CN103980820B - Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet Download PDFInfo
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- CN103980820B CN103980820B CN201410049516.5A CN201410049516A CN103980820B CN 103980820 B CN103980820 B CN 103980820B CN 201410049516 A CN201410049516 A CN 201410049516A CN 103980820 B CN103980820 B CN 103980820B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25B—TOOLS OR BENCH DEVICES NOT OTHERWISE PROVIDED FOR, FOR FASTENING, CONNECTING, DISENGAGING OR HOLDING
- B25B27/00—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for
- B25B27/02—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for for connecting objects by press fit or detaching same
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25B—TOOLS OR BENCH DEVICES NOT OTHERWISE PROVIDED FOR, FOR FASTENING, CONNECTING, DISENGAGING OR HOLDING
- B25B27/00—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for
- B25B27/02—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for for connecting objects by press fit or detaching same
- B25B27/023—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for for connecting objects by press fit or detaching same using screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25B—TOOLS OR BENCH DEVICES NOT OTHERWISE PROVIDED FOR, FOR FASTENING, CONNECTING, DISENGAGING OR HOLDING
- B25B27/00—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for
- B25B27/02—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for for connecting objects by press fit or detaching same
- B25B27/06—Hand tools, specially adapted for fitting together or separating parts or objects whether or not involving some deformation, not otherwise provided for for connecting objects by press fit or detaching same inserting or withdrawing sleeves or bearing races
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25B—TOOLS OR BENCH DEVICES NOT OTHERWISE PROVIDED FOR, FOR FASTENING, CONNECTING, DISENGAGING OR HOLDING
- B25B33/00—Hand tools not covered by any other group in this subclass
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Abstract
The invention provides a pressure-sensitive adhesive composition, a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet which have excellent durability when being applied to optical members such as a polarizing plate. In order to solve the above problems, there is provided a pressure-sensitive adhesive composition comprising: a (meth) acrylate polymer (A) containing 1.5 mass% or more of a monomer having a hydroxyl group as a monomer unit constituting the polymer; an isocyanate-based crosslinking agent (B); and a silane coupling agent (C) having a mercapto group as a functional group that reacts with the organic material; and an active energy ray-curable component (D).
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive (a material for curing a pressure-sensitive adhesive composition), and a pressure-sensitive adhesive sheet, and particularly relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet suitable for use as an optical member such as a polarizing plate.
[ background of the invention ]
In recent years, a touch panel having both a display device and an input device is widely used in various electronic devices. Touch panels are mainly of resistive type, capacitive type, optical type, and ultrasonic type. The resistive touch screen includes an analog data resistive film type and a matrix resistive film type, and the capacitive touch screen includes a surface type and a projection type.
Recently, a projection-type capacitive touch screen is widely used as a touch screen of a mobile electronic device such as a smart phone or a tablet terminal. As a projection type capacitive touch panel of the mobile electronic device, for example, a touch panel in which a liquid crystal display device (LCD), a pressure-sensitive adhesive layer, a transparent conductive film (tin-doped indium oxide: ITO), a glass substrate, a transparent conductive film (ITO), and a protective layer such as a tempered glass are laminated in this order from below has been proposed.
As an optical member constituting the liquid crystal display device, a liquid crystal module is generally used. In general, a liquid crystal module is a module in which alignment layers of two transparent electrode substrates forming the alignment layers are disposed at predetermined intervals via spacers so as to be on the inner side, the periphery of the liquid crystal module is sealed, and a liquid crystal material is sandwiched between the two transparent electrode substrates. Generally, polarizing plates are attached to the outer sides of two transparent electrode substrates in a liquid crystal module with pressure-sensitive adhesives, respectively.
As a pressure-sensitive adhesive used in a touch panel, for example, a pressure-sensitive adhesive shown in patent document 1 is known. The pressure sensitive adhesive comprises: the resin composition comprises a (meth) acrylic polymer containing, as a copolymerization component, 100 parts by weight of an alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms as a monomer unit and 0.2 to 20 parts by weight of a monomer having a carboxyl group, and 0.02 to 2 parts by weight of a peroxide as a crosslinking agent and 0.005 to 5 parts by weight of an epoxy crosslinking agent, based on 100 parts by weight of the (meth) acrylic polymer.
[ Prior art documents ]
[ patent document ]
[ patent document 1 ] Japanese patent laid-open No. 2009-242786
[ summary of the invention ]
[ problem to be solved by the invention ]
With the recent reduction in thickness of mobile electronic devices, the reduction in thickness of polarizing plates as constituent members has been advanced, and polarizing plates using protective films that are likely to cause outgassing of cycloolefin polymers and the like have been used. Therefore, higher reliability (durability) is required for the pressure-sensitive adhesive than ever before. However, the pressure-sensitive adhesive in patent document 1 has a problem that the pressure-sensitive adhesive is low in durability and is likely to bulge or peel with time or under high-temperature conditions or moist-heat conditions.
The present invention has been made in view of such a situation, and an object thereof is to provide a highly durable pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet which are suitable for use in optical members such as a polarizing plate.
[ MEANS FOR SOLVING PROBLEMS ] to solve the problems
In order to achieve the above object, the present invention provides, in a first aspect, a pressure-sensitive adhesive composition comprising: a (meth) acrylate polymer (A) containing 1.5% by mass or more of a monomer having a hydroxyl group as a monomer unit constituting the polymer; an isocyanate-based crosslinking agent (B); a silane coupling agent (C) having a mercapto group as a functional group that reacts with the organic material; and an active energy ray-curable component (D) (invention 1).
When the pressure-sensitive adhesive composition according to the invention (invention 1) is cured, the (meth) acrylate polymer (a), the isocyanate-based crosslinking agent (B) and the silane coupling agent (C) are crosslinked to form the 1 st three-dimensional network structure, and the plurality of active energy ray-curable components (D) are bonded to each other to form the 2 nd three-dimensional network structure, and it is presumed that they are entangled with each other to form an integral three-dimensional network structure. The pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition has excellent durability, and particularly excellent adhesion durability under high-temperature conditions and moist-heat conditions, due to the above structure.
In the above invention (invention 1), the (meth) acrylate polymer (a) preferably has a weight average molecular weight of 100 to 250 ten thousand and contains 1.8 to 10 mass% of a monomer having a hydroxyl group as a monomer unit constituting the polymer (invention 2).
In the above inventions (inventions 1 and 2), the (meth) acrylate polymer (a) preferably contains 1 to 10 mass% of a monomer having an aromatic ring as a monomer unit constituting the polymer (invention 3).
In the above invention (invention 3), the monomer having an aromatic ring is preferably 2-phenylethyl (meth) acrylate (invention 4).
In the above inventions (inventions 1 to 4), the (meth) acrylate polymer (a) preferably does not contain a monomer having a carboxyl group as a monomer unit constituting the polymer (invention 5).
In the above inventions (inventions 1 to 5), the isocyanate crosslinking agent (B) is preferably trimethylolpropane-modified xylylene diisocyanate (invention 6).
In the above inventions (inventions 1 to 6), the active energy ray-curable component (D) is preferably a polyfunctional acrylate monomer having a molecular weight of less than 1000 (invention 7).
In the above invention (invention 7), the polyfunctional acrylate monomer preferably has a cyclic structure (invention 8).
In the above inventions (inventions 1 to 8), the content of the active energy ray-curable component (D) in the pressure-sensitive adhesive composition is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylate polymer (a) (invention 9).
The second invention provides a pressure-sensitive adhesive (invention 10) obtained by curing the pressure-sensitive adhesive composition (invention 1 to invention 9) by irradiation with an active energy ray.
In the above invention (invention 10), it is preferable that the gel fraction after 7 days of storage in an environment of 23 ℃ and 50% RH from the formation of the pressure-sensitive adhesive layer is 75 to 95% (invention 11).
