JP2009209257A - Resin for use in pressure-sensitive adhesive, and pressure-sensitive adhesive composition using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin for use in pressure-sensitive type adhesives which is low in the surface resistivity, is excellent in the antistatic property, and is decreased in the staining property to adherends, and is excellent in the adhesion reliability; a pressure-sensitive type adhesive composition using it which is excellent in the antistatic property, peelability, and tackiness characteristics; a surface protection film which has a pressure-sensitive type adhesive layer formed with this pressure-sensitive type adhesive composition; and a laminate in which a pressure-sensitive type adhesive layer comprising the pressure-sensitive type adhesive composition and an optical member are laminated. <P>SOLUTION: The resin for use in pressure-sensitive type adhesives which has a glass transition temperature of -80 to 0°C, is formed by the graft reaction of an antistatic agent (D) which has a radically polymerizable functional group, with at least one resin selected from an acrylic-based resin (A), a urethane-based resin (B) and a polyester-based resin (C), by means of a peroxide-based initiator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive resin having a low surface resistance value, excellent antistatic properties, reduced contamination to an adherend, and further excellent adhesion reliability. The present invention relates to a pressure-sensitive adhesive composition using a pressure-sensitive adhesive resin, and a laminate of an optical member and a surface protective film excellent in antistatic properties using the pressure-sensitive adhesive composition.

  Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays. A polarizing film and a retardation film are laminated on the liquid crystal cell member constituting the LCD. Also, these display devices use an antireflection film for preventing reflection from an external light source, a protective film (protection film) for preventing scratches on the surface of the display device, and the like. In addition to using the FPD as a display device, a touch panel function may be provided on the surface of the FPD to be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, and the like are also used for this touch panel.

  Various films used in the display device are used by being attached to an adherend with a pressure-sensitive adhesive. Since pressure sensitive adhesives are required to have excellent transparency, pressure sensitive adhesives based mainly on acrylic resins, urethane resins and polyester resins are generally used because they are used in display devices. Has been.

  Of these various films, the surface protective film often finishes the role of surface protection after the incorporation of a liquid crystal display or the like is completed, and is often peeled off. When the surface protective film is peeled off from the display, there may be a problem that peeling electrification occurs to destroy the liquid crystal or the electronic circuit.

  In addition, after laminating a polarizing film on the glass surface for a liquid crystal cell, the polarizing film is peeled off from the glass cell surface in the inspection process for air and dust entrainment in the laminating process. Then, a new polarizing film or the like is pasted again. At this time, the above-described peeling charge is generated, and the liquid crystal is destroyed.

  In order to solve these problems, various studies have been made and proposed for pressure-sensitive adhesives. For example, in Patent Document 1, a charge-sensitive adhesive based on poly (meth) acrylate is blended with an organic salt containing a cation containing an organic substituent and an anion containing a weakly coordinating organic substituent. A preventive pressure sensitive adhesive is disclosed.

  Patent Document 2 discloses an example in which a charge control agent is added to an acrylic pressure-sensitive adhesive. Examples of the charge control agent include metal complex types, imides, bisphenols, phosphates, carboxylic acids, quaternary amines, oniums, and imidazoles.

  Patent Document 3 discloses an antistatic polyurethane pressure-sensitive 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. Examples are disclosed.

  Patent Document 4 discloses an antistatic pressure-sensitive adhesive composition in which an alkali metal salt is blended with a (meth) acrylic polymer having an acid value of 1.0 or less.

  Patent Document 5 discloses a pressure-sensitive adhesive composition for a surface protective film in which a cationic surfactant and a perchlorate are blended in an acrylic copolymer.

  In Patent Document 6, an antistatic agent in which an ionic substance is blended with a polymer having a polyoxyalkylene structure and a hydroxyl group and having a number average molecular weight of 300 to 1500 is added to a (meth) acrylic polymer having a weight average molecular weight of 1 million or more. A blended adhesive composition is disclosed.

