KR20200001990A - Adhesive composition, adhesive sheet, and optical member - Google Patents

Abstract

The present invention provides an adhesive composition capable of obtaining an adhesive sheet (adhesive layer) with excellent antistatic properties when peeling the adhesive sheet from the surface of an optical member (for example, a polarizing film or the like) to which an adhesive sheet used for surface protection is attached, and with excellent adhesion (adhesive properties) with the surface of the optical member and a layer such as an interlayer filler or the like when providing a new layer such as an interlayer filler or the like on the surface of the optical member after peeling the adhesive sheet, an adhesive sheet having an adhesive layer formed by the adhesive composition, and an optical member attached (protected) to the adhesive sheet. The adhesive composition of the present invention comprises: an adhesive polymer; a polyether compound containing at least three polyoxyalkylene chains in a molecule and not containing a silicone chain; and an ionic compound.

Description

Adhesive composition, adhesive sheet, and optical member {ADHESIVE COMPOSITION, ADHESIVE SHEET, AND OPTICAL MEMBER}

This invention relates to an adhesive composition, an adhesive sheet, and an optical member. In particular, the adhesive sheet obtained by the said adhesive composition is used for affixing on the plastic product etc. which are easy to generate static electricity (for example, a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescent (EL) display, etc.). Especially, the surface of an optical member (for example, a polarizing film, a wavelength plate, a retardation plate, an optical compensation film, a reflection sheet, a brightness enhancement film, a touch panel member) etc. which are used for a liquid crystal display etc. can be especially protected. It is useful as a surface protection film used for the purpose.

The adhesive sheet (surface protective film) generally has the structure in which the adhesive layer was provided on the film-form base film. Such an adhesive sheet is bonded to a to-be-adhered body (protected body) through the said adhesive layer, and is used for the purpose of protecting a to-be-adhered body from a scratch and contamination at the time of processing, conveyance, etc. by this. For example, the panel of a liquid crystal display is formed by bonding optical members, such as a polarizing film and a wavelength plate, to a liquid crystal cell through an adhesive layer. In manufacture of such a liquid crystal display panel, once the polarizing film bonded to a liquid crystal cell is manufactured in roll shape, it is unwound from this roll, and it cuts to the desired size according to the shape of a liquid crystal cell, and is used. Here, since at the time of processing, conveyance, etc. of a polarizing film, a polarizing film may be rubbed and damaged by a conveyance roll etc., in order to prevent this, it adhere | attaches on one side or both surfaces (typically one side) of a polarizing film. The measures to bond and protect a sheet are taken. And this adhesive sheet is peeled off and removed in the step which became unnecessary.

Generally, since the adhesive sheet (surface protection film) and the optical member are comprised by the plastic material, electrical insulation is high and generate static electricity by friction and peeling. For this reason, static electricity is easy to generate | occur | produce also when peeling an adhesive sheet from optical members, such as a polarizing film, and when a voltage is applied to a liquid crystal in the state which remained this static electricity, the orientation of a liquid crystal molecule will be lost, or the defect of a panel will be lost. There is a possibility to occur. In addition, the presence of static electricity may be a factor that attracts dust or degrades workability. From such a situation, in order to provide antistatic property to the adhesive layer itself which comprises an adhesive sheet, what contains polyether modified silicone and an ionic compound which function as an antistatic agent in an adhesive (adhesive composition) is performed (patent document 1). Reference).

Moreover, after peeling an adhesive sheet (surface protective film) from an optical member surface, the layer which has another function may be provided in the optical member surface. For example, in order to adhere | attach the surface of optical members, such as a layer which has a polarizing film and a touch panel function, the protective layer comprised from glass, plastics, etc., layers, such as an interlayer filler, may be provided (refer patent document 2). ).

Japanese Patent Laid-Open No. 2011-236266 Japanese Patent Publication No. 2016-113467

However, if the adhesive sheet (adhesive layer) formed of the adhesive containing polyether modified silicone is peeled off at an unnecessary stage after affixing to an optical member such as a polarizing film, the polyether modified silicone contained in the adhesive sheet (adhesive layer) The component transfers to the optical member surface, and the problem that the adhesiveness (adhesiveness) of the layer, such as an interlayer filler provided on the optical member surface from behind, and the optical member surface after peeling the said adhesive sheet falls has arisen.

Therefore, in view of the above circumstances, the present invention, as a result of intensive studies, charging when the adhesive sheet is peeled off from the surface of an optical member (for example, a polarizing film or the like) affixing the adhesive sheet used for surface protection. Adhesive sheet excellent in adhesiveness (excellent adhesiveness) of the optical member surface and layers, such as an interlayer filler, when providing a layer, such as an interlayer filler, on the optical member surface after peeling the said adhesive sheet newly (adhesive agent) It is an object to provide a pressure-sensitive adhesive composition having a layer), a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition, and an optical member affixed (protected) to the pressure-sensitive adhesive sheet.

That is, the adhesive composition of this invention contains a polyether compound which contains three or more polyoxyalkylene chains in an adhesive polymer, a molecule | numerator, and does not contain a silicone chain, and an ionic compound, It is characterized by the above-mentioned.

It is preferable that the said adhesive polymer of the adhesive composition of this invention is a (meth) acrylic-type polymer and / or a urethane-type polymer.

It is preferable that the adhesive composition of this invention contains at least 1 selected from the group which the terminal of the said polyoxyalkylene chain consists of a linear or branched alkyl group, a saturated fatty acid residue, and an unsaturated fatty acid residue.

It is preferable that the adhesive sheet of this invention has the adhesive layer formed by the said adhesive composition on at least one side of a base film.

It is preferable that the said adhesive sheet is affixed on the optical member of this invention.

The present invention, after the adhesive sheet having a pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive polymer, an ionic compound that is an antistatic agent and a specific polyether compound on the surface of an optical member such as a polarizing film, at a step of becoming unnecessary It is excellent in antistatic property at the time of peeling, and excellent in adhesiveness (adhesiveness) between the optical member surface after peeling the said adhesive sheet, and layers, such as an interlayer filler newly provided in the said optical member surface, and is useful. .

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows one structural example of the adhesive sheet (surface protective film) which concerns on this invention.
2 is a schematic diagram of a potential measuring unit.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<Overall structure of adhesive sheet (surface protection film)>

The adhesive sheet disclosed herein is generally in the form of an adhesive tape, adhesive label, adhesive film, or the like, and is particularly used as a liquid crystal display panel component such as an optical component (eg, a polarizing film, a wave plate, etc.). It is suitable as a surface protection film which protects the surface of an optical component at the time of processing and conveyance of an optical component). Although the adhesive layer in the said surface protection film is typically formed continuously, it is not limited to this form, For example, the adhesive layer formed in regular or random pattern, such as a dot form and a stripe form, may be sufficient. In addition, roll shape may be sufficient as the adhesive sheet (surface protection film) disclosed here, and a sheet shape may be sufficient as it.

<Substrate film>

It is preferable that the adhesive sheet (surface protective film) of this invention has a base film. In the technique disclosed herein, the resin material constituting the base film can be used without particular limitation, but is excellent in properties such as transparency, mechanical strength, thermal stability, moisture shielding, isotropy, flexibility, dimensional stability, and the like. It is preferable to use one. In particular, when a base film has flexibility, an adhesive composition can be apply | coated with a roll coater etc., it can be wound up in roll shape, and it is useful.

As said base film, For example, Polyester type polymers, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate; Cellulose polymers such as diacetyl cellulose and triacetyl cellulose; Polycarbonate-based polymers; Acrylic polymers such as polymethyl methacrylate; The plastic film comprised from the resin material which makes a cycloolefin type polymer etc. a main resin component (main component in a resin component, typically 50 mass% or more) can be used suitably as said base film. As another example of the said resin material, Styrene-type polymers, such as a polystyrene and an acrylonitrile-styrene copolymer; Olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic to norbornene structure, and ethylene-propylene copolymers; Vinyl chloride polymers; Amide polymers such as nylon 6, nylon 6,6 and aromatic polyamides; The resin material etc. are mentioned. As another example of the resin material, an imide polymer, a sulfone polymer, a polyether sulfone polymer, a polyether ether ketone polymer, a polyphenylene sulfide polymer, a vinyl alcohol polymer, a vinylidene chloride polymer, vinyl buty Lal polymer, an arylate polymer, a polyoxymethylene polymer, an epoxy polymer, etc. are mentioned. The base film which consists of 2 or more types of blends of the above-mentioned polymer may be sufficient.

As the base film, a plastic film made of a transparent thermoplastic resin material can be preferably used. Among the said plastic films, it is a more preferable aspect to use a polyester film. Here, the polyester film is a polymer material (polyester resin) having a main skeleton based on ester bonds such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate as a main resin component. I say that. Such a polyester film has preferable characteristics as a base film of an adhesive sheet (surface protective film), etc. which are excellent in an optical characteristic or dimensional stability, and has the property which is easy to be charged as it is.

Various additives, such as antioxidant, a ultraviolet absorber, a plasticizer, and a coloring agent (pigment, dye, etc.), may be mix | blended with the resin material which comprises the said base film. For example, known or conventional surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of a primer and the like may be performed. Such surface treatment can be a process for improving adhesiveness (the adhesiveness of an adhesive layer) of a base film and an adhesive layer, for example.