In the above-mentioned invention (invention 10, invention 11), it is preferable that the storage modulus (G ') at 23 ℃ is from 0.05MPa to 0.20MPa, and the storage modulus (G') at 80 ℃ is from 0.05MPa to 0.15MPa (invention 12).
Third, the present invention provides a pressure-sensitive adhesive sheet characterized in that: the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive (invention 10 to invention 12) (invention 13).
In the above invention (invention 13), the substrate is preferably an optical member (invention 14).
In the above invention (invention 14), the optical member is preferably a polarizing plate (invention 15).
Fourth, the present invention provides a pressure-sensitive adhesive sheet characterized in that: the pressure-sensitive adhesive sheet comprises two release sheets and a pressure-sensitive adhesive layer sandwiching the release sheets so that release surfaces of the two release sheets are in contact with each other, wherein the pressure-sensitive adhesive layer comprises the pressure-sensitive adhesive (invention 10 to invention 12) (invention 16).
[ Effect of the invention ]
The pressure-sensitive adhesive composition according to the present invention contains the components (a) to (D), and thus the pressure-sensitive adhesive obtained has high durability and is suitably used for optical members such as polarizing plates.
[ brief description of the drawings ]
Fig. 1 is a sectional view of a pressure-sensitive adhesive sheet according to embodiment 1 of the present invention.
Fig. 2 is a sectional view of a pressure-sensitive adhesive sheet according to embodiment 2 of the present invention.
[ description of reference ]
1A, 1B … pressure-sensitive adhesive sheet
11 … pressure sensitive adhesive layer
12,12a,12b … release sheet
13 … base material
[ embodiments of the invention ]
Hereinafter, embodiments of the present invention will be described.
[ pressure-sensitive adhesive composition ]
The pressure-sensitive adhesive composition according to the present embodiment (hereinafter referred to as "pressure-sensitive adhesive composition P") contains a (meth) acrylate polymer (a) containing 1.5 mass% or more of a monomer having a hydroxyl group as a monomer unit constituting a polymer, an isocyanate-based crosslinking agent (B), a silane coupling agent (C) having a mercapto group as a functional group that reacts with an organic material, and an active energy ray-curable component (D). In the present specification, the term (meth) acrylate refers to both acrylate and methacrylate. Other similar terms are also used. In addition, the term "polymer" also includes the term "copolymer".
When the pressure-sensitive adhesive composition P is cured, the mercapto group of the silane coupling agent (C) is easily bonded to the isocyanate group of the isocyanate-based crosslinking agent (B) to form a thiocarbamate, and the other isocyanate group of the isocyanate-based crosslinking agent (B) reacts with the hydroxyl group of the (meth) acrylate polymer (a) to crosslink the (meth) acrylate polymer (a) to form a 1 st three-dimensional network structure. It is also presumed that the alkoxysilyl group of the silane coupling agent (C) is suspended from the (meth) acrylate polymer (a) at an appropriate distance. On the other hand, it is presumed that a plurality of active energy ray-curable components (D) are bonded to each other to form a 2 nd three-dimensional network structure. The 1 st three-dimensional network structure and the 2 nd three-dimensional network structure are mutually wound to form an integrated three-dimensional network structure. (the structure is hereinafter referred to as "structure X").
The pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition P becomes a highly durable adhesive by the structure X. It is presumed that, in particular, the alkoxysilyl group of the silane coupling agent (C) is present at an appropriate distance from the (meth) acrylate polymer (a) and the structure X, and thus, an excellent coupling effect can be exhibited. Thus, the pressure-sensitive adhesive obtained is also excellent in adhesion durability under high temperature conditions and moist heat conditions.
(1) (meth) acrylate ester Polymer (A)
The (meth) acrylate polymer (a) contains a monomer having a hydroxyl group (hydroxyl group-containing monomer) as a monomer unit constituting the polymer. Thus, the (meth) acrylate polymer (a) has a hydroxyl group. Since the hydroxyl group is highly reactive with the isocyanate group of the isocyanate crosslinking agent (B), the (meth) acrylate polymer (a) is crosslinked by the isocyanate crosslinking agent (B) by the reaction thereof.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and among them, 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of reactivity with the isocyanate-based crosslinking agent (B). These may be used alone or in combination of two or more.
The (meth) acrylate polymer (a) needs to contain 1.5% by mass or more of a monomer having a hydroxyl group, preferably 1.8% by mass to 10% by mass, particularly preferably 2% by mass to 7% by mass, and further preferably 2% by mass to 5% by mass as a monomer unit constituting the polymer. The content of the hydroxyl group-containing monomer is in the above range, and thus, the formed crosslinked structure is good, and the resulting pressure-sensitive adhesive has excellent durability. If the content of the hydroxyl group-containing monomer is less than 1.5% by mass, the crosslinking point is too small, and the resulting pressure-sensitive adhesive cannot exhibit excellent durability. On the other hand, if the content of the hydroxyl group-containing monomer exceeds 10 mass%, the crosslinking points become too large, and the resulting pressure-sensitive adhesive may not be flexible and may have reduced stress relaxation properties.
The (meth) acrylate polymer (a) preferably contains a monomer having an aromatic ring (aromatic ring-containing monomer) as a monomer unit constituting the polymer. Thus, the (meth) acrylate polymer (a) has appropriate hardness, and the obtained pressure-sensitive adhesive is more excellent in durability.
Examples of the aromatic ring-containing monomer include phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, ethoxylated o-phenylphenol acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified cresol (meth) acrylate, Ethylene Oxide (EO) -modified nonylphenol (meth) acrylate, and the like, and among them, 2-phenylethyl (meth) acrylate is preferable from the viewpoint of polymerizability. These may be used alone or in combination of two or more.
The (meth) acrylate polymer (a) preferably contains 1 to 10% by mass, particularly preferably 2 to 8% by mass, and further preferably 3 to 6% by mass of a monomer having an aromatic ring as a monomer unit constituting the polymer. By having the content of the aromatic ring-containing monomer in the above range, the resulting pressure-sensitive adhesive has more excellent durability. If the content of the aromatic ring-containing monomer is less than 1% by mass, the resultant pressure-sensitive adhesive may have a problem of light leakage when used for polarizing plate applications or the like. On the other hand, if the content of the aromatic ring-containing monomer exceeds 10 mass%, there is a possibility that the durability of the resulting pressure-sensitive adhesive is lowered.
The (meth) acrylate polymer (A) preferably contains an alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms as a monomer unit constituting the polymer, and particularly preferably contains the alkyl (meth) acrylate as a main component. Thus, the pressure-sensitive adhesive obtained has more excellent adhesiveness.
Examples of the alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms include methyl (meth) 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, and stearyl (meth) acrylate. Among these, from the viewpoint of improving the adhesion, preferred are (meth) acrylates having an alkyl group having 1 to 4 carbon atoms, and particularly preferred are methyl (meth) acrylate and n-butyl (meth) acrylate. These may be used alone or in combination of two or more.
The (meth) acrylate polymer (a) preferably contains, as a monomer unit constituting the polymer, an alkyl (meth) acrylate having 1 to 20 carbon atoms, which contains 50 to 97.5% by mass, particularly preferably 80 to 96% by mass, and further preferably 85 to 95% by mass of an alkyl group.
The (meth) acrylate polymer (a) may contain, as a monomer unit constituting the polymer, another monomer, if necessary. The other monomer may be a monomer having a reactive functional group (a monomer having a reactive functional group) or a non-reactive monomer.
Examples of the reactive functional group-containing monomer include a monomer having a carboxyl group (carboxyl group-containing monomer), a monomer having an amino group (amino group-containing monomer), and the like.
Examples of the carboxyl group-containing monomer include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These may be used alone or in combination of two or more.
