JP6606334B2 - Adhesive composition, adhesive layer, adhesive sheet, optical member with adhesive layer, and image display device - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive composition. The present invention also relates to an adhesive layer composed of the adhesive composition, an adhesive sheet including the adhesive layer, and an optical member with an adhesive layer. The present invention also relates to an image display device including at least one optical member with such an adhesive layer.

  A pressure-sensitive adhesive composition containing a specific polyrotaxane has been reported as a pressure-sensitive adhesive composition constituting a pressure-sensitive adhesive layer having excellent stress relaxation properties and durability (Patent Document 1). This specific polyrotaxane is a special polymer called Selum (registered trademark) superpolymer known as a sliding ring material of Advanced Soft Materials Co., Ltd., and is a direct polymer penetrating through the opening of the cyclic molecule. A polyrotaxane having a chain molecule and blocking groups arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule.

  When applying a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition containing such a specific polyrotaxane to an optical member, the haze value of the pressure-sensitive adhesive layer is lowered in order not to deteriorate the optical properties of the optical member. It is required to do.

  In response to such a request, in addition to the specific polyrotaxane as described above, a (meth) acrylic acid ester-based polymer having no carboxyl group and a (meth) acrylic acid ester-based polymer having a carboxyl group are included. In addition to the pressure-sensitive adhesive composition (Patent Document 2) and the specific polyrotaxane as described above, a pressure-sensitive adhesive composition (Patent Document 3) containing a chelate compound has been reported.

  However, in the pressure-sensitive adhesive composition reported in Patent Document 2 and Patent Document 3, the haze value of the pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition is not sufficiently low. In Patent Document 2, among 25 examples, 23 have a haze value of 1.0 or more, 11 have a haze value of 1.5 or more, and have a haze value of 2.0 or more. Since there are five, the effect is not sufficient. In Patent Document 3, among 21 examples, all 21 have a haze value of 1.0 or more, 17 have a haze value of 1.5 or more, and have a haze value of 2.0 or more. Since there are nine, there are not enough effects.

  In addition, in the pressure-sensitive adhesive composition reported in Patent Documents 2 and 3, the newly added component for suppressing haze does not participate in the cross-linking formation of the pressure-sensitive adhesive layer, so that the gel fraction is sufficiently high. There is a possibility that a problem that the component that does not rise or the added component bleeds out to the surface of the pressure-sensitive adhesive layer and affects the pressure-sensitive adhesive properties may occur.

JP 2007-224133 A JP 2013-05662 A JP 2013-203854 A

  The subject of this invention is providing the adhesive composition which comprises the adhesive layer which can express a sufficiently low haze value while being excellent in stress relaxation property and durability. Moreover, it is providing the adhesive layer comprised from such an adhesive composition. Furthermore, it is providing the adhesive sheet containing such an adhesive layer and an optical member with an adhesive layer. Moreover, the image display apparatus containing at least 1 such an optical member with an adhesive layer can be provided.

The pressure-sensitive adhesive composition of the present invention is
(Meth) acrylic polymer, a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. A pressure-sensitive adhesive composition comprising a polyrotaxane having a blocking group.
The (meth) acrylic polymer includes a structural unit derived from a monomer having no aromatic ring structure and a structural unit derived from a monomer having an aromatic ring structure.

  In preferable embodiment, the content rate of the said (meth) acrylic-type polymer in the said adhesive composition is 70 weight%-99.9 weight% in a weight ratio.

  In preferable embodiment, the content rate of the said polyrotaxane in the said adhesive composition is 0.1 weight%-30 weight% in a weight ratio.

  In preferable embodiment, the content rate of the structural unit derived from the monomer which has the said aromatic ring structure in the said (meth) acrylic-type polymer is 1 weight%-35 weight% in a weight ratio.

  In a preferred embodiment, the monomer having an aromatic ring structure contains at least one selected from benzyl acrylate and phenoxyethyl acrylate.

  The pressure-sensitive adhesive layer of the present invention is composed of the pressure-sensitive adhesive composition of the present invention.

  The pressure-sensitive adhesive sheet of the present invention includes the pressure-sensitive adhesive layer of the present invention and a base material layer.

  The optical member with an adhesive layer of the present invention includes the adhesive layer of the present invention and an optical member.

  The image display device of the present invention includes at least one optical member with an adhesive layer of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in stress relaxation property and durability, the adhesive composition which comprises the adhesive layer which can express a sufficiently low haze value can be provided. Moreover, the adhesive layer comprised from such an adhesive composition can be provided. Furthermore, the adhesive sheet containing such an adhesive layer and an optical member with an adhesive layer can be provided. Moreover, the image display apparatus containing at least 1 such an optical member with an adhesive layer can be provided.

≪Adhesive composition≫
The pressure-sensitive adhesive composition of the present invention comprises a (meth) acrylic polymer, a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and the cyclic molecule so that the cyclic molecule is not detached from the linear molecule. And a polyrotaxane having blocking groups arranged at both ends of the linear molecule. Hereinafter, in the present specification, the (meth) acrylic polymer contained in the pressure-sensitive adhesive composition of the present invention is simply referred to as “(meth) acrylic polymer”, and the polyrotaxane contained in the pressure-sensitive adhesive composition of the present invention is referred to as “(meth) acrylic polymer”. It is simply referred to as “polyrotaxane”.

  In the present specification, “(meth) acryl” means acryl and / or methacryl, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acryloyl” It means acryloyl and / or methacryloyl.

  The content ratio of the (meth) acrylic polymer in the pressure-sensitive adhesive composition of the present invention is preferably 70% to 99.9% by weight, more preferably 75% to 99.5% by weight. %, More preferably 80% to 99% by weight, and particularly preferably 85% to 99% by weight. By adjusting the content ratio of the (meth) acrylic polymer in the pressure-sensitive adhesive composition of the present invention within the above range, a pressure-sensitive adhesive layer that is more excellent in stress relaxation and durability and can express a sufficiently lower haze value. While providing the adhesive composition to comprise, the adhesive layer comprised from such an adhesive composition, the adhesive sheet containing such an adhesive layer, and an optical member with an adhesive layer can be provided.

  The content ratio of the polyrotaxane in the pressure-sensitive adhesive composition of the present invention is, by weight, preferably 0.01% to 30% by weight, more preferably 0.05% to 25% by weight, Preferably they are 1 weight%-20 weight%, Especially preferably, they are 1 weight%-15 weight%. By adjusting the content ratio of the polyrotaxane in the pressure-sensitive adhesive composition of the present invention within the above range, a pressure-sensitive adhesive composition constituting a pressure-sensitive adhesive layer that is more excellent in stress relaxation and durability and can exhibit a sufficiently sufficiently lower haze value. A pressure-sensitive adhesive layer composed of such a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet including such a pressure-sensitive adhesive layer, and an optical member with a pressure-sensitive adhesive layer can be provided.

<(Meth) acrylic polymer>
The (meth) acrylic polymer includes a structural unit derived from a monomer having no aromatic ring structure and a structural unit derived from a monomer having an aromatic ring structure. Preferably, the (meth) acrylic polymer includes a structural unit derived from a monomer having no aromatic ring structure and a structural unit derived from a monomer having an aromatic ring structure. The (meth) acrylic polymer contains a structural unit derived from a monomer that does not have an aromatic ring structure and a structural unit derived from a monomer that has an aromatic ring structure. A pressure-sensitive adhesive composition constituting a pressure-sensitive adhesive layer capable of exhibiting a low haze value can be provided, a pressure-sensitive adhesive layer composed of such a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet comprising such a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive An optical member with an agent layer may be provided.

