JP5526646B2 - Antistatic pressure-sensitive adhesive composition, and antistatic pressure-sensitive adhesive sheet and laminate using the same - Google Patents

Description

  The present invention relates to an antistatic pressure-sensitive adhesive composition suitably used for laminating optical members such as optical films, and further, an antistatic pressure-sensitive adhesive sheet using the antistatic pressure-sensitive adhesive composition, a laminate The present invention relates to a body and a liquid crystal cell member.

  In recent years, display devices have been used in home and commercial appliances such as electronic computers, electronic watches, mobile phones, and televisions, in-vehicle devices, etc., and are used under harsh conditions according to each application. Opportunities are increasing. And various optical films, such as a polarizing film and a phase difference film, are used for the display member which comprises these display apparatuses.

  By the way, the polarizing film is a state in which a polyvinyl alcohol film dyed and stretched with a pigment is sandwiched between a triacetyl cellulose-based protective film or a cycloolefin-based protective film. The triacetylcellulose-based protective film and the cycloolefin-based protective film used for the polarizing film are difficult to bond with a general pressure-sensitive adhesive. In addition, the polarizing film has poor dimensional stability because of the characteristics of these materials, and the dimensional change due to the shrinkage of the film is particularly severe under high temperature or high temperature and high humidity conditions.

  When a laminate comprising an optical film / pressure-sensitive adhesive layer / adhered body is placed under high temperature or high temperature / high humidity conditions, and the dimensions of the optical film change, the pressure-sensitive adhesive layer and the adherend are adhered. Bubbles are generated at the interface (foaming), and the optical film is lifted from the adherend and peeled off. By adjusting the molecular weight of the base resin, which is the main component of the pressure-sensitive adhesive used, and the degree of crosslinking of the pressure-sensitive adhesive, and by increasing the adhesive force, even in harsh environments against dimensional changes in the optical film Attempts have been made in the past to prevent foaming, floating and peeling.

  However, if an attempt is made to resist the dimensional change of the optical film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the optical film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, and the stress is reduced. Concentrate at the four corners of the optical film or at the peripheral edge. As a result, when the optical film is a polarizing film used in a liquid crystal display device, there is a problem that a so-called “light leakage phenomenon” occurs in which light leaks from the four corners and peripheral edges of the liquid crystal display device.

  In addition, when a polarizing plate is attached to an optical component such as a liquid crystal cell in a manufacturing process of a liquid crystal display or the like, the polarizing plate is peeled off after a certain period of time has elapsed since the attachment position has shifted. It may be necessary to reuse expensive liquid crystal cells. Therefore, a pressure-sensitive adhesive with good reworkability that can be peeled off from a liquid crystal cell relatively easily even after a certain period of time after being pasted via a pressure-sensitive adhesive applied to a polarizing plate. Was demanded.

  Further, various optical films such as a polarizing film and a retardation film are attached to an adherend (glass or other optical film constituting a liquid crystal cell) using a pressure-sensitive adhesive. Specifically, the release sheet that covered the surface of the pressure-sensitive adhesive layer is peeled off from the pressure-sensitive adhesive sheet in the laminated state of various optical films / pressure-sensitive adhesive layers / release sheets, and the pressure-sensitive adhesive layer is interposed therebetween. A polarizing film, a retardation film, or the like is attached to a liquid crystal cell glass or the like that is an adherend. When peeling off the release sheet, static electricity may be generated, and the static electricity sucks dust and debris at the time of sticking. The liquid crystal and electronic circuits that are stopped may be damaged.

  As described above, the pressure-sensitive adhesive used for laminating a polarizing film on a glass member for a liquid crystal cell has good optical properties (transparency), heat resistance and moist heat resistance, light leakage prevention properties, and reworkability. In addition, antistatic properties are required. And the same performance is calculated | required also for the pressure sensitive adhesive for laminating | stacking the retardation film and the cover film of various displays. Therefore, even under harsh conditions, it is a pressure-sensitive adhesive for optical film sticking that does not cause foaming at the interface with the adherend and does not float or peel off. Various pressure-sensitive adhesives having excellent optical properties and reworkability have been proposed.

  As a resin component, a monomer having a reactive functional group and a copolymer (A) having a weight average molecular weight of 1,000,000 to 2,000,000 formed by radical copolymerization of another monomer, and the above copolymer A monomer having a carboxyl group in the presence thereof, and a copolymer (B) having a weight average molecular weight of 10,000 to 100,000 formed by radical copolymerization of the other monomer, and the copolymer (A) and / Or a pressure-sensitive adhesive comprising a polyfunctional compound having at least two reactive functional groups capable of reacting with the copolymer (B), and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive further comprises at least an optical member. An optical member formed on one surface has been proposed (Patent Document 1).

  In addition, it has been proposed to use a pressure-sensitive adhesive composition containing a urethane resin or a urethane urea resin (Patent Documents 2, 3, and 4).

  On the other hand, with respect to imparting the antistatic function of the pressure-sensitive adhesive, an example in which a charge control agent is added to the acrylic pressure-sensitive adhesive is disclosed. Examples of charge control agents include metal complex types, imides, bisphenols, phosphates, carboxylic acids, quaternary amines, oniums, imidazoles, and the like (Patent Document 5).

  Further, an antistatic pressure-sensitive adhesive in which a cationic surfactant and lithium perchlorate are blended with a pressure-sensitive adhesive based on poly (meth) acrylate is disclosed (Patent Document 6).

  Also disclosed is an antistatic polyurethane adhesive containing a hydroxyl group-containing polyurethane resin obtained by reacting a polyol component having an alkylene oxide chain, a polyester polyol component, and a diisocyanate component, an ionic compound, and a trifunctional isocyanate compound. (Patent Document 7).

  Furthermore, an antistatic pressure-sensitive adhesive composed of an ionic liquid that is in a liquid state at room temperature and a urethane resin or urethane urea resin is disclosed (Patent Documents 8 and 9).

  Further, an antistatic pressure-sensitive adhesive composed of an ionic compound containing a fluorine atom-containing anion as a constituent component and an acrylic resin is disclosed (Patent Document 10).

  Further, an antistatic pressure-sensitive adhesive composed of an ionic compound containing a fluorine atom-containing anion as a constituent component and a urethane resin is disclosed (Patent Document 11).

  All of the pressure-sensitive adhesive films using the pressure-sensitive adhesives described in Patent Documents 1 to 4 are attached to the adherend and then for a long time under high temperature and high pressure, high temperature, or high temperature and high humidity. Even if exposed, foaming does not occur at the sticking interface with the adherend, and neither floating nor peeling occurs, and no light leakage phenomenon occurs. However, in further enhancement of performance and size of the liquid crystal display device, durability under high temperature and high humidity and optical function maintaining characteristics were insufficient. In addition, no effective method is described for imparting antistatic properties. In particular, the pressure-sensitive adhesives described in Patent Documents 2 to 4 sometimes have a sticking force that increases with time after application, making rework difficult. Moreover, when it is used for an optical use as it is the method described in patent documents 5-7, the heat-and-moisture resistance will fall under the influence of the antistatic agent to be used. Furthermore, in the case of the pressure-sensitive adhesives described in Patent Documents 8, 9, and 11, good antistatic properties and transparency can be obtained, but when used for optical film applications, floating and peeling under high temperature and high humidity conditions. There was a problem that occurred. Furthermore, in the case of the pressure-sensitive adhesive described in Patent Document 10, it is necessary to use a large amount of an antistatic agent in order to develop a good antistatic ability, causing a deterioration in durability.

JP 2004-331697 A JP 2003-292928 A JP 2002-38119 A JP 2009-8859 A JP 2004-155977 A JP 2006-2140 A JP 2005-154491 A JP 2007-238766 A JP 2007-277484 A JP 2009-155585 A JP 2006-182794 A

  The object of the present invention is to provide good adhesion to an optical film, and after sticking the optical film to an adherend, even if it is exposed to high temperature and pressure, high temperature, or high temperature and high humidity for a long time, It is an object of the present invention to provide an antistatic pressure-sensitive adhesive composition that not only causes foaming, floats and peels, does not cause light leakage, but also has excellent reworkability and good antistatic properties.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the pressure-sensitive adhesive composition shown below, and have completed the present invention. That is, the first invention is a weight average obtained by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) having a polypropylene glycol skeleton or a polyester skeleton with a polyisocyanate (b). With respect to 100 parts by weight of urethane urea resin (A) having a molecular weight (Mw) of 70,000 to 200,000,
0.05 to 10 parts by weight of an ionic compound (B) having a fluorine atom-containing anion as a component,
Hardener (C) 0.3-3 parts by weight,
And an antistatic pressure-sensitive adhesive composition comprising 0.01 to 3 parts by weight of a silane coupling agent (D) having an alkoxysilyl group.

  In the second invention, the amount of polyisocyanate (b) used is 8 to 16% by weight in 100% by weight of urethane urea resin (A), and the amount of polyamino compound (c) used is urethane urea resin. (A) It relates to the antistatic pressure-sensitive adhesive composition of the first invention, which is 0.5 to 11% by weight in 100% by weight.

  In the third invention, the anion of the ionic compound (B) having a fluorine atom-containing anion as a component is bis (fluorosulfonyl) imide or bis (trifluoromethanesulfonyl) imide. The present invention relates to an antistatic pressure-sensitive adhesive composition of the invention of 2.

  The fourth invention relates to the antistatic pressure-sensitive adhesive composition according to any one of the first to third inventions, wherein the curing agent (C) is a hexamethylene diisocyanate trimethylolpropane adduct.

  The fifth invention relates to the antistatic pressure-sensitive adhesive composition of any one of the first to fourth inventions containing polyalkylene glycol (E).

  The sixth invention is the antistatic property feeling of the fifth invention, wherein the polyalkylene glycol (E) is polypropylene glycol and is contained in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the urethane urea resin (A). The present invention relates to a pressure-sensitive adhesive composition.