Examples of the amino group-containing monomer include aminoethyl (meth) acrylate and n-butylaminoethyl (meth) acrylate. These may be used alone or in combination of two or more.
In the case where the object to which the pressure-sensitive adhesive obtained is applied is, for example, a transparent conductive film or a metal film, the (meth) acrylate polymer (a) preferably does not contain a monomer having a carboxyl group as a monomer unit constituting the polymer, because of the problem of generation of acid. Thus, for example, when the object to be pasted is a transparent conductive film, it is possible to suppress corrosion of the transparent conductive film or to change the resistance value of the transparent conductive film. Further, the silane coupling agent (C) having a mercapto group effectively functions also in such an acid-free system.
Examples of the non-reactive monomer include (meth) acrylic acid esters having an alicyclic ring such as (meth) acrylic acid esters having an alkylalkoxy ester such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate, non-crosslinkable acrylamides such as acrylamide and methacrylamide, (meth) acrylic acid esters having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate, vinyl acetate, and styrene. These may be used alone or in combination of two or more.
The polymerization form of the (meth) acrylate polymer (a) may be a random copolymer or a block copolymer.
The weight average molecular weight of the (meth) acrylate polymer (a) is preferably 100 to 250 ten thousand, particularly preferably 140 to 220 ten thousand, and further preferably 170 to 200 ten thousand. The weight average molecular weight in the present specification is a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
If the weight average molecular weight of the (meth) acrylate polymer (a) is less than 100 ten thousand, the durability of the resulting pressure-sensitive adhesive is poor. Further, if the weight average molecular weight of the (meth) acrylate polymer (a) exceeds 250 ten thousand, there is a possibility that the stress relaxation property of the obtained pressure-sensitive adhesive is deteriorated.
In the pressure-sensitive adhesive composition P, the (meth) acrylate polymer (a) may be used alone or in combination of two or more.
(2) Isocyanate-based crosslinking agent (B)
The isocyanate-based crosslinking agent (B) has an advantage of excellent reactivity with the mercapto group of the silane coupling agent (C). Further, the (meth) acrylate polymer (a) has an advantage of excellent reactivity with the hydroxyl group.
The isocyanate-based crosslinking agent (B) contains at least a crosslinking agent of a polyisocyanate compound. Examples of 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, and biuret and isocyanurate compounds thereof, and adducts of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like as reactants with a low-molecular active hydrogen-containing compound, and among them, trimethylolpropane-modified aromatic polyisocyanates are preferable from the viewpoint of improving durability, and trimethylolpropane-modified xylylene diisocyanate is particularly preferable. The isocyanate-based crosslinking agent (B) may be used alone or in combination of two or more.
The content of the isocyanate-based crosslinking agent (B) in the pressure-sensitive adhesive composition P is preferably 0.1 to 1 part by mass, particularly preferably 0.2 to 0.8 part by mass, and further preferably 0.2 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). When the content of the isocyanate-based crosslinking agent (B) is in the above range, the pressure-sensitive adhesive obtained has a crosslinked structure which does not impair stress relaxation property, and is more excellent in durability.
(3) Silane coupling agent (C)
In the present embodiment, the silane coupling agent (C) has a mercapto group as a functional group that reacts with an organic material, but since this mercapto group is likely to react with an isocyanate group of the isocyanate-based crosslinking agent (B), even if the crosslinkable functional group of the (meth) acrylate polymer (a) is only a hydroxyl group that is difficult to function in a general silane coupling agent, (even if the (meth) acrylate polymer (a) does not contain a carboxyl group as a crosslinkable functional group), the coupling effect by the silane coupling agent (C) can be obtained.
As described above, in the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition P, it is presumed that the alkoxysilyl group of the silane coupling agent (C) is kept at an appropriate distance from the (meth) acrylate polymer (a), that is, in the isocyanate-based crosslinking agent (B), a plurality of isocyanate groups are kept at a distance from each other, and a form in which the isocyanate groups are suspended in the (meth) acrylate polymer (a) is formed. In this way, the presence of the alkoxysilyl group at an appropriate distance from the (meth) acrylate polymer (a) and the structure X exerts an excellent coupling effect, and the pressure-sensitive adhesive obtained thereby is excellent in adhesion durability under high-temperature conditions and moist-heat conditions. This effect is particularly remarkable when the object to which the pressure-sensitive adhesive is applied is an inorganic material such as glass or metal.
The silane coupling agent (C) is an organosilicon compound having at least one mercapto group and at least one alkoxysilyl group in the molecule, and is preferably an organosilicon compound having good compatibility with the pressure-sensitive adhesive component and light transmittance, for example, a substantially transparent organosilicon compound.
Specific examples of the silane coupling agent (C) include mercapto group-containing low-molecular-weight silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane; and mercapto group-containing oligomer-type silane coupling agents such as cocondensates of mercapto group-containing silane compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane with alkyl group-containing silane compounds such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane. Among these, from the viewpoint of improving durability, a mercapto group-containing oligomer-type silane coupling agent is preferable, a cocondensate of a mercapto group-containing silane compound and an alkylsilane compound is particularly preferable, and a cocondensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane is further preferable. These may be used alone or in combination of two or more.
The content of the silane coupling agent (C) in the pressure-sensitive adhesive composition P is preferably 0.05 to 1 part by mass, particularly preferably 0.1 to 0.8 part by mass, and further preferably 0.2 to 0.5 part by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). If the content of the silane coupling agent (C) is less than 0.05 part by mass, it is difficult to obtain the effect of improving durability by the silane coupling agent (C). On the other hand, if the content of the silane coupling agent (C) exceeds 1 part by mass, the reaction with the crosslinking agent (B) and the (meth) acrylate polymer (a) may be inhibited.
(4) Active energy ray-curable component (D)
The active energy ray-curable component (D) is not particularly limited as long as it does not inhibit the effect of the present invention, and may be any of a monomer, an oligomer, or a polymer, or a mixture thereof. Among them, preferred are polyfunctional acrylate monomers having a molecular weight of less than 1000 and excellent compatibility with the (meth) acrylate polymer (a) and the like.
Examples of the polyfunctional acrylate monomer having a molecular weight of less than 1000 include 2-functional types such as 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, di (acryloyloxyethyl) isocyanurate, and allylated cyclohexyl di (meth) acrylate; 3-functional types such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate; 4-functional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; 5-functional types such as propionic acid-modified dipentaerythritol penta (meth) acrylate; 6-functional types such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.
Among the above-mentioned polyfunctional acrylate monomers, a monomer having a cyclic structure in the skeleton is preferable from the viewpoint of improving durability. The cyclic structure may be a carbon ring structure, a heterocyclic structure, a monocyclic structure, or a polycyclic structure. Examples of such a polyfunctional acrylate monomer include bis (acryloyloxyethyl) isocyanurate, tris (acryloyloxyethyl) isocyanurate and the like having an isocyanurate structure, dimethylol dicyclopentane diacrylate, ethylene oxide-modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, adamantane diacrylate and the like.
As the active energy ray-curable component (D), an active energy ray-curable acrylate oligomer may also be used. The acrylate oligomer preferably has a weight average molecular weight of 50,000 or less. Examples of such acrylate oligomers include polyester acrylates, epoxy acrylates, polyurethane acrylates, polyether acrylates, polybutadiene acrylates, and silicone acrylates.
Here, the polyester acrylate oligomer can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, which is obtained by condensing a polycarboxylic acid with a polyhydric alcohol, with (meth) acrylic acid; alternatively, the hydroxyl group at the end of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid may be esterified with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a bisphenol epoxy resin or a novolac epoxy resin having a relatively low molecular weight and esterifying the resulting product. In addition, a carboxyl-modified epoxy acrylate oligomer obtained by partially modifying the epoxy acrylate oligomer with a dicarboxylic acid anhydride may be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a urethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid. The polyol acrylate oligomer can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth) acrylic acid.