  The “monomer-derived structural unit” is a repeating structural unit derived from a monomer by a polymerization reaction. For example, when the monomer is represented by “Ra (Rb) = Rc (Rd)”, the structural unit derived from the monomer is “—Ra (Rb) —Rc (Rd) —”. Here, Ra, Rb, Rc, and Rd are arbitrary groups bonded to the unsaturated double bond of the monomer.

  The content ratio of the structural unit derived from the monomer having an aromatic ring structure in the (meth) acrylic polymer is a weight ratio, preferably 1% to 35% by weight, more preferably 3% to 30% by weight. %, More preferably 5% to 28% by weight, particularly preferably 8% to 25% by weight, and most preferably 10% to 23% by weight. By adjusting the content ratio of the structural unit derived from the monomer having an aromatic ring structure in the (meth) acrylic polymer within the above range, it is possible to develop a sufficiently sufficiently low haze value as well as excellent stress relaxation and durability. An adhesive composition that constitutes an adhesive layer can be provided, and an adhesive layer composed of such an adhesive composition, an adhesive sheet including such an adhesive layer, and an optical member with an adhesive layer are provided Can do.

  In the present invention, the content ratio of the structural unit derived from the monomer having an aromatic ring structure in the (meth) acrylic polymer is substantially the same as that used for producing the (meth) acrylic polymer. It is treated as being the same as the content ratio of the monomer having an aromatic ring structure in the monomer component.

  The content ratio of the structural unit derived from the monomer having no aromatic ring structure in the (meth) acrylic polymer is, by weight, preferably 65% to 99% by weight, more preferably 70% by weight to It is 97% by weight, more preferably 72% by weight to 95% by weight, particularly preferably 75% by weight to 92% by weight, and most preferably 77% by weight to 90% by weight. By adjusting the content ratio of the structural unit derived from the monomer having no aromatic ring structure in the (meth) acrylic polymer within the above range, the stress relaxation property and the durability are excellent and the haze value is sufficiently lower. A pressure-sensitive adhesive composition constituting a pressure-sensitive adhesive layer that can be expressed can be provided, a pressure-sensitive adhesive layer composed of such a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet including such a pressure-sensitive adhesive layer, and an optical member with a pressure-sensitive adhesive layer Can provide.

  In addition, in this invention, the content rate of the structural unit derived from the monomer which does not have an aromatic ring structure in a (meth) acrylic-type polymer is used in order to manufacture a (meth) acrylic-type polymer substantially. It is treated as the same as the content ratio of the monomer having no aromatic ring structure in all monomer components.

  The monomer having no aromatic ring structure is a polymerizable monomer having an unsaturated double bond, and any monomer that does not have an aromatic ring structure may be used as long as the effects of the present invention are not impaired. Any suitable monomer may be employed. The aromatic ring structure may be a monocyclic structure or a bicyclic (fused ring) structure.

  As a monomer having no aromatic ring structure, for the purpose of improving adhesiveness and heat resistance, for example, it has a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. One or more types of copolymerization monomers may be mentioned.

  Specific examples of such copolymerizable monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 Hydroxyl group-containing monomers such as -hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate; Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Group-containing monomer A caprolactone adduct of acrylic acid; styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxy Sulfonic acid group-containing monomers such as naphthalene sulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate;

  Examples of such a copolymerization monomer include a modification monomer for modification purposes. Examples of such a modified monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methylolpropane (meth) acrylamide. (N-substituted) amide monomers such as aminoethyl (meth) acrylate, alkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate Aminoalkyl monomers; (meth) acrylic acid alkoxyalkyl monomers such as (meth) acrylic acid methoxyethyl and (meth) acrylic acid ethoxyethyl; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6 -Oxyhexamethylenesuccin Succinimide monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide and N-acryloylmorpholine; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide Itaconimide monomers such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide; Etc.

  Further, examples of such modifying monomers include vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, and vinyl oxazole. , Vinyl morpholine, N-vinyl carboxylic acid amides, vinyl monomers such as styrene, α-methyl styrene, N-vinyl caprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy such as glycidyl (meth) acrylate Group-containing acrylic monomers; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, ( T) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate, 2-methoxyethyl acrylate, etc. Also mentioned. Furthermore, examples of such a modified monomer include isoprene, butadiene, isobutylene, and vinyl ether.

  Furthermore, examples of the copolymerization monomer include silane monomers containing silicon atoms. Examples of such silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyl. Examples include trimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like. It is done.

  Moreover, as a copolymerization monomer, for example, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) (Meth) such as esterified products of (meth) acrylic acid and polyhydric alcohol such as acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate Multifunctional monomer having 2 or more unsaturated double bonds such as acryloyl group and vinyl group; 2 or more unsaturated double bonds such as (meth) acryloyl group and vinyl group in polyester skeleton, epoxy skeleton and urethane skeleton Added polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, etc.

  The monomer having no aromatic ring structure is preferably a (meth) acrylic monomer such as (meth) acrylic acid ester, (meth) acrylic acid or a salt thereof (such as sodium salt or potassium salt) as a main monomer. Including. The content ratio of the (meth) acrylic monomer in the monomer having no aromatic ring structure is preferably 50% by weight or more, more preferably 70% by weight to 100% by weight, and further preferably 90% by weight to 100% by weight. Particularly preferred is 95 to 100% by weight. By adjusting the content ratio of the (meth) acrylic monomer in the monomer having no aromatic ring structure within the above range, the pressure-sensitive adhesive is excellent in stress relaxation and durability and can exhibit a sufficiently low haze value. While providing the adhesive composition which comprises a layer, it can provide the adhesive layer comprised from such an adhesive composition, the adhesive sheet containing such an adhesive layer, and an optical member with an adhesive layer. .

  The (meth) acrylic monomer preferably includes (meth) acrylic acid ester, (meth) acrylic acid or a salt thereof (such as sodium salt or potassium salt).

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms (including cycloalkyl groups), hydroxyl group-containing (meth) acrylic acid esters, and the like. Only one (meth) acrylic acid ester may be used, or two or more may be used.

  Examples of the alkyl (meth) acrylate alkyl ester having 1 to 30 carbon atoms (including a cycloalkyl group) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Amyl acid, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( T) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, (meth) And (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms (including cycloalkyl groups) such as nonadecyl acrylate, eicosyl (meth) acrylate, and lauryl (meth) acrylate. Among these (meth) acrylic acid esters, a (meth) acrylic acid alkyl ester of an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferable, and 4 to 18 carbon atoms are more preferable. (Meth) acrylic acid alkyl ester of an alkyl group (including a cycloalkyl group).

  Examples of the hydroxyl group-containing (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

  The monomer having no aromatic ring structure preferably includes (meth) acrylic acid alkyl ester of an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group). In this case, the content ratio of the (meth) acrylic acid alkyl ester of an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) in the monomer having no aromatic ring structure is preferably a weight ratio, 50 wt% to 99.999 wt%, more preferably 70 wt% to 99.99 wt%, still more preferably 80 wt% to 99.9 wt%, particularly preferably 90 wt% to 99 wt%. 0.5 wt%, most preferably 95 wt% to 99.5 wt%. Stress relaxation by adjusting the content ratio of (meth) acrylic acid alkyl ester of alkyl group having 1 to 30 carbon atoms (including cycloalkyl group) in the monomer having no aromatic ring structure within the above range. A pressure-sensitive adhesive composition that constitutes a pressure-sensitive adhesive layer that is excellent in properties and durability and that can exhibit a sufficiently low haze value, and a pressure-sensitive adhesive layer that is composed of such a pressure-sensitive adhesive composition, An adhesive sheet including an adhesive layer and an optical member with an adhesive layer can be provided.