  The seventh invention is a charge formed by forming a pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition of any one of the first to sixth inventions on one side or both sides of a sheet-like substrate. The present invention relates to a preventive pressure-sensitive adhesive sheet.

  The eighth invention relates to a laminate in which a pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition of any one of the first to sixth inventions is laminated on an optical member.

  Moreover, 9th invention is related with the laminated body of 8th invention whose optical member is a polarizing plate.

  In the tenth invention, a glass member for a liquid crystal cell, a pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition of any one of the first to sixth inventions, and an optical member are sequentially laminated. This relates to a liquid crystal cell member.

  The eleventh invention also relates to a liquid crystal cell member according to the tenth invention, wherein the optical member is a polarizing plate.

  According to the present invention, the adhesiveness to the optical film is good. After the optical film is stuck to the adherend, foaming at the sticking interface is possible even if it is exposed to high temperature, high pressure, high temperature, or high temperature and humidity for a long time. In addition, the anti-static pressure-sensitive adhesive composition not only did not float or peel off and did not cause light leakage but also had excellent reworkability and good antistatic properties.

  The urethane urea resin (A) used in the present invention will be described. The urethane urea resin (A) of the present invention is obtained by reacting a polyamino compound (c) with a urethane prepolymer obtained by reacting a polyol (a) having a polypropylene glycol skeleton or a polyester skeleton with a polyisocyanate (b). The resin having a weight average molecular weight of 70,000 to 200,000.

  The present invention is characterized in that a polyol (a) having a polypropylene glycol skeleton or a polyester skeleton is used as a polyol used for the synthesis of the urethane urea resin (A). By using the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton, the polypropylene glycol skeleton or the polyester skeleton can be introduced into the urethane urea resin (A), which makes the antistatic property and heat-resistant heat resistance of the pressure-sensitive adhesive layer. Compatibility with characteristics is possible. In the present invention, other polyols (d) can be used in combination with the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton. For the above reasons, the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton. The amount of the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton is preferably 80 to 100% by weight in a total of 100% by weight of the polyol and the other polyol (d). Further, in 100% by weight of the polyol (a) having a polypropylene glycol skeleton or polyester skeleton, the amount of the polyether polyol (a-1) having a polypropylene glycol skeleton is more preferably 70 to 100% by weight, more preferably 100% by weight. Is particularly preferred. If it is less than 70% by weight, the optical properties may be deteriorated or the expression of antistatic properties may be difficult.

  The polypropylene glycol skeleton or polyester skeleton introduced into the urethane urea resin (A) forms a complex (composite) with an ionic compound (B) having a fluorine atom-containing anion, which will be described later, as a constituent, and has a micro Brownian mobility. A high polypropylene glycol skeleton or polyester skeleton is considered to produce good antistatic properties because the generated ions are easily carried.

  A well-known thing can be used as a polyol (a) which has the polypropylene glycol frame | skeleton or polyester frame | skeleton used for this invention. Hereinafter, examples of the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton are divided into a polyol (a-1) having a polypropylene glycol skeleton and a polyol (a-2) having a polyester skeleton.

  Examples of the polyol (a-1) having a polypropylene glycol skeleton include polypropylene glycol, copolymers of propylene glycol and alkylene glycols other than various propylene glycols, and the like. In the present invention, a copolymer of polypropylene glycol and polyester polyol is also included in the range of the polyol (a-1) having a polypropylene glycol skeleton.

  As the polyol (a-2) having a polyester skeleton, a known polyester polyol can be used. Examples of the polyester polyol include a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component. Examples of the polyfunctional alcohol component include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3 ′. -Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexane Examples include compounds having two hydroxyl groups such as diol, cyclohexanediol, bisphenol A, and bisphenol F, and three or more hydroxyl acids such as glycerin, trimethylolpropane, and pentaerythritol. Compounds having the like.

  Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.

  Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

  Among the polyols (a-2) having a polyester skeleton, aliphatic polyester polyols are preferable from the viewpoint of adhesion and antistatic properties, and those having low crystallinity are preferable from the viewpoint of transparency.

  Among the polyols (a) having a polypropylene glycol skeleton or a polyester skeleton, polypropylene glycol is most preferable from the viewpoint that both the antistatic property and the heat-and-moisture resistance of the pressure-sensitive adhesive layer can be achieved at a high level.

  The weight average molecular weight of the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton is preferably 100 to 5,000, more preferably 500 to 3,500. If it is less than 100, the concentration of urethane and urea bonds in the resin is increased, and not only the adhesive strength is lowered, but also the optical properties of the pressure-sensitive adhesive may be impaired. If it exceeds 5,000, the urethane bond and urea bond that impart cohesive force to the pressure-sensitive adhesive may be reduced, and the heat resistance of the pressure-sensitive adhesive may be impaired.

  The urethane urea resin (A) used in the present invention can be produced by using a polyol (a) having a polypropylene glycol skeleton having a polypropylene glycol skeleton or a polyester skeleton and other polyols (d) in combination. As other polyols (d), polyether polyols, polycarbonate polyols, and other glycols other than the polyol (a-1) having a known polypropylene glycol skeleton can be used.

  Among the other polyols (d), examples of polyether polyols other than the polyol (a-1) having a polypropylene glycol skeleton include, for example, polymers of alkylene oxides such as tetrahydrofuran, ethylene oxide, butylene oxide, copolymers, and Graft copolymers: those having two or more hydroxyl groups such as hexanediol, methylhexanediol, heptanediol, octanediol or polyether polyols obtained by condensation of a mixture thereof can be used. Furthermore, glycols obtained by adding alkylene oxide excluding propylene oxide such as ethylene oxide to bisphenols such as bisphenol A and bisphenol F can be used.

  Among the other polyols (d), the polycarbonate polyol has a structure represented by the following general formula [1] in its molecule, and a known polycarbonate polyol can be used.

General formula [1]
− [— O—R ¹ —O—CO—] _m —
(In the formula, R ¹ represents a divalent organic residue, and m represents an integer of 1 or more.)

  The polycarbonate polyol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

  Specific examples of the carbonic acid ester used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Examples of the glycol or bisphenol used in the production methods (1) and (2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, or Scan bisphenols such as bisphenol A, bisphenol F, ethylene oxide bisphenol, bisphenol obtained by adding alkylene oxide such as propylene oxide or the like can also be used. These compounds can be used as one kind or a mixture of two or more kinds.

  Specifically, the Kuraray polyol C series of Kuraray Co., Ltd. can be used in the polycarbonate polyol. Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are flexible, and polypropylene is used as a raw material for the urethane urea resin (A). It can be preferably used in combination with a polyol (a) having a glycol skeleton or a polyester skeleton.

  As other glycols among the other polyols (d), two glycols such as ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentylglycol, cyclohexanedimethanol, etc. Examples thereof include compounds having a hydroxyl group, compounds having three or more hydroxyl groups such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and methylglucoside.

  Furthermore, as other glycols, polyols containing at least one ionic functional group can also be used. Examples of the ionic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a primary to tertiary amino group, a quaternary ammonium group, a phosphonium group, and a quaternary sulfonium group.

  The polyol containing at least one ionic functional group makes the urethane urea resin of the present invention aqueous, increases the reaction rate at the time of synthesizing the urethane prepolymer, and further improves the film formability. It is also preferably used in terms of points.

  For example, when a polyol having a carboxyl group is used as a polyol containing at least one ionic functional group, a carboxyl group can be introduced into the urethane urea resin (A), and the carboxyl group can be converted into a curing agent (C) described later. It can be used as a reaction point. Examples of the polyol containing at least one ionic functional group include dioxycarboxylic acids such as dimethylolpropionic acid and dimethylolbutanoic acid.

  In addition, a urethane polyol having a terminal hydroxyl group obtained by reacting an isocyanate group in the following polyisocyanate (b) with less than an equivalent amount to a hydroxyl group in the other glycols described above may be used.

  In order to satisfy the performance as a pressure-sensitive adhesive composition, the polyol (a) having the polypropylene glycol skeleton or the polyester skeleton described above and the other polyol (d) have a glass transition temperature (Tg) of the urethane urea resin (A). ) Is preferably selected so as to be 0 to -80 ° C. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  As the polyisocyanate (b) used in the present invention, conventionally known ones can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. It is done.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As the alicyclic polyisocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2 , 6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

  Further, a trimethylolpropane adduct of the above polyisocyanate (b), a trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as the polyisocyanate (b).

  Examples of the polyisocyanate (b) used in the present invention include 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (also known as IPDI), xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ( It is preferable from the viewpoint of weather resistance to use a non-yellowing type or hardly yellowing type polyisocyanate compound such as another name: hydrogenated MDI).

  Furthermore, as the polyisocyanate (b) described above, it is preferable to use isophorone diisocyanate (also known as IPDI) in terms of controlling the optical properties and reactivity of the pressure-sensitive adhesive composition.

  The amount of polyisocyanate (b) used is 100% by weight of urethane urea resin (A) [polyol having a polypropylene glycol skeleton or polyester skeleton used for the synthesis of urethane urea resin (A) (a), used as necessary. The other polyol (d), polyisocyanate (b), polyamino compound (c), and reaction stopper (e) to be used if necessary in a total of 100% by weight], preferably a ratio of 8 to 16% by weight More preferably, it is 10 to 13% by weight. If it is less than 8% by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, and it may be difficult to impart durability. On the other hand, if it exceeds 16% by weight, the flexibility of the resin is lowered, so that the stress relaxation property of the pressure-sensitive adhesive is impaired, the optical properties are deteriorated, and the molecular motion of the urethane urea resin (A) is suppressed. In other words, the mobility of ions generated from the ionic compound (B) having a fluorine atom-containing anion, which will be described later, as a constituent component is lowered, and sufficient antistatic properties may not be obtained.