The adhesive sheet (surface protective film) of this invention can also use the plastic film in which antistatic process is given as said base film. Since the charging of the adhesive sheet itself at the time of peeling is suppressed by using the said base film, it is preferable. In addition, when the base film is a plastic film and the antistatic treatment is performed on the plastic film, it is possible to reduce the charging of the pressure sensitive adhesive sheet itself and to provide an excellent antistatic ability to the adherend. In addition, there is no restriction | limiting in particular as a method of providing an antistatic function, A conventionally well-known method can be used, For example, electroconductive resin containing antistatic resin, an electroconductive polymer, and an electroconductive substance which consist of an antistatic agent and a resin component The method of apply | coating, the method of depositing or plating a conductive material, the method of mixing an antistatic agent, etc., the method of forming an antistatic layer, etc. are mentioned.

As thickness of the said base film, it is 5-200 micrometers normally, Preferably it is about 10-100 micrometers. When the thickness of the said base film exists in the said range, since it is excellent in the bonding workability to a to-be-adhered body, and peeling work property from an to-be-adhered body, it is preferable.

In addition to a base film and an adhesive layer, the adhesive sheet disclosed here can be implemented also in the aspect containing an antistatic layer and another layer. As said other layer, the undercoat layer (anchor layer) etc. which raise the anchoring property of an antistatic layer and an adhesive layer are mentioned.

<Adhesive Composition>

If the adhesive composition of this invention contains the adhesive polymer which has adhesiveness, it can use without a restriction | limiting especially, and an adhesive layer can be formed with the said adhesive composition. As the pressure-sensitive adhesive composition, for example, an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a synthetic rubber pressure-sensitive adhesive, a natural rubber pressure-sensitive adhesive, or the like may be used. Among these, the pressure-sensitive adhesive polymer is more preferably a (meth) acrylic polymer and / or a urethane-based adhesive. It is more preferable to use (containing) an acrylic pressure sensitive adhesive containing a (meth) acrylic polymer and / or a urethane pressure sensitive adhesive containing a urethane polymer, and particularly preferably, a (meth) acrylic polymer that is the adhesive polymer. The acrylic adhesive to be used is used.

<Acrylic adhesive>

When the said adhesive layer uses an acrylic adhesive, the (meth) acrylic-type polymer which is the adhesive polymer which comprises the said acrylic adhesive is a raw material monomer which comprises this as a (meth) acrylic-type monomer which has a C1-C14 alkyl group, It can be used as a monomer. As said (meth) acrylic-type monomer, 1 type, or 2 or more types can be used. By using the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, it is easy to control the peeling force (adhesive force) to the adherend (protected body) low, and the adhesive having excellent light peelability and re-peelability A sheet (surface protective film) is obtained. In addition, the (meth) acrylic-type polymer in this invention means an acryl-type polymer and / or a methacryl-type polymer, and (meth) acrylate means an acrylate and / or a methacrylate.

As a specific example of the (meth) acrylic-type monomer which has the said C1-C14 alkyl group, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) Acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth ) Acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n- Tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. are mentioned.

Especially, when using the adhesive sheet of this invention as a surface protection film, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) Acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl ( (Meth) acrylic-type monomer which has a C4-C14 alkyl group, such as a meth) acrylate, n-tridecyl (meth) acrylate, and n- tetradecyl (meth) acrylate, is mentioned as a suitable thing. In particular, by using the (meth) acrylic monomer having an alkyl group having 4 to 14 carbon atoms, it becomes easy to control the peeling force (adhesive force) to the adherend low, and it becomes excellent in re-peelability.

In particular, it is preferable to contain 70 mass% or more of the (meth) acrylic-type monomer which has a C1-C14 alkyl group with respect to 100 mass% of monomer components whole quantity which comprises the said (meth) acrylic-type polymer, More preferably, it is 80 It is mass% or more, More preferably, it is 85-99.9 mass%, Especially preferably, it is 90-99.5 mass%. When it is less than 70 mass%, moderate wettability of an adhesive composition and the cohesion force of an adhesive layer will fall, and it is unpreferable.

Moreover, in the adhesive composition of this invention, it is preferable that the said (meth) acrylic-type polymer contains a hydroxyl group containing (meth) acrylic-type monomer as a raw material monomer. As said hydroxyl group containing (meth) acrylic-type monomer, 1 type, or 2 or more types can be used. By using the hydroxyl group-containing (meth) acrylic monomer, it is easy to control the crosslinking of the pressure-sensitive adhesive composition and the like, and furthermore, to control the balance of improvement of wettability by flow and reduction of peeling force (adhesive force) in peeling. Easier

As said hydroxyl group containing (meth) acrylic-type monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-, for example Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclo Hexyl) methyl acrylate, N-methylol (meth) acrylamide, etc. are mentioned. In particular, the use of a hydroxyl group-containing (meth) acrylic monomer having 4 or more carbon atoms in the alkyl group facilitates light peeling during high-speed peeling and is preferable.

It is preferable to contain 30 mass% or less of said hydroxyl group containing (meth) acrylic-type monomers with respect to 100 mass% of monomer components whole quantity which comprise the said (meth) acrylic-type polymer, More preferably, it is 20 mass% or less Preferably it is 0.1-15 mass%, Especially preferably, it is 0.5-10 mass%. When it exists in the said range, since it becomes easy to control the balance of the wettability of an adhesive composition and the cohesion force of the adhesive layer obtained, it is preferable.

Moreover, as another polymerizable monomer component, it is easy to take the balance of adhesion performance, and Tg is set to 0 degrees C or less (usually -100 degrees C or more), and the glass transition temperature and peelability of a (meth) acrylic-type polymer are adjusted. The polymerizable monomer to be used can be used within a range that does not impair the effects of the present invention.

As a (meth) acrylic-type monomer which has the said C1-C14 alkyl group used in the said (meth) acrylic-type polymer, and other polymerizable monomers other than the said hydroxyl group containing (meth) acrylic-type monomer, it is carboxyl group-containing (meth) acrylic-type Monomers can be used. By using the said carboxyl group-containing (meth) acrylic-type monomer, the raise of the adhesive force with time-lapse of an adhesive sheet (adhesive layer) can be suppressed, and it is excellent in re-peelability, adhesive force rise prevention property, and workability, and an adhesive layer Along with the cohesive force of, the shear force is also excellent, which is preferable.

As said carboxyl group-containing (meth) acrylic-type monomer, (meth) acrylic acid, carboxyl ethyl (meth) acrylate, carboxypentyl (meth) acrylate, etc. are mentioned, for example.

It is preferable that it is 0-3 mass% with respect to 100 mass% of monomer components whole quantity which comprises the said (meth) acrylic-type polymer, It is more preferable that it is 0-2 mass%, 0 It is more preferable that it is 1 mass%, and 0.001-0.5 mass% is especially preferable. When it exists in the said range, since it becomes easy to control the balance of the wettability of an adhesive composition and the cohesion force of the adhesive layer obtained, it is preferable.

In addition, when using together the said hydroxyl group containing (meth) acrylic-type monomer and a carboxyl group-containing (meth) acrylic-type monomer, it is containing the said carboxyl group with respect to 100 mass% of monomer components whole quantity which comprises the said (meth) acrylic-type polymer ( It is preferable to contain 0.005-0.1 mass% of a meth) acrylic-type monomer. By adjusting in the said range, the adhesive sheet (adhesive layer) excellent in re-peelability and adhesive force rise prevention property is obtained, and it is effective.

In addition, as another polymerizable monomer, if it is in the range which does not impair the characteristic of this invention, it can use without a limitation. For example, the cohesion force and heat resistance improvement components, such as a cyano group containing monomer, a vinyl ester monomer, and an aromatic vinyl monomer, an amide group containing monomer, an imide group containing monomer, an amino group containing monomer, an epoxy group containing monomer, and N-acryloyl morpholine The component which has a functional group which acts as an improvement of peeling force (adhesive force), such as a vinyl ether monomer, and a crosslinking origin can be used suitably. Especially, it is preferable to use nitrogen-containing monomers, such as a cyano group containing monomer, an amide group containing monomer, an imide group containing monomer, an amino group containing monomer, and N-acryloyl morpholine. By using a nitrogen-containing monomer, since the moderate peeling force (adhesive force) which does not generate | occur | produce a lifting, peeling, etc. can be ensured, and the adhesive sheet (surface protective film) excellent in shear force can be obtained, it is useful. These polymerizable monomers may be used alone or in combination of two or more.

As said cyano group containing monomer, an acrylonitrile and methacrylonitrile are mentioned, for example.

As said amide group containing monomer, acrylamide, methacrylamide, diethyl acrylamide, N-vinylpyrrolidone, N, N- dimethyl acrylamide, N, N- dimethyl methacrylamide, N, N- Diethylacrylamide, N, N-diethylmethacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, diacetone acrylamide Etc. can be mentioned.

As said imide group containing monomer, cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, itaciconimide etc. are mentioned, for example.

As said amino-group containing monomer, aminoethyl (meth) acrylate, N, N- dimethylaminoethyl (meth) acrylate, N, N- dimethylaminopropyl (meth) acrylate, etc. are mentioned, for example.

As said vinyl ester monomer, vinyl acetate, a vinyl propionate, a vinyl laurate etc. are mentioned, for example.