  Patent Document 7 discloses a pressure-sensitive adhesive composition having an antistatic property obtained by blending an ionic liquid with a polyester having a carbonate structural unit and a number average molecular weight of 5000 or more.

  Patent Document 8 discloses a surfactant selected from a polyalkylene oxide-based nonionic surfactant and a trialkylammonium ethosulphate-based cationic surfactant in an acrylic copolymer having a glass transition temperature of -80 to -35 ° C. And a pressure-sensitive adhesive composition containing an ionic liquid.

  In any of the above patent documents, antistatic properties are imparted by blending various antistatic agents having a relatively low molecular weight with acrylic, urethane, and polyester resins as the main ingredients. In Patent Document 6, a polymerized antistatic agent is used, but its number average molecular weight is 300 to 1500, which is hardly a high molecular weight.

As described above, various films used in display devices are used by being attached to an adherend with a pressure-sensitive adhesive. Because it is used for display devices, pressure-sensitive adhesives are required to have heat resistance and heat-and-moisture resistance, and it is also required that no residue of pressure-sensitive adhesive remains on the liquid crystal surface or glass surface after peeling. Is done. When the above-mentioned relatively low molecular weight antistatic agent is blended, the heat resistance and heat-and-moisture resistance decrease, and peeling or misalignment occurs between the polarizing film and the glass surface, or the surface protective film is peeled off. In addition, the residue of the pressure-sensitive adhesive may remain on the display surface, which may cause problems such as a reduction in commercial value.
Special Table 2004-536940 JP 2004-155977 A JP 2005-154491 A JP 2005-298568 A JP 2006-002140 A JP 2006-199873 A JP 2007-008985 A JP 2007-063298 A

  The object of the present invention is to eliminate the problems in the conventional antistatic pressure-sensitive adhesives, to prevent charging to the adherend when peeled, and to reduce contamination to the adherend. An object of the present invention is to provide a pressure-sensitive adhesive resin having excellent adhesion reliability and antistatic properties. Further, a pressure-sensitive adhesive composition having excellent antistatic properties, peelability and adhesive properties using the same, a surface protective film having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and pressure-sensitive type thereof An object of the present invention is to provide a laminate in which a pressure-sensitive adhesive layer formed from an adhesive composition and an optical member are laminated.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the first invention is the antistatic having a radical polymerizable functional group for at least one resin selected from the acrylic resin (A), the urethane resin (B), and the polyester resin (C). The present invention relates to a pressure-sensitive adhesive resin having a glass transition temperature of −80 to 0 ° C. obtained by grafting the agent (D) with a peroxide-based initiator.

  Further, in the second invention, the antistatic agent (D) having a radical polymerizable functional group comprises an ionic solid (d1) having a radical polymerizable functional group, and a surfactant (d2) having a radical polymerizable functional group. The pressure-sensitive adhesive resin according to the first aspect of the present invention is at least one selected from the group consisting of:

  The third invention is the pressure-sensitive adhesive resin according to the first or second invention, wherein the acrylic resin (A) has a weight average molecular weight of 500,000 to 1,500,000. About.

  The fourth invention relates to the pressure-sensitive adhesive resin according to the first or second invention, wherein the urethane-based resin (B) has a weight average molecular weight of 30,000 to 500,000.

  The fifth invention relates to the pressure-sensitive adhesive resin according to the first or second invention, wherein the polyester resin (C) has a weight average molecular weight of 30,000 to 500,000.

  Moreover, 6th invention contains the reactive compound (E) which can react with the resin for pressure sensitive adhesives of any one of 1st-5th invention, and the said resin for pressure sensitive adhesives. The present invention relates to a pressure-sensitive adhesive composition.

  In the seventh invention, the reactive compound (E) is selected from the group consisting of a polyfunctional epoxy compound, a polyfunctional aziridine compound, a polyfunctional carbodiimide compound, a polyfunctional oxazoline compound, a polyfunctional isocyanate compound, and a metal chelate compound. It is related with the pressure sensitive adhesive composition of 6th invention characterized by being at least 1 sort.

  The eighth invention also relates to a surface protective film comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the sixth or seventh invention on the surface of a plastic film substrate. .

