。すなわち、本発明の粘着シートは、アクリル系粘着剤層Aとともに基材を有してもよい。この基材は、単層構造を有してもよく、積層構造を有してもよい。
本発明の粘着シートは、本発明の効果を損なわない範囲で、その他の粘着剤層(アクリル系粘着剤層A以外の粘着剤層)を有していてもよい。当該その他の粘着剤層としては、特に限定されないが、例えば、ウレタン系粘着剤、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、エポキシ系粘着剤、ビニルアルキルエーテル系粘着剤、フッ素系粘着剤などの粘着剤から形成された粘着剤層が挙げられる。その他の粘着剤層を形成するうえでは、1種類の粘着剤を用いてもよいし、2種類以上の粘着剤の混合物を用いてもよい。
本発明の粘着シートは、その使用時まで、粘着面にセパレーター(剥離ライナー)が設けられていてもよい。セパレーターは、粘着シートの粘着剤層が露出しないように保護するための部材であり、粘着シートを被着体に貼付する際に当該粘着シートから剥がされる。セパレーターによる保護形態は特に限定されないが、本発明の粘着シートが両面粘着シートである場合、2枚のセパレーターによって粘着シートが挟まれる形態をとってもよいし、粘着シートとセパレーターとが交互に配されるように粘着シートがセパレーターを伴ってロール状に巻回された形態をとってもよい。
本発明の粘着シートは、上述の構成を具備するアクリル系粘着剤層Aを少なくとも有する。このため、本発明の粘着シートは、良好な接着力を有しつつ、外力が作用した場合にその力の緩和ないし減衰を抑制可能であって効率よく力を伝達するのに適する。本発明の粘着シートは、接着性と力の伝達性との両方を実現するのに適するのである。
攪拌羽根、温度計、窒素ガス導入管、および冷却器を備えた4つ口のフラスコに、2-エチルヘキシルアクリレート(2EHA)63質量部と、N-ビニルピロリドン(NVP)15質量部と、メチルメタクリレート(MMA)9質量部と、2-ヒドロキシエチルアクリレート(HEA)13質量部と、熱重合開始剤としての2,2'-アゾビスイソブチロニトリル(AIBN)0.2質量部とを、重合溶媒としての酢酸エチル177.8質量部と共に投入した。そして、フラスコ内の溶液において、23℃にて窒素雰囲気下で2時間攪拌した後、65℃で5時間反応させ、続いて70℃で2時間反応させた。このようにして、ポリマーを含有するポリマー溶液(調整粘着剤溶液)を得た。このポリマー溶液を「ポリマー溶液(A)」とした。ポリマー溶液(A)中のポリマーの固形分濃度は36.0%(質量%)であり、ポリマーの重量平均分子量は85万であった。
攪拌羽根、温度計、窒素ガス導入管、および冷却器を備えた4つ口のフラスコに、アクリル酸(AA)2.9質量部と、酢酸ビニル(VAc)5質量部と、アクリル酸ブチル(BA)92質量部と、ヒドロキシエチルアクリレート(HEA)0.1質量部とを、重合溶媒としての酢酸エチル30質量部およびトルエン120質量部と共に投入した。次に、フラスコ内の溶液を、窒素ガスを導入しながら2時間攪拌した。このようにして重合系内の酸素を除去した後、フラスコ内の溶液において、熱重合開始剤としての2,2'-アゾビスイソブチロニトリル(AIBN)0.2質量部を加え、60℃に昇温して6時間重合反応を行った。このようにして、ポリマーを含有するポリマー溶液(調整粘着剤溶液)を得た。このポリマー溶液を「ポリマー溶液(B)」とした。ポリマー溶液(B)中のポリマーの固形分濃度は40.0%(質量%)であり、ポリマーの重量平均分子量は50万であった。
攪拌羽根、温度計、窒素ガス導入管、および冷却器を備えた4つ口のフラスコに、アクリル酸(AA)10質量部と、2-エチルヘキシルアクリレート(2EHA)90質量部とを、重合溶媒としての酢酸エチル199質量部と共に投入した。次に、フラスコ内の溶液を、窒素ガスを導入しながら2時間攪拌した。このようにして重合系内の酸素を除去した後、フラスコ内の溶液において、熱重合開始剤としてのベンゾイルパーオキサイド(商品名「ナイパーBW」,日本油脂株式会社製)0.6質量部を加え、60℃に昇温して6時間重合反応を行った。反応停止後にトルエン137質量部を加えることによって、ポリマーを含有するポリマー溶液(調整粘着剤溶液)を得た。このポリマー溶液を「ポリマー溶液(C)」とした。ポリマー溶液(C)中のポリマーの固形分濃度は23.0%(質量%)であり、ポリマーの重量平均分子量は80万であった。