  The monomer having no aromatic ring structure preferably contains a hydroxyl group-containing (meth) acrylic acid ester. In this case, the content ratio of the hydroxyl group-containing (meth) acrylic acid ester in the monomer having no aromatic ring structure is a weight ratio, preferably 0.001 to 50% by weight, more preferably 0. 0.01 wt% to 30 wt%, more preferably 0.1 wt% to 20 wt%, particularly preferably 0.5 wt% to 10 wt%, most preferably 0.5 wt% to 5% by weight. By adjusting the content ratio of the hydroxyl group-containing (meth) acrylic acid ester in the monomer having no aromatic ring structure within the above range, it is possible to develop a sufficiently sufficiently low haze value as well as excellent stress relaxation properties and durability. An adhesive composition that constitutes an adhesive layer can be provided, and an adhesive layer composed of such an adhesive composition, an adhesive sheet including such an adhesive layer, and an optical member with an adhesive layer are provided Can do.

  The monomer having no aromatic ring structure preferably includes (meth) acrylic acid or a salt thereof (such as sodium salt or potassium salt). In this case, the content ratio of (meth) acrylic acid or a salt thereof (such as sodium salt or potassium salt) in the monomer having no aromatic ring structure is a weight ratio, preferably 0 wt% to 50 wt%. More preferably 0.01 wt% to 40 wt%, still more preferably 0.1 wt% to 30 wt%, particularly preferably 0.5 wt% to 20 wt%, most preferably 1% by weight to 10% by weight. By adjusting the content ratio of (meth) acrylic acid or a salt thereof (sodium salt, potassium salt, etc.) in the monomer having no aromatic ring structure within the above range, it has excellent stress relaxation properties and durability. A pressure-sensitive adhesive composition constituting a pressure-sensitive adhesive layer capable of expressing a sufficiently low haze value can be provided, a pressure-sensitive adhesive layer composed of such a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet comprising such a pressure-sensitive adhesive layer, and An optical member with an adhesive layer can be provided.

  As the monomer having an aromatic ring structure, any appropriate monomer within the range of not impairing the effects of the present invention as long as it is a polymerizable monomer having an unsaturated double bond and has an aromatic ring structure. Can be adopted. The aromatic ring structure may be a monocyclic structure or a bicyclic (fused ring) structure.

  Examples of the monomer having an aromatic ring structure include benzyl acrylate, phenoxyethyl acrylate, phenyl acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and ethylene oxide. Examples thereof include modified nonylphenol (meth) acrylate, hydroxyethylated β-naphthol acrylate, biphenyl (meth) acrylate and the like. Furthermore, for example, phenol ethylene oxide modified (meth) acrylate, 2-naphthoethyl (meth) acrylate, 2-naphthoxyethyl acrylate, 2- (4-methoxy-1-naphthoxy) ethyl (meth) acrylate, phenoxypropyl (meth) Examples include acrylate, phenoxydiethylene glycol (meth) acrylate, thiol acrylate, pyridyl acrylate, pyrrole acrylate, phenyl acrylate, and polystyryl (meth) acrylate. The monomer having an aromatic ring structure may be only one type or two or more types.

  The monomer having an aromatic ring structure preferably contains at least one selected from benzyl acrylate and phenoxyethyl acrylate. Adhesive that constitutes a pressure-sensitive adhesive layer that is excellent in stress relaxation and durability and that can express a sufficiently haze value when the monomer having an aromatic ring structure contains at least one selected from benzyl acrylate and phenoxyethyl acrylate While providing an adhesive composition, the adhesive layer comprised from such an adhesive composition, the adhesive sheet containing such an adhesive layer, and an optical member with an adhesive layer can be provided.

  The (meth) acrylic polymer can be produced by any appropriate method. As a manufacturing method of (meth) acrylic-type polymer, well-known manufacturing methods, such as solution polymerization, block polymerization, emulsion polymerization, various radical polymerization, can be selected suitably, for example. Further, the obtained (meth) acrylic polymer may be a random copolymer, a block copolymer, a graft copolymer, or the like. In solution polymerization, for example, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of solution polymerization, for example, a polymerization initiator is added under an inert gas stream such as nitrogen, and the solution polymerization is usually performed at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours. Etc.

  Any appropriate polymerization initiator, chain transfer agent, emulsifier, and the like used for radical polymerization can be selected as long as the effects of the present invention are not impaired. In addition, the weight average molecular weight of the (meth) acrylic polymer (A) can be controlled by, for example, the amount of polymerization initiator used, the amount of chain transfer agent used, reaction conditions, and the like. Their usage is adjusted.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2). -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 '-Azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, VA-057) and other azo initiators, and persulfates such as potassium persulfate and ammonium persulfate , Di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butyl -Oxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3 , 3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) ) Peroxides such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides and sodium bisulfite, peroxides and sodium ascorbate Redox initiators combined with Not intended to be.

  A polymerization initiator may be used independently and may use 2 or more types together.

  The amount of the polymerization initiator used is preferably from 0.005 to 1 part by weight, more preferably from 0.005 to 1 part by weight, based on 100 parts by weight of all monomer components used to produce the (meth) acrylic polymer. 02 parts by weight to 0.5 parts by weight.

  In order to produce a (meth) acrylic polymer using, for example, 2,2′-azobisisobutyronitrile as a polymerization initiator, the amount of polymerization initiator used is a (meth) acrylic polymer. Preferably it is 0.06 weight part-0.2 weight part with respect to 100 weight part of all the monomer components used in order to manufacture, More preferably, it is 0.08 weight part-0.175 weight part.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. A chain transfer agent may be used independently and may use 2 or more types together.

  The amount of the chain transfer agent used is preferably 0.1 parts by weight or less with respect to 100 parts by weight of the total monomer components used for producing the (meth) acrylic polymer.

  Examples of the emulsifier used for emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxyethylene alkyl And nonionic emulsifiers such as ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer; and the like. These emulsifiers may be used independently and may use 2 or more types together.

  Furthermore, as the emulsifier, a reactive emulsifier into which a radical polymerizable functional group such as a propenyl group or an allyl ether group is introduced can also be used. Examples of such reactive emulsifiers include Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria There is a soap SE10N (Asahi Denka Kogyo Co., Ltd.). Reactive emulsifiers are preferred because they are incorporated into the polymer chain after polymerization and thus have improved water resistance.

  The amount of the emulsifier is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total monomer components used for producing the (meth) acrylic polymer, from the viewpoint of polymerization stability and mechanical stability. Parts by weight, more preferably 0.5 parts by weight to 1 part by weight.

  The (meth) acrylic polymer in the present invention that can be obtained by the method described above usually has a weight average molecular weight in the range of 500,000 to 3,000,000. Considering durability, particularly heat resistance, the weight average molecular weight of the (meth) acrylic polymer in the present invention is preferably 700,000 to 2,700,000, more preferably 800,000 to 2,500,000. When the weight average molecular weight of the (meth) acrylic polymer in the present invention is smaller than 500,000, it is not preferable in terms of heat resistance. In addition, when the weight average molecular weight of the (meth) acrylic polymer in the present invention is larger than 3 million, a large amount of a diluting solvent is required to adjust the viscosity for coating, which is not preferable. . The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

<Polyrotaxane>
The polyrotaxane comprises a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and blocking groups disposed at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. Have.