  The ninth invention relates to a laminate in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the sixth or seventh invention is laminated on an optical member.

  The tenth invention is a liquid crystal cell member comprising a glass member for a liquid crystal cell, a pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition according to the sixth or seventh aspect, and an optical member. About.

  According to the present invention, a pressure-sensitive adhesive resin having excellent antistatic properties can be provided. By using this resin, it is possible to prevent static charge on the adherend when it is peeled off, the contamination of the adherend is reduced, and the adhesion reliability is excellent and the pressure sensitive adhesive has antistatic properties. An agent resin could be provided. Further, a pressure-sensitive adhesive composition having excellent antistatic properties, peelability and adhesive properties using the pressure-sensitive adhesive resin, and surface protection having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition It was possible to provide a laminate comprising a film and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition and an optical member.

  The present invention relates to an antistatic agent (D) having a radical polymerizable functional group for at least one resin selected from an acrylic resin (A), a urethane resin (B), and a polyester resin (C). [Hereinafter referred to as “antistatic agent (D)”] is a pressure-sensitive adhesive resin obtained by graft reaction using a peroxide-based initiator. That is, the pressure-sensitive adhesive resin of the present invention is a resin having pressure-sensitive adhesive properties [at least one selected from acrylic resin (A), urethane resin (B), and polyester resin (C)]. Has a structure in which a compound having antistatic properties is introduced as a side chain.

  First, the acrylic resin (A) of the present invention will be described. The acrylic resin (A) of the present invention can be produced by polymerization by a conventionally known method. Although not particularly limited, for example, after introducing an acrylic monomer described later into a reaction solvent and replacing the air in the reaction system with an inert gas such as nitrogen gas, if necessary, in the presence of a reaction initiator, It can be produced by heating and stirring to cause a polymerization reaction.

  As the monomer for forming the acrylic resin (A) of the present invention, conventionally known monomers can be arbitrarily used, but the respective monomers are used so that the glass transition temperature of the obtained resin is -80 to 0 ° C. In consideration of the glass transition temperature of the homopolymer formed from, one kind is used alone, or two or more kinds are used in combination. When the glass transition temperature of the acrylic resin is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the acrylic resin is reduced, and floating is caused. On the other hand, when the glass transition temperature exceeds 0 ° C., the pressure-sensitive adhesive layer becomes too hard and does not exhibit sufficient tack, or the adhesive strength is weak when plastics or a glass plate and a plastic film are laminated. In addition, the solubility in a solvent is reduced, and the viscosity of the pressure-sensitive adhesive is increased, which makes it difficult to handle during coating, which is not preferable. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

Specific examples of the monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2 -Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate;
(Meth) acrylic monomers such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, alkoxyalkyl (meth) acrylates such as methoxytriethylene glycol (meth) acrylate; .

  The resin for pressure sensitive adhesives of this invention mix | blends the reactive compound (E) which can react with this resin, and forms a pressure sensitive adhesive layer by bridge | crosslinking this resin. For this reason, the acrylic resin (A) needs to contain a reactive functional group. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, and an amide group. In obtaining the acrylic resin (A), monomers having these functional groups are appropriately used.

Specific examples of the monomer having a hydroxyl group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
Halogenated hydroxyalkyl (meth) acrylates such as chloro-2-hydroxypropyl (meth) acrylate;
Examples include diethylene glycol mono (meth) acrylate and allyl alcohol. These may be used alone or in combination of two or more.

  These monomers having a hydroxyl group are usually supplied in an amount of 0.3 to 5 parts by weight, preferably 1 to 3 parts by weight, when the total amount of monomers used for copolymerization is 100 parts by weight.

Examples of the monomer having a carboxyl group include unsaturated groups such as (meth) acrylic acid, β-carboxyethyl acrylate, crotonic acid, α-methylcrotonic acid, α-ethylcrotonic acid, isocrotonic acid, tiglic acid and ungelic acid. Monocarboxylic acid;
Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid and hydromuconic acid.