As said aromatic vinyl monomer, styrene, chloro styrene, chloromethyl styrene, (alpha) -methylstyrene, other substituted styrene, etc. are mentioned, for example.

As said epoxy group containing monomer, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, allyl glycidyl ether, etc. are mentioned, for example.

As said vinyl ether monomer, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc. are mentioned, for example.

In this invention, it is preferable that it is 0-30 mass% with respect to 100 mass% of monomer components whole quantity which comprise the said (meth) acrylic-type polymer, and, as for the said other polymerizable monomer, it is more preferable that it is 0-20 mass%. Do. The said other polymerizable monomer can be suitably adjusted in order to acquire desired characteristic.

Moreover, the said (meth) acrylic-type polymer may further contain the alkylene oxide group containing reactive monomer as a monomer component. By using the (meth) acrylic polymer containing the alkylene oxide group-containing reactive monomer as a monomer component as a base polymer, the compatibility between the base polymer and the polyether compound is improved and bleeding to the adherend is suitably suppressed. The adhesive composition of the stainproof (low pollution) is obtained.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 100,000 to 2 million, more preferably 200,000 to 1 million, still more preferably 300,000 to 800,000, particularly preferably 300,000 to 700,000. When the weight average molecular weight is smaller than 100,000, the cohesive force of the pressure-sensitive adhesive layer decreases, and thus there is a tendency to generate pressure-sensitive adhesive residue. On the other hand, when a weight average molecular weight exceeds 2 million, the fluidity | liquidity of a polymer falls and wet to an to-be-adhered body (for example, a polarizing film) will become inadequate, and between the to-be-adhered body and the adhesive layer of an adhesive sheet (surface protective film). There is a tendency to cause expansion that occurs. In addition, a weight average molecular weight says what was obtained by measuring by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C or lower, more preferably -20 ° C or lower, still more preferably -40 ° C or lower, and particularly preferably -50 It is below ° C (usually -100 ° C or more). When the glass transition temperature is higher than 0 ° C., the polymer hardly flows, for example, the wetness to the polarizing film which is an optical member becomes insufficient, and the expansion of the expansion that occurs between the pressure-sensitive adhesive layer of the polarizing film and the adhesive sheet (surface protective film) is performed. It tends to be the cause. Especially, by making glass transition temperature into -60 degrees C or less especially, the adhesive layer excellent in the wettability with respect to an optical member (for example, a polarizing film), and light peelability becomes easy to be obtained. In addition, the glass transition temperature of a (meth) acrylic-type polymer can be adjusted in the said range by suitably changing the monomer component and composition ratio to be used.

Although the polymerization method of the said (meth) acrylic-type polymer is not restrict | limited, It can superpose | polymerize by well-known methods, such as solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, Especially, from a viewpoint of workability, a to-be-adhered body (protected Solution polymerization is a more preferred aspect in view of properties such as low fouling resistance to the sieve). In addition, the polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

<Urethane Adhesive>

When using a urethane type adhesive for the said adhesive layer, arbitrary appropriate urethane type adhesives can be employ | adopted. As such a urethane type adhesive, what consists of a urethane type polymer which is preferably an urethane type polymer which is an adhesive polymer obtained by making a polyol and a polyfunctional isocyanate compound react, or an adhesive polymer obtained by making a urethane prepolymer and a polyfunctional isocyanate compound react is mentioned.

As a polyol, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil type polyol etc. are mentioned, for example. One type of polyol may be sufficient and two or more types may be sufficient as it.

As polyester polyol, it can obtain by esterification of a polyol component and an acid component, for example.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, and the like. As the acid component, for example, succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanediic acid, dimer acid, 2-methyl-1 , 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4 '-Biphenyl dicarboxylic acid, these acid anhydrides, etc. are mentioned.

Examples of the polyether polyol include water, low molecular polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and the like), bisphenols (such as bisphenol A), dihydroxybenzene (catechol, resorcin, Hydroquinone etc.) etc. are mentioned, The polyether polyol obtained by addition-polymerizing alkylene oxides, such as ethylene oxide, a propylene oxide, butylene oxide, is mentioned. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

Examples of the polycaprolactone polyol include caprolactone polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

As a polycarbonate polyol, For example, Polycarbonate polyol obtained by carrying out polycondensation reaction of the said polyol component and phosgene; And dicarbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate and dibenzyl carbonate. Polycarbonate polyols obtained by transesterification of esters; Copolymerized polycarbonate polyol obtained by using 2 or more types of said polyol components together; Polycarbonate polyol obtained by esterifying the said various polycarbonate polyol and carboxyl group-containing compound; Polycarbonate polyols obtained by etherification of the various polycarbonate polyols and hydroxyl group-containing compounds; Polycarbonate polyol obtained by transesterifying the said various polycarbonate polyol and ester compound; Polycarbonate polyol obtained by transesterifying the said various polycarbonate polyol and hydroxyl group containing compound; Polyester-based polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols with a dicarboxylic acid compound; Copolymerized polyether polycarbonate polyol obtained by copolymerizing the said various polycarbonate polyol and alkylene oxide; Etc. can be mentioned.

As a castor oil type | system | group polyol, the castor oil type | system | group polyol obtained by making a castor oil fatty acid and the said polyol component react is mentioned, for example. Specifically, the castor oil type polyol obtained by making a castor oil fatty acid and polypropylene glycol react is mentioned, for example.

The number average molecular weight (Mn) of the polyol is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, and particularly preferably 500 to 30000. By adjusting the number average molecular weight (Mn) of a polyol in the said range, since the wettability of an adhesive layer can be improved, affixing becomes possible without rolling up a bubble.

As said polyfunctional isocyanate compound, For example, aliphatic polyisocyanates, such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone Alicyclic isocyanates such as diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate ( Aromatic isocyanates such as XDI), allophanate bonds, biuret bonds, isocyanurate bonds, uretodione bonds, urea bonds, carbodiimide bonds, uretonimine imine, oxadiazinetrione bonds, etc. Polyisocyanate modified substance modified by . For example, as a commercial item, brand names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, Mitsui Chemical Industries, Ltd.), Sumidule T80, Sumidule L, Death module N3400 (above, Smica Bayer urethane company), Milionate MR, Milionate MT, Coronate L, Coronate HL, Coronate HX (above, Tosoh Corporation), etc. are mentioned. These isocyanate compounds may be used independently, may be used in mixture of 2 or more types, and can also use together and use a bifunctional isocyanate compound and a trifunctional or more isocyanate compound.

As an equivalent ratio (NCO group / OH group) of NCO group and OH group in a polyol and a polyfunctional isocyanate compound, Preferably it is 5.0 or less, More preferably, it is 0.1-3.0, More preferably, it is 0.2-2.5, Especially preferably, it is 0.3-2.25, Most preferably, it is 0.5-2.0. Since the delamination of adhesive force can be suppressed by adjusting the equivalence ratio of NCO group / OH group in the said range, it is preferable.

<Polyether compound which contains three or more polyoxyalkylene chains in a molecule and does not contain a silicone chain>

The adhesive composition of this invention contains the polyether compound which contains three or more polyoxyalkylene chains in a molecule | numerator, and does not contain a silicone chain, It is characterized by the above-mentioned. When the said adhesive composition contains the said polyether compound, the adhesive sheet (adhesive layer) excellent in antistatic property is obtained by interaction with an ionic compound, and also the adhesive sheet is a to-be-adhered body (for example, a polarizing film). After peeling from such an optical member), since it is excellent in adhesiveness (adhesiveness) of layers, such as an interlayer filler provided on the to-be-adhered body surface, and the to-be-adhered body surface after peeling the said adhesive sheet, it becomes a preferable aspect. In addition, a "silicone chain" is a structure containing a siloxane bond, As a compound containing a silicone chain, polydimethylsiloxane etc. are mentioned, for example.

The polyether compound contains three or more polyoxyalkylene chains in the molecule, preferably four or more, more preferably five or more, even more preferably six or more. When the said polyoxyalkylene chain is three or more, since interaction with an ionic compound becomes strong and it is excellent in antistatic property, it is preferable. In addition, the said polyoxyalkylene chain is what contains two or more oxyalkylene units, and although the said polyoxyalkylene chain exists three or more, each polyoxyalkylene chain may be same or different.

The oxyalkylene unit is not particularly limited, but may be linear or branched. For example, an oxymethylene group, an oxyethylene group, an oxyalkylene group, an oxypropylene group, an oxybutylene group, or an oxyethylene- An oxypropylene block copolymer, an oxyethylene-oxybutylene block copolymer, an oxyethylene-oxypropylene random copolymer, etc. are mentioned, Preferably, they are an oxyethylene group or an oxypropylene group.

The repeating number of the polyoxyalkylene unit is preferably 2 or more and 200 or less, and it is not preferable because the repetition number exceeds 200 because it causes crystallization and the antistatic property is lowered.

Moreover, although the terminal of the said polyoxyalkylene chain may be linear or branched alkyl groups, such as hydrogen, a methyl group, an ethyl group, unsaturated fatty acid residues, such as an oleic acid residue, saturated fatty acid residues, such as isostearic acid residue, a carboxyl group, etc. may be more preferable. The terminal of the polyoxyalkylene chain includes at least one selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues and unsaturated fatty acid residues.