  A cyclic molecule is a molecule in which a straight-chain molecule is included in a skewered manner in the opening and is movable on the straight-chain molecule, and has a hydroxyl group or an active energy ray-polymerizable group. Any appropriate cyclic molecule may be employed as long as the effects of the invention are not impaired. In the present specification, “cyclic” of “cyclic molecule” means substantially “cyclic”. That is, the cyclic molecule may not be completely closed as long as it can move on the linear molecule.

  Specific examples of the cyclic molecule preferably include cyclic polymers such as cyclic polyether, cyclic polyester, cyclic polyetheramine, and cyclic polyamine, and cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. It is done. Among these, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferable because they are relatively easily available and a large number of types of blocking groups can be selected. Two or more cyclic molecules may be mixed in the polyrotaxane.

  In the polyrotaxane, the cyclic molecule preferably has a hydroxyl group. Moreover, a part of such hydroxyl groups may be substituted with other groups. Examples of such other groups include a hydrophilic group, a hydrophobic group, and a photoreactive group.

  As a linear molecule, a molecule or substance that is included in a cyclic molecule and can be integrated by a mechanical bond rather than a chemical bond such as a covalent bond, It is not limited. In the present specification, “linear” of “linear molecule” means substantially “linear”. That is, the linear molecule may have a branched chain as long as the cyclic molecule can move on the linear molecule.

  As the linear molecule, for example, polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polytetrahydrofuran, polyacrylic acid ester, polydimethylsiloxane, polyethylene, polypropylene and the like are preferable. There may be only one kind of linear molecule, or two or more kinds.

  The number average molecular weight of the linear molecule is preferably 1000 to 300000, more preferably 2000 to 200000, and further preferably 4000 to 100000.

  As the blocking group, any appropriate group can be adopted as long as the cyclic molecule is a group that can keep a skewered form with a linear molecule as long as the effect of the present invention is not impaired. Such groups include, for example, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, anthracene, main chain or side chain of a polymer having a number average molecular weight of 1,000 to 1,000,000. Etc. Only one type of blocking group may be used, or two or more types may be used.

  In the polyrotaxane, the cyclic molecule is preferably 0 when the amount (maximum inclusion amount) by which the cyclic molecule is included to the maximum when the cyclic molecule is clasped with the linear molecule is 100%. 0.1% to 60%, more preferably 1% to 50%, and even more preferably 5% to 40% in a chain-like inclusion in linear molecules. The maximum inclusion amount of the cyclic molecule can be determined by the length of the linear molecule and the thickness of the cyclic molecule. For example, when the linear molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount is experimentally determined (see Macromolecules 1993, 26, 5698-5703).

  As the polyrotaxane, for example, polyrotaxanes described in JP-A-2005-154675, JP-A-2009-270119, WO2009 / 145073 and the like can be employed.

  The polyrotaxane can be obtained, for example, by the method described in JP-A-2005-154675, JP-A-2009-270119, WO2009 / 145073, and the like. Commercially available products (for example, “Celum (registered trademark) superpolymer” series manufactured by Advanced Soft Materials Co., Ltd.) can also be employed.

<Crosslinking agent>
The pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent. Examples of such a crosslinking agent include organic crosslinking agents and polyfunctional metal chelates.

  Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Etc. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.

  As the crosslinking agent, an isocyanate-based crosslinking agent is preferable. Examples of isocyanate crosslinking agents include tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate. Diisocyanates such as isophorone diisocyanate; polyisocyanate compounds derived from these diisocyanates; adducts obtained by adding these diisocyanates with trimethylolpropane, etc .; isocyanurates which are trimers of these diisocyanates; hexamethylene diisocyanate and water or tertiary alcohol The reaction product of the burette body; Ol, polyester polyols, acrylic polyols, polybutadiene polyols, obtained by addition reaction and polyisoprene polyol, a urethane prepolymer type isocyanates; and the like.

  The isocyanate-based crosslinking agent is preferably tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene. And diisocyanates such as diisocyanate and isophorone diisocyanate; and polyisocyanate compounds derived from these diisocyanates.

  The diisocyanate is more preferably hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, or isophorone diisocyanate.

  The polyisocyanate compound derived from diisocyanate is more preferably polyol-modified hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer type hydrogenated xylylene diisocyanate, or polyol-modified isophorone diisocyanate.

  Isocyanate-based crosslinking agents are derived from diisocyanates in that the reaction with hydroxyl groups can contribute to the speed of crosslinking, especially because the acid or base contained in the polymer acts as a catalyst and proceeds rapidly. Polyisocyanate compounds are particularly preferred.

  When a crosslinking agent is used, the amount is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight based on the (meth) acrylic polymer. %, More preferably 0.03% to 3% by weight, particularly preferably 0.03% to 2% by weight, most preferably 0.05% to 1.5% by weight. . By adjusting the use ratio of the cross-linking agent within the above range, an appropriate cross-linking reaction can be caused, and a pressure-sensitive adhesive layer capable of developing a sufficiently sufficiently low haze value while being excellent in stress relaxation property and durability is constituted. While providing an adhesive composition, the adhesive layer comprised from such an adhesive composition, the adhesive sheet containing such an adhesive layer, and an optical member with an adhesive layer can be provided.

<Other ingredients>
The pressure-sensitive adhesive composition of the present invention may contain other components. The pressure-sensitive adhesive composition of the present invention may contain any appropriate additive as long as the effects of the present invention are not impaired. Examples of such additives include powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, and antioxidants. , Antistatic agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, and the like. In addition, a reducing agent may be added as an additive to make a redox system as long as the effects of the present invention are not impaired.

  The pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent. By including a silane coupling agent, the durability of the pressure-sensitive adhesive composition of the present invention can be improved.

  Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, Epoxy group-containing silane coupling agents such as 4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N- (1,3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltri (Meth) axes such as ethoxysilane Isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane; Le group-containing silane coupling agent and the like.

As the silane coupling agent, a general formula: —SiR _a M _3-a (wherein R is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent, and M is a hydroxyl group or A is a hydrolyzable group, and a is an integer of 0 to 2. However, when a plurality of Rs are present, the plurality of Rs may be the same as or different from each other. May be the same as or different from each other.) And those having a reactive silyl group and an acetoacetyl group. Examples of commercially available silane coupling agents having a reactive silyl group and an acetoacetyl group as described above include A100 manufactured by Soken Chemical Co., Ltd.

  A silane coupling agent may be used only by 1 type, and may use 2 or more types together.

  As content of a silane coupling agent, 0.001 weight part-5 weight part are preferable with respect to 100 weight part of (meth) acrylic-type polymers, 0.01 weight part-1 weight part are more preferable, and 0.02 Part by weight to 1 part by weight is more preferable, and 0.05 part by weight to 0.6 part by weight is particularly preferable. By adjusting the content of the silane coupling agent in the above range, the durability of the pressure-sensitive adhesive composition of the present invention can be improved, and the adhesive force to an optical member such as a liquid crystal cell can be appropriately maintained.

  However, the pressure-sensitive adhesive composition of the present invention can provide a pressure-sensitive adhesive composition that constitutes a pressure-sensitive adhesive layer that is excellent in stress relaxation and durability and can exhibit a low haze value even if it does not contain other components. An adhesive layer composed of such an adhesive composition, an adhesive sheet including such an adhesive layer, and an optical member with an adhesive layer can be provided. Therefore, in order to suppress a decrease in gel fraction and bleed out, it is preferable that other components are not included more than necessary.

  With the pressure-sensitive adhesive composition of the present invention, a pressure-sensitive adhesive layer can be formed. In forming the pressure-sensitive adhesive layer, the addition amount of the entire crosslinking agent is adjusted, and the crosslinking treatment temperature and the crosslinking treatment during the crosslinking treatment are performed. It is preferable to fully consider the influence of time.

