WO2015151209A1 - 粘着剤および粘着シート - Google Patents
粘着剤および粘着シート Download PDFInfo
- Publication number
- WO2015151209A1 WO2015151209A1 PCT/JP2014/059583 JP2014059583W WO2015151209A1 WO 2015151209 A1 WO2015151209 A1 WO 2015151209A1 JP 2014059583 W JP2014059583 W JP 2014059583W WO 2015151209 A1 WO2015151209 A1 WO 2015151209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- acid ester
- acrylic acid
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Definitions
- the present invention relates to an adhesive and an adhesive sheet that can be used for a touch panel or the like.
- Various mobile electronic devices such as mobile phones and tablet terminals in recent years include a display using a display module having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, and the like. Is increasingly becoming a touch panel.
- a display module having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, and the like.
- a protective panel is usually provided on the surface side of the display module.
- the protective panel has been changed from a conventional glass plate to a plastic plate such as an acrylic plate or a polycarbonate plate.
- a gap is provided between the protective panel and the display module so that the deformed protective panel does not hit the display module even when the protective panel is deformed by an external force.
- a frame-like printed layer may exist as a step on the display module side of the protective panel. If the pressure-sensitive adhesive layer does not follow the step, the pressure-sensitive adhesive layer floats in the vicinity of the step, thereby causing light reflection loss. For this reason, the pressure-sensitive adhesive layer is required to have a step following ability.
- Patent Document 1 discloses that the shear storage elastic modulus (G ′) at 25 ° C. and 1 Hz is 1.0 as an adhesive layer that fills the gap between the protective panel and the display module.
- ⁇ is at 10 5 Pa or less
- a gel fraction discloses a pressure-sensitive adhesive layer is 40% or more.
- Patent Document 1 an attempt is made to improve the step following property by lowering the storage elastic modulus at normal temperature in the pressure-sensitive adhesive layer.
- the storage elastic modulus at normal temperature is lowered as described above, the storage elastic modulus at high temperature is unnecessarily lowered, causing a problem under durability conditions.
- bubbles may be generated near the step, or outgas may be generated from the plastic plate, which is a protective panel, and blisters such as bubbles, floats, and peeling may occur.
- the pressure-sensitive adhesive layer is hardened in order to improve the blister resistance, the step following ability is lowered.
- the present invention has been made in view of the above-described actual situation, and an object thereof is to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that are excellent in both blister resistance and level difference followability.
- the present invention comprises (meth) acrylic acid ester polymer (A) containing 8 to 30% by mass of a monomer having a reactive functional group as a monomer unit constituting the polymer. And an adhesive composition containing an abietic acid ester-based tackifying liquid (B), wherein the adhesive has a gel fraction of 30 to 95%.
- A acrylic acid ester polymer
- B an adhesive composition containing an abietic acid ester-based tackifying liquid (B), wherein the adhesive has a gel fraction of 30 to 95%.
- invention 1 the wettability improvement effect by an abietic acid ester-type tackifying liquid (B), the reactive functional group of an (meth) acrylic acid ester polymer (A), and an abietic acid ester-type tackifying Due to the interaction of the ionic liquid (B), the adhesiveness of the adhesive to the adherend is improved and the blister resistance is excellent.
- the pressure-sensitive adhesive does not need to be hardened to improve blister resistance, and the gel fraction is within the above range, so that the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is excellent in step following ability. .
- the said (meth) acrylic acid ester polymer (A) contains the hard monomer whose glass transition temperature as a homopolymer is 70 degreeC or more as a monomer unit which comprises the said polymer. Is preferred (Invention 2).
- the (meth) acrylic acid ester polymer (A) preferably contains 2-ethylhexyl (meth) acrylate as a monomer unit constituting the polymer (Invention). 3).
- the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 200,000 to 1,200,000 (Invention 4).
- the adhesive composition preferably further contains a crosslinking agent (C) (Invention 5).
- the present invention includes two release sheets and an adhesive layer sandwiched between the release sheets so as to be in contact with the release surfaces of the two release sheets, and the adhesive layer is the adhesive.
- a pressure-sensitive adhesive sheet comprising (Inventions 1 to 5) is provided (Invention 6).
- the said adhesive layer is arrange
- the pressure-sensitive adhesive and pressure-sensitive adhesive sheet according to the present invention are excellent in both blister resistance and step following ability.
- the pressure-sensitive adhesive comprises a (meth) acrylic acid ester polymer containing 8 to 30% by mass of a monomer having a reactive functional group (reactive functional group-containing monomer) as a monomer unit constituting the polymer (A pressure-sensitive adhesive obtained by crosslinking a pressure-sensitive adhesive composition containing A) and an abietic acid ester-based tackifying liquid (B) (hereinafter sometimes referred to as “pressure-sensitive adhesive composition P”), The fraction is 30-95%.
- the adhesive composition P preferably further contains a crosslinking agent (C).
- (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester.
- polymer includes the concept of “copolymer”.
- the abietic acid ester-based tackifying liquid (B) is liquid at room temperature.
- the pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition P containing the abietic acid ester-based tackifying liquid (B) has improved wettability and improved adhesion to the adherend.
- the (meth) acrylic acid ester polymer (A) contains a relatively large amount of the reactive functional group-containing monomer as a monomer unit constituting the polymer as described above, so that the reactive functional group and abietin Interaction with the acid ester-based tackifying liquid (B) occurs, and the adhesion to the adherend is further improved. Thereby, the adhesive layer which consists of the said adhesive becomes the thing excellent in blister resistance.
- the pressure-sensitive adhesive does not need to be hardened to improve blister resistance, and the gel fraction is within the above range, so that the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is excellent in step following ability. .
- the pressure-sensitive adhesive according to the present embodiment it is possible to achieve both the blister resistance and the step following ability that are normally in a trade-off relationship.
- the pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive when applied to the surface on the side where the level difference of the plastic plate is present, the pressure-sensitive adhesive layer follows the level difference, so there are no floating or bubbles in the vicinity of the level difference. It will be a thing.
- generation of bubbles or the like in the vicinity of the step is suppressed, and even if outgas is generated from the plastic plate, bubbles, floats, Generation
- the reactive functional group-containing monomer contained in the (meth) acrylic acid ester polymer (A) as a monomer unit constituting the polymer includes a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer) and a carboxyl in the molecule.
- Preferred examples include a monomer having a group (carboxyl group-containing monomer) and a monomer having an amino group in the molecule (amino group-containing monomer).
- a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable, and a hydroxyl group-containing monomer is particularly preferable.
- the resulting adhesive has more excellent blister resistance. It becomes.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth And (meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate.
- 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of the reactivity of the resulting (meth) acrylic acid ester polymer (A) with the crosslinking agent (C) of the hydroxyl group and the copolymerizability with other monomers. Is preferred. These may be used alone or in combination of two or more.