ポリマー溶液(A)に、ポリマー溶液中のポリマー100質量部に対して10質量部となる割合で多官能アクリルオリゴマーとしての多官能ウレタンアクリレート(商品名「紫光UV-7650B」,重量平均分子量2300,官能基数4~5,固形分濃度99質量%,日本合成化学株式会社製)を添加し、更に、ポリマー溶液中のポリマー100質量部に対して0.2質量部となる割合で光重合開始剤(商品名「イルガキュア184」,BASFジャパン株式会社製)を添加して、これらが溶解するまで当該溶液を十分に攪拌した。攪拌後、当該溶液に、ポリマー溶液中のポリマー100質量部に対して0.3質量部となる割合でシランカップリング剤としての3-グリシドキシプロピルトリメトキシシラン(商品名「KBM403」,信越化学工業株式会社製)を添加し、更に、ポリマー溶液中のポリマー100質量部に対して0.2質量部となる割合で架橋剤としてのキシリレンジイソシアネートのトリメチロールプロパン付加物(商品名「タケネートD-110N」,固形分濃度75質量%,三井化学株式会社製)を添加した。そして、当該溶液について、固形分濃度が30.0質量%となるように酢酸エチルで希釈して十分に攪拌し、粘着剤組成物(溶剤型の粘着剤組成物)を得た。次に、セパレーター(表面がシリコーン系剥離処理されている剥離ライナー,ポリエチレンテレフタレート製,厚さ38μm,商品名「MRF38」,三菱樹脂株式会社製)の剥離処理された面に、乾燥後に得られる粘着剤層の厚さ(乾燥塗膜厚さ)が50μmとなるように上記粘着剤組成物を塗布し、塗布層(粘着剤組成物層)を得た。次に、100℃で2分間の乾燥を行い、セパレーター上に粘着剤層を形成した。次に、得られた粘着剤層の表面(粘着面)に、セパレーター(表面がシリコーン系剥離処理されている剥離ライナー,ポリエチレンテレフタレート製,厚さ38μm,商品名「MRE38」,三菱樹脂株式会社製)を、剥離処理された面と粘着剤層の粘着面とが接する形態で貼り合わせ、セパレーター(MRF)/粘着剤層/セパレーター(MRE)の積層構造を有する基材レス両面粘着シートを得た。このようにして作製された両面粘着シートについて下記の評価や測定を行う前には、当該粘着シートを、光が当たらないように遮光シート内で、50℃雰囲気下で24時間放置した。
実施例1において用いた多官能アクリルオリゴマーの種類と添加量、シランカップリング剤の配合量、および架橋剤の配合量を表1に示すように変えたこと以外は、実施例1と同様の操作を行い、粘着シートを作製した。
ポリマー溶液(A)に、ポリマー溶液中のポリマー100質量部に対して10質量部となる割合で多官能アクリルオリゴマーとしての多官能ウレタンアクリレート(商品名「紫光UV-7650B」,重量平均分子量2300,官能基数4~5,固形分濃度99質量%,日本合成化学株式会社製)を添加し、更に、ポリマー溶液中のポリマー100質量部に対して0.2質量部となる割合で光重合開始剤(商品名「イルガキュア184」,BASFジャパン株式会社製)を添加して、これらが溶解するまで当該溶液を十分に攪拌した。攪拌後、当該溶液に、ポリマー溶液中のポリマー100質量部に対して5質量部となる割合で塩基性モノマーとしてのN-(3-ジメチルアミノプロピル)メタクリルアミド(商品名「DMAPMA」,エボニック・ジャパン社製)を添加した。次に、当該溶液について、固形分濃度が30.0質量%となるように酢酸エチルで希釈して十分に攪拌して、粘着剤組成物(溶剤型の粘着剤組成物)を得た。そして、この粘着剤組成物を用いたこと以外は実施例1と同様にして、基材レス両面粘着シートを作製した。
塩基性モノマーとしてのN-(3-ジメチルアミノプロピル)メタクリルアミドの添加量について5質量部に代えて10質量部とした以外は実施例16と同様にして、基材レス両面粘着シートを作製した。