  The crosslinking treatment temperature and the crosslinking treatment time can be adjusted depending on the crosslinking agent used. The crosslinking treatment temperature is preferably 170 ° C. or lower.

  The crosslinking treatment may be performed at the temperature during the drying step of the pressure-sensitive adhesive layer, or may be performed by providing a crosslinking treatment step in which a crosslinking treatment is separately performed after the drying step.

  The crosslinking treatment time can be set in consideration of productivity and workability. Such a crosslinking treatment time is preferably 0.2 minutes to 20 minutes, more preferably 0.5 minutes to 10 minutes.

  As an example of the pressure-sensitive adhesive layer, in the case of the pressure-sensitive adhesive layer in the polarizing film with a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is formed on at least one surface of the polarizing film with the pressure-sensitive adhesive composition of the present invention.

  As a method for forming the pressure-sensitive adhesive layer, for example, a method in which the pressure-sensitive adhesive composition of the present invention is applied to a release-treated separator and the like, and a polymerization solvent is dried and removed to form a pressure-sensitive adhesive layer, which is then transferred to a polarizing film. Or the method of apply | coating the adhesive composition of this invention to a polarizing film, drying and removing a polymerization solvent etc., and forming the adhesive layer in a polarizing film etc. are mentioned. In applying the pressure-sensitive adhesive composition of the present invention, one or more solvents other than the polymerization solvent may be added as appropriate.

<Method for producing pressure-sensitive adhesive composition>
The pressure-sensitive adhesive composition of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired. As such a production method, for example, a (meth) acrylic polymer, a polyrotaxane, and other components as required, together with any appropriate solvent as necessary, are put into a stirrer or the like and stirred and mixed. Furthermore, a method of adding and stirring a cross-linking agent as necessary may be mentioned.

≪Adhesive layer≫
The pressure-sensitive adhesive layer of the present invention is composed of the pressure-sensitive adhesive composition of the present invention.

  The pressure-sensitive adhesive layer of the present invention is preferably formed by curing the pressure-sensitive adhesive composition of the present invention.

  The pressure-sensitive adhesive layer of the present invention can be preferably formed by applying the pressure-sensitive adhesive composition of the present invention on any appropriate substrate and curing it.

  Arbitrary appropriate means can be employ | adopted as a means of hardening. For example, thermosetting and photocuring.

  As the thickness of the pressure-sensitive adhesive layer of the present invention, any appropriate thickness can be adopted depending on the purpose. The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 100 μm, more preferably 2 μm to 50 μm, still more preferably 2 μm to 40 μm, and particularly preferably 5 μm to 35 μm.

  The haze value of the pressure-sensitive adhesive layer of the present invention is preferably less than 1.0, more preferably 0.95 or less, still more preferably 0.90 or less, still more preferably 0.85 or less, More preferably, it is 0.80 or less, Especially preferably, it is 0.75 or less, Most preferably, it is 0.70 or less.

≪Adhesive sheet≫
The pressure-sensitive adhesive sheet of the present invention includes the pressure-sensitive adhesive layer of the present invention and a base material layer. The pressure-sensitive adhesive sheet of the present invention may contain any appropriate other layer as long as the effects of the present invention are not impaired. The pressure-sensitive adhesive sheet of the present invention is preferably a laminate of the pressure-sensitive adhesive layer and the base material layer of the present invention.

  As the thickness of the pressure-sensitive adhesive sheet of the present invention, any appropriate thickness can be adopted depending on the purpose. The thickness of such an adhesive sheet is preferably 10 μm to 1000 μm, more preferably 10 μm to 500 μm, still more preferably 20 μm to 500 μm, and particularly preferably 30 μm to 400 μm.

  The base material layer may be a single layer or a laminate of two or more layers. The base material layer may be stretched.

  As a base material layer, arbitrary appropriate base material layers can be employ | adopted in the range which does not impair the effect of this invention. Examples of the material for the base material layer include plastic, paper, metal film, and non-woven fabric. Preferably, it is a plastic. The base material layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, you may be comprised from 2 or more types of plastics.

  Examples of the plastic include a polyester resin, a polyamide resin, and a polyolefin resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include olefin monomer homopolymers, olefin monomer copolymers, and the like. Specific examples of polyolefin resins include homopolypropylene; block-type, random-type, and graft-type propylene copolymers having an ethylene component as a copolymer component; reactor TPO; low density, high density, linear Low density, ultra-low density, etc. ethylene polymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid And ethylene copolymers such as butyl copolymer, ethylene / methacrylic acid copolymer, and ethylene / methyl methacrylate copolymer.

  The base material layer may contain any appropriate additive as required. Examples of the additive that can be contained in the base material layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, and a pigment. The kind, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration. From the viewpoint of improving weather resistance and the like, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

  The pressure-sensitive adhesive sheet of the present invention may include a release liner on the surface of the pressure-sensitive adhesive layer.

  Any appropriate separator can be adopted as the release liner. As such a release liner, for example, a base material having a release layer such as a plastic film or paper surface-treated with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based, molybdenum sulfide; polytetrafluoroethylene, Low-adhesive substrate made of a fluoropolymer such as polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer; And a low-adhesive substrate made of a nonpolar polymer such as a resin (for example, polyethylene, polypropylene, etc.).

  The pressure-sensitive adhesive sheet of the present invention can be produced by any appropriate method. Examples of such a production method include a method in which the pressure-sensitive adhesive composition of the present invention is applied to a release liner and the like, and a polymerization solvent and the like are removed by drying. In applying the pressure-sensitive adhesive composition of the present invention, one or more solvents other than the polymerization solvent may be added as appropriate. In such a process, as a method for drying the pressure-sensitive adhesive composition of the present invention, any appropriate method can be adopted depending on the purpose. As such a method, Preferably, the method of heat-drying the coating film obtained by apply | coating the adhesive composition of this invention is mentioned. The heating and drying temperature in such a method is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and further preferably 70 ° C to 170 ° C. By adjusting the heating and drying temperature within the above range, an adhesive sheet having excellent adhesive properties can be obtained. Any appropriate time can be adopted as the heat drying time. Such heat drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and further preferably 10 seconds to 5 minutes.

  Various methods are used as a method of forming the pressure-sensitive adhesive layer. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.

≪Optical member with adhesive layer≫
The optical member with an adhesive layer of the present invention includes the adhesive layer of the present invention and an optical member. The optical member with an adhesive layer of the present invention may contain any appropriate other layer as long as the effects of the present invention are not impaired. The optical member with an adhesive layer of the present invention is preferably a laminate of the adhesive layer of the present invention and an optical member.

  As thickness of the optical member with an adhesive layer of this invention, arbitrary appropriate thickness can be employ | adopted according to the objective. The thickness of such an optical member with an adhesive layer is preferably 10 μm to 1000 μm, more preferably 30 μm to 750 μm, still more preferably 40 μm to 500 μm, and particularly preferably 50 μm to 400 μm.

  The optical member may be a single layer or a laminate of two or more layers. The optical member may be stretched.

  Examples of the optical member include a polarizing plate, a retardation plate, an optical compensation plate, a brightness enhancement plate, a liquid crystal display device, an organic EL display device, and an image display device such as a PDP.

  The optical member with an adhesive layer of the present invention may include a release liner on the surface of the adhesive layer.