  Examples of the monomer having an amino group include dimethylaminoethyl (meth) acrylate and diethylamino (meth) acrylate.

  Examples of the monomer having an amide group include (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide and the like, and a monomer having an amino group and an amide group such as dimethylaminopropyl (meth) acrylamide. Etc. can also be used.

  These monomers having reactive functional groups can be used singly or in combination of two or more.

In addition, when manufacturing the said acrylic resin (A), other monomers other than the monomer shown above can also be used for a copolymerization as needed. Examples of other monomers include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, Styrenic monomers such as bromostyrene, dibromostyrene iodostyrene, nitrostyrene, acetylstyrene, methoxystyrene;
Examples thereof include vinyl monomers such as vinyl pyrrolidone, vinyl carbazole, divinyl benzene, vinyl acetate, and acrylonitrile. These monomers can be used alone or in combination of two or more.

  As the reaction initiator used for producing the acrylic resin (A), a commonly used azo initiator or peroxide initiator can be arbitrarily used. As the azo initiator, for example, azobisisobutyronitrile is preferably used, and as the peroxide initiator, for example, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy- Examples thereof include 2-ethylhexanoate and cumene hydroperoxide.

  As the reaction solvent, an organic solvent that does not affect the graft reaction described later is used. Specifically, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as n-hexane. And esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol, and ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.

  The polymerization reaction temperature is usually 50 to 90 ° C., and the reaction time is usually 2 to 20 hours, preferably 4 to 12 hours. The reaction solvent is used in an amount of 50 to 300 parts by weight with respect to 100 parts by weight of the total amount of monomers, and the reaction initiator is usually used in an amount of 0.01 to 10 parts by weight. The weight average molecular weight (Mw) of the acrylic resin (A) of the present invention is preferably 500,000 to 1,500,000, and the amount of reaction solvent and reaction initiator are adjusted so that the weight average molecular weight falls within this range. Set volume, reaction temperature and reaction time. When the Mw is less than 500,000, the cohesive force as the pressure-sensitive adhesive layer becomes difficult to develop, and the heat resistance and the heat and humidity resistance are reduced. On the other hand, if Mw exceeds 1,500,000, the fluidity of the pressure-sensitive adhesive becomes poor even when diluted with a solvent, and when preparing a pressure-sensitive adhesive sheet, the coatability is reduced. Absent. After the completion of the polymerization reaction, it is subjected to a graft reaction to obtain a pressure-sensitive adhesive resin having antistatic properties. In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this invention are the values of polystyrene conversion by GPC (gel permeation chromatography) measurement.

  Next, the urethane resin (B) of the present invention will be described. The urethane resin (B) of the present invention can be produced by a conventionally known method. That is, it can be obtained by reacting a polyol component such as polyester polyol, polyether polyol or polycarbonate polyol with a diisocyanate compound. In the reaction, the polyol component and the diisocyanate compound are appropriately selected and used so that the glass transition temperature of the urethane resin (B) is -80 to 0 ° C. When the glass transition temperature of the urethane resin is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the urethane resin is reduced, and the float-off occurs. On the other hand, when the glass transition temperature exceeds 0 ° C., the pressure-sensitive adhesive layer becomes too hard and does not exhibit sufficient tack, or when the plastics or glass plates and plastic films are laminated, the adhesive strength is low. In addition to weakening, the solubility in a solvent decreases, and the viscosity of the pressure-sensitive adhesive increases, which makes it difficult to handle during coating. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

As polyester polyol, as an acid component, for example, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, trimellitic anhydride;
Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2-butylethyl-1 , 3-propanediol, trimethylolpropane, glycerin, pentaerythritol;
It can be obtained by a dehydration condensation reaction between an acid component such as a glycol component. Further, polyester polyol obtained by ring-opening polymerization of ε-caprolactone, γ-valerolactone, or the like can also be used. As the number average molecular weight of the polyester polyol, those having a relatively low molecular weight are used because of easy handling. A number average molecular weight of 500 to 6,000 is preferably used.