  Next, the polyamino compound (c) used in the present invention will be described. The polyamino compound (c) of the present invention is a compound having two or more amino groups, and known compounds can be used. In the case where the polyamino compound (c) is used, it becomes easy to introduce a urea bond into the resin, and when the ionic compound (B) having a fluorine atom-containing anion as a part of the constituent component is blended with the pressure-sensitive adhesive, Also, the durability of the pressure sensitive adhesive can be improved. In addition, the urea bonding portion introduced by the polyamino compound (c) is microlayer-separated in the pressure-sensitive adhesive layer, so that both durability and optical properties can be achieved.

Examples of the polyamino compound (c) include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2 , 2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2- Hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropyl) Styrene) diamines, aliphatic such as piperazine polyamine;
Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( sec-butyl) aromatic diamines such as diphenylmethane;
And dimer diamine obtained by converting the carboxyl group of dimer acid into an amino group, a dendrimer having a primary or secondary amino group at the terminal, and a propoxyamine at both terminals, and represented by the following general formula [2] Etc. can also be used.

General formula [2]
_{H 2 N-CH 2 -CH 2} -CH 2 -O- (C m H 2m -O) n -CH 2 -CH 2 -CH 2 -NH 2
(In the formula, m represents an arbitrary integer of 2 to 4, and n represents an arbitrary integer of 2 to 50.)

  The polyamino compound (c) used in the present invention is a compound (c3) obtained by Michael addition reaction of an ethylenically unsaturated compound (c2) with a compound (c1) having two or more primary amino groups, particularly from the viewpoint of reaction control. In addition, as the ethylenically unsaturated compound (c2), an ethylenically unsaturated compound having a hydroxyl group is preferably used from the viewpoint of introducing a crosslinking point into the urethane urea resin (A). By using an ethylenically unsaturated compound having a hydroxyl group, the durability and optical properties of the pressure-sensitive adhesive can be further improved.

  As the compound (c1) having two or more primary amino groups, compounds having two or more primary amino groups among the above-mentioned compounds having two or more amino groups can be used. , 2,4-trimethylhexamethylenediamine and hexamethylenediamine are easy to control the Michael addition reaction, and the urethane urea resin (A) obtained using the resulting Michael addition reaction compound (c3) It is preferable because of its excellent transparency.

  Examples of the ethylenically unsaturated compound having a hydroxyl group in the ethylenically unsaturated compound (c2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl alcohol, Daicel Chemical Industries Plaxel FA, Plaxel FA2D, Plaxel FA3, Plaxel FA5, Plaxel FA10L, Plaxel FM1D, Plaxel FM2D, Unsaturated compounds having a polyester chain terminated with a hydroxyl group, such as PLACCEL FM3, PLACCEL FM3X, PLACCEL FM5, PLACCEL FM5L, polyethylene glycol (meth) acrylate Over DOO, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, an unsaturated compound having a polyether chain having a hydroxyl group such as hexaethylene glycol (meth) acrylate at the terminal thereof.

  The above compounds can be used alone or in combination of two or more, but 4-hydroxybutyl acrylate is particularly preferred from the standpoint of reactivity with the curing agent (C) described later and optical properties of the pressure-sensitive adhesive. Is preferably used.

  Examples of ethylenically unsaturated compounds (c2) that do not have a hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate , Tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate Nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkyl (meth) acrylates having 1 to 22 carbon atoms such as docosyl (meth) acrylate. In the case of adjusting the polarity, an alkyl group-containing acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, or a corresponding methacrylate is exemplified. When aiming at adjustment of leveling property, etc., it is preferable to have 6 or more carbon atoms.

Furthermore, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, propoxypolyethyleneglycol (meth) acrylate, n-butoxypolyethyleneglycol (meth) acrylate, n-pentoxypolyethyleneglycol (meth) acrylate, phenoxypolyethyleneglycol Alkoxy polyalkylene glycol mono (meth) acrylates such as (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate;
Fatty acid vinyls such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate;
Vinyl ethers such as butyl vinyl ether and ethyl vinyl ether;
Α-olefins such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene;
Maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid carboxyl group-containing unsaturated compounds such as β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid;
Nitrogen-containing unsaturated compounds such as amide group-containing unsaturated compounds, dialkylamino group-containing unsaturated compounds, and quaternary ammonium base-containing unsaturated compounds can be used in combination.

  Examples of the amide group-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- (meth). Monoalkylol (meth) acrylamide such as acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethyl methacrylamide N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide and the like can be mentioned.

  Dialkylamino group-containing unsaturated compounds include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate , Dimethylaminostyrene, diethylaminostyrene and the like.

The quaternary ammonium base-containing unsaturated compound can be obtained by quaternizing the dialkylamino group-containing unsaturated compound. Examples of the quaternary ammonium base-containing unsaturated compound having a Cl ⁻ , Br ⁻ , I ⁻ halogen ion or QSO ₃ ⁻ (Q: an alkyl group having 1 to 12 carbon atoms) as a counter ion include dimethylaminoethyl (meth) acrylate. Methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, and trimethyl-3- (1- (Meth) acrylamide-1,1-dimethylethyl) ammonium chloride and the like.

Furthermore, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meta ) Acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl Perfluoro having a C 1-20 perfluoroalkyl group such as (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Alkyl (meth) acrylates; perfluorobutyl ethylene, perfluorohexylethylene, perfluorooctylethylene, perfluoroalkyl group-containing unsaturated compound of the perfluoroalkyl alkylene, and the like, such as perfluorodecyl ethylene;
Unsaturated compounds having an alkoxysilyl group such as vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, and derivatives thereof;
Epoxy group-containing unsaturated compounds such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate;
Allyl compounds such as allyl acetate, allylbenzene, allyl cyanide;
Vinyl compounds such as vinyl cyanide, vinylcyclohexane, vinylmethylketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene;
Ethynyl compounds such as acetylene, ethynylbenzene and ethynyltoluene can also be used in combination.

  In the Michael addition reaction between the compound (c1) having two or more primary amino groups and the ethylenically unsaturated compound (c2), 1 mol of active hydrogen of the amino group in the compound (c1) having two or more primary amino groups Reacts with 1 mol of ethylenically unsaturated groups in the ethylenically unsaturated compound (c2). Since the amino group in the compound (c1) having two or more primary amino groups is easily Michael-added to the ethylenically unsaturated group of the compound having an electron-withdrawing group, the ethylenically unsaturated compound (c2) Is preferably a (meth) acrylic compound, and particularly preferably an acrylate compound from the viewpoint of the efficiency of the Michael addition reaction.

  As a synthesis method of the compound (c3) obtained by subjecting the compound (c1) having two or more primary amino groups to the Michael addition reaction of the ethylenically unsaturated compound (c2), a known method relating to the Michael addition reaction can be used as it is. When the ethylenically unsaturated compound (c2) is a (meth) acrylic compound, particularly an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst such as alcohol as necessary. Although depending on the type of the ethylenically unsaturated compound (c2) used, a reaction temperature of 40 to 80 ° C. is preferred. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. Further, when the ethylenically unsaturated compound (c2) does not have an electron-withdrawing group, the reaction becomes possible in the presence of a metal catalyst. In this case, if the reaction is performed at 60 to 100 ° C. while heating in the presence of the catalyst. A moderate reaction rate is preferable. The synthetic solvent may or may not be used, and the kind thereof is not particularly limited, but known solvents such as methyl ethyl ketone, toluene, acetone, and benzene can be used. The solution concentration in the case of using a solvent is preferably 20% by weight or more, more preferably 50% by weight or more. If it is more dilute than this, it is not preferable because the reaction hardly proceeds. The reaction time varies depending on the type of ethylenically unsaturated compound (c2) to be used, but is completed in 30 minutes to 5 hours.

  The ratio of ethylenically unsaturated compound (c2) to be added to compound (c1) having two or more primary amino groups is at least two primary or secondary amino groups in compound (c3) subjected to Michael addition reaction. Is preferably 0.1 to 1 mol, more preferably 0.2 to 1 mol, with respect to 1 mol of the primary amino group of the compound (c1) having two or more primary amino groups. It is preferable to react the ethylenically unsaturated group in the ethylenically unsaturated compound (c2). If it is less than this, the effect of introducing the ethylenically unsaturated compound (c2) may not be obtained, and it is not preferable because the storage stability is low. More than this does not contribute to the reaction.

  The amount of the polyamino compound (c) used is 100% by weight of the urethane urea resin (A) [the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton having a polypropylene glycol skeleton used for the synthesis of the urethane urea resin (A), Other polyols (d) to be used as necessary, polyisocyanate (b), amino compound (c), and reaction terminator (e) to be used if necessary in a total of 100% by weight], 0.5 to A ratio of 11% by weight is preferable, and 1.0 to 4% by weight is more preferable. If it is less than 0.5% by weight, the cohesive force is lowered, and it may be difficult to impart durability. On the other hand, if it exceeds 11% by weight, the flexibility of the resin is lowered, so that it may be difficult to impart antistatic properties or optical characteristics may be deteriorated.

  The urethane urea resin (A) of the present invention is obtained by reacting a urethane prepolymer whose terminal is an isocyanate group and a polyamino compound (c), and further, if necessary, a monoamino compound as a reaction terminator (e). Can be reacted.

  The reaction terminator (e) plays a role of controlling the molecular weight or reacting with an unreacted isocyanate group at the end of the urethane urea resin (A) to stabilize the reaction activity of the resin.

  Examples of the reaction terminator (e) used in the present invention include, for example, diethanolamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine, diisononylamine, monoethanolamine, diethanolamine, 2 -Monoamine having a hydroxyl group such as amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol, monomethylhydrazine, 1,1-dimethylhydrazine, Alkyl hydrazines such as benzylhydrazine, hydrazides such as form hydrazide, acetohydrazide, lauric hydrazide, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine and the like Primary amino group and primary amino group Compounds, monoamino compounds with a γ- aminopropyl triethoxysilane alkoxysilyl group can be used. Furthermore, amino compounds having only one primary or secondary amino group can also be used as a reaction terminator.