ポリマー溶液(A)に、ポリマー溶液中のポリマー100質量部に対して10質量部となる割合で多官能アクリルオリゴマーとしての多官能ウレタンアクリレート(商品名「UA-306H」,ウレタンポリマー(ペンタエリスリトールトリアクリレート・ヘキサメチレンジイソシアネート),官能基数:6,重量平均分子量:1350,硬度:6H,共栄社化学株式会社製)」を添加し、更に、ポリマー溶液中のポリマー100質量部に対して0.4質量部となる割合で光重合開始剤(商品名「イルガキュア184」,BASFジャパン株式会社製)を添加し、更に、ポリマー溶液中のポリマー100質量部に対して0.4質量部となる割合で光重合開始剤(商品名「イルガキュア819」,BASFジャパン株式会社製)を添加して、これらが溶解するまで当該溶液を十分に攪拌した。次に、当該溶液について、固形分濃度が30.0質量%となるように酢酸エチルで希釈して十分に攪拌して、粘着剤組成物(溶剤型の粘着剤組成物)を得た。そして、この粘着剤組成物を用いたこと以外は実施例1と同様にして、基材レス両面粘着シートを得た。
ポリマー溶液(A)の代わりにポリマー溶液(C)を用いたこと、シランカップリング剤は添加しなかったこと、架橋剤として、キシリレンジイソシアネートのトリメチロールプロパン付加物(商品名「タケネートD-110N」,固形分濃度75質量%,三井化学株式会社製)の代わりに、ポリマー溶液中のポリマー100質量部に対して1.0質量部となる割合で芳香族ポリイソシアネート(商品名「コロネートL」,固形分濃度75質量%,日本ポリウレタン工業株式会社製)を添加したこと以外は、実施例1と同様にして、粘着剤組成物(溶剤型の粘着剤組成物)を得た。そして、この粘着剤組成物を用いたこと以外は実施例1と同様にして、基材レス両面粘着シートを得た。
実施例1において用いた多官能アクリルオリゴマーの種類と添加量、シランカップリング剤の配合量、および架橋剤の配合量を表2に示すように変えたこと以外は実施例1と同様の操作を行い、粘着シートを作製した。
ポリマー溶液(B)に、ポリマー溶液中のポリマー100質量部に対して4質量部となる割合でロジン樹脂(商品名「ペンセルD-125」,固形分100%,荒川化学工業株式会社製)を添加し、ポリマー溶液中のポリマー100質量部に対して4質量部となる割合でロジン樹脂(商品名「スーパーエステルA-100」,固形分100%,荒川化学工業株式会社製)を添加し、ポリマー溶液中のポリマー100質量部に対して2質量部となる割合でロジン樹脂(商品名「フォーラリン8020F」,固形分100%,イーストマンケミカル社製)を添加し、ポリマー溶液中のポリマー100質量部に対して6質量部となる割合でテルペンフェノール樹脂(商品名「タマノル803L」,固形分100%,荒川化学工業株式会社製)を添加し、これらが溶解するまで当該溶液を十分に攪拌した。攪拌後、当該溶液において、ポリマー溶液中のポリマー100質量部に対して1.1質量部となる割合で架橋剤としての芳香族ポリイソシアネート(商品名「コロネートL」,固形分濃度75質量%,日本ポリウレタン工業株式会社製)を添加して十分に攪拌して、粘着剤組成物(溶剤型の粘着剤組成物)を得た。そして、この粘着剤組成物を用いたこと以外は実施例1と同様にして、基材レス両面粘着シートを得た。
上記の実施例および比較例で得られた両面粘着シートについて、以下の測定または評価を行った。その測定結果または評価を表3、表4、および表5に示す。
得られたポリマーの重量平均分子量は、以下に列記する仕様にてGPC(ゲル・パーミエーション・クロマトグラフィー)によって測定した。測定に付するサンプル液としては、ポリマー試料をテトラヒドロフランに溶解して0.1質量%の溶液を調製し、これを一晩静置した後、0.45μmのメンブレンフィルターで濾過した濾液を用いた。
・分析装置:HLC-8120GPC(東ソー株式会社製)
・カラム:TSKgel GMHHR-H(S)(東ソー株式会社製)
・カラムサイズ:7.8mmφ×30cm
・溶離液:テトラヒドロフラン(濃度0.1質量%)
・流量:0.5ml/min
・検出器:示差屈折率計(RI)
・カラム温度:40℃
・注入量:100μl
・標準試料:ポリスチレン