  Any appropriate separator can be adopted as the release liner. As such a release liner, for example, a base material having a release layer such as a plastic film or paper surface-treated with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based, molybdenum sulfide; polytetrafluoroethylene, Low-adhesive substrate made of a fluoropolymer such as polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer; And a low-adhesive substrate made of a nonpolar polymer such as a resin (for example, polyethylene, polypropylene, etc.).

≪Image display device≫
As the optical member with the pressure-sensitive adhesive layer of the present invention, those used for forming an image display device such as a liquid crystal display device are preferably used, and the type thereof is arbitrary appropriate as long as the effects of the present invention are not impaired. The type can be adopted. That is, the image display device of the present invention includes at least one optical member with an adhesive layer of the present invention. As an optical member, Preferably, a polarizing plate is mentioned. The polarizing plate can be produced by any appropriate method.

  As the polarizing plate, one having a transparent protective film on one side or both sides of a polarizer is generally used. Any appropriate polarizer can be adopted as the polarizer as long as the effects of the present invention are not impaired. Examples of such a polarizer include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, ethylene / vinyl acetate copolymer partially saponified films, iodine and dichroic dyes. Examples thereof include those obtained by adsorbing a dichroic substance and uniaxially stretched, and polyene-based oriented films such as a dehydrated polyvinyl alcohol product and a dehydrochlorinated polyvinyl chloride product. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. Any appropriate thickness can be adopted as the thickness of these polarizers as long as the effects of the present invention are not impaired. The thickness is preferably 5 μm to 80 μm.

  As a material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include, for example, cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Cyclic polyolefin resins (for example, norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.

  The content of the thermoplastic resin in the transparent protective film is preferably 50% to 100% by weight, more preferably 50% to 99% by weight, and further preferably 60% to 98% by weight. It is particularly preferably 70 to 97% by weight. When content of the said thermoplastic resin in a transparent protective film is less than 50 weight%, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

  A transparent protective film is bonded to one or both sides of the polarizer by an adhesive layer. On at least one surface of the polarizer, a thermosetting resin such as a (meth) acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, a silicone resin, or an ultraviolet curable resin is used as a transparent protective film. Can be used. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.

  An adhesive is used for the adhesion treatment between the polarizer and the transparent protective film. Examples of the adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, and water-based polyesters. The adhesive is usually used as an adhesive made of an aqueous solution, and preferably contains 0.5 to 60% by weight of a solid content. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable adhesive exhibits suitable adhesion to the various transparent protective films. The adhesive used in the present invention can contain a metal compound filler.

  The polarizing plate can be laminated with other optical films. Examples of other optical films include formation of liquid crystal display devices such as reflectors, anti-transmission plates, retardation plates (including wavelength plates such as 1/2 and 1/4), visual compensation films, and brightness enhancement films. And an optical layer that may be used in the above. These can be laminated on a polarizing plate for practical use, and one layer or two or more layers can be used.

  An optical film in which an optical layer is laminated on a polarizing plate can also be formed in a method of laminating separately sequentially in the manufacturing process of a liquid crystal display device or the like. As such an optical film, an optical film laminated in advance is excellent in quality stability, assembly work, and the like, and has an advantage of improving the manufacturing process of a liquid crystal display device and the like. Arbitrary suitable adhesion means, such as an adhesion layer, can be used for lamination. When the polarizing plate and the optical layer are bonded, their optical axes can be set to any appropriate arrangement angle in accordance with the target retardation characteristics.

  The optical member with an adhesive layer of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device generally has a polarizing plate with an adhesive layer disposed on one side or both sides of a display panel such as a liquid crystal cell, and appropriately assembles components such as an illumination system as necessary to provide a drive circuit. It can be formed by incorporating or the like. When providing a polarizing plate with an adhesive layer on both sides of the display panel, they may be the same or different. As the liquid crystal cell, for example, any appropriate type such as a TN type, an STN type, a π type, a VA type, and an IPS type can be adopted.

  When forming a liquid crystal display device, for example, any appropriate component such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, and any appropriate position One layer or two or more layers can be disposed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In Examples, unless otherwise specified, “parts” and “%” are based on weight. “Weight” may be read as “mass”.

In addition, the meaning of the symbol in Table 1 is as follows.
BA: Butyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
AA: Acrylic acid (Mitsubishi Chemical Corporation)
NVP: N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.)
HEA: Hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HBA: Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
BzA: benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
PEA: Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Measurement of weight average molecular weight Mw>
The weight average molecular weight of the obtained (meth) acrylic polymer was measured by GPC (gel permeation chromatography). The sample was prepared by dissolving the sample in dimethylformamide to give a 0.1% by weight solution, which was allowed to stand overnight and then filtered through a 0.45 μm membrane filter.
・ Analyzer: HLC-8120GPC manufactured by Tosoh Corporation
Column: Super AWM-H, AW4000, AW2500, manufactured by Tosoh Corporation
・ Column size: 6.0mmφ × 150mm each
・ Eluent: 30 mM-lithium bromide, 30 mM-phosphoric acid in dimethylformamide solution ・ Flow rate: 0.4 ml / min
・ Detector: Differential refractometer (RI)
-Column temperature: 40 ° C
・ Injection volume: 20 μl

<Measurement of haze value>
The obtained adhesive sheet was bonded to a micro slide glass (thickness 1.0 mmt to 1.2 mmt, manufactured by Matsunami Glass Industry Co., Ltd., product number S1112). Thus, the separator on one side of the pressure-sensitive adhesive sheet bonded to the micro slide glass was peeled off, and the haze value of the pressure-sensitive adhesive layer was measured with a haze meter (HM-150, manufactured by murakami color research laboratory).

<Appearance evaluation of optical member with adhesive layer>
The obtained polarizing plate with the pressure-sensitive adhesive layer was bonded to a 10 inch liquid crystal panel so as to be crossed Nicol, and after the backlight (B / L) was turned on, the appearance after driving the liquid crystal was visually observed.
○ ・ ・ ・ No problem in practical use × ・ ・ ・ There is a problem affecting the appearance

[Synthesis Example 1]
(Preparation of slide ring material solution)
Advanced Soft Materials Co., Ltd. slide ring material (Celum (registered trademark) superpolymer, product number: SH3400P) (linear molecule: polyethylene glycol, cyclic molecule: α-cyclodextrin having a hydroxypropyl group and a caprolactone chain, Blocking group: adamantane group, weight average molecular weight (Mw) = 600,000, hydroxyl value = 72 mgKOH / g, solid content concentration 100% by mass) mixed with ethyl acetate, adjusted to 50 ° C., dissolved with stirring for 60 min An 11 wt% ethyl acetate solution of the slide ring material was prepared.

[Example 1]
(Preparation of acrylic polymer)
Monomer blended in a mixing ratio (weight ratio) shown in Table 1 in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube: 100 parts by weight, ethyl acetate: 200 parts by weight, and 2 2,2′-Azobisisobutyronitrile: 0.1 part by weight was charged, and the air in the reaction vessel was replaced with nitrogen gas. Thereafter, while stirring in a nitrogen atmosphere, the reaction solution was heated to 60 ° C., reacted for 12 hours, and then cooled to room temperature. As a result, an ethyl acetate solution of the acrylic polymer (1) having a weight average molecular weight (Mw) = 20.4 million was obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (1), and diluted so that the solid content of the acrylic polymer (1) becomes 12% by weight, and the ethyl acetate of the acrylic polymer (1) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
An 11 wt% ethyl acetate solution of the slide ring material obtained in Synthesis Example 1 and an ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (1) were converted into an acrylic polymer (1) / slide ring material = It mix | blended in reaction container so that it might become 90/10 (weight ratio), and it stirred and mixed with the stirrer. Thereafter, 0.6 parts by weight of an isocyanate-based crosslinking agent (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) is added to the reaction vessel with respect to 100 parts by weight of the total solid content of the acrylic polymer (1) and the sliding ring material. Then, the mixture was stirred again to obtain an adhesive composition (1).