Terminals of the polyoxyalkylene chain may be the same or different in the molecule, respectively. By the presence of an alkyl group, an unsaturated fatty acid residue, and a saturated fatty acid residue that is a low polar component (low polar group), the ionic compound that interacts with the polyoxyalkylene chain moiety is the surface of the adhesive layer (the interface between the adhesive layer and air, or Since it is easy to segregate in the interface of an adhesive layer and a separator, and is excellent in antistatic property, and wettability, such as an interlayer filler, improves, since it is excellent in residual adhesive force, such as an interlayer filler, it is preferable. In addition, the alkyl group preferably has 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, isononyl group, and a saturated fatty acid. As the residue, those having 1 to 20 carbon atoms, such as butyric acid residue, caproic acid residue, lauric acid residue, myristic acid residue, palmitic acid residue, stearic acid residue and isostearic acid residue, are preferable. C1-C20 is preferable, for example, an acid residue, a myristoleic acid residue, a palmitoleic acid residue, an oleic acid residue, an oleic acid residue, and a gadoleic acid residue.

Formulas 1 to 9 below illustrate the polyether compounds, Formula 1 is glycerin, Formula 2 is trimethylolpropane, Formula 3 is diglycerin, Formula 4 is pentaerythritol, Formula 5 is methylglucoside And Formula 6 and Formula 7 are sorbitan fatty acid esters, Formula 8 is sorbitan, and Formula 9 is castor oil-based polyether compound.

In addition, R <1> in following General formulas 1-9 is a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group), may be individual, may be a block copolymer, or may be a random copolymer do. In addition, the repeating number of the oxyalkylene units is preferably 2 to 200. If the number of repetitions exceeds 200, crystallization is liable to occur, and the antistatic property is lowered. If the repetition number is less than 2, the interaction with the ionic compound is lowered and the antistatic property is lowered, which is not preferable. In addition, all structures of R1 may be the same in the molecule | numerator of the said polyether compound, and may differ.

R2 in the formulas (1) to (9) may be a linear or branched alkyl group such as hydrogen, methyl or ethyl group, unsaturated fatty acid residue such as oleic acid residue, saturated fatty acid residue such as isostearic acid residue, carboxyl group or the like, more preferably R2 is , At least one selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues and unsaturated fatty acid residues. In addition, all of R <2> may have the same structure in a molecule | numerator of the said polyether compound, and may differ.

As a specific example of the said polyether compound, as a compound with three polyoxyalkylene chains, GP250, GP400, GP600, GP1000, GP1500, GP3000, GP4000 which are polyoxypropylene glyceryl ether (above, Sanyo Kasei Co., Ltd. make), polyoxy Ethylene glycerine G-450, G-750, G-1200, TD-4S which is polyoxyethylene trimethylol propane distearic acid, GT-10IS which is polyoxyethylene glyceryl triisostearic acid, GT-20IS, GT-30IS, S-753 which is polyoxyethylene glyceryl isostearic acid GM-8IS, GM-10IS, GM-15IS, GM-20IS, GM-30IS, GM-60IS, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether, As a compound whose number of polyoxyethylene polyoxypropylene trimethylol propane which is 43TT-2500, 10TT-4500, polyoxyethylene polyoxypropylene glyceryl ether 50TG-32 (above, Nichi Corporation), and the number of polyoxyalkylene chain is four, DG which is oxypropylene diglyceryl ether P-700, DGP-950, 5TP-300KB which is polyoxyethylene polyoxypropylene pentaerythritol ether, RC-9050 which is polyoxybutylene polyoxyethylene pentaerythritol ether, MG-10E which is polyoxyethylene methyl glucoside, MG-20E, MG-2070, polyoxybutylene polyoxyethylene polyoxypropylene methylglucoside, OT-521, ST-521, ST-5160, LT-221, PT-221, polyoxyethylene sorbitan fatty acid ester As a compound whose number of polyoxyalkylene chains is MG-120TIS (above, Nichi Corporation) which is OT-206, OT-221, ST-206, LT-210, IST-221, polyoxyethylene methyl glucotriisostearic acid (above, Nichi Corporation) , Polyoxyethylene sorbitol tetraoleic acid ST-6E, ST-30E, ST-30EC, ST-40E, ST-60E, polyoxyethylene sorbitol pentaoleic acid SP-40E, polyoxyethylene sorbitol tetraisostearic acid ST-30IS, HS-1600D, polyoxypropylene sorbent, HS-2000D, C-35, HC-2, polyoxyethylene castor oil 0M (above, Nichi Corporation) etc. are mentioned. These polyether compounds may be used independently, and may mix and use 2 or more types.

As for content of the said polyether compound, 0.01-20 mass parts is preferable with respect to 100 mass parts of adhesive polymers [it is a base polymer, for example, a (meth) acrylic-type polymer, a urethane type polymer, etc.] which comprise the said adhesive composition, More preferably, Preferably it is 0.02-15 mass parts, More preferably, it is 0.04-10 mass parts, Especially preferably, it is 0.08-5 mass parts, Most preferably, it is 0.1-2 mass parts. If it exists in the said range, since it is excellent in antistatic property and low pollution property, it is preferable.

<Ionic compound>

The pressure-sensitive adhesive composition of the present invention is characterized by containing an ionic compound. As the ionic compound, it is preferable to use an alkali metal salt and / or an ionic liquid. By containing the said ionic compound, the outstanding antistatic property and peeling antistatic property can be provided.

Since the said alkali metal salt has high ion dissociation property, even if it is a trace amount addition, it is preferable at the point which expresses the outstanding antistatic ability. Examples of the alkali metal salts include cations composed of Li ⁺ , Na ⁺ , K ⁺ , Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , and SCN ^{−. _{, ClO 4 -, NO 3 -}} , CH 3 COO -, C 9 H 19 COO -, CF 3 COO -, C 3 F 7 COO -, CH 3 SO 3 -, CF 3 SO 3 -, C 4 F 9 SO _{^{3 -, C 2 H 5 OSO}} 3 -, C 6 H 13 OSO 3 -, C 8 H 17 OSO 3 - 2 N, (C 2 F 5 SO 2) - -, (CF 3 SO 2) 2 N, ( _{C 3 F 7 SO 2) 2} N -, (C 4 F 9 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F ^{_{(HF) n -, (CN}} ) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CH 3) 2 PO 4 -, (C 2 H 5) 2 PO 4 -, CH 3 ( _{OC 2 H 4) 2 OSO 3} -, C 6 H 4 (CH 3) SO 3 -, (C 2 F 5) 3 PF 3 -, CH 3 CH (OH) COO -, and (FSO _{2) 2} N ^- Metal salts composed of anions consisting of are suitably used. More preferably, LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (FSO _{2) 2 N, Li (CF} 3 SO 2) 3 lithium salt, such as C, and more preferably from _{LiCF 3 SO 3, Li (CF} 3 SO 2) 2 N, Li (C 2 F 5 SO 2) 2 N, Li (C ₃ F ₇ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (FSO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C are used. These alkali metal salts may be used alone, or may be used by mixing two or more kinds.

As for the said ionic liquid, what consists of the organic cation component represented by following formula (A)-(E) and an anion component is used preferably. Among the ionic liquids having these cations, those having a melting point of 100 ° C. or less can be obtained that are more excellent in antistatic ability.

R _<a> in said Formula (A) represents _a C4-C20 hydrocarbon group, the functional group in which one part of the said hydrocarbon group was substituted by the hetero atom may be sufficient, R <_b> and R <_c> are the same or different, and hydrogen or C1-C16 May be a functional group substituted with a hetero atom. Provided that when the nitrogen atom contains a double bond, R _c is absent.

R <_d> in said Formula (B) represents a C2-C20 hydrocarbon group, the functional group in which one part of the said hydrocarbon group was substituted by the hetero atom may be sufficient, R <_e> , R <_f> and R <_g> are the same or different, and hydrogen or carbon number The functional group in which the hydrocarbon group of 1-16 is shown and one part of the said hydrocarbon group was substituted by the hetero atom may be sufficient.

R <_h> in said Formula (C) represents a C2-C20 hydrocarbon group, the functional group in which one part of the said hydrocarbon group was substituted by the hetero atom may be sufficient, and R <_i> , R <_j> and R <_k> are the same or different, and hydrogen or carbon number The functional group in which the hydrocarbon group of 1-16 is shown and one part of the said hydrocarbon group was substituted by the hetero atom may be sufficient.

Z in said formula (D) represents a nitrogen, sulfur, or phosphorus atom, R <_1> , R <_m> , R <_n>, and R <_o> represent the same or different, C1-C20 hydrocarbon group, and a part of said hydrocarbon group is The functional group substituted by the hetero atom may be sufficient. However, when Z is a sulfur atom, there is no R _o .

R <_P> in said Formula (E) may represent a C1-C18 hydrocarbon group, and the functional group in which one part of the said hydrocarbon group was substituted by the hetero atom may be sufficient.

As a cation represented by Formula (A), a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, the cation which has a pyrroline skeleton, the cation which has a pyrrole skeleton, a morpholinium cation, etc. are mentioned, for example.

As a specific example, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl- 1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1- Heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpy Lolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, Pyrrolidinium-2-one cation, 1-pro Peelpiperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1- Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl- 1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1- Heptylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1, 2-dimethylindole cation, 1-ethylcarbazole cation, N-ethyl-N-methylmorpholinium cation, etc. are mentioned.