The weight average molecular weight of the acrylate oligomer is preferably 50,000 or less, particularly preferably 500 to 50,000, and more preferably 3,000 to 40,000. These acrylate oligomers may be used alone or in combination of two or more.
Further, as the active energy ray-curable component (D), an adduct acrylate polymer having a group having a (meth) acryloyl group introduced into a side chain thereof may be used. Such an adduct acrylate polymer can be obtained by reacting a compound having a group reactive with a (meth) acryloyl group and a crosslinkable functional group with a part of the crosslinkable functional group of a copolymer of a (meth) acrylate and a monomer having a crosslinkable functional group in a molecule.
The (meth) acrylic acid ester is preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms and containing an alkyl group, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate. These may be used alone or in combination of two or more.
The monomer having a crosslinkable functional group in the molecule preferably contains at least 1 kind of functional group selected from a hydroxyl group, a carboxyl group, an amino group and an amide group as the functional group. Examples of the monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; acrylamides such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; monoalkylaminoalkyl (meth) acrylates such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate; and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These monomers may be used alone or in combination of two or more.
Examples of the compound having a group that reacts with a (meth) acryloyl group and a crosslinkable functional group include acryloyloxyethyl isocyanate, acryloyloxypropyl isocyanate, methacryloyloxyethyl isocyanate, methacryloyloxypropyl isocyanate, and the like. These may be used alone or in combination of two or more.
The weight average molecular weight of the acrylate polymer adduct is preferably about 50 to 200 ten thousand.
The active energy ray-curable component (D) may be used by selecting one from the above-mentioned polyfunctional acrylate monomers, acrylate oligomers and adduct acrylate polymers, or may be used in combination of two or more kinds thereof, or may be used in combination with other active energy ray-curable components.
The content of the active energy ray-curable component (D) in the pressure-sensitive adhesive composition P is preferably 5 to 20 parts by mass, particularly preferably 6 to 15 parts by mass, and further preferably 7 to 12 parts by mass, based on 100 parts by mass of the (meth) acrylate polymer (a). It is presumed that the pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition P containing the active energy ray-curable component (D) in this range is a pressure-sensitive adhesive that well forms the structure X.
(5) Photopolymerization initiator (E)
Here, when ultraviolet rays are used as the active energy rays to be irradiated to the pressure-sensitive adhesive composition P, the pressure-sensitive adhesive composition P preferably further contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E) in this manner, the active energy ray-curable component (D) can be cured efficiently, and the polymerization curing time and the irradiation dose of the active energy ray can be reduced.
Examples of such photopolymerization initiators (E) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinyl-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4' -diethylaminobenzophenone, Dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoate, oligo [ 2-hydroxy-2-methyl-1 [ 4- (1-methylvinyl) phenyl ] acetone ], 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like. These may be used alone or in combination of two or more.
The photopolymerization initiator (E) is preferably used in an amount in the range of 2 to 15 parts by mass, particularly preferably 5 to 12 parts by mass, based on 100 parts by mass of the active energy ray-curable component (D).
(6) Various additives
Various additives generally used in acrylic pressure-sensitive adhesives, for example, antistatic agents, adhesion imparting agents, antioxidants, ultraviolet absorbers, light stabilizers, softening agents, fillers, refractive index adjusting agents, and the like may be added to the pressure-sensitive adhesive composition P as needed.
Examples of the antistatic agent include ionic liquids, ionic solids, anionic surfactants, alkali metal salts, cationic surfactants, nonionic surfactants, and the like, and among these, at least one selected from ionic liquids, ionic solids, and alkali metal salts is preferably used.
The ionic liquid and the ionic solid are preferably a nitrogen-containing onium salt, a sulfur-containing onium salt, a phosphorus-containing onium salt, or the like. The alkali metal salt is preferably a lithium salt, a potassium salt, or the like. These may be used alone or in combination of two or more.
The content of the antistatic agent in the pressure-sensitive adhesive composition P is preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass. By the content of the antistatic agent being within the above range, the balance of the antistatic property and the durability of the pressure-sensitive adhesive becomes good.
[ method for producing pressure-sensitive adhesive composition ]
The pressure-sensitive adhesive composition P can be produced by producing the (meth) acrylate polymer (a), mixing the obtained (meth) acrylate polymer (a), the isocyanate-based crosslinking agent (B), the silane coupling agent (C), and the active energy ray-curable component (D), and adding the photopolymerization initiator (E), additives, and the like at an optional stage as needed.
The (meth) acrylate polymer (a) can be produced by polymerizing monomers constituting the polymer (in the case of a copolymer, a mixture of monomers) by a general radical polymerization method. The polymerization of the (meth) acrylate polymer (a) may be carried out by a solution polymerization method or the like using a polymerization initiator as needed. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and two or more kinds thereof may be used in combination.
The polymerization initiator may, for example, be an azo compound or an organic peroxide, and two or more kinds may be used simultaneously. Examples of the azo compound include 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane 1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2 ' -azobis (2-methylpropionate), 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (2-hydroxymethylpropionitrile), and 2,2 ' -azobis [ 2- (2-imidazolin-2-yl) propane ].
Examples of the organic peroxide include benzoyl peroxide, t-butyl peroxybenzoate, cumyl hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3, 5, 5-trimethylhexanoyl) peroxide, dipropyl peroxide, and diacetyl peroxide.
In the polymerization step, the weight average molecular weight of the obtained polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
After the (meth) acrylate polymer (a) is obtained, an isocyanate-based crosslinking agent (B), a silane coupling agent (C), an active energy ray-curable component (D), and if necessary, a photopolymerization initiator (E), additives and the like are added to a solution of the (meth) acrylate polymer (a) and sufficiently mixed to obtain a pressure-sensitive adhesive composition P (coating solution) diluted with a solvent.
As the diluting solvent of the coating solution for diluting the pressure-sensitive adhesive composition P, for example, aliphatic hydrocarbons such as hexane, heptane, cyclohexane, etc.; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate, and cellosolve-based solvents such as ethyl cellosolve.
The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as they are within the range in which coating can be performed, and may be appropriately selected depending on the case. For example, the concentration of the pressure-sensitive adhesive composition P may be diluted to 10 to 40 mass%. In addition, when obtaining the coating solution, the addition of a diluting solvent or the like is not an essential condition, and the pressure-sensitive adhesive composition P may not be added with a diluting solvent as long as it has a viscosity capable of being coated. In this case, the pressure-sensitive adhesive composition P may be used as it is as a coating solution.
[ pressure-sensitive adhesive ]
The pressure-sensitive adhesive according to the present embodiment can be preferably obtained by coating and drying the pressure-sensitive adhesive composition P to a desired object, and then curing the pressure-sensitive adhesive composition P by irradiation with an active energy ray.
The drying of the pressure-sensitive adhesive composition P may be carried out by air drying, but is usually carried out by heat treatment (preferably by hot air drying). When the heat treatment is performed, the heating temperature is preferably 50 to 150 ℃, and particularly preferably 70 to 120 ℃. The heating time is preferably 10 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes.
Ultraviolet rays, electron beams, and the like are generally used as the active energy rays. The dose of the active energy ray varies depending on the type of the energy ray, but in the case of ultraviolet rays, for example, the dose is preferably 50mJ/cm in a light meter2～1000mJ/cm2Particularly preferably 100mJ/cm2～500mJ/cm2. In the case of electron beam, it is preferably about 10 to 1000 krad.