- carboxyl group-containing monomer examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
- carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
- acrylic acid is preferred from the viewpoint of the reactivity of the resulting (meth) acrylic acid ester polymer (A) with the crosslinking agent (C) of the carboxyl group and the copolymerizability with other monomers.
- acrylic acid is preferred from the viewpoint of the reactivity of the resulting (meth) acrylic acid ester polymer (A) with the crosslinking agent (C) of the carboxyl group and the copolymerizability with other monomers.
- amino group-containing monomer examples include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
- the (meth) acrylic acid ester polymer (A) contains 8 to 30% by mass of a reactive functional group-containing monomer as a monomer unit constituting the polymer.
- a reactive functional group-containing monomer is less than 8% by mass, the interaction with the abietic acid ester-based tackifying liquid (B) hardly occurs, and the resulting pressure-sensitive adhesive is inferior in blister resistance.
- the content of the reactive functional group-containing monomer exceeds 30% by mass, desired tackiness cannot be obtained.
- the (meth) acrylic acid ester polymer (A) contains a hydroxyl group-containing monomer as a reactive functional group-containing monomer constituting the polymer
- its content is preferably 10 to 25% by mass, In particular, the content is preferably 15 to 20% by mass.
- the content thereof is 8 to 25% by mass. It is particularly preferable that the content is 10 to 15% by mass.
- the reactive functional group is usually a hydrophilic group, and when such a hydrophilic group is present in the pressure-sensitive adhesive layer in a predetermined amount, even when the pressure-sensitive adhesive layer is placed under high-temperature and high-humidity conditions, The compatibility with the moisture that has entered the pressure-sensitive adhesive layer below is good, and as a result, whitening of the pressure-sensitive adhesive layer is suppressed, and the pressure-sensitive adhesive layer is excellent in resistance to moist heat whitening.
- the (meth) acrylic acid ester polymer (A) preferably contains a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a monomer unit constituting the polymer.
- the obtained adhesive can express preferable adhesiveness.
- the below-mentioned hard monomer is removed from the (meth) acrylic acid alkyl ester.
- alkyl ester having 1 to 20 carbon atoms in the alkyl group examples include methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, ( N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate , Myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
- (meth) acrylic acid esters having an alkyl group having 1 to 8 carbon atoms are preferred, and n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferred. More preferred is 2-ethylhexyl (meth) acrylate. According to 2-ethylhexyl (meth) acrylate, the dielectric constant of the obtained adhesive can be lowered, and the response accuracy of the touch panel can be improved. In addition, these may be used independently and may be used in combination of 2 or more type.
- the (meth) acrylic acid ester polymer (A) contains 30 to 90% by mass of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms as a monomer unit constituting the polymer.
- the content is preferably 40 to 75% by mass, more preferably 50 to 65% by mass.
- the (meth) acrylic acid ester polymer (A) preferably contains a hard monomer having a glass transition temperature (Tg) of 70 ° C. or more as a homopolymer as a monomer unit constituting the polymer.
- Tg glass transition temperature
- the glass transition temperature (Tg) of the hard monomer as a homopolymer is preferably 75 to 200 ° C., particularly preferably 80 to 180 ° C.
- Examples of the hard monomer include methyl methacrylate (Tg 105 ° C.), isobornyl acrylate (Tg 94 ° C.), isobornyl methacrylate (Tg 180 ° C.), acryloylmorpholine (Tg 145 ° C.), adamantyl acrylate (Tg 115 ° C.), and adamantyl methacrylate. (Tg 141 ° C.), dimethylacrylamide (Tg 89 ° C.), acrylamide (Tg 165 ° C.) and the like. These may be used alone or in combination of two or more.
- methyl methacrylate, isobornyl acrylate and acryloyl morpholine are more preferable from the viewpoint of exerting the performance of the hard monomer while preventing adverse effects on other properties such as adhesion and transparency, and methacrylic acid. Methyl is particularly preferred.
- the (meth) acrylic acid ester polymer (A) preferably contains 10 to 45% by mass, and particularly preferably 15 to 30% by mass of the hard monomer as a monomer unit constituting the polymer.
- the hard monomer in an amount of 10% by mass or more, an effect of improving blister resistance by the monomer unit can be expected.
- the hard monomer content is set to 45% by mass or less, the relative shortage of other monomer units in the (meth) acrylic acid ester polymer (A) is prevented, and the pressure-sensitive adhesive obtained The adhesiveness and the step following ability can be made excellent.
- the (meth) acrylic acid ester polymer (A) may contain other monomers as a monomer unit constituting the polymer, if desired.
- the other monomer is preferably a monomer that does not contain a reactive functional group so as not to interfere with the action of the reactive functional group-containing monomer.
- Such other monomers include, for example, (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, and aliphatic rings such as cyclohexyl (meth) acrylate (meta ) Acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, etc. (meth) acrylic acid ester having acetic acid tertiary amino group, acetic acid Examples include vinyl and styrene. These may be used alone or in combination of two or more.
- the polymerization mode of the (meth) acrylic acid ester polymer (A) may be a random copolymer or a block copolymer.
- the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 200,000 to 1,200,000, particularly preferably 300,000 to 900,000, and more preferably 400,000 to 700,000. .
- the weight average molecular weight in this specification is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is within a relatively low range as described above, a pressure-sensitive adhesive excellent in both blister resistance and step followability can be obtained.
- the weight average molecular weight of the (meth) acrylate polymer (A) is less than 200,000, the blister resistance may be deteriorated, and the weight average molecular weight of the (meth) acrylate polymer (A) is 1,200,000. If it exceeds, step following ability may be deteriorated.
- the (meth) acrylic acid ester polymer (A) may be used alone or in combination of two or more.
- the abietic acid ester-based tackifying liquid (B) in the present embodiment is an abietic acid ester having a melting point of 20 ° C. or lower.
- the abietic acid ester-based tackifying liquid (B) becomes a liquid at room temperature and is based on the above-described wettability improving action and interaction with the reactive functional group of the (meth) acrylic acid ester polymer (A). Adhesion improvement effect is produced and excellent blister resistance is achieved.
- the melting point of the abietic acid ester-based tackifying liquid (B) is preferably 0 ° C. or lower.
- abietic acid ester-based tackifying liquid (B) having the above melting point for example, “Pine Crystal ME-G” (trade name) manufactured by Arakawa Chemical Industries, Ltd. can be used.
- 1 type may be used independently for an abietic acid ester-type tackifying liquid (B), and it may be used in combination of 2 or more type.
- the content of the abietic acid ester tackifying liquid (B) in the adhesive composition P is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). In particular, the amount is preferably 7 to 20 parts by mass, and more preferably 10 to 15 parts by mass.
- the content of the abietic acid ester-based tackifying liquid (B) is 5 parts by mass or more, the above-described adhesion improving effect is exhibited, and the resulting adhesive has excellent blister resistance.