  Among the above reaction terminators (e), a monoamine compound having a hydroxyl group such as 2-amino-2-methyl-propanol is to obtain a urethane urea resin (A) having a terminal hydroxyl group and excellent in storage stability. Can do. Furthermore, the urethane urea resin (A) whose terminal is a hydroxyl group is preferable because this hydroxyl group can be used as a reaction point with the curing agent (C) described later. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the urethane prepolymer, but the reactivity of the amino group is higher, and it reacts preferentially with the isocyanate group. .

  The reaction terminator (e) is a polyol (a) having a polypropylene glycol skeleton or a polyester skeleton having a polypropylene glycol skeleton used for the synthesis of the urethane urea resin (A) in 100% by weight of the urethane urea resin (A). 0.05 parts by weight of a total of 100% by weight of other polyol (d), polyisocyanate (b), polyamino compound (c), and reaction terminator (e) used if necessary -2.0% by weight is preferred, and if it is less than 0.05 parts by weight, the reaction stability of the resin may be impaired. May impair sex.

  Furthermore, it can be modified by ring-opening addition of a cyclic ester compound and / or a cyclic ether compound to the hydroxyl group of the urethane urea resin (A) thus obtained.

  The production method of the urethane urea resin (A) used in the present invention is as follows. First, a polyol (a) having a polypropylene glycol skeleton or a polyester skeleton, and other polyol (d) used as necessary, and a polyisocyanate (b) ) To produce a urethane prepolymer having at least one isocyanate group. Next, the urethane urea resin (A) can be produced by reacting the obtained urethane prepolymer, the polyamino compound (c) and a reaction terminator (e) as necessary.

  A known catalyst can be used for the synthesis of the urethane prepolymer. Examples thereof include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and may be used alone or in combination in some cases. it can.

  Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Examples include acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurate (also known as DOTDL), and tin 2-ethylhexanoate.

  Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Examples include iron series such as iron ethylhexanoate and iron acetylacetonate, cobalt series such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc series such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. It is done.

  Among the above catalysts, dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Catalysts such as tertiary amine compounds and organometallic compounds can be used alone in some cases, but can also be used in combination. Especially when polyester diols and polyether diols are used in combination as polyol components, Use of dibutyltin dilaurate and tin 2-ethylhexanoate in combination is preferable because a uniform urethane prepolymer can be obtained stably.

  The organometallic compound catalyst used when synthesizing the urethane prepolymer significantly accelerates the reaction when the urethane prepolymer reacts with the polyamino compound (c). The reaction between an isocyanate group and an amino group is very fast from the beginning, but in the presence of an organometallic compound catalyst, the reaction may be further promoted and may be difficult to control. At this time, if a chelate compound is present, a chelate is formed with the organometallic compound catalyst, the catalytic ability is adjusted, and the reaction with the polyamino compound (c) is easily controlled.

  Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxyacids such as ethylenediaminetetraacetic acid (also known as EDTA), oxycarboxylic acids such as citric acid, and condensed phosphoric acid. Among the chelate compounds, acetylacetone is soluble in an organic solvent, has volatility, and is preferably easy to remove if necessary.

  The chelate compound remains in the urethane urea resin (A) even after the reaction. A curing agent (C) is added to the antistatic pressure-sensitive adhesive composition containing the urethane urea resin (A) of the present invention. At this time, the chelate compound comprises the urethane urea resin (A) and the curing agent (C ) And the reaction rate can be adjusted, and as a result, an antistatic pressure-sensitive adhesive composition having excellent storage stability can be provided.

  A known solvent is suitably used for the synthesis of the urethane prepolymer of the present invention. The use of a solvent serves to facilitate reaction control. Examples of the solvent used for such purpose include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like. It is done. In view of the solubility of the urethane urea resin (A), the boiling point of the solvent, the solubility of the polyamino compound (c), etc., ethyl acetate, toluene, methyl ethyl ketone or a mixed solvent thereof is particularly preferable. The concentration in the urethane prepolymer reaction system when using a solvent is preferably 50 to 95% by weight, more preferably 60 to 90% by weight of the resin solid content, and if the concentration is too low, the reactivity decreases. It is not preferable because it is too much.

  The urethanization reaction for synthesizing the urethane prepolymer in the present invention can be carried out in various ways, but is roughly classified into the following two methods. [I] A method in which the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton and the polyisocyanate (b), and, if necessary, the other polyol (d), a solvent, and a catalyst are all charged. [Ii] A polyol (a) having a polypropylene glycol skeleton or a polyester skeleton and, if necessary, other polyol (d) and a solvent are charged into a flask, and a polyisocyanate (b) is dropped, and then a catalyst is used if necessary. How to add. [Ii] is preferable when the reaction is precisely controlled. The reaction temperature for obtaining the urethane prepolymer is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 120 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined weight average molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed in the presence of a catalyst at 50 to 110 ° C. for 1 to 20 hours.

  The blending ratio of the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton and the polyisocyanate (b) greatly depends on the reactivity of the compound, the abundance ratio of the trivalent or higher compound, the use of the obtained resin, and the like. . In order for the urethane prepolymer to have at least one isocyanate group, 1 mol of the isocyanate group in the polyisocyanate (b) is 1 mol of the hydroxyl group in the polyol (a) having a polypropylene glycol skeleton or a polyester skeleton. It is necessary to increase the amount, preferably 1.01 to 4 mol, more preferably 1.1 to 2 mol.

  Moreover, the urea reaction of the isocyanate group in the urethane prepolymer which is an isocyanate group-containing compound obtained as described above and the primary or secondary amino group of the polyamino compound (c) has the following two types. Broadly divided into methods. [Iii] A method in which a urethane prepolymer is charged into a flask and the polyamino compound (c) is dropped. [Iv] A method in which the polyamino compound (c) is charged into a flask and a urethane prepolymer is dropped. If there is no problem in the reaction, the method [iii] that is easy to operate is preferred. The temperature of the urea reaction of the present invention is preferably 100 ° C. or lower. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin (A) having a predetermined weight average molecular weight and structure. When an alcohol solvent is used as the synthesis solvent for the polyamino compound (c), the temperature in the reaction system should be 50 ° C. or lower, more preferably 40 ° C. or lower when the polyamino compound (c) is dropped. Is preferred.

  The amount of the reaction terminator (e) used varies depending on whether it is mixed and added with the polyamino compound (c) or when it is added alone at the end, but when mixed and added, it is added to 1 mol of isocyanate groups in the urethane prepolymer. On the other hand, it is desirable to use an amount in which the amino group in the reaction terminator (e) is preferably 0.5 mol or less, more preferably 0.3 mol or less. Is 0.5 to 3 moles with respect to 1 mole of isocyanate groups finally present, and preferably 1 to 3 moles for the purpose of stabilizing the urethane urea resin (A). Outside this range, adverse effects such as a decrease in film formability or discoloration may be observed.

  The end point of the reaction is judged from the disappearance of the isocyanate peak by the measurement of isocyanate% due to titration and IR measurement.

  The urethane urea resin (A) having a carboxyl group or a tertiary amino group can be ionized in order to disperse or dissolve in water.

  The molecular weight of the urethane urea resin (A) needs to be 70,000 to 200,000 as a weight average molecular weight in terms of standard polystyrene by GPC. Preferably, it is 80,000-140,000. If the weight average molecular weight is less than 70,000, the balance between the durability as a pressure-sensitive adhesive and the optical function maintaining characteristics deteriorates. On the other hand, if it exceeds 200,000, the viscosity is too high and it becomes difficult to handle.

  The solution viscosity of the obtained urethane urea resin (A) is not particularly limited and is selected depending on the use of the resin, but is preferably 3000 to 25000 mPa · s (25 ° C.) at a solid content of 50% by weight. If the viscosity is too high, coating may be difficult. If the viscosity is too low, a resin having a sufficient molecular weight may not be formed.

  Next, the ionic compound (B) having the fluorine atom-containing anion used in the present invention as a part of the constituent components will be described.

  The ionic compound (B) having a fluorine atom-containing anion as a constituent component used in the present invention is a salt composed of an anion and a cation, and is a solid even if it is liquid at room temperature (20 ° C.). Also good.

  When the anion of the ionic compound (B) of the present invention contains a fluorine atom, the degree of ion dissociation in the pressure-sensitive adhesive is improved, and good antistatic properties can be exhibited.

  Examples of the fluorine atom-containing anion constituting the ionic compound (B) having the fluorine atom-containing anion as a constituent component include, for example, fluorinated aryl sulfonate, perfluoroalkane sulfonate, cyanoperfluoroalkanesulfonylamide, bis ( Examples include cyano) perfluoroalkanesulfonylmethide, bis (perfluoroalkanesulfonyl) imide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, and the like. More specifically, for example, trifluoromethanesulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, trifluoroacetate, heptafluorobutyrate, tris (trifluoromethanesulfonyl) ) Methide, (trifluoromethanesulfonyl) trifluoroacetamide and the like.

  Among the fluorine atom-containing anions, bis (fluorosulfonyl) imide and bis (trifluoromethanesulfonyl) imide do not contain carbon atoms in the molecule and have a small molecular size. Therefore, in the urethane urea resin (A) used in the present invention, When mixed, it is easy to move in the resin and can be preferably used because it exhibits particularly excellent antistatic properties.

  On the other hand, the cation component constituting the ionic compound (B) having a fluorine atom-containing anion as a constituent component has a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton and a pyrrole skeleton. A cation, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a tetraalkylammonium cation in which a part of the alkyl group is substituted with an alkenyl group, Examples thereof include metal cations.