As a cation represented by Formula (B), an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, etc. are mentioned, for example.

As a specific example, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethyl Imidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1- (2-methoxyethyl) -3-methylimidazolium cation, 1,3-dimethyl-1,4,5,6 Tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6- Tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,3-dimethyl-1,4 -Dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3- Trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6- Dihydropyrimidinium cation etc. are mentioned.

As a cation represented by Formula (C), a pyrazolium cation, a pyrazolinium cation, etc. are mentioned, for example.

As a specific example, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl -2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3 , 5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation, and the like.

As the cation represented by the formula (D), for example, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation or a part of the alkyl group substituted with an alkenyl group, an alkoxyl group, or an epoxy group, etc. Can be mentioned.

As specific examples, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecyl Ammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, Trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, Tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, Decyl methyl phosphonium cation, a diallyl dimethyl ammonium cation, tributyl (2-methoxyethyl) phosphonium cation and the like. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylphosphonium cation and tributylethylforce Asymmetric tetraalkylammonium cations such as phosphium cations and trimethyldecylphosphonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations and N, N-diethyl-N-methyl-N- (2-methoxyethyl) Ammonium cation, glycidyltrimethylammonium cation, diaryldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N- Dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylarm Cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl-N-propyl-N-hexylammonium Cation, N, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation , N, N-dimethyl-N-pentyl-N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N- Propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N -Pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl -N-pentylammonium cation, N, N-dipropyl-N-butyl-N-hexylammonium cation, N, N-dipropyl-N, N- Hexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N- Ethyl-N-propyl-N-pentylammonium cation is preferably used.

As a cation represented by Formula (E), a sulfonium cation etc. are mentioned, for example. Moreover, as a specific example of R <_P> in said formula (E), a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, an octadecyl group Etc. can be mentioned.

On the other hand, as the anionic component, if it satisfies that an ionic liquid is not particularly limited, for ^{example, Cl -, Br -, I} -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, _{^{SCN -, ClO 4 -, NO}} 3 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, C 4 F 9 SO 3 -, (CF 3 SO 2) 2 N - _{, (C 2 F 5 SO 2} ) 2 N -, (C 3 F 7 SO 2) 2 N -, (C 4 F 9 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 - _{^{, SbF 6 -, NbF 6 -}} , TaF 6 -, F (HF) n -, (CN) 2 n -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 n -, C 3 F _{^{7 COO -, (CF 3 SO}} 2) (CF 3 CO) N -, C 9 H 19 COO -, (CH 3) 2 PO 4 -, (C 2 H 5) 2 PO 4 -, CH 3 OSO 3 - ^{_{, C 2 H 5 OSO 3 -}} , C 4 H 9 OSO 3 -, C 6 H 13 OSO 3 -, C 8 H 17 OSO 3 -, CH 3 (OC 2 H 4) 2 OSO 3 -, C 6 H 4 ^{_{(CH 3) SO 3 -,}} (C 2 F 5) 3 PF 3 -, CH 3 CH (OH) COO -, (FSO 2) 2 N -, B (CN) 4 -, C (CN) 3 -, N (CN) ₂ ^-, p- toluenesulfonate anion, a 2- (2-methoxy-ethyl) and the like ethyl sulfate anion.

These ionic liquids may be used independently, and may mix and use 2 or more types.

As for content of the said ionic compound, 0.01-5 mass parts is preferable with respect to 100 mass parts of adhesive polymers [it is a base polymer, for example, (meth) acrylic-type polymer, a urethane type polymer, etc.] which comprise the said adhesive composition, More preferably, Preferably it is 0.05-3 mass parts, More preferably, it is 0.1-2 mass parts, Especially preferably, it is 0.2-1 mass part. If it exists in the said range, since the adhesive sheet of this invention becomes easy to make both antistatic property and low pollution, it is preferable.

<Bridge school>

As for the adhesive sheet (surface protective film) of this invention, it is preferable that the said adhesive composition contains a crosslinking agent. Moreover, in this invention, it can be set as an adhesive layer using the said adhesive composition. For example, when the said adhesive composition is an acrylic adhesive containing the said (meth) acrylic-type polymer, it bridge | crosslinks by adjusting the structural unit of a said (meth) acrylic-type polymer, a structural ratio, the selection and addition ratio of a crosslinking agent, etc. suitably, Furthermore, the adhesive sheet (adhesive layer) excellent in heat resistance can be obtained.

As a crosslinking agent used for this invention, an isocyanate compound, an epoxy compound, a melamine type resin, an aziridine derivative, a metal chelate compound, etc. may be used, Especially use of an isocyanate compound becomes a preferable aspect. In addition, these compounds may be used independently and may be used in mixture of 2 or more type.

As said isocyanate compound, Aliphatic polyisocyanates, such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, for example Alicyclic isocyanates such as (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI) Aromatic isocyanates, such as an isocyanate compound, are modified by an allophanate bond, a biuret bond, an isocyanurate bond, a uretodione bond, a urea bond, a carbodiimide bond, a uretonimine bond, an oxadiazinetrione bond, and the like. One polyisocyanate modified body is mentioned. For example, as a commercial item, brand names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (above, Mitsui Chemical Industries, Ltd.), Sumidule T80, Sumidule L, Death module N3400 (above, Smica Bayer urethane company), Milionate MR, Milionate MT, Coronate L, Coronate HL, Coronate HX (above, Tosoh Corporation), etc. are mentioned. These isocyanate compounds may be used independently, may be used in mixture of 2 or more types, and can also use together and use a bifunctional isocyanate compound and a trifunctional or more isocyanate compound. By using together and using a crosslinking agent, it becomes possible to make adhesiveness and repulsion resistance (adhesiveness with respect to a curved surface) compatible, and the adhesive sheet excellent in the adhesive characteristic can be obtained further.

As said epoxy compound, N, N, N ', N'- tetraglycidyl-m-xylenediamine (brand name TETRAD-X, Mitsubishi Gas Chemical Co., Ltd.) and 1, 3-bis (N, N-, for example) are mentioned, for example. Diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

Hexamethylol melamine etc. are mentioned as said melamine type resin. As an aziridine derivative, brand name HDU, TAZM, TAZO (above, the Sogo Yakugosha Co., Ltd.) etc. as a commercial item are mentioned, for example.

As said metal chelate compound, aluminum, iron, tin, titanium, nickel etc. as a metal component, acetylene, methyl acetoacetate, ethyl lactate, etc. are mentioned as a chelate component.

It is preferable that content of the crosslinking agent used for this invention is 0.01-30 mass parts with respect to 100 mass parts of said (meth) acrylic-type polymers, for example, it is more preferable that it is 0.1-25 mass parts, and it is 0.5-20 mass parts More preferably, it is especially preferable that it is 1-18 mass parts. When the said content is less than 0.01 mass part, crosslinking formation by a crosslinking agent becomes inadequate, the cohesion force of the adhesive layer obtained becomes small, sufficient heat resistance may not be obtained, and there exists a tendency which becomes a cause of adhesive residue. On the other hand, when content exceeds 30 mass parts, the cohesion force of a polymer is large, fluidity | liquidity falls, and wet to an adherend (for example, a polarizing film) becomes inadequate, and between an adherend and an adhesive layer (adhesive composition layer) It tends to be the cause of expansion that occurs.

The pressure-sensitive adhesive composition may further contain a crosslinking catalyst for more effectively carrying out any of the above-described crosslinking reactions. As such a crosslinking catalyst, for example, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris (acetylacetonato) iron, tris (hexane-2,4-dionato) iron, tris (heptane- 2,4-dionato) iron, tris (heptane-3,5-dionato) iron, tris (5-methylhexane-2,4-dionato) iron, tris (octane-2,4-dionato) iron , Tris (6-methylheptan-2,4-dionato) iron, tris (2,6-dimethylheptan-3,5-dionato) iron, tris (nonane-2,4-dionato) iron, tris ( Nonane-4,6-dionato) iron, tris (2,2,6,6-tetramethylheptan-3,5-dionato) iron, tris (tridecane-6,8-dionato) iron, tris ( 1-phenylbutane-1,3-dionato) iron, tris (hexafluoroacetylacetonato) iron, tris (acetoacetic acid) iron, tris (acetoacetic acid-n-propyl) iron, tris (acetoacetic acid isopropyl) Iron, tris (acetoacetic acid-n-butyl) iron, tris (acetoacetic acid-sec-butyl) , Tris (acetoacetic acid-tert-butyl) iron, tris (methyl propionyl acetate) iron, tris (ethyl propionyl acetate) iron, tris (propionyl acetate-n-propyl) iron, tris (propionyl acetate isopropyl) Iron, tris (propionyl acetate-n-butyl) iron, tris (propionyl acetate-sec-butyl) iron, tris (propionyl acetate-tert-butyl) iron, tris (acetoacetic acid benzyl) iron, tris (malonic acid) Iron catalysts, such as dimethyl) iron, tris (diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, and ferric chloride, can be used. These crosslinking catalysts may be one type, or may use 2 or more types together.