It is presumed that, by drying the pressure-sensitive adhesive composition P and irradiation of the active energy ray, the (meth) acrylate polymer (a) having a hydroxyl group is crosslinked by the isocyanate-based crosslinking agent (B) to form a 1 st three-dimensional network structure, and the plurality of active energy ray-curable components (D) are bonded to each other to form a 2 nd three-dimensional network structure, which is intertwined with each other to form the structure X. The mercapto group of the silane coupling agent (C) is likely to react with the isocyanate group of the isocyanate crosslinking agent (B), and it is presumed that the remaining isocyanate group of the isocyanate crosslinking agent (B) also reacts with the hydroxyl group of the (meth) acrylate polymer (a). Thus, the alkoxysilyl group of the silane coupling agent (C) is present at an appropriate distance from the (meth) acrylate polymer (a) and the structure X by the isocyanate crosslinking agent (B), and exhibits an excellent coupling effect.
The pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition P has high durability due to the above structure X, and particularly exhibits excellent adhesion durability even under high-temperature conditions and moist-heat conditions, due to the excellent coupling effect of the silane coupling agent (C). For example, when the sheet is left to stand at a high temperature of 80 ℃ and a moist heat of 60 ℃ and 90% RH for 250 hours, the occurrence of swelling, peeling, and blisters can be prevented or suppressed.
The gel fraction of the pressure-sensitive adhesive according to the present embodiment is preferably 75% to 95%, and particularly preferably 80% to 92%. If the gel fraction is less than 75%, the cohesive force of the pressure-sensitive adhesive is insufficient, and the durability and reworkability may be reduced. When the gel fraction is more than 90%, the adhesive force may be too low, and the durability may be reduced. The gel fraction is a value obtained after storage for 7 days (after aging) at 23 ℃ and 50% RH from the formation of the pressure-sensitive adhesive layer. When it is not determined whether or not the aging period has elapsed, the gel fraction may be within the above range if it is stored again at 23 ℃ and 50% RH for 7 days.
The pressure-sensitive adhesive according to the present embodiment preferably has a storage modulus (G') at 23 ℃ of 0.05 to 0.20MPa, particularly preferably 0.08 to 0.17MPa, and more preferably 0.10 to 0.16 MPa. The pressure-sensitive adhesive according to the present embodiment preferably has a storage modulus (G') at 80 ℃ of 0.05 to 0.15MPa, particularly preferably 0.08 to 0.14MPa, and more preferably 0.10 to 0.12 MPa. When the storage modulus (G') at 23 ℃ and 80 ℃ is within the above range, the desired adhesion to the substrate and the desired cohesive strength are obtained, and when the composition is applied to an optical member such as a polarizing plate, swelling, peeling, and the like at the interface with the optical member or the interface with the glass substrate can be effectively prevented in a durable environment (for example, at a high temperature of 80 ℃). The storage modulus is a value measured by the torsional shear method at a measurement frequency of 1Hz in accordance with JIS K7244-6.
[ pressure-sensitive adhesive sheet ]
As shown in fig. 1, the pressure-sensitive adhesive sheet 1A according to embodiment 1 is composed of a release sheet 12, a pressure-sensitive adhesive layer 11 laminated on the release surface of the release sheet 12, and a base material 13 laminated on the pressure-sensitive adhesive layer 11 in this order from below.
As shown in fig. 2, the pressure-sensitive adhesive sheet 1B according to embodiment 2 is composed of two release sheets 12a and 12B, and a pressure-sensitive adhesive layer 11 sandwiched between the two release sheets 12a and 12B so as to be in contact with the release surfaces of the two release sheets 12a and 12B. The release surface of the release sheet in the present specification means a surface having releasability in the release sheet, and includes any of a surface subjected to a release treatment and a surface showing releasability even if the release treatment is not performed.
In either of the pressure- sensitive adhesive sheets 1A, 1B, the pressure-sensitive adhesive layer 11 includes a pressure-sensitive adhesive formed by curing the above-described pressure-sensitive adhesive composition.
The thickness of the pressure-sensitive adhesive layer 11 is appropriately determined depending on the purpose of use of the pressure- sensitive adhesive sheets 1A and 1B, but is usually in the range of 5 μm to 100 μm, preferably 10 μm to 60 μm. For example, when used as an optical member, particularly as a pressure-sensitive adhesive layer for a polarizing plate, it is preferably 10 to 50 μm, and particularly preferably 15 to 30 μm.
The substrate 13 is not particularly limited, and any substrate used as a substrate sheet of a general pressure-sensitive adhesive sheet can be used. Examples of the optical member include a woven fabric or a nonwoven fabric using fibers such as rayon, acrylonitrile, and polyester; synthetic paper; paper systems such as coated paper, cellophane paper, impregnated paper, and coated paper; metal foils of aluminum, copper, and the like; foams such as polyurethane foam and polyethylene foam; polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyurethane film, polyethylene film, polypropylene film, cellulose film such as triacetyl cellulose; plastic films such as polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, norbornene resin film, cycloolefin resin film; laminates of two or more of these. The plastic film may be a uniaxially or biaxially stretched film.
Examples of the optical member include a polarizing plate (polarizing film), a polarizing element, a retardation plate (retardation film), a viewing angle compensation film, a luminance improvement film, a contrast improvement film, a liquid crystal polymer film, a diffusion film, and a semi-transmissive reflection film. As the polarizing plate, a polarizing plate in which triacetyl cellulose (TAC) films are attached to both surfaces of a polyvinyl alcohol polarizing element, a polarizing plate in which one TAC film is changed to a cycloolefin polymer film (hereinafter, referred to as a "COP polarizing plate"), or the like is used. The pressure-sensitive adhesive layer 11 according to the present embodiment exhibits excellent adhesiveness to the above-described substrate, particularly a polarizing plate, particularly a COP polarizing plate.
The thickness of the substrate 13 varies depending on the type thereof, but in the case of an optical member, for example, the thickness is usually 10 to 500 μm, preferably 50 to 300 μm, and particularly preferably 80 to 150 μm.
Examples of the release sheets 12,12a, and 12b include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate film, an ionomer resin film, an ethylene- (meth) acrylic acid copolymer film, an ethylene- (meth) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, and a fluororesin film. In addition, crosslinked films thereof may also be used. Further, a laminate film thereof may be used. The release sheet 12,12a,12b is preferably active energy ray-permeable.
The release surface of the release sheet (particularly, the surface in contact with the pressure-sensitive adhesive layer 11) is preferably subjected to a release treatment. Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
The thickness of the release sheets 12,12a,12b is not particularly limited, and is usually about 20 μm to 150 μm.
In the production of the pressure-sensitive adhesive sheet 1A, a solution (coating solution) containing the pressure-sensitive adhesive composition P is applied and dried to the release surface of the release sheet 12, and after a coating layer of the pressure-sensitive adhesive composition P is formed, the substrate 13 is laminated on the coating layer. Then, the pressure-sensitive adhesive layer 11 is formed by irradiating the coating layer with an active energy ray across the release sheet 12. The irradiation conditions for the active energy rays are as described above.
In the production of the pressure-sensitive adhesive sheet 1B, a coating solution containing the pressure-sensitive adhesive composition is applied and dried to the release surface of one release sheet 12a (or 12B), and after a coating layer of the pressure-sensitive adhesive composition P is formed, the other release sheet 12B (or 12a) is laminated on the coating layer. The pressure-sensitive adhesive layer 11 is formed by irradiating the coating layer with active energy rays across the release sheet 12a (or 12 b).
Alternatively, instead of irradiating the release sheet with the active energy ray to form the pressure-sensitive adhesive layer 11 as described above, a coating film layer of the pressure-sensitive adhesive composition P may be formed on the release sheet, the pressure-sensitive adhesive layer 11 may be formed by irradiating the active energy ray in a state where the coating film layer is exposed, and then the pressure-sensitive adhesive layer 11 may be laminated with a substrate or a release sheet. Further, a coating layer of the pressure-sensitive adhesive composition P may be directly formed on the substrate, and the pressure-sensitive adhesive layer 11 may be formed by irradiating the coating layer with an active energy ray.