  Specific examples of a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton include 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-octyl-3-methylpyridinium cation, 1-lauryl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpiperidinium cation, 1-ethyl-1-methylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl- -Octylpiperidinium cation, 1-methyl-1-laurylpiperidinium cation, 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidi Cation, 1-methyl-1-octylpyrrolidinium cation, 1-methyl-1-laurylpyrrolidinium cation, 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1,2- Examples thereof include dimethylindole cation and 1-ethylcarbazole cation.

  Specific examples of imidazolium cation, tetrahydropyrimidinium cation and dihydropyrimidinium cation include 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 -Dimethylimidazoli Cation, 1-hexyl-2,3-dimethylimidazolium 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-dihydride Pyrimidinium cation, and a 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation.

  Specific examples of the pyrazolium cation and the virazolinium cation include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation and the like.

  Specific examples of the tetraalkylammonium cation, trialkylsulfonium cation, and tetraalkylphosphonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrahexylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, and trimethyl. Decylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-dimethyl -N, N-dihexyl ammonium cation, N, N-dipropyl-N, N-dihexyl ammonium cation , Trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium Examples include cations, triethylmethylphosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations, diallyldimethylammonium cations, and the like. Among them, 1-octyl-3-methylpyridinium cation, 1-lauryl-3-methylpyridinium cation, 1,1-dimethylpiperidinium cation, 1-ethyl-1-methylpiperidinium cation, 1-methyl-1- Propylpiperidinium cation, 1-methyl-1-octylpiperidinium cation, 1-methyl-1-laurylpiperidinium cation, 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium Cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-octylpyrrolidinium cation, 1-methyl-1-laurylpyrrolidinium cation, 1,3-dimethylimidazolium cation, 1,3 -Diethylimidazolium cation, 1-ethyl-3-methylimi Zolium 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 Pyridinium, piperidinium, pyrrolidinium, and imidazolium cations such as −2,3-dimethylimidazolium cation and 1-hexyl-2,3-dimethylimidazolium cation are preferably used, and pyridinium and imidazolium cations are more preferable. It is.

  Examples of the metal cation include a lithium cation, a sodium cation, and a potassium cation.

  Specific examples of the ionic compound (B) having a fluorine atom-containing anion used in the present invention as a constituent component are appropriately selected from a combination of the anion component and the cation component.

  Examples of the ionic compound (B) having a fluorine atom-containing anion used in the present invention as a constituent component include, for example, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoro) (Romethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpi Ridinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl- 1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (to Trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoro) Lomethanesulfonyl) imide, 1-pentylpiberidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethane) Sulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pe Tilpiberidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiberidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) Imido, 1-ethyl-1-propylpiberidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (Trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-di Propylpiberidiniu Bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoro) Ethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1- Butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) Imido, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium Bis (pentafluoroe Sulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiberidinium bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) ) Imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiberidinium Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1 Hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) ) Imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpi Peridinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1 -Propyl-1- Butyl piperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methyl Imidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methyl Midazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1- Butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1- Ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-butyl 2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5 -Trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide;

  N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N- Heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) Imido, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N- Dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl- N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- Propyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) Imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N- Dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexyl Ammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N Methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetra Hexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyl dimethyl Ruammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl -N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, Glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) ) Imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanetansulfonyl) imide;

  1-butylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 2-methyl-1-pyrroline tetrafluoroborate, 1,2-dimethyl Indoletetrafluoroborate, 1-ethyl-2-phenylindoletetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-2, 3-dimethylimidazolium tetrafluoroborate, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, diallyldimethylammonium tetrafluoroborate;

  1-hexyl-3-methylimidazolium chloride, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium hepta Fluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methyl Imidazolium dicyanamide, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3- Tyrimidazolium perfluorobutanesulfonate, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl -3-methylimidazolium hexafluorophosphate, diallyldimethylammonium trifluoromethanesulfonate;

1-butyl-3-methylimidazolium hexafluorophosphate;
1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl- 2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3 -Methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide 1-ethyl-3-methylimidazole Potassium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate;

  Lithium bis (trifluoromethanesulfone) imide, potassium bis (trifluoromethanesulfone) imide, sodium bis (trifluoromethanesulfone) imide, lithium bis (fluorosulfonyl) imide, potassium bis (fluorosulfonyl) imide, sodium bis (fluorosulfonyl) imide Lithium bis (trifluoromethanesulfone) imide, lithium tetrafluoroborate and the like.

  Among the above, lithium bis (trifluoromethanesulfone) imide and lithium bis (fluorosulfonyl) imide are solid compounds at room temperature, but have good solubility in the urethane urea resin of the present invention, and the ionic compounds over time. Bleed out is suppressed and the durability of the pressure sensitive adhesive is improved.

  As the ionic compound (B) having a fluorine atom-containing anion as a constituent component as described above, a commercially available one may be used, but it can also be synthesized by a known method as described below. . The method for synthesizing the ionic compound (B) having a fluorine atom-containing anion as a constituent component is not particularly limited as long as the ionic compound (B) having the target fluorine atom-containing anion as a constituent component is obtained. However, in general, the halide method, hydroxide method, acid ester method as described in the document “ionic liquids—the forefront and future of development” [published by CMC Publishing Co., Ltd.] , Complex formation method, neutralization method and the like are used.

  In addition, the pressure-sensitive adhesive composition of the present invention may use other antistatic agents in combination with the ionic compound (B) having the above-described fluorine atom-containing anion as a component. Although it does not specifically limit as a compound to use together, A well-known surfactant and organic salt of alkali metal are mentioned, These can be used individually or in combination.

  The pressure-sensitive adhesive composition of the present invention is 0.05 to 10 to 10 parts by weight of the ionic compound (B) having the fluorine atom-containing anion as a component as a constituent component. Including 0.5 parts by weight, preferably 0.5-4 parts by weight. If the amount is less than 0.05 parts by weight, sufficient antistatic properties cannot be obtained, and even if it is added in excess of 10 parts by weight, it is difficult to obtain further antistatic properties as well as poor heat resistance. .

  Next, the curing agent (C) and the silane coupling agent (D) having an alkoxysilyl group will be described.

  The pressure-sensitive adhesive composition of the present invention has the urethane urea resin (A), an ionic compound (B) having the fluorine atom-containing anion as a component, a curing agent (C), and an alkoxysilyl group. It contains a silane coupling agent (D). Examples of the reactive functional group present in the urethane urea resin (A) include a hydroxyl group and a carboxyl group. Therefore, as a functional group which the hardening | curing agent (C) used for this invention has, an isocyanate group, an epoxy group, an alkoxysilyl group, a methylol group, an aziridine group, a carbodiimide group etc. are mentioned. Examples of the curing agent (C) include polyisocyanate compounds, polyfunctional epoxy compounds, high molecular weight polycarbodiimides, N-methylol group-containing compounds, polyfunctional aziridine compounds, and metal chelates. In order to act as an agent, a compound having two or more functional groups capable of reacting with the hydroxyl group of the urethane urea resin (A) in the molecule is preferably used. In particular, polyisocyanate compounds are preferably used because they are excellent in adhesion after the crosslinking reaction and adhesion to the coating layer.

  The polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule. Examples of polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene. Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and further these polyisocyanate compounds Known polyether polyols and polyesters Ether polyols, acrylic polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.

  The polyfunctional epoxy compound is not particularly limited as long as it is a compound having a plurality of epoxy groups in the molecule. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N ′, N Examples include '-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, and the like.

  Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

  Examples of the polyfunctional aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.

  Examples of metal chelates include coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and acetylacetone and ethyl acetoacetate. It is done.

  The said hardening | curing agent (C) can be used individually or in combination. As said hardening | curing agent (C), a polyisocyanate compound is preferable from the reactivity, a pot life, and the optical characteristic of a pressure sensitive adhesive layer, etc., and especially a hexamethylene diisocyanate trimethylol propane adduct body is preferable.

  The antistatic pressure-sensitive adhesive composition of the present invention is characterized by containing 0.3 to 3 parts by weight of the curing agent (C) with respect to 100 parts by weight of the urethane urea resin (A). It is more preferable to contain 0.5-2 weight part especially. If it exceeds 3 parts by weight, the cross-linked structure of the pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition becomes dense, the tack of the pressure-sensitive adhesive layer tends to decrease, and the adhesion to the adherend is reduced. In addition to a decrease in flexibility, the optical properties such as light leakage prevention properties are impaired when used in pressure sensitive adhesives for optical films such as polarizing plates. On the other hand, if the amount is less than 0.3 parts by weight, a sufficient cross-linked structure cannot be obtained, so that the cohesive force is lowered, and the heat resistance and heat and humidity resistance are lowered. By the reaction between the reactive functional group of the urethane urea resin (A) and the functional group in the curing agent (C), the resin composition is three-dimensionally cross-linked to ensure adhesion with various substrates and adherends. In addition, since the heat resistance and heat-and-moisture resistance under conditions severer than before can be improved, it can be preferably used for an optical member.

  The antistatic pressure-sensitive adhesive composition of the present invention contains a silane coupling agent (D) having an alkoxysilyl group for the purpose of improving wet heat resistance. It is considered that the silane coupling agent (D) is particularly easy to form an inclined structure in the pressure-sensitive adhesive layer of the present invention, is unevenly distributed on the surface of the adhesive layer, and is particularly effective in improving wet heat resistance.

A well-known thing can be used as a silane coupling agent (D). For example, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltributoxysilane, Silane compounds having a (meth) acryloxy group and an alkoxy group such as γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane;
Alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane;
Alkoxysilanes such as 5-hexenyltrimethoxysilane, 9-decenyltrimethoxysilane, styryltrimethoxysilane;
Silanes having aminoalkyl groups and alkoxy groups such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane;
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6 A compound having a mercapto group such as mercaptohexyltrimethoxysilane, 10-mercaptodecyltrimethoxysilane;
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane , Phenyltrimethoxysilane, hexamethylsilazane, diphenyldimethoxysilane, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl)- Examples include 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. Any one or more of these can be used alone or in combination.