- the content of the abietic acid ester-based tackifying liquid (B) is 25 parts by mass or less, the cohesive force of the obtained adhesive becomes preferable, and the obtained adhesive has durability. .
- the adhesive composition P preferably further contains a crosslinking agent (C).
- the crosslinking agent (C) reacts with the reactive functional group of the (meth) acrylic acid ester polymer (A).
- the (meth) acrylic acid ester polymer (A) is cross-linked by the cross-linking agent (C), and the resulting pressure-sensitive adhesive has improved cohesive force and is more excellent in blister resistance.
- the crosslinking agent (C) may be any one that reacts with the reactive functional group of the (meth) acrylic acid ester polymer (A).
- an isocyanate crosslinking agent for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, and an amine crosslinking agent.
- Melamine crosslinking agent aziridine crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline crosslinking agent, metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, ammonium salt crosslinking agent, etc. Is mentioned.
- the reactive functional group of the (meth) acrylic acid ester polymer (A) is a hydroxyl group
- an isocyanate-based crosslinking agent that is excellent in reactivity with the hydroxyl group
- (meth) acrylic acid when the reactive functional group which the ester polymer (A) has is a carboxyl group, it is preferable to use an epoxy-based crosslinking agent having excellent reactivity with the carboxyl group.
- a crosslinking agent (C) can be used individually by 1 type or in combination of 2 or more types.
- the isocyanate-based crosslinking agent contains at least a polyisocyanate compound.
- the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, etc.
- biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
- low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
- trimethylolpropane-modified aromatic polyisocyanate particularly trimethylolpropane-modified tolylene diisocyanate and trimethylolpropane-modified xylylene diisocyanate are preferable from the viewpoint of reactivity with hydroxyl groups.
- epoxy-based crosslinking agent examples include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl.
- examples include ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like.
- the content of the crosslinking agent (C) in the pressure-sensitive adhesive composition P is preferably 0.001 to 10 parts by mass, particularly 0, relative to 100 parts by mass of the (meth) acrylic acid ester polymer (A).
- the amount is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 1 part by mass.
- the blister resistance can be improved without hindering the step following ability of the obtained pressure-sensitive adhesive.
- additives usually used for acrylic pressure-sensitive adhesives such as silane coupling agents, refractive index adjusters, antistatic agents, tackifiers, Antioxidants, ultraviolet absorbers, light stabilizers, softeners, fillers, and the like can be added.
- the (meth) acrylic acid ester polymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by an ordinary radical polymerization method.
- the polymerization of the (meth) acrylic acid ester polymer (A) can be performed by a solution polymerization method or the like using a polymerization initiator as desired.
- the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like, and two or more kinds may be used in combination.
- Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more kinds may be used in combination.
- Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
- organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
- organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
- examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
- the weight average molecular weight of the resulting polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
- the solution of the (meth) acrylic acid ester polymer (A) is added to the abietic acid ester-based tackifying liquid (B) and optionally a crosslinking agent (C).
- the adhesive composition P (coating solution) diluted with the solvent is obtained by adding the additive and the diluting solvent and mixing them well.
- the dilution solvent examples include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolve solvents such as ethyl cellosolve and the like are used.
- aliphatic hydrocarbons such as hexane, heptane, and cyclohexane
- aromatic hydrocarbons such as toluene and xylene
- halogenated hydrocarbons such as methylene chloride and
- the concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, dilution is performed so that the concentration of the adhesive composition P is 10 to 60% by mass.
- a dilution solvent etc. is not a necessary condition, and if a viscosity etc. which can be coated with the adhesive composition P are not necessary, a dilution solvent does not need to be added.
- the adhesive composition P becomes a coating solution using the polymerization solvent of the (meth) acrylic acid ester polymer (A) as a dilution solvent.
- the pressure-sensitive adhesive according to this embodiment is obtained by crosslinking the pressure-sensitive adhesive composition P.
- the crosslinking of the pressure-sensitive adhesive composition P can be usually performed by heat treatment.
- this heat processing can also serve as the drying process at the time of volatilizing the dilution solvent of the adhesive composition P, etc.
- the heating temperature is preferably 50 to 150 ° C., particularly preferably 70 to 120 ° C.
- the heating time is preferably 30 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes.
- a curing period of about 1 to 2 weeks may be provided at normal temperature (for example, 23 ° C., 50% RH).
- the (meth) acrylic acid ester polymer (A) is sufficiently crosslinked and can exhibit excellent blister resistance.
- the gel fraction of the pressure-sensitive adhesive according to this embodiment is 30 to 95%, preferably 40 to 80%, and particularly preferably 45 to 70%.
- the gel fraction is less than 30%, the cohesive force of the pressure-sensitive adhesive is insufficient and blister resistance is lowered.
- the gel fraction exceeds 95%, the adhesive strength becomes too low and the durability is lowered or the step following performance is lowered.
- the measuring method of a gel fraction is as showing to the test example mentioned later.
- the pressure-sensitive adhesive sheet 1 As shown in FIG. 1, the pressure-sensitive adhesive sheet 1 according to this embodiment includes two release sheets 12a and 12b and the two release sheets 12a so as to be in contact with the release surfaces of the two release sheets 12a and 12b. , 12b and an adhesive layer 11 sandwiched between the two layers.
- the release surface of the release sheet in this specification refers to a surface having peelability in the release sheet, and includes both a surface that has been subjected to a release treatment and a surface that exhibits peelability without being subjected to a release treatment. .
- Adhesive layer 11 is comprised from the adhesive mentioned above, ie, it is comprised from the adhesive formed by bridge
- the thickness of the pressure-sensitive adhesive layer 11 is preferably 10 to 400 ⁇ m, more preferably 20 to 300 ⁇ m, even more depending on the height of the step. It is preferable that the thickness be ⁇ 250 ⁇ m. When the thickness of the pressure-sensitive adhesive layer 11 is 10 ⁇ m or more, good step followability is exhibited, and when the thickness of the pressure-sensitive adhesive layer 11 is 400 ⁇ m or less, workability is improved.
- the pressure-sensitive adhesive layer 11 may be formed as a single layer or may be formed by laminating a plurality of layers.
- the release sheets 12a and 12b are not particularly limited, and known plastic films can be used.
- plastic films polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene acetate
- a vinyl film, an ionomer resin film, an ethylene / (meth) acrylic acid copolymer film, an ethylene / (meth) acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, or the like is used.
- These crosslinked films are also used.
- these laminated films may be sufficient.
- the release surface of the release sheets 12a and 12b (particularly the surface in contact with the pressure-sensitive adhesive layer 11) is preferably subjected to a release treatment.
- the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
- one release sheet is preferably a heavy release release sheet having a high release force
- the other release sheet is preferably a light release release sheet having a low release force.
- the thickness of the release sheets 12a and 12b is not particularly limited, but is usually about 20 to 150 ⁇ m.