Examples of the method of applying the coating solution include a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, and a gravure roll coating method.
The haze value (value measured according to JIS K7136: 2000) of the pressure-sensitive adhesive layer 11 in the pressure- sensitive adhesive sheets 1A, 1B is preferably 1.0% or less, particularly preferably 0.9% or less, and more preferably 0.8% or less. When the haze value is 1.0% or less, the transparency is extremely high, and the pressure-sensitive adhesive layer is suitable for optical applications.
Here, for example, in the manufacture of a liquid crystal display device including a liquid crystal module and a polarizing plate, the release sheet 12 of the pressure-sensitive adhesive sheet 1A may be peeled off using a polarizing plate as the substrate 13 of the pressure-sensitive adhesive sheet 1A, and the exposed pressure-sensitive adhesive layer 11 and the liquid crystal module may be bonded to each other.
For example, in manufacturing a liquid crystal display device in which a retardation plate is disposed between a liquid crystal module and a polarizing plate, as an example, first, one release sheet 12a (or 12B) of the pressure-sensitive adhesive sheet 1B is peeled off, and the exposed pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1B and the retardation plate are bonded. Then, the release sheet 12 of the pressure-sensitive adhesive sheet 1A using the polarizing plate as the substrate 13 was peeled off, and the pressure-sensitive adhesive layer 11 exposed from the pressure-sensitive adhesive sheet 1A and the above-mentioned retardation plate were bonded. Further, the other release sheet 12B (or 12a) is peeled from the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet B, and the exposed pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet B is bonded to the liquid crystal module.
According to the pressure- sensitive adhesive sheets 1A and 1B described above, the pressure-sensitive adhesive layer 11 is excellent in durability, and therefore, even under high-temperature conditions or wet-heat conditions, it is possible to prevent or suppress the occurrence of swelling, peeling, foaming, or the like between the pressure-sensitive adhesive layer and the substrate 13 such as a COP polarizing plate or an adherend.
The pressure- sensitive adhesive sheets 1A and 1B according to the present embodiment preferably have a transparent conductive film as an adherend. In this case, the (meth) acrylate polymer (a) in the pressure-sensitive adhesive composition P preferably does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. This can suppress adverse effects on the transparent conductive film due to the acid component. Specifically, the transparent conductive film can be inhibited from being corroded, or the resistance value of the transparent conductive film can be inhibited from being changed.
Examples of the transparent conductive film include metals such as platinum, gold, silver, and copper; oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide, and zinc oxide; tin-doped indium oxide (ITO), zinc oxide-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, and the like; a chalcogen compound, lanthanum hexaboride, titanium nitride, titanium carbide, or other non-oxide compound.
The pressure-sensitive adhesive sheet 1A using a polarizing plate as the substrate 13 (hereinafter, referred to as "polarizing plate with a pressure-sensitive adhesive layer") has an adhesive strength to alkali-free glass of preferably 0.1N/25mm to 25N/25mm, and particularly preferably 2N/25mm to 20N/25 mm. When the adhesive strength is within the above range, swelling, peeling, or the like can be prevented between the sheet and an adherend such as a glass plate. The adhesive force referred to herein is basically a force obtained by a method based on JIS Z0237: 2009 adhesion force measured by 180 ° peel method, a measurement sample was cut into a width of 25mm and a length of 100mm, the measurement sample was attached to an adherend under pressure of 0.5MPa and 50 ℃ for 20 minutes, and then left for 24 hours under conditions of normal pressure of 23 ℃ and 50% RH, and the obtained adhesion force was measured at a peel speed of 300 mm/min.
The polarizing plate having the pressure-sensitive adhesive layer is adhered to the adherend and the adhesive strength after leaving the plate under normal pressure at 50 ℃ and 50% RH for 2 days is preferably 0.1N/25mm to 25N/25mm, and particularly preferably 2N/25mm to 20N/25 mm. As described above, the increase in adhesive force with time was suppressed, and thus a polarizing plate having excellent reworkability could be evaluated. Further, the adhesive force referred to herein also means an adhesive force obtained by adhering a base material to a substrate according to JIS Z0237: 2009, the adhesive force measured by the 180 ° peel method, the adhesive force obtained by cutting a measurement sample into pieces having a width of 25mm and a length of 100mm, applying the measurement sample to an adherend under pressure at 0.5MPa and 50 ℃ for 20 minutes, leaving the measurement sample under the above conditions (normal pressure, 50 ℃ and 50% RH) for 2 days, and measuring the adhesive force at a peel speed of 300 mm/min.
The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiments includes all design changes and equivalents that fall within the technical scope of the present invention.
For example, the release sheet 12 of the pressure-sensitive adhesive sheet 1A may be omitted, and either one of the release sheets 12a and 12B of the pressure-sensitive adhesive sheet 1B may be omitted.
[ examples ] A method for producing a compound
The present invention will be further specifically described below with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
[ example 1 ]
Preparation of (meth) acrylate Polymer
88 parts by mass of n-butyl acrylate, 5 parts by mass of methyl acrylate, 5 parts by mass of 2-phenylethyl acrylate, 2 parts by mass of 2-hydroxyethyl acrylate, 200 parts by mass of ethyl acetate and 0.08 part by mass of 2, 2' -azobisisobutyronitrile were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device and a nitrogen gas inlet tube, and the air in the reaction vessel was replaced with nitrogen gas. The reaction solution was heated to 60 ℃ with stirring in the nitrogen atmosphere, and the reaction was allowed to proceed for 16 hours, followed by cooling to room temperature. Here, it was confirmed that a part of the obtained solution was measured for molecular weight by the method described later, and a (meth) acrylate polymer (a) having a weight average molecular weight of 200 ten thousand was produced.
2. Preparation of pressure-sensitive adhesive composition
100 parts by mass (solid content equivalent; the same applies hereinafter) of the (meth) acrylic ester polymer (A) obtained in the above step (1); as the isocyanate-based crosslinking agent (B), 0.3 parts by mass of trimethylolpropane-modified xylylene diisocyanate (product of mitsui wutian 12465 ミカ ル, trade name "タケネート D110N"); 0.2 part by mass of a co-condensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane (trade name "X41-1810" manufactured by shin-Etsu chemical Co., Ltd.) as a silane coupling agent (C) having a mercapto group as a functional group which reacts with an organic material; 5 parts by mass of a mixture of bis (acryloyloxyethyl) isocyanurate and tris (acryloyloxyethyl) isocyanurate (product of Toyo Synthesis Co., Ltd.; trade name: アロニックス M315) as the active energy ray-curable component (D); as the photopolymerization initiator (E), benzophenone and 1-hydroxycyclohexyl benzophenone were polymerized in a ratio of 1: 1 (イルガキュア 500, manufactured by チバ & ス ペ シ ャ リ テ ィ ケ ミカ ル ズ)0.5 parts by mass (corresponding to 10 parts by mass per 100 parts by mass of the component D) of the obtained mixture was mixed, sufficiently stirred, and diluted with ethyl acetate to obtain a coating solution of the pressure-sensitive adhesive composition.
Here, compounding of the pressure-sensitive adhesive composition is shown in table 1. The abbreviations and the like shown in table 1 are described in detail below.
[ (meth) acrylate Polymer ]
BA: acrylic acid n-butyl ester
MA: acrylic acid methyl ester
PhEA: acrylic acid 2-phenoxyethyl
HEA: 2-hydroxyethyl acrylate
4 HBA: acrylic acid 4-hydroxybutyl ester
3. Production of polarizing plate with pressure-sensitive adhesive layer
The obtained coating solution of the pressure-sensitive adhesive composition was applied to a release-treated surface of a release sheet (manufactured by Linekec corporation, SP-PET 3811, thickness: 38 μm) having one surface of a polyethylene terephthalate film subjected to a release treatment with a silicone-based release agent, using a blade coater, and then subjected to a heat treatment at 90 ℃ for 1 minute to form a pressure-sensitive adhesive layer.