粘着シートにおける粘着剤層のゲル分率は、次のようにして求めた。粘着シートの粘着剤層から約0.1g(質量:W1mg)の粘着剤サンプルを採取して平均孔径0.2μmのテトラフルオロエチレン樹脂製多孔質膜(質量:W2mg)で巾着状に包み、口を凧糸(質量:W3mg)で縛り、包みを得た。この包みを容量50mLのスクリュー管に入れ、当該スクリュー管に酢酸エチルを満たした(包み毎に1本のスクリュー管を使用した)。これを室温(典型的には23℃)にて7日間静置した後、包みをスクリュー管から取り出して130℃で2時間乾燥させた。その後に当該包みの質量(W4mg)を測定した。そして、W1~W4の値を下記式に代入することによって粘着剤層のゲル分率を算出した。
粘着シートにおける粘着剤層のヤング率(UV照射前)は、次のようにして求めた。まず、紫外線照射前の粘着シートから粘着剤層を採取し、当該粘着剤層を円柱状に巻くことによって、直径が3mmで長さが30mmの円柱状の測定サンプルを作製した。次に、温度が23℃で相対湿度が50%RHの測定環境下、引張試験機(商品名「引張圧縮試験機TG-1kN」,ミネベア株式会社製)を使用して、試験機においてチャック間の長さ(測定に係る初期サンプル長さに相当する)が10mmになるように測定サンプルを試験機にセットし、測定サンプルを引張速度10mm/分の条件で引っ張った。そして、得られた変位と応力の結果からヤング率を算出した。このような測定に付されることとなる測定サンプルについては、測定時まで、光が当たらないように遮光シートで覆って保管した。
粘着シートにおける粘着剤層のヤング率(UV照射後)は、次のようにして求めた。まず、粘着シート(セパレーター(MRF)/粘着剤層/セパレーター(MRE)の積層構造を有する基材レス両面粘着シート)に対し、セパレーター(MRE)の側から、メタルハライドランプ(M3000L/22,株式会社東芝製)を使用して、照度300mW/cm2で、積算照射量が3000mJ/cm2となるように紫外線を照射して、粘着剤層を硬化させた。次に、紫外線照射後の粘着シートから硬化粘着剤層を採取し、当該粘着剤層を円柱状に巻くことによって、直径が3mmで長さが30mmの円柱状の測定サンプルを作製した。次に、23℃かつ50%RHの測定環境下、引張試験機(商品名「引張圧縮試験機TG-1kN」,ミネベア株式会社製)を使用して、試験機においてチャック間の長さ(測定に係る初期サンプル長さに相当する)が10mmになるように測定サンプルを試験機にセットし、測定サンプルを引張速度10mm/分の条件で引っ張った。そして、得られた変位と応力の結果からヤング率を算出した。このような測定に付されることとなる測定サンプルについては、測定時まで、光が当たらないように遮光シートで覆って保管した。
粘着シートのヘーズ(UV照射前)は、次のようにして求めた。まず、粘着シートの一方の面のセパレーター(MRE)を剥がし、当該粘着シートをスライドガラス(商品名「スライドガラスS1112」,松浪硝子工業株式会社製)に貼り合わせ、その後に他方のセパレーター(MRF)を剥がし、測定サンプルを作製した。この測定サンプルについて、測定機器として村上色彩技術研究所社製の「HAZE METER HM-150」を使用して、ヘーズを測定した。測定には、光が当たらないように遮光シートで覆って保管していた粘着シートを使用した。
粘着シートのヘーズ(UV照射後)は、次のようにして求めた。まず、粘着シートの一方の面のセパレーター(MRE)を剥がし、当該粘着シートをスライドガラス(商品名「スライドガラスS1112」,松浪硝子工業株式会社製)に貼り合わせ、他方のセパレーター(MRF)で覆われた面の側から、照度300mW/cm2で、積算照射量が3000mJ/cm2となるように紫外線を照射して、粘着剤層を硬化させた。その後、セパレーター(MRF)を剥がし、測定サンプルを作製した。この測定サンプルについて、測定機器として村上色彩技術研究所社製の「HAZE METER HM-150」を使用して、ヘーズを測定した。測定には、測定時までは光が当たらないように遮光シートで覆って保管していた粘着シートを使用した。