- a coating liquid of the above-mentioned pressure-sensitive adhesive composition P is applied to the release surface of one release sheet 12a (or 12b), and heat treatment is performed for adhesion. After cross-linking the composition P and forming a coating layer, the release surface of the other release sheet 12b (or 12a) is overlaid on the coating layer.
- a curing period is required, a curing period is set, and when the curing period is unnecessary, the coating layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained.
- the conditions for the heat treatment and curing are as described above.
- a coating liquid of the above-mentioned pressure-sensitive adhesive composition P is applied to the release surface of one release sheet 12 a, a heat treatment is performed to cross-link the pressure-sensitive adhesive composition P, and a coating layer To obtain a release sheet 12a with a coating layer.
- the coating liquid of the said adhesive composition P is apply
- a release sheet 12b is obtained. And the peeling sheet 12a with an application layer and the peeling sheet 12b with an application layer are bonded together so that both application layers may mutually contact.
- the curing period is necessary, the curing period is set, and when the curing period is unnecessary, the above-mentioned laminated application layer becomes the pressure-sensitive adhesive layer 11 as it is. Thereby, the said adhesive sheet 1 is obtained. According to this production example, even when the pressure-sensitive adhesive layer 11 is thick, it can be stably produced.
- a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
- the pressure-sensitive adhesive layer 11 in the present embodiment preferably has a haze value (measured according to JIS K7136: 2000) of 3% or less, particularly preferably 2% or less. Further, it is preferably 1% or less. When the haze value is 3% or less, the transparency is very high, which is suitable for optical applications.
- the pressure-sensitive adhesive layer 11 in the present embodiment preferably has a total light transmittance (value measured according to JIS K7105: 1981) of 90% or more, particularly 95% or more. It is preferable that it is 98% or more. When the total light transmittance is 98% or more, the transparency is very high and it is suitable for optical use.
- the touch panel 2 includes a display module 3, a first film sensor 5 a laminated thereon via an adhesive layer 4 a, and a second film sensor 5 b laminated thereon via an adhesive layer 4 b. And the cover material 6 laminated
- the pressure-sensitive adhesive layer 11 in the touch panel 2 is the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1.
- Examples of the display module 3 include a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper.
- LCD liquid crystal
- LED light emitting diode
- organic EL organic electroluminescence
- the pressure-sensitive adhesive layers 4a and 4b may be formed of the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1, or may be formed of other pressure-sensitive adhesives or pressure-sensitive adhesive sheets.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 4 includes an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, and a polyvinyl ether-based pressure-sensitive adhesive.
- an acrylic pressure-sensitive adhesive is preferable.
- the first film sensor 5a and the second film sensor 5b are each generally composed of a base film 51 and a patterned transparent conductive film 52, respectively. Although it does not specifically limit as the base film 51, For example, a polyethylene terephthalate film, an acrylic film, a polycarbonate film etc. are used.
- Examples of the transparent conductive film 52 include metals such as platinum, gold, silver and copper, oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
- oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide and zinc dioxide, tin-doped indium oxide (ITO), and zinc oxide-doped oxide.
- Examples include composite oxides such as indium, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide, and non-oxidized compounds such as chalcogenide, lanthanum hexaboride, titanium nitride, and titanium carbide. Among these, those made of tin-doped indium oxide (ITO) are preferable.
- One of the transparent conductive film 52 of the first film sensor 5a and the transparent conductive film 52 of the second film sensor 5b normally constitutes a circuit pattern in the X-axis direction, and the other constitutes a circuit pattern in the Y-axis direction. .
- the transparent conductive film 52 of the second film sensor 5b in the present embodiment is located above the second film sensor 5b in FIG. 2, but is not limited to this, and the second film sensor It may be located below 5a. Moreover, although the transparent conductive film 52 of the 1st film sensor 5a is located in the upper side of the 1st film sensor 5a in FIG. 2, it is not limited to this, The 1st film sensor 5a It may be located on the lower side.
- the cover material 6 is mainly composed of a glass plate or a plastic plate.
- the glass plate is not particularly limited. For example, chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass. Etc.
- the plastic plate is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate and the like, and a polycarbonate plate.
- a functional layer such as a hard coat layer, an antireflection layer, or an antiglare layer may be provided on one side or both sides of the glass plate or plastic plate, or a hard coat film, an antireflection film, or an antiglare film.
- Such optical members may be laminated.
- the cover material 6 has a step on the surface on the pressure-sensitive adhesive layer 11 side, and specifically has a step due to the presence or absence of the printing layer 7.
- the print layer 7 is generally formed in a frame shape on the pressure-sensitive adhesive layer 11 side of the cover material 6.
- the material constituting the printing layer 7 is not particularly limited, and a known material for printing is used.
- the thickness of the printing layer 7, that is, the height of the step, is preferably 3 to 45 ⁇ m, more preferably 5 to 35 ⁇ m, particularly preferably 7 to 25 ⁇ m, and preferably 7 to 15 ⁇ m. Further preferred.
- the thickness (height of the step) of the printing layer 7 is preferably 3 to 30% of the thickness of the pressure-sensitive adhesive layer 11, particularly preferably 3.2 to 20%, and more preferably 3 It is preferably 5 to 15%.
- the pressure-sensitive adhesive layer 11 can easily follow the step formed by the printing layer 7, and the occurrence of floating or bubbles in the vicinity of the step is suppressed.
- One release sheet 12a is peeled from the pressure-sensitive adhesive sheet 1, and the exposed pressure-sensitive adhesive layer 11 is bonded to the second film sensor 5b so as to be in contact with the patterned transparent conductive film 52 of the second film sensor 5b.
- the pressure-sensitive adhesive layer 4b provided on the release sheet is bonded to the first film sensor 5a so as to be in contact with the patterned transparent conductive film 52 of the first film sensor 5a.
- the release film remaining on the pressure-sensitive adhesive layer 4b is peeled off, and the exposed pressure-sensitive adhesive layer 4b is opposite to the surface on which the pressure-sensitive adhesive layer 11 is laminated in the second film sensor 5b (second surface). Both are bonded so that it may touch the exposed surface of the base film 51 of the film sensor 5b. Thereby, the laminated body by which the peeling sheet 12b, the adhesive layer 11, the 2nd film sensor 5b, the adhesive layer 4b, and the 1st film sensor 5a are laminated
- the pressure-sensitive adhesive layer 4a provided on the release sheet is bonded to the surface of the laminate on the first film sensor 5a side (exposed surface of the base film 51 of the first film sensor 5a).
- the other release sheet 12b is peeled from the laminate, and the cover material 6 is pasted so that the printed layer 7 side of the cover material 6 contacts the pressure-sensitive adhesive layer 11 with respect to the exposed pressure-sensitive adhesive layer 11. Match.