Next, a COP polarizing plate having a thickness of 100 μm, which was obtained by protecting one surface of a polarizing element formed of a polyvinyl alcohol film with a triacetyl cellulose film and the other surface with a cycloolefin polymer film, was laminated to the pressure-sensitive adhesive layer so that the exposed surface of the pressure-sensitive adhesive layer was in contact with the surface of the cycloolefin polymer film, and then, the pressure-sensitive adhesive layer was formed by irradiating ultraviolet light under the following conditions over a release sheet, thereby obtaining a polarizing plate with a pressure-sensitive adhesive layer. In addition, the thickness of the pressure-sensitive adhesive layer was 20 μm.
< ultraviolet irradiation conditions >
H bulb for electrodeless lamp manufactured by Fusion
Illuminance 600mW/cm2Light quantity of 150mJ/cm2
The UV illuminance/photometer used was "UVPF-36" manufactured by アイグラフィックス Co "
[ examples 2 to 8, comparative examples 1 to 3 ]
A polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in example 1, except that the kinds and proportions of the monomers constituting the (meth) acrylate polymer (a), the weight average molecular weight of the (meth) acrylate polymer (a), the isocyanate-based crosslinking agent (B), the silane coupling agent (C), and the blending amount of the active energy ray-curable component (D) were changed as shown in table 1. Further, in example 5, as the antistatic agent, a pressure-sensitive adhesive composition further mixed with 2.3 parts by mass of a pyridinium-based ionic liquid (product name "IL-P18" of Kyowa Kagaku Co., Ltd.) as a nitrogen-containing onium salt was used.
Here, the weight average Molecular Weight (MW) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC) under the following conditions (GPC measurement).
< measurement Condition >
GPC measurement apparatus: HLC-8020 manufactured by Toho ソー K
GPC column (passage in the following order): manufactured by Tokyo ソー K
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Determination of the solvent: tetrahydrofuran (THF)
Measurement temperature: 40 deg.C
[ test example 1 ] (measurement of gel fraction)
In examples or comparative examples, a pressure-sensitive adhesive sheet was produced using a release sheet (SP-PET 3801, manufactured by Linekekeko Co., Ltd., thickness: 38 μm) obtained by peeling one surface of a polyethylene terephthalate film with a silicone-based release agent, instead of the polarizing plate used for producing the polarizing plate having a pressure-sensitive adhesive layer. Specifically, the above-mentioned release sheet was laminated so that the release-treated surface side was in contact with the exposed pressure-sensitive adhesive layer of the construct comprising the release sheet/pressure-sensitive adhesive layer (thickness: 25 μm) obtained in the production process of the examples or comparative examples. Thus, a pressure-sensitive adhesive sheet having a release sheet/pressure-sensitive adhesive layer/release sheet structure was produced.
The pressure-sensitive adhesive sheet thus obtained was aged at 23 ℃ and 50% RH for 7 days. Thereafter, the pressure-sensitive adhesive sheet was prepared into a sample of 80mm × 80mm in size, the pressure-sensitive adhesive layer was wrapped with a polyester net (net size 200), and only the mass of the pressure-sensitive adhesive was weighed with a precision balance. The mass at this time was taken as M1.
Subsequently, the pressure-sensitive adhesive wrapped with 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 at a temperature of 23 ℃ and a relative humidity of 50% for 24 hours, and further dried in an oven at 80 ℃ for 12 hours. Only the mass of the pressure-sensitive adhesive after drying was weighed with a precision balance. The mass at this time was taken as M2. Gel fraction (%) is represented by (M2/M1). times.100. The results are shown in Table 1.
[ test example 2 ] (measurement of haze value)
As a measurement sample, a pressure-sensitive adhesive sheet (aged for 7 days) similar to the pressure-sensitive adhesive sheet used for measuring the gel fraction was prepared. The pressure-sensitive adhesive layer (thickness: 25 μm) of this pressure-sensitive adhesive sheet was measured using a haze meter (NDH 2000, manufactured by japan electro-chromatic industries, inc., JIS K7136: 2000, haze value (%) was measured. The results are shown in Table 1.
[ test example 3 ] (measurement of storage modulus)
A pressure-sensitive adhesive sheet composed of a release sheet, a pressure-sensitive adhesive layer, and a release sheet was produced in the same manner as in test example 1. The release sheet was peeled from the pressure-sensitive adhesive sheet so that the thickness of the pressure-sensitive adhesive layer became 3mm, and multilayer lamination was performed. Holes of a cylinder (height 3mm) having a diameter of 8mm were punched out of the obtained laminate of the pressure-sensitive adhesive layer as a sample.
The storage modulus (MPa) of the above sample was measured by a torsional shear method using a viscoelasticity measuring instrument (available from REMOMETRIC, DYNAMICALANALAYER) in accordance with JIS K7244-6 under the following conditions. The results are shown in Table 1.
Measuring frequency: 1Hz
Measuring temperature: 23 ℃ and 80 DEG C
[ test example 4 ] (evaluation of durability)
The polarizing plate with the pressure-sensitive adhesive layer obtained in example or comparative example was cut to prepare a sample having a size of 233mm × 309 mm. As a sample, a sample was prepared after storing the polarizing plate with the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer formation) at 23 ℃ and 50% RH for 7 days. The release sheet was peeled from the sample, and after being stuck to alkali-free glass (イーグル XG, manufactured by コーニング Co.) through the exposed pressure-sensitive adhesive layer, the sheet was pressed at 0.5MPa and 50 ℃ for 20 minutes in an autoclave manufactured by King.
After that, the glass was put into an environment under the following durable conditions, and after 250 hours, the presence or absence of swelling or peeling was checked using a 10-fold loupe. The evaluation criteria are as follows. The results are shown in Table 1.
◎ No bulging or peeling was observed.
○, swelling or peeling of a size of 0.5mm or less was observed.
X: swelling or peeling of a size of 0.6mm or more was observed.
< endurance Condition >
Drying at 80 ℃
60 ℃ relative humidity 90% RH
[ test example 5 ] (measurement of surface resistivity)
The polarizing plate with the pressure-sensitive adhesive layer obtained in example 5 was cut in a size of 50mm × 50mm, and the obtained sample was left at 23 ℃ and 50% RH for 24 hours. Thereafter, the release sheet was peeled off, and the surface resistance value (Ω/sq) was measured on the exposed surface of the pressure-sensitive adhesive layer based on JIS K6911 using a resistivity meter (manufactured by Mitsubishi chemical アナリテッ ク, model ハイレスタ UP MCP-HT 450). The results are shown in Table 1.
In addition, the surface resistance value is preferably 3.0 × 1011Omega/sq or less, particularly preferably 1.0X 1011Omega/sq or less, more preferably 8.0X 1010Omega/sq ofThe following steps. When the surface resistance value is less than the above value, good antistatic property is exhibited.
As is clear from table 1, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer obtained in the examples was excellent in durability and had good storage modulus at 23 ℃ and 80 ℃.
[ industrial applicability ]
The pressure-sensitive adhesive of the present invention is suitable for adhesion of an optical member, particularly a polarizing plate, and the pressure-sensitive adhesive sheet of the present invention is suitable for use as a pressure-sensitive adhesive sheet for an optical member, particularly for use as a polarizing plate.