Although content in particular of the said crosslinking catalyst is not restrict | limited, For example, it is preferable to set it as about 0.0001-1 mass part with respect to 100 mass parts of said (meth) acrylic-type polymers, and 0.001-0.5 mass part is more preferable. When it exists in the said range, at the time of forming an adhesive layer, the speed | rate of a crosslinking reaction will be quick and the pot life of an adhesive composition will become long, and it becomes a preferable aspect.

In addition, the pressure-sensitive adhesive composition may contain a compound that generates keto-enol intervariability. For example, in the adhesive composition containing a crosslinking agent or the adhesive composition which can be used in combination with a crosslinking agent, the aspect containing the said compound which produces the said keto-enol mutual variability can be employ | adopted preferably. Thereby, the effect of suppressing excessive viscosity increase and gelation of the adhesive composition after crosslinking agent mixing | mixing, and extending the pot life of an adhesive composition can be implement | achieved. In the case where at least an isocyanate compound is used as the crosslinking agent, it is particularly important to include a compound that generates keto-enol intervariability. This technique can be preferably applied, for example, when the pressure-sensitive adhesive composition is in the form of an organic solvent solution or a solvent-free.

As the compound for generating the keto-enol intervariability, various β-dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-3 Β-diketones such as, 5-dione; Acetoacetic acid esters, such as acetoacetic acid methyl, acetoacetic acid ethyl, acetoacetic acid isopropyl, and acetoacetic acid tert-butyl; Propionyl acetate esters such as ethyl propionyl acetate, ethyl propionyl acetate, propionyl acetate isopropyl, and propionyl acetate tert-butyl; Isobutyryl acetate esters such as ethyl isobutyryl acetate, isobutyryl acetate, isobutyryl acetate isopropyl, and isobutyryl acetate tert-butyl; Malonic acid esters such as methyl malonate and ethyl malonate; Etc. can be mentioned. Among these, suitable compounds include acetylacetone and acetoacetic acid esters. The compounds which generate such keto-enol intervariability may be used alone or in combination of two or more thereof.

Content of the compound which produces the said keto-enol mutual variability can be 0.1-20 mass parts with respect to 100 mass parts of said (meth) acrylic-type polymers, for example, and 0.5-15 mass parts (for example, 1 to 10 parts by mass) is appropriate. When there is too little quantity of the said compound, sufficient use effect may become difficult to be exhibited. On the other hand, when the said compound is used more than necessary, it may remain in an adhesive layer and may reduce cohesion force.

Moreover, the said adhesive composition may contain other well-known additives, For example, powder, such as a lubricating agent, a coloring agent, and a pigment, a plasticizer, a tackifier, a low molecular weight polymer, a surface lubricant, a leveling agent, antioxidant, and a corrosion inhibitor And light stabilizers, ultraviolet absorbers, polymerization inhibitors, softeners, anti-aging agents, heat stabilizers, silane coupling agents, inorganic or organic fillers, metal powders, particulates, thin substances, solvents, and the like. .

<Adhesive layer and adhesive sheet (surface protective film)>

It is preferable that the adhesive sheet of this invention has the adhesive layer formed from the said adhesive composition on at least single side | surface of the said base film. Moreover, although the said adhesive layer is obtained by bridge | crosslinking of the said adhesive composition, and is generally performed after application | coating of an adhesive composition, it is also possible to transfer the adhesive layer which consists of an adhesive composition after crosslinking to a base film etc.

In addition, the method of forming an adhesive layer on a base film does not matter in particular, For example, it is produced by apply | coating the said adhesive composition (solution) to a base film, drying and removing a polymerization solvent, etc., and forming an adhesive layer on a base film. do. Thereafter, curing may be performed for the purpose of adjusting the component transition of the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like. In addition, when apply | coating an adhesive composition on a base film and manufacturing an adhesive sheet, you may add a 1 or more types of solvent other than a polymerization solvent newly in the said adhesive composition so that it may apply | coat uniformly on a base film.

Moreover, as a formation method of the adhesive layer at the time of manufacturing the adhesive sheet of this invention, the well-known method used for manufacture of adhesive tapes is used. Specifically, the extrusion coat method using a roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, an air knife coat method, a die coater, etc. are mentioned, for example.

The adhesive sheet of this invention is produced normally so that the thickness of the said adhesive layer is about 0.1-100 micrometers, Preferably it is about 1-80 micrometers. When the thickness of an adhesive layer exists in the said range, since it is easy to obtain a suitable balance of re peelability and adhesiveness, it is preferable.

Moreover, it is preferable that the total thickness of the adhesive sheet of this invention is 8-300 micrometers, It is more preferable that it is 10-200 micrometers, It is most preferable that it is 20-100 micrometers. If it is in the said range, it will be excellent in adhesive characteristic (repeelability, adhesiveness, etc.), workability, and an external appearance characteristic, and will be a preferable aspect. In addition, the said total thickness means the sum total of the thickness containing all layers, such as a base film, an adhesive layer, and other layers.

<Separator>

It is preferable that a separator is affixed on the adhesive sheet of this invention on the surface opposite to the surface which contacts the said base film of the said adhesive layer. The said separator can join a separator to the adhesive layer surface in order to protect an adhesive surface as needed.

As a material which comprises the said separator, although there exists a plastic film, a plastic film is used suitably from the point which is excellent in surface smoothness. It will not specifically limit, if it is a film which can protect the said adhesive layer, For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethyl pentene film, a polyvinyl chloride film, vinyl chloride air A copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned.

The thickness of the separator is usually 5 to 200 µm, preferably about 10 to 100 µm. Since it is excellent in the bonding workability | operativity with respect to an adhesive layer, and peeling workability from an adhesive layer in it being in the said range, it is preferable. The separator may be subjected to antistatic treatment such as a release agent, antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, or the like, or a coating type, a mixed type, or a deposition type.

<Optical member>

It is preferable that the said adhesive sheet is affixed (protected) in the optical member of this invention. The said adhesive sheet is an interlayer filler newly provided in the surface of optical members, such as a polarizing film, etc., and is newly provided in the antistatic property at the time of peeling after sticking, the optical member surface after peeling off the said adhesive sheet, and the optical member surface after peeling off. Since the adhesiveness (adhesiveness) of layers, etc. is excellent, it can be used for surface protection uses (surface protection film), such as at the time of processing, conveyance, and shipment, and is useful in order to protect the surface of the said optical member.

<Interlayer Filler>

In an image display device such as a liquid crystal display, when a shock is applied from an outer surface, the impact is transmitted to an optical member such as a polarizing film and is prevented from being broken. Front transparent plates (also referred to as "window layers"), such as plates and glass plates, may be provided. In the image display apparatus provided with such a front transparent plate, when an air layer exists between an optical member such as a polarizing film and the front transparent plate, reflection loss occurs due to a difference in refractive index at the interface with the air layer. Visibility may fall, for example, an image may appear double. Therefore, both may be bonded through the layer (layer of an interlayer filler) formed with an interlayer filler so that an air layer may not exist between optical members, such as a polarizing film, and a front transparent plate. As a layer (adhesive layer, adhesive sheet) of the said interlayer filler, liquid interlayers, such as a model number "SVR7000 series" made by Decerials Corporation, and the brand name "WORLD ROCK HRJ-21" made by Kyoritsu Chemical Co., Ltd. Filler, optical transparent adhesive tape (brand name "LUCIACS series") made by Nitto Denko Corporation, etc. are mentioned. Among them, the optical transparent adhesive tape (brand name "LUCIACS series") made by the said Nitto Denko Corporation which contains the acrylic polymer which is easy to handle because it is a tape state, etc. is used, and if it is the adhesive sheet in this invention, the said display panel ( Even if the layer of the said interlayer filler is provided on the surface of the optical member after affixing on the surface etc. and peeling at the step which became unnecessary, it is excellent in adhesiveness (adhesiveness) and becomes a preferable aspect.

EXAMPLE

Hereinafter, although some Example concerning this invention is described, it is not what intended limiting this invention to what is shown in this specific example. In addition, "part" and "%" are mass references | standards unless there is particular notice in the following description.

In addition, in the following description, each characteristic was measured or evaluated as follows, respectively.

<Measurement of weight average molecular weight (Mw)>

The weight average molecular weight (Mw) of the polymer used was measured using the GPC apparatus (HLC-8220GPC) by the Tosoh Corporation. Measurement conditions are as follows.

Sample concentration: 0.2 mass% (THF solution)

Sample injection volume: 10 μl

Eluent: THF

Flow rate: 0.6ml / min

Measuring temperature: 40 ℃

column:

Sample column; TSKguardcolumn SuperHZ-H (one) + TSKgel SuperHZM-H (two)

Reference column; TSKgel SuperH-RC (one)

Detector: Differential Refractometer (RI)

In addition, the weight average molecular weight was calculated | required in polystyrene conversion value.

<Theoretical value of glass transition temperature (Tg)>

Glass transition temperature Tg (degreeC) was calculated | required by the following formula using the following literature value as glass transition temperature Tgn (degreeC) of the homopolymer by each monomer.

Formula: 1 / (Tg + 273) = Σ [Wn / (Tgn + 273)] [wherein, Tg (° C) is the glass transition temperature of the copolymer, Wn (−) is the mass fraction of each monomer, and Tgn (° C) is The glass transition temperature of the homopolymer by each monomer, n represents the kind of each monomer.]

Literature value:

2-ethylhexyl acrylate (2EHA): -70 deg.