- the release sheet is peeled from the structure, and the structure is bonded to the display module 3 so that the exposed adhesive layer 4a is in contact with the display module 3. Thereby, the touch panel 2 shown in FIG. 2 is manufactured.
- the pressure-sensitive adhesive layer 11 and the cover material 6 are bonded in the above process, since the pressure-sensitive adhesive layer 11 is excellent in step following ability, it is difficult to form a gap between the step formed by the printing layer 7 and the pressure-sensitive adhesive layer 11.
- the agent layer 11 can fill the step. Further, even when the touch panel 2 is placed under a high temperature and high humidity condition, it is possible to prevent bubbles, floats, peeling, and the like from occurring near the step.
- the cover material 6 is a plastic plate
- the pressure-sensitive adhesive layer 11 is excellent in blister resistance, and thus blisters such as bubbles, floats, and peeling. Is suppressed from occurring.
- the pressure-sensitive adhesive layer 11 is excellent in moisture and heat whitening resistance, whitening when the touch panel 2 returns to room temperature after being placed in a high temperature and high humidity condition is suppressed.
- one of the release sheets 12a and 12b in the pressure-sensitive adhesive sheet 1 may be omitted.
- Example 1 Preparation of (meth) acrylic acid ester polymer 60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized to give a (meth) acrylic acid ester polymer ( A) was prepared. When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method described later, it was a weight average molecular weight (Mw) of 600,000.
- Adhesive Composition 100 parts by mass of the (meth) acrylic acid ester polymer (A) obtained in the above step (1) (solid content converted value; the same applies hereinafter) and an abietic acid ester-based tackifying liquid (B ) 10 parts by mass of abietic acid ester compound (made by Arakawa Chemical Co., Ltd., product name “Pine Crystal ME-G”) as (tackifier) and tolylene diisocyanate compound (made by Toyochem Co., Ltd.) as crosslinking agent (C) , Product name “BHS8515”) 0.25 parts by mass, sufficiently stirred, and diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition having a solid content concentration of 36% by mass.
- Table 1 shows the composition of the adhesive composition. Details of the abbreviations and the like described in Table 1 are as follows. [(Meth) acrylic acid ester polymer (A)] 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate BA: n-butyl acrylate AA: acrylic acid MA: methyl acrylate [Crosslinking agent (C)] Isocyanate: Tolylene diisocyanate compound (Toyochem, product name “BHS8515”) Epoxy series: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (product name “TC-5” manufactured by Taisei Kayaku Co., Ltd.)
- the heavy release type release sheet with the coating layer obtained above and the light release type release sheet with the coating layer obtained above were bonded so that both coating layers were in contact with each other.
- a pressure-sensitive adhesive sheet having a structure of heavy release type release sheet / pressure-sensitive adhesive layer (thickness: 50 ⁇ m) / light release type release sheet was produced.
- the thickness of the pressure-sensitive adhesive layer is a value measured using a constant pressure thickness measuring instrument (manufactured by Teclock, product name “PG-02”) in accordance with JIS K7130.
- the above-mentioned weight average molecular weight (Mw) is a polystyrene-reduced weight average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
- GPC measurement device manufactured by Tosoh Corporation, HLC-8020 GPC column (passed in the following order): TSK guard column HXL-H manufactured by Tosoh Corporation TSK gel GMHXL ( ⁇ 2) TSK gel G2000HXL ⁇ Measurement solvent: Tetrahydrofuran ⁇ Measurement temperature: 40 ° C.
- the pressure-sensitive adhesive wrapped in the polyester mesh was immersed in ethyl acetate at room temperature (23 ° C.) for 24 hours. Thereafter, the pressure-sensitive adhesive was taken out, air-dried for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and further dried in an oven at 80 ° C. for 12 hours. After drying, the mass was weighed with a precision balance, and the mass of the pressure sensitive adhesive alone was calculated by subtracting the mass of the mesh alone. The mass at this time is M2. The gel fraction (%) is represented by (M2 / M1) ⁇ 100. The results are shown in Table 2.
- Test Example 2 (Blister resistance evaluation) Polyethylene terephthalate film (manufactured by Oike Kogyo Co., Ltd., ITO film, thickness) provided with a transparent conductive film made of tin-doped indium oxide (ITO) on one side of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples 125 ⁇ m) transparent conductive film and an acrylic plate made of polymethyl methacrylate (PMMA) (Mitsubishi Gas Chemical Co., Ltd., Iupilon sheet MR200, thickness: 1 mm) to obtain a laminate.
- ITO tin-doped indium oxide
- the obtained laminate was autoclaved for 30 minutes at 50 ° C. and 0.5 MPa, and then allowed to stand at normal pressure, 23 ° C. and 50% RH for 24 hours. Subsequently, it was stored for 72 hours under 85 ° C. and 85% RH durability conditions. Thereafter, it was visually confirmed whether or not the pressure-sensitive adhesive layer had bubbles, floating or peeling, and blister resistance was evaluated according to the following criteria. The results are shown in Table 2. A: There were no bubbles, no floating, and no peeling. ⁇ : Only bubbles with a diameter of 0.1 mm or less were generated. X: Bubbles with a diameter of more than 0.1 mm, floating or peeling occurred.
- a stepped glass plate having a thickness of any one of 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, and 20 ⁇ m was produced.
- the light release type release sheet was peeled off from the pressure sensitive adhesive sheets obtained in Examples and Comparative Examples, and the exposed pressure sensitive adhesive layer was easily made of a polyethylene terephthalate film (PET A4300, thickness: 100 ⁇ m) having an easy adhesion layer. Bonded to the adhesive layer. Next, the heavy release type release sheet was peeled off to expose the pressure-sensitive adhesive layer. Then, using a laminator (product name “LPD3214”, manufactured by Fuji Plastics Co., Ltd.), the laminate is laminated on each stepped glass plate so that the adhesive layer covers the entire frame-like print, and this is used as an evaluation sample. did.
- PET A4300 polyethylene terephthalate film
- step following property was evaluated as a step following rate (%) according to the following criteria. The results are shown in Table 2.
- Step follow-up rate (%) ⁇ (height of printing step filled without gaps or bubbles ( ⁇ m)) / (thickness of adhesive layer: 50 ⁇ m) ⁇ ⁇ 100
- the pressure-sensitive adhesive sheets obtained in the examples were excellent in both step following ability and blister resistance, and had good optical properties.