粘着シートの「粘着力(UV照射前)」は、次のようにして求めた。まず、粘着シートの一方の面のセパレーター(MRE)を剥がした後、露出した粘着面を厚さ50μmのポリエチレンテレフタレート(PET)フィルムに貼り付けて、粘着シートを裏打ちした。この裏打ちされた粘着シートから、試験片(幅20mm×長さ100mm)を切り出した。この試験片からもう一方の面のセパレーター(MRF)を剥がし、これによって露出した粘着面にて試験片を被着体に貼り合わせ、2kgのローラーを1往復させることによって試験片と被着体とを圧着させた。その後、24時間保管した。保管後、引張試験機(商品名「引張圧縮試験機TG-1kN」,ミネベア株式会社製)を使用して、引張速度300mm/分、引張角度180°の条件で、被着体から試験片を剥離し、剥離強度(N/20mm)を測定した。その剥離強度をUV照射前の粘着力とした。試験片の作製、試験片の保管、および剥離強度の測定は、23℃かつ50%RHの環境下で行った。試験片の作製および保管は、光が当たらないように遮光シートで覆った状態で行った。以上のような粘着力測定は、実施例ごと及び比較例ごとに、ステンレス板(SUS304)を被着体とする場合についても、PC板(ポリカーボネート樹脂板)を被着体とする場合についても行った。
粘着シートの「粘着力(UV照射後)」は、次のようにして求めた。まず、粘着シートの一方の面のセパレーター(MRE)を剥がした後、露出した粘着面を厚さ50μmのポリエチレンテレフタレート(PET)フィルムに貼り付けて、粘着シートを裏打ちした。この裏打ちされた粘着シートから、試験片(幅20mm×長さ100mm)を切り出した。この試験片からもう一方の面のセパレーターを剥がし、試験片を被着体に貼り合わせ、2kgのローラーを1往復させることによって試験片と被着体とを圧着させた。その後、12時間保管した。保管後、試験片に対してPETフィルム側から紫外線を照射し、試験片の粘着剤層を硬化させた。紫外線照射には、メタルハライドランプ(M3000L/22,株式会社東芝製)を使用し、紫外線の照度は300mW/cm2とし、積算照射量は3000mJ/cm2とした。このような紫外線照射後、試験片を更に12時間保管した。保管後、引張試験機(商品名「引張圧縮試験機TG-1kN」,ミネベア株式会社製)を使用して、引張速度300mm/分、引張角度180°の条件で、被着体から試験片を剥離し、剥離強度(N/20mm)を測定した。その剥離強度をUV照射後の粘着力とした。試験片の作製、試験片の保管、紫外線の照射、および剥離強度の測定は、23℃かつ50%RHの環境下で行った。試験片の作製および保管は、光が当たらないように遮光シートで覆った状態で行った。以上のような粘着力測定は、実施例ごと及び比較例ごとに、ステンレス板(SUS304)を被着体とする場合についても、PC板(ポリカーボネート樹脂板)を被着体とする場合についても行った。
粘着シートに外力が作用した場合に当該粘着シートが効率よくその力を伝達できるかどうかについては、粘着シートに外力が作用した場合における当該粘着シートの変形量(変形の程度)に基づいて評価することができる。すなわち、粘着シートに外力が作用した際、当該粘着シートの変形量が小さいほど、変形エネルギー(粘着シートに蓄えられるエネルギー)が小さく、その分の力のロスが小さい。具体的には、後記のように「荷重に対する伸び率」を測定し、その測定結果に基づき、下記基準で力の伝達性を評価した。
(力の伝達性の評価基準)
とても良好:荷重に対する伸び率が30%以下
良好:荷重に対する伸び率が30%を超えて50%以下
やや良好:荷重に対する伸び率が50%を超えて100%以下
不良:荷重に対する伸び率が100%を超える
まず、紫外線照射前の粘着シートから粘着剤層を採取し、当該粘着剤層を円柱状に巻くことによって、直径が3mmで長さが30mmの円柱状の測定サンプルを作製した。次に、23℃かつ50%RHの測定環境下、引張試験機(商品名「引張圧縮試験機TG-1kN」,ミネベア株式会社製)を使用して、試験機においてチャック間の長さ(測定に係る初期サンプル長さに相当する)が10mmになるように測定サンプルを試験機にセットし、測定サンプルを引張速度10mm/分の条件で引っ張った。そして、得られた変位と応力の結果を分析し、荷重が0.5N/mm2であるときの測定サンプルの変位量から、下記式より伸び率を算出した。