  As the polyether polyol, a polyol having a repeating unit of alkylene oxide such as methylene oxide, ethylene oxide, propylene oxide, butylene oxide can be used. As the number average molecular weight of the polyether polyol, one having a relatively low molecular weight is used for ease of handling. A number average molecular weight of 500 to 6,000 is preferably used.

  Polycarbonate polyols include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5-pentane. Examples thereof include polycarbonate diols obtained by dealcoholization reaction with polyhydric alcohols such as diol 1,9-nonanediol, and carbonate diols such as propylene carbonate diol and hexamethylene carbonate diol. The number average molecular weight of the polycarbonate polyol is a relatively low molecular weight because of easy handling. A number average molecular weight of 500 to 6,000 is preferably used.

  Further, as the polyol component, a compound having a carboxyl group with two hydroxyl groups, for example, dioxycarboxylic acid such as dimethylolpropionic acid and dimethylolbutanoic acid can be used. By using such a compound, not only a hydroxyl group but also a carboxyl group can be introduced as a reactive functional group of the urethane resin.

  Furthermore, a compound having two or more low molecular weight hydroxyl groups can be used in combination as the polyol component. For example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,2 -Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl- 2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-, methyl-2,4-pentanediol, 2 , 4-diethyl-1,5-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl 1,6-hexanediol, 2-methyl-1,8-octanediol, 2-methyl-1,9-nonanediol, dimer diol, 2-methyl-1,4-cyclohexanediol, glycerin, trimethylolpropane 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol and the like.

  Examples of the diisocyanate compound include conventionally known diisocyanate compounds such as aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  As aromatic diisocyanates, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Examples thereof include isocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.

  Aliphatic diisocyanates include trimethylene diisocyanate, tetremethylene diisocyanate, hexamethylene diisocyanate, pentemethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4 , 4'-trimethylhexamethylene diisocyanate and the like.

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

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5′-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2,4. -Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, etc. it can.

  The reaction between the polyol component and the diisocyanate component is a reaction between a hydroxyl group and an isocyanate group. In carrying out this reaction, an organic solvent that does not affect the reaction can be used. As such an organic solvent, hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferably used.

  In the reaction of the polyol component and the diisocyanate component, the equivalent ratio of the hydroxyl group to the isocyanate group is preferably OH / NCO = 65/35 to 50/50. If the ratio of OH exceeds 65, the amount of unreacted hydroxyl components increases, and it exists as a monomer even after the urethane reaction is completed, so the cohesive force of the pressure-sensitive adhesive may be reduced. On the other hand, if the equivalent ratio of hydroxyl groups is less than 50, excess isocyanate groups remain in the urethane resin, so the stability of the resin solution may deteriorate.

  When the polyol component and the diisocyanate component are reacted, it is preferable to use a catalyst. As the catalyst used in the present invention, a conventionally known catalyst can be used. For example, a tertiary amine compound or an organic metal salt is used. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N′-dimethylbenzylamine, N-methylmorpholine, 1,8-diaza-bicyclo (5,4,0) undecene.

  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, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin Examples include ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 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.

  The manufacturing method of the urethane type resin (B) of this invention is demonstrated. The polyol component, the diisocyanate component and, if necessary, an organic solvent are charged and reacted in a lump under a hydroxyl group-excess condition. Or you may make it react by dripping a diisocyanate component. Since the urethane-based resin (B) of the present invention preferably has a glass transition temperature of −80 to 0 ° C. and a weight average molecular weight of 30,000 to 500,000, the polyol component has a glass transition during polymerization. It is appropriately selected and used so that the temperature becomes −80 to 0 ° C. Further, the weight average molecular weight can be set to the target molecular weight by adjusting the reaction conditions and the excess ratio of the hydroxyl group.