  The antistatic pressure-sensitive adhesive composition of the present invention is characterized by containing 0.01 to 3 parts by weight of the silane coupling agent (D) with respect to 100 parts by weight of the urethane urea resin (A). In particular, it is more preferable to contain 0.1 to 2.5 parts by weight. If it exceeds 3 parts by weight, the optical function maintaining characteristics are impaired. Moreover, if it is less than 0.01 weight part, sufficient improvement in heat-and-moisture resistance is not seen. Any one or more of the above may be used alone or in combination.

  Next, the polyalkylene glycol (E) of the present invention will be described. The antistatic pressure-sensitive adhesive composition of the present invention preferably contains (E) a polyalkylene glycol for the purpose of imparting reworkability. Furthermore, it becomes possible to control the adhesive force of the antistatic pressure-sensitive adhesive composition of the present invention by the plastic effect of the polyalkylene glycol (E). Examples of the polyalkylene glycol (E) of the present invention include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Those which are liquid at room temperature are preferred. In particular, polypropylene glycol is preferable in terms of compatibility with the resin and transparency.

  The amount of polyalkylene glycol added is preferably 0.5 to 10 parts by weight, particularly preferably 1 to 8 parts by weight, based on 100 parts by weight of the urethane urea resin (A). If it is less than 0.5 part by weight, reworkability may not be imparted. On the other hand, if it exceeds 10 parts by weight, heat resistance may be deteriorated.

  In the antistatic pressure-sensitive adhesive composition according to the present invention, other resins such as acrylic resin, polyester resin, amino resin, epoxy resin, and polyurethane resin can be used in combination as necessary. Furthermore, additives such as organic / inorganic pigments, fillers, colorants, ultraviolet absorbers, antioxidants, antifoaming agents, light stabilizers and the like may be blended depending on the application.

  Using the antistatic pressure-sensitive adhesive composition of the present invention, a laminated product composed of a pressure-sensitive adhesive layer and a sheet-like substrate (hereinafter referred to as “antistatic pressure-sensitive adhesive sheet”) can be obtained. it can. For example, an antistatic pressure-sensitive adhesive sheet can be obtained by coating, drying and curing the antistatic pressure-sensitive adhesive composition of the present invention on one side or both sides of various sheet-like substrates. Since the pressure-sensitive adhesive layer constituting the antistatic pressure-sensitive adhesive sheet is “pressure-sensitive”, it has tack at about room temperature. In applying the antistatic pressure-sensitive adhesive composition, an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, or water is further added, The viscosity can be adjusted, or the antistatic pressure-sensitive adhesive composition can be heated to lower the viscosity. However, care should be taken because adding water or alcohol in a large amount may cause reaction inhibition between the urethane urea resin (A) and the curing agent (C).

  Sheet-like substrates include cellophane, various plastic sheets, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plates, metal plates, wood, optical films such as polarizing plates, etc. Can be mentioned. Various base materials can be used alone or in a multi-layered state in which a plurality of base materials are laminated. Furthermore, the surface of which has been subjected to a peeling treatment or an antistatic treatment can also be used.

  Various plastic sheets are also referred to as various plastic films, such as polyvinyl alcohol films, triacetyl cellulose films, films of polyolefin resins such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate. Polyester resin film such as polyethylene naphthalate, polycarbonate resin film, polynorbornene resin film, polyarylate resin film, acrylic resin film, polyphenylene sulfide resin film, polystyrene resin film, vinyl Resin film, polyamide resin film, polyimide resin film, epoxy resin, cycloolefin Films such emissions resins.

  When the antistatic pressure-sensitive adhesive composition contains a liquid medium such as an organic solvent or water after the antistatic pressure-sensitive adhesive composition is applied to the sheet-like substrate by an appropriate method according to a conventional method When the liquid medium is removed or the antistatic pressure-sensitive adhesive composition does not contain a liquid medium to be volatilized, the adhesive layer in a molten state is cooled and solidified, and An adhesive layer can be formed thereon. The thickness of the pressure sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 5 μm to 50 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

  The method for applying the antistatic pressure-sensitive adhesive composition of the present invention to a sheet-like substrate is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma. Various coating methods such as a coater, knife coater, reverse coater, spin coater and the like can be mentioned. There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the cured form of the adhesive composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

  The laminate of the present invention has various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film, so-called sheet (also referred to as a film as described above) in an optical member, A pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition of the present invention is laminated. On the other surface of the pressure-sensitive adhesive layer, a sheet-like base material subjected to a release treatment can be laminated.

  In the laminate of the present invention, (a) an antistatic pressure-sensitive adhesive composition is applied to the release-treated surface of the release-treated sheet-like substrate and dried, and the sheet-like optical member is formed on the pressure-sensitive adhesive layer. The surface of the sheet-like base material that has been laminated on the surface or (a) a sheet-like optical member is coated with an antistatic pressure-sensitive adhesive composition, dried, and then peeled off on the surface of the pressure-sensitive adhesive layer Can be obtained by laminating.

  By peeling off the release-treated sheet-like substrate covering the surface of the pressure-sensitive adhesive layer from the laminate thus obtained, for example, by sticking the pressure-sensitive adhesive layer to the glass member for liquid crystal cells , A liquid crystal cell member having a configuration of “sheet-like optical member / pressure-sensitive adhesive layer / liquid crystal cell glass member” can be obtained.

  Further, the use of the antistatic pressure-sensitive adhesive sheet or laminate of the present invention is not particularly limited, but it can also be applied to various electronics-related members such as liquid crystal displays, plasma displays, touch panels, electrode peripheral members, and protective film applications.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

  The weight average molecular weight (Mw) of each resin obtained in Synthesis Examples 4 to 23 was determined according to the following method.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured by using GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation. GPC is liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

[Synthesis of amino compounds]
Synthesis example 1
A 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 25.0 parts of isophoronediamine (IPDA) and 25.0 parts of toluene. 19.1 parts of 4-hydroxybutyl acrylate and 18.8 parts of butyl acrylate were added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours, and then 37.9 parts of toluene was added. Further, ethyl acetate was added to adjust the solid content to 50% to obtain a compound (1) solution.

Synthesis example 2
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 40.0 parts of isophoronediamine (IPDA) and 40.0 parts of toluene. 67.8 parts of 4-hydroxybutyl acrylate was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours, and 67.8 parts of toluene was added. Further, ethyl acetate was added to adjust the solid content to 50% to obtain a compound (2) solution.

Synthesis example 3
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 30.0 parts of isophoronediamine (IPDA) and 30.0 parts of toluene. 18.4 parts of 4-hydroxyethyl acrylate and 17.6 parts of ethyl acrylate were added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours, and then 36.0 parts of toluene was added. Further, ethyl acetate was added to adjust the solid content to 50% to obtain a compound (3) solution.

[Synthesis of urethane urea resin]
Synthesis example 4
In a 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 790 parts Sanix PP-2000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries Ltd.), 110 parts isophorone diisocyanate, toluene 220 parts and 0.074 part of dioctyltin dilaurate as a catalyst were charged, and the temperature was gradually raised to 100 ° C., followed by reaction for 2 hours. After cooling to 40 ° C., 787 parts of ethyl acetate and 2.5 parts of acetylacetone were added, 48.7 parts of the compound (1) solution was added dropwise over 1 hour, and further aged for 1 hour. After confirming the remaining amount of isocyanate groups by titration, 2.3 parts of 2-amino-2-methyl-propanol and 90 parts of ethyl acetate were added, and the NCO characteristic absorption (2,270 cm- ¹ ) of the IR chart disappeared. It was confirmed that the reaction was completed. The urethane urea resin (A-1) had a weight average molecular weight Mw of 125,000.

[Synthesis of urethane urea resin]
Synthesis Examples 5-13, 15-17, 19, 20, 22
According to the formulation shown in Table 1, urethane urea resins (A-2) to (A-10), (A-12) to (A-14), (A-16), (A-) in the same manner as in Synthesis Example 4 17) and (A-19) were obtained.

[Synthesis of urethane urea resin]
Synthesis Example 14
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 774 parts Sanix PP-2000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.), 126 parts isophorone diisocyanate, toluene 225 parts, 0.075 part of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out the reaction for 2 hours. After confirming the remaining amount of isocyanate groups by titration, the mixture was cooled to 40 ° C., 486 parts of ethyl acetate and 8.1 parts of acetylacetone were added, and 107 parts of the compound (2) solution dissolved in 180 parts of ethyl acetate was added for 1 hour. After ripening for 1 hour and further aging for 1 hour, 2.9 parts of 2-amino-2-methyl-propanol was added, and it was confirmed that NCO characteristic absorption (2,270 cm- ¹ ) of the IR chart disappeared. The reaction was terminated. It was the weight average molecular weight Mw82,900 of this urethane urea resin (A-11).

[Synthesis of urethane urea resin]
Synthesis Example 18
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 49 parts of PCDLT5650J (polycarbonate polyol, manufactured by Asahi Kasei Chemical), Denacol DA350 (acrylic acid modified form of polyethylene glycol diglycidyl ether) , Manufactured by Nagase ChemteX Corporation), 0.5 part, 0.05 part of dibutyltin dilaurate, and 60 parts of toluene were charged, and the temperature was raised to 50 ° C. Subsequently, 10.7 parts of xylylene diisocyanate was added dropwise to the flask to initiate the reaction. After reacting for 2 hours as it was, 3 parts of ethylenediamine was added as a chain extender, and it was confirmed that the NCO characteristic absorption (2,270 cm- ¹ ) of the IR chart had disappeared, and the reaction was terminated. The urethane urea resin (A-15) had a weight average molecular weight Mw of 110,000.