まず、粘着シート(セパレーター(MRF)/粘着剤層/セパレーター(MRE)の積層構造を有する基材レス両面粘着シート)に対し、セパレーター(MRE)の側から、メタルハライドランプ(M3000L/22,株式会社東芝製)を使用して、照度300mW/cm2で、積算照射量が3000mJ/cm2となるように紫外線を照射して、粘着剤層を硬化させた。次に、紫外線照射後の粘着シートから硬化粘着剤層を採取し、当該粘着剤層を円柱状に巻くことによって、直径が3mmで長さが30mmの円柱状の測定サンプルを作製した。次に、23℃かつ50%RHの測定環境下、引張試験機(商品名「引張圧縮試験機TG-1kN」,ミネベア株式会社製)を使用して、試験機においてチャック間の長さ(測定に係る初期サンプル長さに相当する)が10mmになるように測定サンプルを試験機にセットし、測定サンプルを引張速度10mm/分の条件で引っ張った。そして、得られた変位と応力の結果からヤング率を算出した。このような測定に付されることとなる測定サンプルについては、測定時まで、光が当たらないように遮光シートで覆って保管した。そして、得られた変位と応力の結果を分析し、荷重が0.5N/mm2であるときの測定サンプルの変位量から、下記式より伸び率を算出した。
後記のように「抵抗値変化率」を測定し、その測定結果に基づき、下記基準で金属腐食防止性を評価した。
(金属腐食防止性の評価基準)
良好:抵抗値変化率が10%未満
不良:抵抗値変化率が10%以上
まず、ガラス板(幅25mm,長さ25mm,厚さ7mm)の一方の面に、両面粘着テープ(セパレーター/粘着剤層/基材/粘着剤層の積層構成を有する基材付き両面粘着テープ,商品名「No.5606」,日東電工株式会社製)から切り出した両面粘着シート(幅25mm,長さ25mm)を貼り合わせて、積層体(積層体1)を得た。次に、積層体1における両面粘着シートのセパレーターを剥がし、露出した粘着面の中央に、ITOフィルム(ハードコート処理(アンチグレア処理)されたPETフィルム(非蒸着面を有するPETフィルム)/粘着剤層/PETフィルム/ITO層の積層構成を有する透明導電性フィルム,商品名「ELECRYSTA」,日東電工株式会社製)から切り出したITOフィルム(幅15mm,長さ15mm)を、その非蒸着面と前記粘着面とが接する形態で貼りあせて、積層体(積層体2)を得た。次に、測定対象の粘着シート(セパレーター(MRF)/粘着剤層/セパレーター(MRE)の積層構造を有する基材レス両面粘着シート)から切り出した測定サンプル(幅8mm,長さ8mm)におけるセパレーター(MRE)を剥がして粘着面を露出させ、積層体2におけるITOフィルムのITO層表面(蒸着面)の中央に、当該測定サンプルを貼り付けて、積層体(積層体3)を得た。次に、ホール効果測定装置(装置名「HL5500PC」,Accent Optical Technologies社製)を使用して、積層体3のITOフィルムのITO層表面(蒸着面)の四隅を測定点として電気抵抗値を測定した。この電気抵抗値を「R1」とした。電気抵抗値R1の測定後、積層体3を60℃かつ95%RHの条件下に500時間放置し、更に、23℃かつ50%RHの条件下に1時間放置した。放置後の積層体3について、上記と同様にして、電気抵抗値を測定した。測定された電気抵抗値を「R2」とした。そして、電気抵抗値変化率を、下記式より算出した。
放射線照射により硬化するアクリル系粘着剤層を有し、
前記アクリル系粘着剤層は、アクリル系ポリマーおよび多官能アクリルオリゴマーを含み、
硬化後の前記アクリル系粘着剤層の23℃におけるヤング率は500kPa以上10000kPa以下であり、
硬化後の前記アクリル系粘着剤層の粘着力は3.0N/20mm以上である、粘着シート。
(付記2)
硬化前の前記アクリル系粘着剤層の粘着力は3.0N/20mm以上である、付記1に記載の粘着シート。
(付記3)
硬化前の前記アクリル系粘着剤層の23℃におけるヤング率は30kPa以上200kPa以下である、付記1または2に記載の粘着シート。
(付記4)