(Manufacture of adhesive layer and adhesive sheet)
The pressure-sensitive adhesive composition (1) is applied to one side of a polyethylene-treated polyethylene terephthalate (PET) film (Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) so that the thickness of the pressure-sensitive adhesive layer after drying is 23 μm. And dried at 155 ° C. for 1 minute to form a pressure-sensitive adhesive sheet (1) having a pressure-sensitive adhesive layer (1).
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
A polyvinyl alcohol film having a thickness of 80 μm was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer. A saponified 80 μm-thick triacetyl cellulose film was bonded to both surfaces of the obtained polarizer with a polyvinyl alcohol-based adhesive to form a polarizing plate. Further, a polarizing plate (B) was prepared in the same manner as described above using an acrylic film (lactone-modified acrylic resin film) having a thickness of 30 μm instead of the triacetyl cellulose film having a thickness of 80 μm. Further, a polarizing plate (C) was prepared in the same manner as described above using a norbornene-based film (Zeonor film ZB12, manufactured by Nippon Zeon Co., Ltd.) having a thickness of 60 μm instead of the triacetylcellulose film having a thickness of 80 μm. Next, the pressure-sensitive adhesive layer (1) was transferred from the pressure-sensitive adhesive sheet (1) to each of the polarizing plates (A) to (C) to prepare pressure-sensitive adhesive layer-attached polarizing plates (1A) to (1C). The polarizing plate (1A) with an adhesive layer is obtained by transferring the adhesive layer (1) from the adhesive sheet (1) to the polarizing plate (A). The polarizing plate (1B) with an adhesive layer is obtained by transferring the adhesive layer (1) from the adhesive sheet (1) to the polarizing plate (B). The polarizing plate (1C) with an adhesive layer is obtained by transferring the adhesive layer (1) from the adhesive sheet (1) to the polarizing plate (C).
The results are shown in Table 1.

[Example 2]
(Preparation of acrylic polymer)
Except having used the monomer mix | blended with the mixture ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (2) of weight average molecular weight (Mw) = 2 million is used. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (2), and diluted so that the solid content of the acrylic polymer (2) becomes 12% by weight, and the ethyl acetate of the acrylic polymer (2) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
The same as Example 1 except that the ethyl acetate solution (solid content = 12% by weight) of the acrylic polymer (2) was used instead of the ethyl acetate solution (solid content = 12% by weight) of the acrylic polymer (1). The pressure-sensitive adhesive composition (2) was obtained.

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (2) was applied on a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The adhesive sheet (2) which has an adhesive layer (2) was produced by throwing into an oven for 1 minute and drying a solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (2) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (2A)-(2C) with an adhesive layer. The polarizing plate (2A) with an adhesive layer is obtained by transferring the adhesive layer (2) from the adhesive sheet (2) to the polarizing plate (A). The polarizing plate (2B) with an adhesive layer is obtained by transferring the adhesive layer (2) from the adhesive sheet (2) to the polarizing plate (B). The polarizing plate (2C) with an adhesive layer is obtained by transferring the adhesive layer (2) from the adhesive sheet (2) to the polarizing plate (C).
The results are shown in Table 1.

Example 3
(Preparation of acrylic polymer)
Except having used the monomer mix | blended with the mixture ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (3) whose weight average molecular weight (Mw) = 920,000 is used. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (3), and diluted so that the solid content of the acrylic polymer (3) is 12% by weight, and the ethyl acetate of the acrylic polymer (3) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
The same as Example 1 except that the ethyl acetate solution (solid content = 12% by weight) of the acrylic polymer (3) was used instead of the ethyl acetate solution (solid content = 12% by weight) of the acrylic polymer (1). The pressure-sensitive adhesive composition (3) was obtained.

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (3) was applied on a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The adhesive sheet (3) which has an adhesive layer (3) was produced by throwing into an oven for 1 minute and drying a solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (3) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (3A)-(3C) with an adhesive layer. A polarizing plate (3A) with an adhesive layer is obtained by transferring the adhesive layer (3) from the adhesive sheet (3) to the polarizing plate (A). The polarizing plate with an adhesive layer (3B) is obtained by transferring the adhesive layer (3) from the adhesive sheet (3) to the polarizing plate (B). A polarizing plate (3C) with an adhesive layer is obtained by transferring the adhesive layer (3) from the adhesive sheet (3) to the polarizing plate (C).
The results are shown in Table 1.

[Comparative Example 1]
(Preparation of acrylic polymer)
Except using the monomer mix | blended with the mixture ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (C1) whose weight average molecular weight (Mw) = 22.2 million is carried out. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (C1), and diluted so that the solid content of the acrylic polymer (C1) is 12% by weight. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
The same as Example 1 except that an ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (C1) was used instead of the ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (1). To obtain an adhesive composition (C1).

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (C1) was applied onto a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The pressure-sensitive adhesive sheet (C1) having the pressure-sensitive adhesive layer (C1) was produced by putting it in an oven for 1 minute and drying the solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (C1) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (C1A)-(C1C) with an adhesive layer. The polarizing plate with pressure-sensitive adhesive layer (C1A) is obtained by transferring the pressure-sensitive adhesive layer (C1) from the pressure-sensitive adhesive sheet (C1) to the polarizing plate (A). The polarizing plate with pressure-sensitive adhesive layer (C1B) is obtained by transferring the pressure-sensitive adhesive layer (C1) from the pressure-sensitive adhesive sheet (C1) to the polarizing plate (B). The polarizing plate with pressure-sensitive adhesive layer (C1C) is obtained by transferring the pressure-sensitive adhesive layer (C1) from the pressure-sensitive adhesive sheet (C1) to the polarizing plate (C).
The results are shown in Table 1.

[Comparative Example 2]
(Preparation of acrylic polymer)
Except using the monomer mix | blended with the mixture ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (C2) whose weight average molecular weight (Mw) = 1.6 million is used. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (C2), and diluted so that the solid content of the acrylic polymer (C2) becomes 12% by weight, and the ethyl acetate of the acrylic polymer (C2) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
The same as Example 1 except that the ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (C2) was used instead of the ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (1). The pressure-sensitive adhesive composition (C2) was obtained.

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (C2) was applied on a separator (Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The adhesive sheet (C2) which has an adhesive layer (C2) was produced by throwing into an oven for 1 minute and drying a solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (C2) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (C2A)-(C2C) with an adhesive layer. The polarizing plate with pressure-sensitive adhesive layer (C2A) is obtained by transferring the pressure-sensitive adhesive layer (C2) from the pressure-sensitive adhesive sheet (C2) to the polarizing plate (A). The polarizing plate with pressure-sensitive adhesive layer (C2B) is obtained by transferring the pressure-sensitive adhesive layer (C2) from the pressure-sensitive adhesive sheet (C2) to the polarizing plate (B). The polarizing plate with pressure-sensitive adhesive layer (C2C) is obtained by transferring the pressure-sensitive adhesive layer (C2) from the pressure-sensitive adhesive sheet (C2) to the polarizing plate (C).
The results are shown in Table 1.

[Comparative Example 3]
(Preparation of acrylic polymer)
Except having used the monomer mix | blended with the mixing | blending ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (C3) whose weight average molecular weight (Mw) = 11.1 million Obtained. To the ethyl acetate solution of the obtained acrylic polymer (C3), ethyl acetate is further added and diluted so that the solid content of the acrylic polymer (C3) becomes 12% by weight, and the ethyl acetate of the acrylic polymer (C3) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
Example 1 except that an ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (C3) was used instead of the ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (1). To obtain an adhesive composition (C3).