2-hydroxyethyl acrylate (HEA): -15 ° C

4-hydroxybutyl acrylate (4HBA): -32 ° C

Acrylic acid (AA): 106 ° C

In addition, as said document value, it referred to "synthesis, design, and reliability expansion of acrylic resin" (issued from the Central Management Development Center Press) and "Polymer Handbook" (John Wiley & Sons).

<Preparation of acrylic polymer (1)>

91 mass parts of 2-ethylhexyl acrylate (2EHA), 9 mass parts of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) to the four neck flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. 0.02 parts by mass, 0.2 parts by mass of 2,2'-azobisisobutyronitrile and 150 parts by mass of ethyl acetate were added as a polymerization initiator, nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was kept at about 65 ° C. The polymerization reaction was carried out for 6 hours to prepare an acrylic polymer (1) solution (40 mass%). The weight average molecular weight (Mw) of the said acrylic polymer (1) was 540,000, and glass transition temperature (Tg) was -67 degreeC.

<Preparation of acrylic polymer (2)>

98.5 parts by mass of 2-ethylhexyl acrylate (2EHA), 1.5 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid (AA) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler. 0.2 parts by mass of 2,2'-azobisisobutyronitrile and 150 parts by mass of ethyl acetate were added as a mass part and a polymerization initiator, nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was kept at about 65 ° C. Time polymerization reaction was performed and the acrylic polymer (2) solution (40 mass%) was prepared. The weight average molecular weight (Mw) of the said acrylic polymer (2) was 480,000, and glass transition temperature (Tg) was -70 degreeC.

<Preparation of acrylic polymer (3)>

96 parts by mass of 2-ethylhexyl acrylate (2EHA), 4 parts by mass of 2-hydroxyethyl acrylate (HEA) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube and a cooler, 0.2 mass part of 2'- azobisisobutyronitrile and 150 mass parts of ethyl acetates are introduce | transduced, nitrogen gas is introduce | transduced with gentle stirring, the liquid temperature in a flask is maintained at 65 degreeC, and it polymerizes for 6 hours, and acryl-type polymer (3) A solution (40 mass%) was prepared. The weight average molecular weight (Mw) of the said acrylic polymer (3) was 480,000, and glass transition temperature (Tg) was -68 degreeC.

<Example 1>

[Preparation of Acrylic Pressure-Sensitive Adhesive Solution] The acrylic polymer (1) solution (40 mass%) was diluted to 20 mass% with ethyl acetate, and polyoxygen was dissolved in 500 mass parts (100 mass parts of solid content) as a polyether compound. 0.5 parts by mass of propylene glyceryl ether (Sannix GP3000, Sanyo Kasei Kogyo Co., Ltd.), an ionic compound, 0.3 parts by mass of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Kasei Kogyo Co., Ltd., LiTFSI), a crosslinking agent, Dioctyl tin (1 mass% acetic acid) as an isocyanurate of hexamethylene diisocyanate (made by Tosoh Corporation, coronate HX: C / HX, trifunctional isocyanate compound) 1.5 mass parts (solid content 1.5 mass parts) and a crosslinking catalyst Ethyl solution) 3 mass parts (0.03 mass part of solid content) was added, the mixture was stirred, and the acrylic adhesive solution was prepared.

[Production of antistatic treatment film]

As a binder, 100 mass parts of polyester resin vironal MD-1480 (25% aqueous solution, the Toyobo Corporation make) by solid amount, and poly (3, 4- ethylene dioxythiophene) (PEDOT) / polystyrene sulfonic acid ( 100 parts by mass of PSS) (manufactured by Baytron P, H, C, Starck Co., Ltd.) as a solid content, and 10 parts by mass of hexamethylolmelamine as a solid content as a crosslinking agent were added to a mixed solvent of water / ethanol (1/1), and about 20 parts by mass. It stirred for minutes and mixed sufficiently. In this manner, an antistatic agent solution of about 0.4% of NV (nonvolatile matter) was prepared.

The obtained antistatic agent solution was applied onto a polyethylene terephthalate (PET) film (thickness: 38 μm) which is a base film using a Mayer bar, and dried at 130 ° C. for 1 minute to remove the solvent to form an antistatic layer (thickness 0.2 μm). It formed and the antistatic process film (base film with an antistatic layer) was produced.

[Production of adhesive sheet (surface protection film)]

The acrylic pressure-sensitive adhesive solution was applied to a surface opposite to the surface (antistatic treatment surface) having the antistatic layer of the antistatic treatment film described above, and heated at 130 ° C. for 1 minute to form an adhesive layer having a thickness of 10 μm. . Next, the siliconized surface of the polyethylene terephthalate (PET) film (separator, 25 micrometers in thickness) which performed the siliconization on one side was bonded to the surface which is not in contact with the PET film which is the base film of the said adhesive layer, and the adhesive sheet ( Surface protective film) was produced (see FIG. 1).

<Examples 2 to 23 and Comparative Examples 1 to 3>

An adhesive sheet (surface protective film) by the same method as Example 1 in the compounding quantity shown in Table 3 except having used the raw material of Table 3 instead of the adhesive polymer, polyether compound, and ionic compound used in Example 1. Made.

<Example 24>

[Preparation of Urethane Adhesive Solution]

As polyol, 100 mass parts of preminol S3011 (made by Asahi Glass Co., Mn = 10000) which is a polyol which has three hydroxyl groups, 8.9 mass parts of isocyanate compounds (Cornate HX: C / HX, Nippon Polyurethane company make) as a crosslinking agent, As a catalyst, 0.04 mass part of iron (III) acetylacetonato (made by Tokyo Kasei Kogyo Co., Ltd.), 0.5 mass part of ST-30E (made by Nichi Corporation) as a polyether compound, AS110 (made by Daiichi Kogyo Seiyaku Co., Ltd.) 0.45 as an ionic compound 210 mass parts of ethyl acetate were mix | blended as a mass part and the diluting solvent, and the urethane type adhesive solution was obtained.

[Production of adhesive sheet (surface protection film)]

The urethane pressure-sensitive adhesive solution was applied to a surface opposite to the antistatic treatment surface of the antistatic treatment film, and heated at 130 ° C. for 1 minute to form an adhesive layer having a thickness of 10 μm. Next, the siliconized surface of the polyethylene terephthalate (PET) film (separator, 25 micrometers in thickness) which performed the siliconization on one side was bonded to the surface which is not in contact with the PET film which is the base film of the said adhesive layer, and the adhesive sheet ( Surface protective film) was produced (see FIG. 1).

<Examples 25 to 28>

An adhesive sheet (surface protective film) was produced by the same method as Example 24 except for using the starting material and the compounding amount described in Table 4.

<Example 29>

[Preparation of Urethane Adhesive Solution]

100 parts by mass of urethane prepolymer SH109 (manufactured by Toyochem Co., Ltd.) and 3.8 parts by mass of isocyanate compound (Coronate L: C / L, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, and iron (III) acetylacetonato (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.04 mass part, 0.5 mass part of ST-30E (made by Nichi Corporation) as a polyether compound, 0.45 mass part of AS110 (made by Daiichi Kogyo Seiyaku Co., Ltd.) as an ionic compound, 210 mass parts of ethyl acetate are mix | blended as a dilution solvent, A solution was obtained.

[Production of adhesive sheet (surface protection film)]

The urethane pressure-sensitive adhesive solution was applied to a surface opposite to the antistatic treatment surface of the antistatic treatment film, and heated at 130 ° C. for 1 minute to form an adhesive layer having a thickness of 10 μm. Next, the siliconized surface of the polyethylene terephthalate (PET) film (separator, 25 micrometers in thickness) which performed the siliconization on one side was bonded to the surface which is not in contact with the PET film which is the base film of the said adhesive layer, and the adhesive sheet ( Surface protective film) was produced (see FIG. 1).

<Example 30>

[Preparation of Urethane Adhesive Solution]

Preminol S3011 (manufactured by Asahi Glass Co., Mn = 10000), which is a polyol having three hydroxyl groups, as a polyol; Sannix GP3000 (manufactured by Sanyo Kasei Co., Ltd., Mn = 3000), which is 85 parts by mass of a polyol having three hydroxyl groups. 13 parts by mass of isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) Part, as a catalyst, 0.04 parts by mass of iron (III) acetylacetonato (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.5 parts by mass of ST-30E (manufactured by Nichiyo Corp.) as a polyether compound, and AS110 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an ionic compound. ) 0.45 mass part and 210 mass parts of ethyl acetate were mix | blended as a diluting solvent, and the urethane type adhesive solution was obtained.

[Production of adhesive sheet (surface protection film)]

The urethane pressure-sensitive adhesive solution was applied to a surface opposite to the antistatic treatment surface of the antistatic treatment film, and heated at 130 ° C. for 1 minute to form an adhesive layer having a thickness of 10 μm. Next, the siliconized surface of the polyethylene terephthalate (PET) film (separator, 25 micrometers in thickness) which performed the siliconization on one side was bonded to the surface which is not in contact with the PET film which is the base film of the said adhesive layer, and the adhesive sheet ( Surface protective film) was produced (see FIG. 1).