Claims (14)
1. A pressure-sensitive adhesive composition comprising:
a (meth) acrylate polymer (A) containing 1.5% by mass or more of a monomer having a hydroxyl group, 1% by mass to 10% by mass of a monomer having an aromatic ring, and 80% by mass to 97.5% by mass of an alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms and not containing a monomer having a carboxyl group as a monomer unit constituting the polymer;
an isocyanate-based crosslinking agent (B);
a silane coupling agent (C) having a mercapto group as a functional group that reacts with the organic material;
and an active energy ray-curable component (D).
2. The pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylate polymer (a) has a weight average molecular weight of 100 to 250 ten thousand, and contains 1.8 to 10 mass% of the monomer having a hydroxyl group as a monomer unit constituting the polymer.
3. The pressure-sensitive adhesive composition according to claim 1, wherein the monomer having an aromatic ring is 2-phenylethyl (meth) acrylate.
4. The pressure-sensitive adhesive composition according to claim 1, wherein the isocyanate-based crosslinking agent (B) is trimethylolpropane-modified xylylene diisocyanate.
5. The pressure-sensitive adhesive composition according to claim 1, wherein the active energy ray-curable component (D) is a polyfunctional acrylate monomer having a molecular weight of less than 1000.
6. The pressure-sensitive adhesive composition according to claim 5, wherein the polyfunctional acrylate-based monomer has a cyclic structure.
7. The pressure-sensitive adhesive composition according to claim 1, wherein the content of the active energy ray-curable component (D) in the pressure-sensitive adhesive composition is 5 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylate polymer (a).
8. A pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition according to any one of claims 1 to 7 by irradiation with an active energy ray.
9. The pressure-sensitive adhesive according to claim 8, wherein the gel fraction is 75 to 95% after storage for 7 days in an environment of 23 ℃ and 50% RH from the formation of the pressure-sensitive adhesive layer.
10. The pressure-sensitive adhesive of claim 8, wherein the storage modulus (G ') at 23 ℃ is 0.05MPa to 0.20MPa and the storage modulus (G') at 80 ℃ is 0.05MPa to 0.15 MPa.
11. A pressure-sensitive adhesive sheet which is a pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer, characterized in that the pressure-sensitive adhesive layer comprises the pressure-sensitive adhesive according to claim 8.
12. The pressure-sensitive adhesive sheet according to claim 11, wherein the substrate is an optical member.
13. The pressure-sensitive adhesive sheet according to claim 12, wherein the optical member is a polarizing plate.
14. A pressure-sensitive adhesive sheet comprising two release sheets and a pressure-sensitive adhesive layer sandwiched between the release sheets so as to be in contact with release surfaces of the two release sheets, wherein the pressure-sensitive adhesive layer comprises the pressure-sensitive adhesive according to claim 8.
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| JP2013-026092 | 2013-02-13 | ||
| JP2013026092A JP6112893B2 (en) | 2013-02-13 | 2013-02-13 | Adhesive composition, adhesive and adhesive sheet |
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| CN103980820A CN103980820A (en) | 2014-08-13 |
| CN103980820B true CN103980820B (en) | 2020-01-17 |
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| JP (1) | JP6112893B2 (en) |
| KR (1) | KR102157557B1 (en) |
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| JP5988889B2 (en) * | 2013-02-15 | 2016-09-07 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| JP6356383B2 (en) * | 2013-02-15 | 2018-07-11 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| KR101927432B1 (en) * | 2015-02-11 | 2018-12-10 | 동우 화인켐 주식회사 | High durable polarizing plate and display device comprising thereof |
| JP6444793B2 (en) * | 2015-03-03 | 2018-12-26 | リンテック株式会社 | Adhesive, adhesive sheet and optical film with adhesive layer |
| JP6438817B2 (en) * | 2015-03-27 | 2018-12-19 | リンテック株式会社 | Adhesive composition, adhesive, adhesive sheet and optical film with adhesive layer |
| JP2016204406A (en) * | 2015-04-15 | 2016-12-08 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| WO2016170875A1 (en) * | 2015-04-22 | 2016-10-27 | Dic株式会社 | Ultraviolet ray-curable adhesive sheet, and adhesive sheet |
| JP6554344B2 (en) * | 2015-06-30 | 2019-07-31 | リンテック株式会社 | Adhesive sheet and display |
| JP6755089B2 (en) * | 2015-11-27 | 2020-09-16 | 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． | Adhesive composition, adhesive layer, adhesive sheet, and image display device |
| JP6232486B2 (en) * | 2016-01-19 | 2017-11-15 | 住友化学株式会社 | Method for producing optical laminate |
| JP6594782B2 (en) * | 2016-01-25 | 2019-10-23 | リンテック株式会社 | Polarizing plate with adhesive layer |
| JP7030436B2 (en) * | 2016-09-29 | 2022-03-07 | 日東電工株式会社 | Polarizing film with adhesive layer and image display device |
| JP6921586B2 (en) * | 2017-03-31 | 2021-08-18 | リンテック株式会社 | Adhesive Compositions, Adhesives, Adhesive Sheets and Labels |
| JP6467548B1 (en) * | 2017-09-28 | 2019-02-13 | 日東電工株式会社 | Reinforcement film |
| JP2020063377A (en) * | 2018-10-18 | 2020-04-23 | 東洋インキＳｃホールディングス株式会社 | Active energy ray polymerizable adhesive, and polarizer |
| TWI714932B (en) * | 2018-12-24 | 2021-01-01 | 明基材料股份有限公司 | Adhesive for flexible optical film |
| CN111978871A (en) * | 2020-06-30 | 2020-11-24 | 南京汇鑫光电材料有限公司 | Processing technological process of pressure-sensitive adhesive for vehicle-mounted display |
| KR102635555B1 (en) * | 2021-06-18 | 2024-02-08 | (주)이녹스첨단소재 | Adhesive sheet for display and display comprising the same |
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| KR100932888B1 (en) * | 2006-07-21 | 2009-12-21 | 주식회사 엘지화학 | Optically compensated acrylic pressure sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| JP5379409B2 (en) * | 2008-02-15 | 2013-12-25 | 日東電工株式会社 | Adhesive composition for optical film, adhesive optical film, and image display device |
| JP5591477B2 (en) | 2008-03-13 | 2014-09-17 | 日東電工株式会社 | Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, transparent conductive laminate, touch panel, and image display device |
| JP5407204B2 (en) * | 2008-07-16 | 2014-02-05 | 王子ホールディングス株式会社 | Adhesive, double-sided adhesive sheet, optical filter, and display |
| WO2010050527A1 (en) * | 2008-10-31 | 2010-05-06 | 日本合成化学工業株式会社 | Adhesive for optical members, optical member having adhesive layer obtained using the same, and adhesive composition for active energy beam-setting and/or thermosetting optical member |
| JP5455362B2 (en) * | 2008-12-25 | 2014-03-26 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition and optical member using the same |
| TW201107437A (en) * | 2009-06-09 | 2011-03-01 | Nippon Synthetic Chem Ind | Adhesive compositions and adhesive, adhesive for optical members and optical member with adhesive layer using it |
| CN102181244B (en) * | 2009-12-29 | 2014-02-12 | 第一毛织株式会社 | Adhesive binder and preparation method thereof, composition, method for manufacturing adhesive binder layer and optical member |
| JP6097473B2 (en) * | 2010-12-13 | 2017-03-15 | 日東電工株式会社 | Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, pressure-sensitive adhesive optical film, and image display device |
| JP2012208248A (en) * | 2011-03-29 | 2012-10-25 | Sumitomo Chemical Co Ltd | Liquid crystal display device |
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| JP2014152318A (en) | 2014-08-25 |
| TWI618767B (en) | 2018-03-21 |
| JP6112893B2 (en) | 2017-04-12 |
| TW201439259A (en) | 2014-10-16 |
| KR102157557B1 (en) | 2020-09-18 |
| CN103980820A (en) | 2014-08-13 |
| KR20140102130A (en) | 2014-08-21 |
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