  The weight average molecular weight (Mw) of the urethane-based resin (B) in the present invention is preferably in the range of 30,000 to 500,000 from the viewpoint of adhesiveness, and in the range of 50,000 to 300,000. Is more preferable. When such a urethane resin (B) is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. If the Mw is less than 30,000, the cohesive force as the pressure-sensitive adhesive layer is hardly expressed, and the heat resistance and heat and humidity resistance are reduced. On the other hand, if Mw exceeds 500,000, the fluidity of the pressure-sensitive adhesive becomes poor even when diluted with a solvent, and the coating property is lowered when a pressure-sensitive adhesive sheet is produced.

  As the reaction conditions for the urethane-based resin (B) of the present invention, conditions for ordinary urethanization reactions can be used. That is, an organic solvent that does not affect the graft reaction described later, a polyol component, and a catalyst as needed are charged all at once, and when the solution becomes sufficiently uniform by stirring, the diisocyanate component is added dropwise. The reaction temperature is preferably 80 ° C. to 100 ° C., the dropping time is preferably 30 minutes to 2 hours, and the reaction time after dropping is preferably 2 to 5 hours. The reaction is completed by confirming the disappearance of the isocyanate group with an infrared spectrophotometer. After completion of the urethanization reaction, it is subjected to a graft reaction to obtain a pressure-sensitive adhesive resin having antistatic properties.

  Next, the polyester resin (C) of the present invention will be described. The polyester resin (C) of the present invention can be obtained by a dehydration condensation reaction between a normal polycarboxylic acid component and a polyhydric alcohol component. When the molecular weight is increased as necessary, a dealcoholization reaction may be performed under high vacuum. During the reaction, a polyvalent carboxylic acid component and a polyhydric alcohol component are appropriately selected and used so that the glass transition temperature of the polyester resin (C) is -80 to 0 ° C. When the glass transition temperature of the polyester resin is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the polyester resin is lowered, and the float-off occurs. On the other hand, when the glass transition temperature exceeds 0 ° C., the pressure-sensitive adhesive layer becomes too hard and does not exhibit sufficient tack, or the adhesive strength is weak when plastics or a glass plate and a plastic film are laminated. In addition, the solubility in a solvent is reduced, and the viscosity of the pressure-sensitive adhesive is increased, which makes it difficult to handle during coating, which is not preferable. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  Examples of the polyvalent carboxylic acid component include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetraundecanedioic acid, and isophthalic acid. Aromatic dicarboxylic acids such as terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Examples thereof include alicyclic dicarboxylic acids such as acids and dimer acids. Examples of the trivalent or higher polyvalent carboxylic acids include trimellitic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, and the like. Can be mentioned. These acid anhydrides and those esterified with a lower alcohol are also used.

  Examples of the polyhydric alcohol component include, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, Linear aliphatic diols such as 1,9-nonanediol, 1,10-decanediol, 1,18-octadecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol And alicyclic diols such as

  Examples of the polyhydric alcohol component having a hydrocarbon group include neopentyl glycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 2-methyl-2-propyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl- 1,5-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 2-methyl-1, Examples include 9-nonanediol, dimer diol, and 2-methyl-1,4-cyclohexanediol. Examples of the trihydric or higher polyhydric alcohol component include, for example, glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, pentaerythritol. And aliphatic polyhydric alcohols such as dipentaerythritol.

  Moreover, in order to easily obtain a resin having a desired molecular weight as the polyhydric alcohol component, commercially available polyester diol, polyether diol, polycaprolactone diol, polycarbonate diol, and the like can be used as the polyhydric alcohol component.

  Examples of commercially available polyester diols include, for example, trade names “Kuraray polyol P-510”, “Kuraray polyol P-1010”, “esterified product of 3-methyl-1,5-pentanediol and adipic acid”, “ Kuraray polyol P-2010 "," Kuraray polyol P-3010 "," Kuraray polyol P-5010 "(manufactured by Kuraray Co., Ltd.) and the like.

  Examples of the polyether diol include, for example, polyethylene glycol and polypropylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like. Commercially available products are polyether diols in which propylene oxide is added to propylene glycol, trade names “Adeka Polyether P-400”, “Adeka Polyether P-1000”, “Adeka Polyether P-2000”, “Adeka Poly”. Ether P-3000 "(manufactured by ADEKA).