About the adhesive sheet which concerns on an Example and a comparative example, the result of having performed the above-mentioned compounding content, various measurement, and evaluation was shown in Table 1-5. In addition, the compounding quantity in Table 3 and Table 4 showed the active ingredient. In Examples 2 to 23 other than Example 1 and Comparative Examples 1 to 3, the same amount as in Example 1 was blended with respect to the crosslinking catalyst and the like which do not describe the compounding amounts in Tables 3 and 4. In addition, the thickness of the obtained adhesive layer was prepared similarly to Example 1.

Below, abbreviated-name of Table 3 and Table 4 is demonstrated below.

(Ionic compound)

LiTFSI: Lithium bis (trifluoromethanesulfonyl) imide (made by Tokyo Kasei Kogyo Co., Ltd.), alkali metal salt

LiTFS: lithium trifluoromethanesulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), alkali metal salts

AS110: 1-ethyl-3-methylimidazolium bis (fluoromethane sulfonyl) imide (made by Daiichi Kogyo Seiyaku Co., Ltd.), ionic liquid

AS210: 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (made by Dai-ichi Kogyo Seiyaku Co., Ltd.), ionic liquid

CIL312: 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide (manufactured by Nippon Khalit), ionic liquid

CIL313: 1-ethyl-3-methylpyridinium trifluoromethanesulfonic acid (manufactured by Nippon Calit), ionic liquid

MTOATFSI: Methyl toric octyl ammonium bis (trifluoromethanesulfonyl) imide (made by Wako Junyaku Kogyo Co., Ltd.), an ionic liquid

(Bridge)

C / HX: isocyanurate body of hexamethylene diisocyanate (made by Tosoh Corporation, brand name: coronate HX)

C / L: trimethylolpropane / tolylene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate L)

C / HL: trimethylolpropane adduct of hexamethylene diisocyanate (made by Tosoh Corporation, brand name: coronate HL)

<Preparation of the film with a hard coat layer>

In urethane acrylate ultraviolet curable resin solution [DIC Corporation make, brand name "Unidick 17-806", solid content concentration 80%], per 100 mass parts of solid content in the solution, a photoinitiator [Shiba Japan Co., Ltd. product, a product name] 5 parts by mass of "IRGACURE906"] and 0.03 parts by mass of a leveling agent (manufactured by DIC Corporation, product name "GRANDIC PC4100") were added. Thereafter, butyl acetate was added to the solution so that the solid content concentration in the solution was 75%, and cyclopentanone was added to the solution so that the solid content concentration in the solution was 50%. Thus, the hard-coat layer formation material for forming a hard-coat layer was prepared.

Subsequently, the said hard-coat layer formation material was apply | coated so that the thickness after hardening might be set to 7.5 micrometers on the triacetyl cellulose film (made by Fujifilm Co., Ltd. product, "TD80UL", thickness of 80 micrometers), and the coating film was formed. The said coating film was dried at 80 degreeC for 2 minutes. Then, the film with a hard-coat layer was produced by irradiating the said coating film with the ultraviolet-ray of accumulated light quantity 300mJ / cm <2> using a high pressure mercury lamp.

<Measurement of peeling band voltage>

The adhesive sheet 10 which concerns on each example was cut into the size of width 70mm and length 130mm, and after peeling a separator, the said film with a hard-coat layer (70mm in width, length 100mm in length) bonded to the glass plate 11 One end of the adhesive sheet 10 was protruded to 30 mm from the end of the film 12 with a hard coat layer on the surface of the lamella (12), and was crimped with a hand roller.

After leaving this sample in the environment of 23 degreeC * 50% RH for 1 day, as shown in FIG. 2, it set to the predetermined position of the sample holder 13 of height 20mm. The edge part of the adhesive sheet 10 which protruded 30 mm from the film 12 with a hard-coat layer was fixed to an automatic winding machine (not shown), and it peeled so that it might become a peeling angle of 150 degrees and a peeling speed of 30 m / min. Dislocation measuring instrument 14 (Shideido Seidoki), where the dislocation of the surface of the adherend (film 12 with hard coat layer) generated at this time is fixed at a position of 30 mm in height from the center of the film 12 with hard coat layer. "Peeling band voltage" was measured by the model "STATIRON DZ-4". The measurement was performed in the environment of 23 degreeC and 50% RH.

As said peeling band voltage (kV, absolute value), Preferably it is 1 kPa or less, More preferably, it is 0.8 kPa or less, More preferably, it is 0.6 kPa or less. By the said peeling band voltage being in the said range, damage of the panel by static electricity, etc. do not occur, and it becomes a preferable aspect.

<Measurement of Residual Adhesion Force>

After peeling the separator of the adhesive sheet which concerns on each example, it pressed on the surface of the said film (70 mm in width, 100 mm in length) 12 with a hard-coat layer with the hand roller.

After leaving this sample in the environment of 23 degreeC x 50% RH for 1 day, an adhesive sheet is peeled off and an acrylic tape (No.31B made from Nitto Denko Co., Ltd., width 19mm,) on the surface of the film 12 with a hard-coat layer, Substrate thickness 25 µm) was pressed with a hand roller. After leaving this sample in an environment of 23 ° C. × 50% RH for 30 minutes, the peel force (N / 19 mm) when peeled at a peel angle of 180 ° and a peel rate of 0.3 m / min was measured, and this was measured as a residual adhesive force ( N / 19 mm).

As said residual adhesive force (N / 19mm), Preferably it is 4.5N / 19mm or more, More preferably, it is 4.8N / 19mm or more, More preferably, it is 5N / 19mm or more, Especially preferably, it is 5.5 N / 19 mm or more. Since the said residual adhesive force exists in the said range, for example, after sticking an adhesive sheet to the surface of an optical member (polarizing film etc.), after peeling, adhesiveness with the interlayer filler etc. newly provided in the optical member surface after peeling (adhesiveness) This does not fall, and problems, such as peeling, do not arise, and it becomes a preferable aspect.

<Residual Adhesion Rate>

The adhesion of No. 31B to the surface of the film with hard coat layer before bonding the pressure sensitive adhesive sheet was measured and calculated by the following formula.

Residual Adhesion Rate (%) = 100 x [(No.31B Adhesion Force after Adhesive Sheet Peeling of Each Example) / (No.31B Adhesion Force Before Bonding Adhesive Sheet)]

As said residual adhesion rate (%), Preferably it is 70% or more, More preferably, it is 75% or more, More preferably, it is 80% or more, Especially preferably, it is 90% or more. Adhesiveness with the interlayer filler etc. newly provided in the optical member surface after peeling, after peeling an adhesive sheet on the surface of an optical member (polarizing film etc.), for example, because the said residual adhesion rate exists in the said range (adhesiveness) ) Does not decrease, and problems such as peeling do not occur, thereby becoming a preferred embodiment. In addition, when the said residual adhesiveness exceeds 100%, although the detail is not clear, a polyether compound is transcribe | transferred on the optical member surface which is a to-be-adhered body, and after that, wettability improves in relationship with the newly provided interlayer filler etc. It is estimated that the said residual adhesion rate becomes high.

From the evaluation result of the said Table 5, in all the Examples, after peeling from the to-be-adhered body (here, a film with a hard-coat layer), it was excellent in antistatic property, and after peeling an adhesive sheet from the to-be-adhered body surface, Adhesive sheet (adhesive layer) which is excellent in the residual adhesive force and the residual adhesive rate in the acrylic tape bonded to the to-be-adhered surface, and excellent in adhesiveness (adhesiveness) with the acrylic tape with respect to the to-be-adhered body surface after peeling the said adhesive sheet. It was confirmed that was obtained.

On the other hand, from the evaluation result of the said Table 5, in the comparative example 1, since the polyether compound containing a silicone chain was used at the time of manufacture of an adhesive solution (composition), residual adhesive force and residual adhesive rate are low, and adhesiveness (adhesiveness) Properties) were inferior, and in Comparative Example 2 and Comparative Example 3, since the number of polyoxyalkylene chains was smaller than the desired range, it was confirmed that the interaction with the ionic compound was weak and the antistatic property was inferior.

The adhesive sheet disclosed here is an optical member corresponding to a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescence (EL) display, a manufacturing method of an optical member used as a component such as a touch panel, and at the time of conveyance. It is suitable as a surface protection film for protecting. It is especially useful as a surface protection film (surface protective film for optics) applied to optical members, such as a polarizing film, a wavelength plate, a retardation plate, an optical compensation film, a brightness enhancement film, a light-diffusion sheet, and a reflection sheet for liquid crystal display panels. .

1: antistatic layer
2: base film
3: adhesive layer
4: Separator
10: adhesive sheet (surface protective film)
11: glass plate
12: adherend (film with hard coat layer)
13: sample holder
14: potential measuring instrument

Claims (5)

Adhesive polymer,
A polyether compound containing at least three polyoxyalkylene chains in a molecule and not containing a silicone chain, and
An adhesive composition containing an ionic compound. The said adhesive polymer is a (meth) acrylic-type polymer and / or a urethane-type polymer, The adhesive composition of Claim 1 characterized by the above-mentioned. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the terminal of the polyoxyalkylene chain comprises at least one selected from the group consisting of linear or branched alkyl groups, saturated fatty acid residues and unsaturated fatty acid residues. At least one side of a base film has an adhesive layer formed of the adhesive composition in any one of Claims 1-3, The adhesive sheet characterized by the above-mentioned. The adhesive sheet of Claim 4 is affixed, The optical member characterized by the above-mentioned.

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