[Synthesis of urethane urea resin]
Synthesis Example 21
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 267.9 parts Hi-Lube D-660 (bifunctional polypropylene glycol, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Polyhardener T -500 (trifunctional polypropylene glycol, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 148.8 parts, isophorone diisocyanate 59.5 parts, toluene 36.2 parts, dioctyltin dilaurate 0.00005 parts as a catalyst, 90 The temperature was gradually raised to ° C and the reaction was carried out for 2 hours. After confirming the isocyanate value, 423.8 parts of toluene was added, cooled to 60 ° C., 23.8 parts of diisopropanolamine (monoaminopolyol) was added dropwise over 30 minutes, and the inside of the dropping funnel was washed with 40 parts of toluene. did. Next, 0.2 part of dioctyltin dilaurate was added, and the mixture was stirred well to make the whole uniform, then heated to 100 ° C. and heated for 3 hours. After confirming that the NCO characteristic absorption (2,270 cm- ¹ ) of the IR chart has disappeared, heating was terminated, and when the temperature became 60 ° C. or less, 3.4 parts of acetylacetone was added and stirred well to urethane urea. Resin (A-18) was obtained. The urethane urea resin (A-18) had a weight average molecular weight Mw of 110,000.

PP1000: Sannix PP-1000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)
PP2000: Sannix PP-2000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)
PP3000: Sannix PP-3000 (bifunctional polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)
PE-62: New Pole PE-62 (polypropylene glycol and polyethylene glycol copolymer, manufactured by Sanyo Chemical Industries, Ltd.)
P-2010: Kuraray polyol P-2010 (bifunctional polyester diol, manufactured by Kuraray Co., Ltd.)
D-660: High lube D-660 (bifunctional polypropylene glycol, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
T-500: Polyhardener T-500 (Trifunctional polypropylene glycol, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
PTMG: PTMG-3000 (bifunctional polytetramethylene glycol, manufactured by Hodogaya Chemical Co., Ltd.)
C1090: Kuraray polyol C-1090 (bifunctional polycarbonate diol, manufactured by Kuraray Co., Ltd.)
PCDLT5650J: PCDLT5650J (polycarbonate polyol, manufactured by Asahi Kasei Chemical Co., Ltd.)
DA350: Denacol DA350 (acrylic acid modified product of polyethylene glycol diglycidyl ether, manufactured by Nagase ChemteX Corporation)
PEG2000: PEG-2000 (bifunctional polyethylene glycol, manufactured by Sanyo Chemical Industries)
IPDI: isophorone diisocyanate HMDI: hexamethylene diisocyanate XDI: xylylene diisocyanate DOTDL: dioctyltin dilaurate DBTDL: dibutyltin dilaurate IPDA: isophoronediamine AMP: 2-amino-2-methyl-propanol

[Synthesis of urethane resin]
Synthesis Example 23
In a four-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel, 100 parts of ADEKA polyether G-4000 (trifunctional polyether polyol, manufactured by ADEKA, Mn = 4,000), bifunctional polyether polyol ( Made by ALDRICH, 100 parts of block copolymer of polypropylene glycol and polyethylene glycol, Mn = 2,700, ethylene glycol ratio: 40% by weight), 85.7 parts of toluene, and 0.04 part of dibutyltin dilaurate as a catalyst are charged. The liquid temperature in the flask was raised to 90 ° C. while starting stirring. While maintaining the liquid temperature in the flask at 90 ° C., 10.2 parts of hexamethylene diisocyanate was added dropwise over 40 minutes, and the reaction was performed at 90 ° C. for 6 hours. It was confirmed that NCO characteristic absorption (2,270 cm ⁻¹ ) on the IR chart had disappeared, and the reaction was terminated to obtain a urethane resin (A-20). The urethane resin (A-20) had a weight average molecular weight Mw of 27,000.

[Synthesis of urethane resin]
Synthesis Example 24
Polyester polyol P-1010 (bifunctional polyester polyol, manufactured by Kuraray Co., Ltd.) 68 parts, polyether polyol G-3000B (3) in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel 265 parts functional polypropylene glycol (manufactured by ADEKA), 125 parts toluene, 0.03 part iron 2-ethylhexanoate and 0.04 part lead naphthenate as a catalyst, 24 parts of methylene diisocyanate was added dropwise over 1 hour, and the reaction was performed at 90 ° C. for 3 hours. It was confirmed that the NCO characteristic absorption (2,270 cm ⁻¹ ) on the IR chart had disappeared, and 115 parts of toluene after the reaction was added to obtain a urethane resin (A-21). The weight average molecular weight Mw of this urethane resin (A-21) was 50,000.

[Synthesis of urethane resin]
Synthesis Example 25
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 521 parts of hexamethylene diisocyanate, 1548 parts of polyhardener D-600 (bifunctional polypropylene glycol, manufactured by Daiichi Kogyo Seiyaku), toluene 1670 parts and 0.3 part of dioctyltin dilaurate as a catalyst were charged, and the temperature was raised to 90 ° C. over 1 hour, followed by reaction at 90 ° C. for 2 hours, and then cooled to 55 ° C. To this, 903 parts of polyhardener T-500 (trifunctional polypropylene glycol, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 170 parts of toluene were added, and the temperature was raised again to 90 ° C. and reacted for 3 hours. It was confirmed that the NCO characteristic absorption (2,270 cm ⁻¹ ) of the IR chart had disappeared, and it was cooled to 70 ° C. After adding 86.8 parts of hexamethylene diisocyanate and 170 parts of toluene, the temperature was raised to 90 ° C., and the reaction was further continued at 90 ° C. for 3 hours. It was confirmed that the NCO characteristic absorption (2,270 cm ⁻¹ ) on the IR chart had disappeared, and when it completely disappeared, the reaction was terminated and cooled. When the temperature became 80 ° C. or lower, 4.9 parts of acetylacetone was added and stirred well for 30 minutes to inactivate the tin catalyst. The urethane resin (A-22) had a weight average molecular weight Mw of 45,000.

[Synthesis of acrylic resin]
Synthesis Example 26
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 99 parts of n-butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 150 parts of acetone, 2,2′-azobisisobutyrate After 0.06 part of nitrile was charged and the air in the reaction vessel was replaced with nitrogen gas, the reaction solution was heated to 60 ° C. in a nitrogen atmosphere with stirring and reacted for 5 hours. After completion of the reaction, 190 parts of toluene, 0.25 part of acrylic acid and 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, the temperature was raised to 70 ° C., and the reaction was continued for 6 hours. I let you. After the reaction, 55 parts of toluene was added and cooled to room temperature to obtain an acrylic resin (A-23). The weight average molecular weight of the obtained acrylic resin (A-23) was 1,600,000.

[Synthesis of acrylic resin]
Synthesis Example 27
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 76 parts of n-butyl acrylate, 22 parts of methyl methacrylate, 1.5 parts of acrylic acid, 100 parts of acetone, 2,2 ′ -After charging 0.03 part of azobisisobutyronitrile and replacing the air in the reaction vessel with nitrogen gas, the conversion rate of the reaction solution is 75% at reflux temperature in a nitrogen atmosphere with stirring. For 4.5 hours to obtain a mixed solution of a copolymer having a weight average molecular weight of 1,000,000 and a monomer. Next, 200 parts of toluene, 0.5 part of acrylic acid, and 0.2 part of 2,2′-azobisisobutyronitrile were added and reacted for another 6 hours until the conversion reached 100%. A solution of acrylic resin (A-24) at 4 ° C. was obtained. The acrylic resin (A-24) has a weight average molecular weight of 1,000,000, a high molecular weight component not containing a polymer having a molecular weight of less than 150,000 having a Tg of −29.9 ° C., a weight average molecular weight of 30,000, and a Tg of −28. And a low molecular weight component not containing a polymer having a molecular weight of 150,000 or more at ° C. The high molecular weight component and the low molecular weight component showed two independent peaks in the GPC discharge curve, and the area ratio between them was 75/25.

[Synthesis of acrylic resin]
Synthesis Example 28
After nitrogen gas is sealed in a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 75 parts of ethyl acetate, 15 parts of acetone, 55 parts of butyl acrylate, 25 parts of 2-ethylhexyl acrylate 2-hydroxyethyl acrylate 5 parts, 2-methoxyethyl acrylate 10 parts and 2,2′-azobisisobutyronitrile 0.2 part. The mixture was reacted at the reflux temperature of the solvent for 7 hours with stirring to obtain a solution of an acrylic resin (A-25). The weight average molecular weight of the obtained acrylic resin (A-25) was 1,000,000.

[Synthesis of acrylic resin]
Synthesis Example 29
After nitrogen gas is sealed in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen inlet tube, 70 parts of ethyl acetate, 15 parts of acetone, 62.5 parts of butyl acrylate, 19 parts of phenoxyethyl acrylate 16 parts of methyl acrylate, 1.5 parts of acrylic acid, 1 part of 2-hydroxyethyl acrylate and 0.1 part of 2,2′-azobisisobutyronitrile were charged. The reaction was carried out for 8 hours at the reflux temperature of the solvent with stirring. After completion of the reaction, 315 parts of toluene was added and cooled to room temperature. The weight average molecular weight of the obtained acrylic resin (A-26) was 1.35 million.

[Synthesis of polyester resin]
Synthesis Example 30
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 116 parts of isophthalic acid, 61 parts of sebacic acid, 30 parts of 1,4-butanediol, 1,6-hexanediol 26 Part, 57 parts neopentyl glycol and 2.5 parts trimethylolpropane. After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring. After maintaining at 100 ° C. for 1 hour, dehydration reaction was performed by gradually raising the temperature to 180 to 240 ° C. over about 8 hours. Next, when the acid value became 15 or less, 0.1 part of tetrabutyl titanate was added as a catalyst, the pressure was gradually reduced, the reaction was carried out at 1 to 3 torr and 260 ° C. for 5 hours, the solution was gradually cooled, and toluene The reaction was terminated by dissolving in a solution / ethyl acetate mixed solution (weight ratio = 1/3). The weight average molecular weight of the obtained polyester resin (A-27) was 90,000.