  Examples of polycaprolactone diols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and γ-valerolactone. Examples of commercially available products include “Placcel L205AL”, “Placcel L212AL”, “Placcel L220PL”, “Placcel L230AL” (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Examples of commercially available carbonate diol include, for example, trade names “PLACCEL CD205”, “PLACCEL CD210”, “PLACCEL 220”, “PLACCEL CD205PL”, “PLACCEL CD210PL”, “PLACCEL 220PL” (hereinafter referred to as Daicel Chemical Industries, Ltd.). Manufactured).

  The polyester-based resin (C) of the present invention can be obtained by polycondensing a polyvalent carboxylic acid component and a polyhydric alcohol component as described above by a conventionally known method. As described above, the polyester resin (C) of the present invention has a glass transition temperature (Tg) so that it can exhibit well-balanced adhesive properties (particularly, both tack and cohesive force) as a pressure-sensitive adhesive layer. The polyvalent carboxylic acid component and the polyhydric alcohol component may be appropriately selected so that the temperature is -80 to 0 ° C, and the glass transition temperature (Tg) of the polyester resin (C) is -60 to -10 ° C. It is more preferable to select each component.

  The weight-average molecular weight (Mw) of the polyester resin (C) in the present invention is preferably in the range of 30,000 to 500,000 from the viewpoint of adhesiveness, and in the range of 50,000 to 300,000. Is more preferable. When such a polyester resin (C) is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. If the Mw is less than 30,000, the cohesive force as the pressure-sensitive adhesive layer is hardly expressed, and the heat resistance and heat and humidity resistance are reduced. On the other hand, if Mw exceeds 500,000, the fluidity of the pressure-sensitive adhesive becomes poor even when diluted with a solvent, and the coating property is lowered when a pressure-sensitive adhesive sheet is produced.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyester resin (C) in the present invention is preferably in the range of 2.0 to 6.0, More preferably, it is in the range of 2.0 to 4.0. When Mw / Mn is less than the lower limit, as in the case of Mw, the cohesive force as the pressure-sensitive adhesive layer is hardly expressed, and heat resistance and moist heat resistance tend to decrease. On the other hand, exceeding the upper limit is not preferable because the fluidity of the pressure-sensitive adhesive is lowered even when diluted with a solvent, and the coating property is lowered when a pressure-sensitive adhesive sheet is produced. Usually, in the case of a pressure-sensitive adhesive, unlike the adhesive, it is preferable that the Mw / Mn ratio is 2.0 or more. That is, when Mw / Mn ratio is large and a low molecular weight component is contained to some extent, when producing a pressure-sensitive adhesive sheet, the affinity (wetting property) to the sheet-like substrate is improved, and the substrate adhesion is improved. Furthermore, when the formed pressure-sensitive adhesive sheet is adhered to an adherend, the pressure-sensitive adhesive layer in a cured state contains a cured component derived from a low molecular weight component, so that the pressure-sensitive adhesive layer is attached. Adhesion to the body can be improved.

  In order to make the weight average molecular weight within this range, it is carried out by adjusting the equivalent ratio of the polyvalent carboxylic acid component and the polyhydric alcohol component, and by selecting the reaction conditions and the catalyst. Furthermore, in order to increase the molecular weight, a method of performing a deglycolization reaction under a reduced pressure of 5 mmHg or less can be employed. It is preferable to use a catalyst when performing the deglycolization reaction. Examples of the catalyst include titanium catalysts such as tetrabutyl titanate and tetraisopropyl titanate, antimony catalysts such as antimony trioxide, germanium catalysts such as germanium oxide, zinc acetate, manganese acetate, and dibutyltin oxide. Can do.