- the pressure-sensitive adhesive and pressure-sensitive adhesive sheet according to the present invention can be suitably used for bonding, for example, a display module in a touch panel and a cover material having a step, particularly a plastic plate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
〔粘着剤〕
本実施形態に係る粘着剤は、重合体を構成するモノマー単位として、反応性官能基を有するモノマー(反応性官能基含有モノマー)を8~30質量%含有する(メタ)アクリル酸エステル重合体(A)と、アビエチン酸エステル系粘着付与性液体(B)とを含有する粘着性組成物(以下「粘着性組成物P」という場合がある。)を架橋してなる粘着剤であって、ゲル分率が30~95%であるものである。粘着性組成物Pは、さらに架橋剤(C)を含有することが好ましい。
(メタ)アクリル酸エステル重合体(A)が、当該重合体を構成するモノマー単位として含有する反応性官能基含有モノマーとしては、分子内に水酸基を有するモノマー(水酸基含有モノマー)、分子内にカルボキシル基を有するモノマー(カルボキシル基含有モノマー)、分子内にアミノ基を有するモノマー(アミノ基含有モノマー)などが好ましく挙げられる。これらの中でも、水酸基含有モノマーおよびカルボキシル基含有モノマーが好ましく、特に水酸基含有モノマーが好ましい。水酸基含有モノマーを使用することにより、特に、水酸基含有モノマーと、後述する架橋剤(C)としてイソシアネート系架橋剤とを組み合わせて使用することにより、得られる粘着剤の耐ブリスター性がより優れたものとなる。
本実施形態におけるアビエチン酸エステル系粘着付与性液体(B)とは、融点が20℃以下であるアビエチン酸エステルである。これにより、アビエチン酸エステル系粘着付与性液体(B)は常温で液体となり、前述した濡れ性向上の作用および(メタ)アクリル酸エステル重合体(A)の反応性官能基との相互作用に基づく密着性向上効果が奏され、優れた耐ブリスター性が達成される。かかる観点から、アビエチン酸エステル系粘着付与性液体(B)の融点は、0℃以下であることが好ましい。
粘着性組成物Pは、さらに架橋剤(C)を含有することが好ましい。粘着性組成物Pを加熱等すると、架橋剤(C)は、(メタ)アクリル酸エステル重合体(A)の反応性官能基と反応する。これにより、架橋剤(C)によって(メタ)アクリル酸エステル重合体(A)が架橋され、得られる粘着剤は凝集力が向上し、耐ブリスター性により優れたものとなる。
粘着性組成物Pには、所望により、アクリル系粘着剤に通常使用されている各種添加剤、例えばシランカップリング剤、屈折率調整剤、帯電防止剤、粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、軟化剤、充填剤などを添加することができる。
粘着性組成物Pは、(メタ)アクリル酸エステル重合体(A)を製造し、得られた(メタ)アクリル酸エステル重合体(A)に、アビエチン酸エステル系粘着付与性液体(B)、ならびに所望により架橋剤(C)および添加剤を加えることで製造することができる。
本実施形態に係る粘着剤は、粘着性組成物Pを架橋してなるものである。粘着性組成物Pの架橋は、通常は加熱処理により行うことができる。なお、この加熱処理は、粘着性組成物Pの希釈溶剤等を揮発させる際の乾燥処理で兼ねることもできる。
本実施形態に係る粘着剤のゲル分率は、30~95%であり、好ましくは40~80%であり、特に好ましくは45~70%である。ゲル分率が30%未満であると、粘着剤の凝集力が不足して、耐ブリスター性が低下する。一方、ゲル分率が95%を超えると、粘着力が低くなり過ぎて耐久性が低下したり、段差追従性能が低下する。なお、ゲル分率の測定方法は後述する試験例に示す通りである。
図1に示すように、本実施形態に係る粘着シート1は、2枚の剥離シート12a,12bと、それら2枚の剥離シート12a,12bの剥離面と接するように当該2枚の剥離シート12a,12bに挟持された粘着剤層11とから構成される。なお、本明細書における剥離シートの剥離面とは、剥離シートにおいて剥離性を有する面をいい、剥離処理を施した面および剥離処理を施さなくても剥離性を示す面のいずれをも含むものである。
粘着剤層11は、前述した粘着剤から構成され、すなわち、粘着性組成物Pを架橋してなる粘着剤から構成される。
剥離シート12a,12bとしては、特に限定されることはなく、公知のプラスチックフィルムを用いることができる。例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニルフィルム、アイオノマー樹脂フィルム、エチレン・(メタ)アクリル酸共重合体フィルム、エチレン・(メタ)アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルム等が用いられる。また、これらの架橋フィルムも用いられる。さらに、これらの積層フィルムであってもよい。
粘着シート1の一製造例としては、一方の剥離シート12a(または12b)の剥離面に、上記粘着性組成物Pの塗布液を塗布し、加熱処理を行って粘着性組成物Pを架橋し、塗布層を形成した後、その塗布層に他方の剥離シート12b(または12a)の剥離面を重ね合わせる。養生期間が必要な場合は養生期間をおくことにより、養生期間が不要な場合はそのまま、上記塗布層が粘着剤層11となる。これにより、上記粘着シート1が得られる。加熱処理および養生の条件については、前述した通りである。
本実施形態における粘着剤層11は、ヘイズ値(JIS K7136:2000に準じて測定した値)が、3%以下であることが好ましく、特に2%以下であることが好ましく、さらには1%以下であることが好ましい。ヘイズ値が3%以下であると、透明性が非常に高く、光学用途として好適なものとなる。
本実施形態における粘着剤層11は、全光線透過率(JIS K7105:1981に準じて測定した値)が、90%以上であることが好ましく、特に95%以上であることが好ましく、さらには98%以上であることが好ましい。全光線透過率が98%以上であると、透明性が非常に高く、光学用途として好適なものとなる。
上記粘着シート1を使用することにより、例えば、図2に示す静電容量方式のタッチパネル2を製造することができる。タッチパネル2は、表示体モジュール3と、その上に粘着剤層4aを介して積層された第1のフィルムセンサー5aと、その上に粘着剤層4bを介して積層された第2のフィルムセンサー5bと、その上に粘着剤層11を介して積層されたカバー材6とを備えて構成される。
粘着シート1から一方の剥離シート12aを剥離し、露出した粘着剤層11を、第2のフィルムセンサー5bのパターニングされた透明導電膜52と接するように、当該第2のフィルムセンサー5bと貼合する。一方、剥離シート上に設けられた粘着剤層4bを、第1のフィルムセンサー5aのパターニングされた透明導電膜52と接するように、当該第1のフィルムセンサー5aと貼合する。
1.(メタ)アクリル酸エステル重合体の調製
アクリル酸2-エチルヘキシル60質量部、メタクリル酸メチル20質量部およびアクリル酸2-ヒドロキシエチル20質量部を共重合させて、(メタ)アクリル酸エステル重合体(A)を調製した。この(メタ)アクリル酸エステル重合体(A)の分子量を後述する方法で測定したところ、重量平均分子量(Mw)60万であった。
上記工程(1)で得られた(メタ)アクリル酸エステル重合体(A)100質量部(固形分換算値;以下同じ)と、アビエチン酸エステル系粘着付与性液体(B)(粘着付与剤)としてのアビエチン酸エステル系化合物(荒川化学社製,製品名「パインクリスタルME-G」)10質量部と、架橋剤(C)としてのトリレンジイソシアネート系化合物(トーヨーケム社製,製品名「BHS8515」)0.25質量部とを混合し、十分に撹拌して、メチルエチルケトンで希釈することにより、固形分濃度36質量%の粘着性組成物の塗布溶液を得た。
[(メタ)アクリル酸エステル重合体(A)]
2EHA:アクリル酸2-エチルヘキシル
MMA:メタクリル酸メチル
HEA:アクリル酸2-ヒドロキシエチル
BA:アクリル酸n-ブチル
AA:アクリル酸
MA:アクリル酸メチル
[架橋剤(C)]