硬化後の前記アクリル系粘着剤層のゲル分率は70質量%以上である、付記1から3のいずれか一つに記載の粘着シート。
(付記5)
前記アクリル系ポリマーは、その構成モノマー成分として、窒素原子含有モノマーを0.5~30質量%含有する、付記1から4のいずれか一つに記載の粘着シート。
(付記6)
前記アクリル系ポリマーは、その構成モノマー成分として、水酸基含有モノマーを1~30質量%含有する、付記1から5のいずれか一つに記載の粘着シート。
(付記7)
前記アクリル系ポリマーは、その構成モノマー成分として、酸性基含有モノマーを実質的に含有しない、付記1から6のいずれか一つに記載の粘着シート。
(付記8)
前記アクリル系ポリマーの重量平均分子量は40万~200万である、付記1から7のいずれか一つに記載の粘着シート。
(付記9)
前記多官能アクリルオリゴマーは、分子内に二つ以上の(メタ)アクリロイル基を有する、付記1から8のいずれか一つに記載の粘着シート。
(付記10)
前記多官能アクリルオリゴマーは、ポリエステル(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、およびビスフェノールAのEO付加物ジアクリレートからなる群より選択される少なくとも一種である、付記1から9のいずれか一つに記載の粘着シート。
(付記11)
前記多官能アクリルオリゴマーの重量平均分子量は400~10000である、付記1から10のいずれか一つに記載の粘着シート。
(付記12)
前記多官能アクリルオリゴマーは、その単独重合物についてJIS K5600-5-4に従って測定される硬度が4B以上である、付記1から11のいずれか一つに記載の粘着シート。
(付記13)
前記アクリル系粘着剤層は更に光重合開始剤を含む、付記1から12のいずれか一つに記載の粘着シート。
(付記14)
前記アクリル系粘着剤層において、前記多官能アクリルオリゴマーの含有量は、前記アクリル系ポリマー100質量部に対して0.05~40質量部であり、前記光重合開始剤の含有量は、前記アクリル系ポリマー100質量部に対して0.05~5質量部である、付記13に記載の粘着シート。
(付記15)
前記アクリル系粘着剤層は、前記アクリル系ポリマー100質量部に対して0.05~5質量部の架橋剤を更に含む、付記1から14のいずれか一つに記載の粘着シート。
(付記16)
前記アクリル系粘着剤層は、前記アクリル系ポリマー100質量部に対して0.01~1質量部のシランカップリング剤を更に含む、付記1から15のいずれか一つに記載の粘着シート。
Claims (16)
- 放射線照射により硬化するアクリル系粘着剤層を有し、
前記アクリル系粘着剤層は、アクリル系ポリマーおよび多官能アクリルオリゴマーを含み、
硬化後の前記アクリル系粘着剤層の23℃におけるヤング率は500kPa以上10000kPa以下であり、
硬化後の前記アクリル系粘着剤層の粘着力は3.0N/20mm以上である、粘着シート。 - 硬化前の前記アクリル系粘着剤層の粘着力は3.0N/20mm以上である、請求項1に記載の粘着シート。
- 硬化前の前記アクリル系粘着剤層の23℃におけるヤング率は30kPa以上200kPa以下である、請求項1または2に記載の粘着シート。
- 硬化後の前記アクリル系粘着剤層のゲル分率は70質量%以上である、請求項1から3のいずれか一つに記載の粘着シート。
- 前記アクリル系ポリマーは、その構成モノマー成分として、窒素原子含有モノマーを0.5~30質量%含有する、請求項1から4のいずれか一つに記載の粘着シート。
- 前記アクリル系ポリマーは、その構成モノマー成分として、水酸基含有モノマーを1~30質量%含有する、請求項1から5のいずれか一つに記載の粘着シート。
- 前記アクリル系ポリマーは、その構成モノマー成分として、酸性基含有モノマーを実質的に含有しない、請求項1から6のいずれか一つに記載の粘着シート。
- 前記アクリル系ポリマーの重量平均分子量は40万~200万である、請求項1から7のいずれか一つに記載の粘着シート。
- 前記多官能アクリルオリゴマーは、分子内に二つ以上の(メタ)アクリロイル基を有する、請求項1から8のいずれか一つに記載の粘着シート。