Examples 1-19
With respect to 100 parts of the solid content of the resins (A-1) to (A-13) obtained in Synthesis Examples 4 to 16, an ionic compound (B) having a fluorine atom-containing anion as a constituent component, a curing agent ( C), a silane coupling agent (D) having an alkoxysilyl group, and a polyalkylene glycol (E) were blended according to Table 2 to obtain an antistatic pressure-sensitive adhesive composition.

Comparative Examples 1-19
100 parts of solid content of resins (A-1), (A-14) to (A-24), (A-26), and (A-27) obtained in Synthesis Examples 4, 17 to 27, 29, and 30 Table 3 shows an ionic compound (B) having a fluorine atom-containing anion as a component, a curing agent (C), a silane coupling agent (D) having an alkoxysilyl group, and a polyalkylene glycol (E). And an antistatic pressure-sensitive adhesive composition was obtained.

Comparative Examples 20-25
Antistatic agent, curing agent (C), silane coupling agent having alkoxysilyl group (D) with respect to 100 parts of solid content of resins (A-1) and (A-25) obtained in Synthesis Examples 4 and 28 ) And polyalkylene glycol (E) were blended according to Table 4 to obtain an antistatic pressure-sensitive adhesive composition.

  The antistatic pressure-sensitive adhesive composition was applied on a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes. A pressure sensitive adhesive layer was formed. After drying, the pressure-sensitive adhesive layer is bonded with one side of a polarizing plate having a multilayer structure in which both sides of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”), A laminate having a configuration of “release film / pressure-sensitive adhesive layer / TAC film / PVA / TAC film” was obtained. Next, the obtained laminate was aged (dark reaction) for one week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the adhesive layer was advanced to obtain a laminate.

  The laminate obtained above is cut into a size of 350 mm × 250 mm, the release film is peeled off, and a laminator is placed on both sides of a 1.1 mm thick float glass plate so that the absorption axes of the respective polarizing plates are orthogonal to each other. Used to stick. Subsequently, the glass plate on which the polarizing plate was attached was held in an autoclave at 50 ° C.-5 atm for 20 minutes, and the polarizing plate was firmly adhered to the glass plate to obtain a liquid crystal cell member. Reworkability, wet heat resistance, optical properties, and antistatic properties were evaluated by the following methods.

<Rework evaluation method>
The laminate is cut to a width of 25 mm, the release film is peeled off, and the exposed pressure-sensitive adhesive layer is attached to a glass plate having a thickness of 0.7 mm at 23 ° C.-50% RH, and 5 kg / 50 ° C. atmosphere. After applying a pressure of cm ² and holding for 15 minutes for bonding, roll pressure bonding was performed according to JIS Z 0237. After 24 hours of pressure bonding, after leaving still at 80 ° C. for 500 hours, the polarizing film was peeled off from the glass plate at a peel tester in a 23 ° C.-50% RH atmosphere at 180 ° peel and a pulling speed of 300 mm / min. The glass plate surface and the pressure-sensitive adhesive layer surface were visually observed. The evaluation criteria are as follows.

4: “The pressure-sensitive adhesive layer has not been transferred to the glass plate surface at all, and the pressure-sensitive adhesive layer surface is also smooth.”
3: “The pressure-sensitive adhesive layer is not transferred to the surface of the glass plate, but the surface of the pressure-sensitive adhesive layer is slightly uneven.”
2: “A part of the pressure-sensitive adhesive layer has been transferred to the surface of the glass plate, and the surface of the pressure-sensitive adhesive layer is also significantly uneven.”
1: “The pressure-sensitive adhesive layer has completely transferred to the glass plate surface.”

<Method for evaluating wet heat resistance>
As evaluation of the heat and moisture resistance, floating peeling and foaming after the liquid crystal cell member was allowed to stand for 1000 hours at 80 ° C. and 90% relative humidity were visually observed. The wet heat resistance was evaluated based on the following three evaluation criteria.
○: “No floating peeling or foaming is observed, and there is no problem in practical use.”
Δ: “Slightly floating peeling / foaming is observed, but there is no practical problem”
×: “There is floating peeling and foaming on the whole surface, which is impractical.”
Means each.

<Evaluation method of optical characteristics>
As an evaluation of optical characteristics, light leakage (white spots) was visually observed when light was transmitted through the liquid crystal cell member after being left at 90 ° C. for 1000 hours. The optical characteristics were evaluated based on the following three evaluation criteria.
○: “No light leakage was observed and there was no problem in practical use.”
Δ: “Slight light leakage is observed, but there is no practical problem”
X: “There is light leakage over the entire surface and it is not practical.”
Means each.

<Antistatic property>
The release film of the laminate was peeled off, and the surface resistance value of the exposed pressure-sensitive adhesive layer surface was measured with a digital ultrahigh resistance / microammeter (manufactured by R8340 ADVANTEST).
A: “The surface resistance value is less than 3.0 × 10 ^9. ”
○: “Surface resistance value is 3.0 × 10 ⁹ or more and less than 9.0 × 10 ^9. ”
Δ: “The surface resistance value is 9.0 × 10 ⁹ or more and less than 3.0 × 10 ^10. ”
×: “Surface resistance value is 3.0 × 10 ¹⁰ or more.”
Means each.

  The evaluation results are shown in Tables 2 to 4.

EMIm: 1-ethyl-3-methylimidazolium cation OMPri: 1-octyl-3-methylpyridinium cation Li: lithium cation Bu4-N: tetrabutylammonium cation FSI: bisfluorosulfonylimide anion TFSI: trifluoromethane sulfonylimide Anion C-1: Hexamethylene diisocyanate trimethylolpropane adduct C-2: Tolylene diisocyanate trimethylolpropane adduct C-3: Hexamethylene diisocyanate burette C-4: Mitec NY710A (aliphatic polyfunctional isocyanate, Mitsubishi Chemical)
Silane coupling agent: 3-glycidoxypropyltrimethoxysilane E-1: Sanniks PP-2000 (polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)
E-2: PEG-600 (polyethylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)
E-3: SANNICS PP-600 (polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)

F-1: Lithium perchlorate F-2: Cationic surfactant [alkylbis (2-hydroxyethyl) methylammonium chloride]
F-3: Charge control agent (Hodogaya Chemical, TN-105)
F-4: Sodium perchlorate F-5: Tetrabutylammonium chloride C-1: Hexamethylene diisocyanate trimethylolpropane adduct C-5: 1: 1 mixture of hexamethylene diisocyanate isocyanurate and acetylacetone Silane coupling agent : 3-Glycidoxypropyltrimethoxysilane E-1: Sannix PP-2000 (polypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.)

As shown in Examples 1 to 19 in Table 2, a specific amount of urethane urea resin (A), an ionic compound (B) having a fluorine atom-containing anion as a constituent component, a curing agent (C), and a silane The antistatic pressure-sensitive adhesive composition of the present invention comprising the coupling agent (D) was excellent in all of rework properties, wet heat resistance, optical properties, and antistatic properties. On the other hand, as shown in Tables 3 and 4, the antistatic pressure-sensitive adhesive compositions of Comparative Examples 1 to 25 are poor in any of reworkability, moist heat resistance, optical properties, and antistatic properties, It was not possible to satisfy the characteristics.

Claims (11)

To a urethane prepolymer obtained by reacting a polyol (a) having a polypropylene glycol skeleton or a polyester skeleton with a polyisocyanate (b),
The weight average molecular weight (Mw) obtained by reacting a hydroxyl group-containing polyamino compound (c) obtained by Michael addition of an ethylenically unsaturated compound having a hydroxyl group to a compound having two or more amino groups is 70,000 to 200. 1,000 parts by weight of urethane urea resin (A),
0.05 to 10 parts by weight of an ionic compound (B) having a fluorine atom-containing anion as a component,
Hardener (C) 0.3-3 parts by weight,
And an antistatic pressure-sensitive adhesive composition comprising 0.01 to 3 parts by weight of a silane coupling agent (D) having an alkoxysilyl group. The amount of the polyisocyanate (b) used is 8 to 16% by weight in 100% by weight of the urethane urea resin (A), and the amount of the polyamino compound (c) used is 100% by weight of the urethane urea resin (A). The antistatic pressure-sensitive adhesive composition according to claim 1, which is 1.0 to 4 % by weight. The antistatic pressure-sensitive adhesive according to claim 1 or 2, wherein the anion of the ionic compound (B) having a fluorine atom-containing anion as a constituent component is bis (fluorosulfonyl) imide or bis (trifluoromethanesulfonyl) imide. Agent composition. The antistatic pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the curing agent (C) is a hexamethylene diisocyanate trimethylolpropane adduct. The antistatic pressure-sensitive adhesive composition according to any one of claims 1 to 4, comprising a polyalkylene glycol (E). The antistatic pressure-sensitive adhesive composition according to claim 5, wherein the polyalkylene glycol (E) is polypropylene glycol and is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the urethane urea resin (A). An antistatic pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition according to any one of claims 1 to 6 formed on one side or both sides of a sheet-like substrate. A laminate in which a pressure-sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition according to any one of claims 1 to 6 is laminated on an optical member. The laminate according to claim 8, wherein the optical member is a polarizing plate. A glass cell member for a liquid crystal cell, a pressure sensitive adhesive layer formed from the antistatic pressure-sensitive adhesive composition according to any one of claims 1 to 6, and a member for a liquid crystal cell in which an optical member is sequentially laminated. The liquid crystal cell member according to claim 10, wherein the optical member is a polarizing plate.