イソシアネート系:トリレンジイソシアネート系化合物(トーヨーケム社製,製品名「BHS8515」)
エポキシ系:1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン(大成化薬社製,製品名「TC-5」)
得られた粘着性組成物の塗布溶液を、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した重剥離型剥離シート(リンテック社製,製品名「SP-PET752150」)の剥離処理面に、乾燥後の厚さが25μmになるようにナイフコーターで塗布したのち、90℃で1分間加熱処理して塗布層を形成した。同様に、得られた粘着性組成物の塗布溶液を、ポリエチレンテレフタレートフィルムの片面をシリコーン系剥離剤で剥離処理した軽剥離型剥離シート(リンテック社製,製品名「SP-PET382120」)の剥離処理面に、乾燥後の厚さが25μmになるようにナイフコーターで塗布したのち、90℃で1分間加熱処理して塗布層を形成した。
(メタ)アクリル酸エステル重合体(A)を構成する各モノマーの割合、(メタ)アクリル酸エステル重合体(A)の重量平均分子量(Mw)、粘着付与剤の種類および配合量、ならびに架橋剤(C)の種類および配合量を表1に示すように変更する以外、実施例1と同様にして粘着シートを製造した。
<測定条件>
・GPC測定装置:東ソー社製,HLC-8020
・GPCカラム(以下の順に通過):東ソー社製
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
・測定溶媒:テトラヒドロフラン
・測定温度:40℃
実施例および比較例で得られた粘着シートを80mm×80mmのサイズに裁断して、その粘着剤層をポリエステル製メッシュ(メッシュサイズ200)に包み、その質量を精密天秤にて秤量し、上記メッシュ単独の質量を差し引くことにより、粘着剤のみの質量を算出した。このときの質量をM1とする。
実施例および比較例で得られた粘着シートの粘着剤層を、片面にスズドープ酸化インジウム(ITO)からなる透明導電膜が設けられたポリエチレンテレフタレートフィルム(尾池工業社製,ITOフィルム,厚さ:125μm)の透明導電膜と、ポリメチルメタクリレート(PMMA)からなるアクリル板(三菱ガス化学社製,ユーピロン・シート MR200,厚さ:1mm)とで挟み、積層体を得た。
◎…気泡、浮きおよび剥がれが全くなかった。
○…直径0.1mm以下の気泡のみが発生した。
×…直径0.1mm超の気泡、浮きまたは剥がれが発生した。
(a)評価用サンプルの作製
ガラス板(NSGプレシジョン社製,製品名「コーニングガラス イーグルXG」,縦90mm×横50mm×厚み0.5mm)の表面に、紫外線硬化型インク(帝国インキ社製,製品名「POS-911墨」)を塗布厚が5μm、10μm、15μm及び20μmのいずれか1つとなるように額縁状(外形:縦90mm×横50mm,幅5mm)にスクリーン印刷した。次いで、紫外線を照射(80W/cm2,メタルハライドランプ2灯,ランプ高さ15cm,ベルトスピード10~15m/分)して、印刷した上記紫外線硬化型インクを硬化させ、印刷による段差(段差の高さ:5μm、10μm、15μm及び20μmのいずれか1つ)を有する段差付ガラス板を作製した。
得られた評価用サンプルを、50℃、0.5MPaの条件下で30分間オートクレーブ処理した後、常圧、23℃、50%RHにて24時間放置した。次いで、85℃、85%RHの湿熱条件下にて72時間保管し、その後、段差追従性を評価した。段差追従性は、粘着剤層により印刷段差が完全に埋められたか否かで判断し、印刷段差と粘着剤層との界面で隙間や気泡などが観察された場合は、印刷段差に追従できなかったと判断される。ここでは、段差追従性は、下記の基準にしたがって段差追従率(%)として評価した。結果を表2に示す。
◎:段差追従率40%
○:段差追従率10%~30%
×:段差追従率10%未満
実施例および比較例で得られた粘着シートの粘着剤層について、JIS K7361-1:1997に準じて、ヘイズメーター(日本電色工業社製,NDH-2000)を用いてヘイズ値(%)および全光線透過率(%)を測定した。結果を表2に示す。
11…粘着剤層
12a,12b…剥離シート
2…タッチパネル
3…表示体モジュール
4a,4b…粘着剤層
5a…第1のフィルムセンサー
5b…第2のフィルムセンサー
51…基材フィルム
52…透明導電膜
6…カバー材
7…印刷層
Claims (7)
- 重合体を構成するモノマー単位として、反応性官能基を有するモノマーを8~30質量%含有する(メタ)アクリル酸エステル重合体(A)と、
アビエチン酸エステル系粘着付与性液体(B)と
を含有する粘着性組成物を架橋してなる粘着剤であって、
ゲル分率が30~95%である
ことを特徴とする粘着剤。 - 前記(メタ)アクリル酸エステル重合体(A)は、当該重合体を構成するモノマー単位として、ホモポリマーとしてのガラス転移温度が70℃以上のハードモノマーを含有することを特徴とする請求項1に記載の粘着剤。
- 前記(メタ)アクリル酸エステル重合体(A)は、当該重合体を構成するモノマー単位として、(メタ)アクリル酸2-エチルヘキシルを含有することを特徴とする請求項1又は2に記載の粘着剤。
- 前記(メタ)アクリル酸エステル重合体(A)の重量平均分子量は、20万~120万であることを特徴とする請求項1~3いずれか一項に記載の粘着剤。
- 前記粘着性組成物は、さらに架橋剤(C)を含有することを特徴とする請求項1~4のいずれか一項に記載の粘着剤。
- 2枚の剥離シートと、
前記2枚の剥離シートの剥離面と接するように前記剥離シートに挟持された粘着剤層とを備え、
前記粘着剤層が、請求項1~5のいずれか一項に記載の粘着剤からなる
ことを特徴とする粘着シート。 - 前記粘着剤層は、2つのパターニングされた透明導電膜の間、またはパターニングされた透明導電膜とカバー材もしくは表示体モジュールとの間に配置されることを特徴とする請求項6に記載の粘着シート。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2014/059583 WO2015151209A1 (ja) | 2014-03-31 | 2014-03-31 | 粘着剤および粘着シート |
JP2016511228A JP6145568B2 (ja) | 2014-03-31 | 2014-03-31 | 粘着剤および粘着シート |
CN201480077600.6A CN106133097B (zh) | 2014-03-31 | 2014-03-31 | 粘着剂及粘着片 |
KR1020167029617A KR102245863B1 (ko) | 2014-03-31 | 2014-03-31 | 점착제 및 점착 시트 |
TW104110395A TWI668281B (zh) | 2014-03-31 | 2015-03-31 | 黏著劑及黏著片 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2014/059583 WO2015151209A1 (ja) | 2014-03-31 | 2014-03-31 | 粘着剤および粘着シート |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015151209A1 true WO2015151209A1 (ja) | 2015-10-08 |
Family
ID=54239577
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/059583 WO2015151209A1 (ja) | 2014-03-31 | 2014-03-31 | 粘着剤および粘着シート |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6145568B2 (ja) |
KR (1) | KR102245863B1 (ja) |
CN (1) | CN106133097B (ja) |
TW (1) | TWI668281B (ja) |
WO (1) | WO2015151209A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7558047B2 (ja) | 2020-12-02 | 2024-09-30 | 日東電工株式会社 | スペーサ |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2886433T3 (es) * | 2017-12-15 | 2021-12-20 | Henkel Ag & Co Kgaa | Cinta adhesiva para unir materiales textiles |