- 前記多官能アクリルオリゴマーは、ポリエステル(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、およびビスフェノールAのEO付加物ジアクリレートからなる群より選択される少なくとも一種である、請求項1から9のいずれか一つに記載の粘着シート。
- 前記多官能アクリルオリゴマーの重量平均分子量は400~10000である、請求項1から10のいずれか一つに記載の粘着シート。
- 前記多官能アクリルオリゴマーは、その単独重合物についてJIS K5600-5-4に従って測定される硬度が4B以上である、請求項1から11のいずれか一つに記載の粘着シート。
- 前記アクリル系粘着剤層は更に光重合開始剤を含む、請求項1から12のいずれか一つに記載の粘着シート。
- 前記アクリル系粘着剤層において、前記多官能アクリルオリゴマーの含有量は、前記アクリル系ポリマー100質量部に対して0.05~40質量部であり、前記光重合開始剤の含有量は、前記アクリル系ポリマー100質量部に対して0.05~5質量部である、請求項13に記載の粘着シート。
- 前記アクリル系粘着剤層は、前記アクリル系ポリマー100質量部に対して0.05~5質量部の架橋剤を更に含む、請求項1から14のいずれか一つに記載の粘着シート。
- 前記アクリル系粘着剤層は、前記アクリル系ポリマー100質量部に対して0.01~1質量部のシランカップリング剤を更に含む、請求項1から15のいずれか一つに記載の粘着シート。
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WO2016167133A1 (ja) * | 2015-04-13 | 2016-10-20 | 日東電工株式会社 | 粘着シートおよび接合体製造方法 |
JP2020151926A (ja) * | 2019-03-19 | 2020-09-24 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
JP2020152797A (ja) * | 2019-03-19 | 2020-09-24 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
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JP2020152798A (ja) * | 2019-03-19 | 2020-09-24 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
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CN114231205A (zh) * | 2021-12-31 | 2022-03-25 | 深圳市云启科技有限公司 | 一种耐热uv减粘胶带 |
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WO2022113410A1 (ja) * | 2020-11-24 | 2022-06-02 | 日東電工株式会社 | 樹脂シート、樹脂シート積層体、フレキシブル積層体、および、フレキシブルデバイス |
CN114231205A (zh) * | 2021-12-31 | 2022-03-25 | 深圳市云启科技有限公司 | 一种耐热uv减粘胶带 |
CN114231205B (zh) * | 2021-12-31 | 2023-09-19 | 深圳市云启科技有限公司 | 一种耐热uv减粘胶带 |
CN114574112B (zh) * | 2022-03-24 | 2024-02-13 | 苏州高泰电子技术股份有限公司 | 亚克力可uv增韧组合物、胶膜以及胶带 |
CN114574112A (zh) * | 2022-03-24 | 2022-06-03 | 苏州高泰电子技术股份有限公司 | 亚克力可uv增韧组合物、胶膜以及胶带 |
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