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (C3) was applied on a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The adhesive sheet (C3) which has an adhesive layer (C3) was produced by throwing into an oven for 1 minute and drying a solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (C3) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (C3A)-(C3C) with an adhesive layer. The polarizing plate with pressure-sensitive adhesive layer (C3A) is obtained by transferring the pressure-sensitive adhesive layer (C3) from the pressure-sensitive adhesive sheet (C3) to the polarizing plate (A). The polarizing plate with pressure-sensitive adhesive layer (C3B) is obtained by transferring the pressure-sensitive adhesive layer (C3) from the pressure-sensitive adhesive sheet (C3) to the polarizing plate (B). The polarizing plate with pressure-sensitive adhesive layer (C3C) is obtained by transferring the pressure-sensitive adhesive layer (C3) from the pressure-sensitive adhesive sheet (C3) to the polarizing plate (C).
The results are shown in Table 1.

[Comparative Example 4]
(Preparation of acrylic polymer)
Except using the monomer mix | blended with the mixture ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (C4) whose weight average molecular weight (Mw) = 950,000 is carried out. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (C4), and diluted so that the solid content of the acrylic polymer (C4) becomes 12% by weight, and the ethyl acetate of the acrylic polymer (C4) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
Example 1 except that an ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (C4) was used instead of the ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (1). To obtain an adhesive composition (C4).

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (C4) was applied on a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The pressure-sensitive adhesive sheet (C4) having the pressure-sensitive adhesive layer (C4) was produced by putting it in an oven for 1 minute and drying the solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (C4) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (C4A)-(C4C) with an adhesive layer. The polarizing plate with pressure-sensitive adhesive layer (C4A) is obtained by transferring the pressure-sensitive adhesive layer (C4) from the pressure-sensitive adhesive sheet (C4) to the polarizing plate (A). The polarizing plate with pressure-sensitive adhesive layer (C4B) is obtained by transferring the pressure-sensitive adhesive layer (C4) from the pressure-sensitive adhesive sheet (C4) to the polarizing plate (B). The polarizing plate with pressure-sensitive adhesive layer (C4C) is obtained by transferring the pressure-sensitive adhesive layer (C4) from the pressure-sensitive adhesive sheet (C4) to the polarizing plate (C).
The results are shown in Table 1.

[Comparative Example 5]
(Preparation of acrylic polymer)
Except having used the monomer mix | blended with the mixture ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (C5) whose weight average molecular weight (Mw) = 840,000 is carried out. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (C5), and diluted so that the solid content of the acrylic polymer (C5) becomes 12% by weight, and the ethyl acetate of the acrylic polymer (C5) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
Example 1 except that an ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (C5) was used instead of the ethyl acetate solution (solid content = 12 wt%) of the acrylic polymer (1). To obtain an adhesive composition (C5).

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (C5) was applied onto a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The adhesive sheet (C5) which has an adhesive layer (C5) was produced by throwing into an oven for 1 minute and drying a solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (C5) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (C5A)-(C5C) with an adhesive layer. The polarizing plate with pressure-sensitive adhesive layer (C5A) is obtained by transferring the pressure-sensitive adhesive layer (C5) from the pressure-sensitive adhesive sheet (C5) to the polarizing plate (A). The polarizing plate with pressure-sensitive adhesive layer (C5B) is obtained by transferring the pressure-sensitive adhesive layer (C5) from the pressure-sensitive adhesive sheet (C5) to the polarizing plate (B). The polarizing plate with pressure-sensitive adhesive layer (C5C) is obtained by transferring the pressure-sensitive adhesive layer (C5) from the pressure-sensitive adhesive sheet (C5) to the polarizing plate (C).
The results are shown in Table 1.

[Reference Example 1]
(Preparation of acrylic polymer)
Except having used the monomer mix | blended with the mixing | blending ratio (weight ratio) shown in Table 1, it carries out similarly to Example 1, and the ethyl acetate solution of the acrylic polymer (R1) whose weight average molecular weight (Mw) = 2.04 million is used. Obtained. Ethyl acetate is further added to the ethyl acetate solution of the obtained acrylic polymer (R1) and diluted so that the solid content of the acrylic polymer (R1) is 12% by weight, and the ethyl acetate of the acrylic polymer (R1) is obtained. A solution (solid content = 12% by weight) was obtained.

(Manufacture of adhesive composition)
Without using the slide ring material obtained in Synthesis Example 1, the acrylic polymer (1) was directly used as the pressure-sensitive adhesive composition (R1).

(Manufacture of adhesive layer and adhesive sheet)
The obtained pressure-sensitive adhesive composition (R1) was applied onto a separator (MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) so that the film thickness after drying was 23 μm with an applicator, and adjusted to 155 ° C. The pressure-sensitive adhesive sheet (R1) having the pressure-sensitive adhesive layer (R1) was produced by putting it in an oven for 1 minute and drying the solvent.
The results are shown in Table 1.

(Manufacture of optical member with adhesive layer)
Except having used the adhesive layer (R1) instead of the adhesive layer (1), it carried out similarly to Example 1 and produced the polarizing plates (R1A)-(R1C) with an adhesive layer. The polarizing plate with pressure-sensitive adhesive layer (R1A) is obtained by transferring the pressure-sensitive adhesive layer (R1) from the pressure-sensitive adhesive sheet (R1) to the polarizing plate (A). The polarizing plate (R1B) with an adhesive layer is obtained by transferring the adhesive layer (R1) from the adhesive sheet (R1) to the polarizing plate (B). The polarizing plate (R1C) with an adhesive layer is obtained by transferring the adhesive layer (R1) from the adhesive sheet (R1) to the polarizing plate (C).
The results are shown in Table 1.

  From the results shown in Table 1, it was found that haze can be significantly suppressed by adding a monomer having an aromatic ring structure in an optimum composition. It was also confirmed that the appearance evaluation can be improved to look almost the same as when no slide ring material is added.

  The pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, optical member with a pressure-sensitive adhesive layer, and image display device of the present invention can be used in the optical field, for example.

Claims (8)

(Meth) acrylic polymer, a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and arranged at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. A pressure-sensitive adhesive composition comprising a polyrotaxane having a blocking group.
The (meth) acrylic polymer, viewed contains a structural unit derived from a monomer having no aromatic ring structure, a structural unit derived from a monomer having an aromatic ring structure,
The content ratio of the structural unit derived from the monomer having an aromatic ring structure in the (meth) acrylic polymer is 1% by weight to 35% by weight .
Adhesive composition.   The pressure-sensitive adhesive composition according to claim 1, wherein a content ratio of the (meth) acrylic polymer in the pressure-sensitive adhesive composition is 70% by weight to 98% by weight.   The pressure-sensitive adhesive composition according to claim 1 or 2, wherein a content ratio of the polyrotaxane in the pressure-sensitive adhesive composition is 2% by weight to 30% by weight. The pressure-sensitive adhesive composition according to any one of claims 1 to 3 , wherein the monomer having an aromatic ring structure contains at least one selected from benzyl acrylate and phenoxyethyl acrylate. The adhesive layer comprised from the adhesive composition in any one of Claim 1 to 4 . An adhesive sheet comprising the adhesive layer according to claim 5 and a base material layer. An optical member with an adhesive layer comprising the adhesive layer according to claim 5 and an optical member. The image display apparatus containing at least 1 the optical member with an adhesive layer of Claim 7 .