CN111187586B (zh) * | 2020-01-21 | 2021-07-20 | 江苏景宏新材料科技有限公司 | 一种特高粘丙烯酸酯乳液压敏胶及其制备方法 |
KR102371171B1 (ko) * | 2020-09-29 | 2022-03-07 | 한국전자기술연구원 | 자외선 경화 탈착형 접착 조성물 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007051271A (ja) * | 2005-07-21 | 2007-03-01 | Nitto Denko Corp | 粘着剤組成物、両面粘着テープ、接着方法及び携帯用電子機器 |
JP2008274243A (ja) * | 2007-03-30 | 2008-11-13 | Dic Corp | 粘着テープおよびlcdモジュール |
JP2009132909A (ja) * | 2007-11-07 | 2009-06-18 | Nippon Synthetic Chem Ind Co Ltd:The | 光学部材用粘着剤及び光学部材 |
JP2011026361A (ja) * | 2009-07-21 | 2011-02-10 | Lintec Corp | 粘着シートおよび液晶表示装置 |
JP2014502293A (ja) * | 2010-11-24 | 2014-01-30 | エルジー・ハウシス・リミテッド | タッチパネル用粘着剤組成物、粘着フィルム及びタッチパネル |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10134261A1 (de) * | 2001-07-18 | 2003-01-30 | Basf Ag | Stabilisatoren enthaltende UV-vernetzbare Schmelzhaftklebstoffe |
US20110111660A1 (en) * | 2007-09-07 | 2011-05-12 | Dic Corporation | Double-sided adhesive tape |
JP2010097070A (ja) | 2008-10-17 | 2010-04-30 | Nitto Denko Corp | フラットパネルディスプレイ用透明粘着シート及びフラットパネルディスプレイ |
JP5479151B2 (ja) * | 2009-02-23 | 2014-04-23 | 日東電工株式会社 | 積層セラミックシート切断用熱剥離型粘着シート及び積層セラミックシートの切断加工方法 |
JP5578835B2 (ja) * | 2009-11-16 | 2014-08-27 | 日東電工株式会社 | 粘着テープ |
JP5732436B2 (ja) * | 2012-06-11 | 2015-06-10 | 綜研化学株式会社 | 粘着シートの製造法およびタッチパネル用積層体の製造方法 |
-
2014
- 2014-03-31 JP JP2016511228A patent/JP6145568B2/ja active Active
- 2014-03-31 KR KR1020167029617A patent/KR102245863B1/ko active IP Right Grant
- 2014-03-31 CN CN201480077600.6A patent/CN106133097B/zh active Active
- 2014-03-31 WO PCT/JP2014/059583 patent/WO2015151209A1/ja active Application Filing
-
2015
- 2015-03-31 TW TW104110395A patent/TWI668281B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007051271A (ja) * | 2005-07-21 | 2007-03-01 | Nitto Denko Corp | 粘着剤組成物、両面粘着テープ、接着方法及び携帯用電子機器 |
JP2008274243A (ja) * | 2007-03-30 | 2008-11-13 | Dic Corp | 粘着テープおよびlcdモジュール |
JP2009132909A (ja) * | 2007-11-07 | 2009-06-18 | Nippon Synthetic Chem Ind Co Ltd:The | 光学部材用粘着剤及び光学部材 |
JP2011026361A (ja) * | 2009-07-21 | 2011-02-10 | Lintec Corp | 粘着シートおよび液晶表示装置 |
JP2014502293A (ja) * | 2010-11-24 | 2014-01-30 | エルジー・ハウシス・リミテッド | タッチパネル用粘着剤組成物、粘着フィルム及びタッチパネル |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7558047B2 (ja) | 2020-12-02 | 2024-09-30 | 日東電工株式会社 | スペーサ |
Also Published As
Publication number | Publication date |
---|---|
CN106133097A (zh) | 2016-11-16 |
KR102245863B1 (ko) | 2021-04-28 |
TWI668281B (zh) | 2019-08-11 |
JP6145568B2 (ja) | 2017-06-14 |
KR20160140778A (ko) | 2016-12-07 |
TW201546216A (zh) | 2015-12-16 |
JPWO2015151209A1 (ja) | 2017-04-13 |
CN106133097B (zh) | 2018-03-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6200065B2 (ja) | 粘着剤および粘着シート | |
JP6356786B2 (ja) | 粘着シートおよび積層体 | |
JP5789350B1 (ja) | 粘着シートおよび積層体 | |
JP6251293B2 (ja) | 粘着シート、および表示体の製造方法 | |
JP6374485B2 (ja) | 粘着シート | |
JP6290377B2 (ja) | 積層体 | |
JP6325653B2 (ja) | 粘着性組成物、粘着剤および粘着シート | |
JPWO2016063405A6 (ja) | 粘着シート、および表示体の製造方法 | |
JP6368410B2 (ja) | タッチパネル | |
JP6145568B2 (ja) | 粘着剤および粘着シート | |
JP6270941B2 (ja) | 粘着剤、粘着シート、および表示体の製造方法 | |
JP6500077B2 (ja) | 積層体 | |
JP6343717B2 (ja) | 粘着剤、粘着シートおよび表示体 | |
JP6934443B2 (ja) | 粘着剤および粘着シート | |
JP2017014378A (ja) | マイグレーション防止剤、粘着剤および粘着シート |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14887846 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016511228 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase | ||
ENP | Entry into the national phase |
Ref document number: 20167029617 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14887846 Country of ref document: EP Kind code of ref document: A1 |