  As a manufacturing method of the polyester-type resin (C) of this invention, the following methods can be shown. The polyvalent carboxylic acid component and the polyhydric alcohol component are charged without a solvent. At this time, the equivalent of the polyhydric alcohol component is charged to be slightly excessive with respect to the equivalent of the carboxylic acid component. A polyester resin (C) is obtained by performing a dehydration reaction or a transesterification reaction at a temperature of 160 to 260 ° C. for 10 to 20 hours. When the molecular weight is difficult to increase and the desired molecular weight cannot be obtained, the above-described catalyst is added and the reaction is further continued under reduced pressure of 5 mmHg or less to obtain a polyester resin (C) having the desired molecular weight. After completion of the reaction, it is dissolved in an organic solvent that does not affect the graft reaction described later, and subjected to a graft reaction to obtain a pressure-sensitive adhesive resin having antistatic properties.

  The pressure-sensitive adhesive resin of the present invention has a radical polymerizable functional group on at least one resin selected from the acrylic resin (A), urethane resin (B), and polyester resin (C). The antistatic agent (D) can be obtained by a graft reaction using a peroxide-based initiator.

  The antistatic agent (D) having a radical polymerizable functional group is a radical polymerizable functional group, for example, a functional group such as a (meth) acryloyl group, a vinyl group, an allyl group, a propenyl group, It is a compound containing a structure having an ability to prevent, for example, a structure such as an ionic functional group or a polyoxyalkylene skeleton. That is, the antistatic agent (D) is a compound obtained by introducing a radical functional group into a compound having an antistatic ability generally used as an additive. Examples of the compound having antistatic ability include an ionic liquid, an ionic solid, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an alkali metal salt. Examples of the ionic liquid include a sulfonium ionic liquid, a phosphonium ionic liquid, an ammonium ionic liquid, a pyridium ionic liquid, an imidazolium ionic liquid, a nitrogen-containing onium salt, a sulfur-containing onium salt, and the like. Examples thereof include phosphonium salts and ionic liquids in which the anion portion contains a fluorine atom. Examples of the anionic surfactant include a sulfonate type surfactant such as dodecylbenzene sulfonate, a sulfate ester type surfactant, and a phosphate type surfactant. Examples of the cationic surfactant include an alkyl ammonium salt type surfactant, an alkyl imidazoline type surfactant, and an alkyl betaine type surfactant. Nonionic surfactants include, for example, alkyl ether type surfactants such as polyoxyalkylene alkyl ethers, polycyclic phenyl ether type surfactants such as polyoxyalkylene polycyclic phenyl ethers, and surfactants obtained from sorbitan derivatives. Etc. Examples of the alkali metal salt include an alkali metal salt of perchloric acid, an alkaline earth metal salt of perchloric acid, an alkali metal salt of an organic boron complex, and an alkaline earth metal salt of an organic boron complex.

  Examples of the antistatic agent (D) having a radical polymerizable functional group used in the present invention include an ionic solid (d1) having a radical polymerizable functional group and a surfactant (d2) having a radical polymerizable functional group. And a polyoxyalkylene compound having a radical polymerizable functional group. In the present invention, from the viewpoint of antistatic performance of the obtained resin, an ionic solid (d1) having a radical polymerizable functional group, radical polymerization. It is preferable to use a surfactant (d2) having a functional functional group.

  Examples of the ionic solid (d1) having a radical polymerizable functional group include compounds represented by the following general formula [1].

  General formula [1]

Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkynyl group that may have a substituent. Represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and adjacent R ^{5 to} R ⁸ may be bonded to each other to form a ring. , At least one of R ^{5 to} R ^{8 is} an alkenyl group which may have a substituent.)

R ^{1 to} R ⁸ of the compound represented by the general formula [1] in the present invention are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents an alkynyl group which may have a group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and adjacent R ^{5 to} R ⁸ are bonded to each other. A ring may be formed. However, at least one of R ^{5 to} R ^{8 is} an alkenyl group which may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3- Torofenashiru group, and the like.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Furthermore, the alkyl group which may have a substituent mentioned above, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the aryl group and the substituent which may have a substituent The hydrogen atom of the heterocyclic group which may have may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Acyloxy such as alkoxycarbonyl groups such as oxy, methoxycarbonyl, butoxycarbonyl, aryloxycarbonyl such as phenoxycarbonyl, alkenyloxycarbonyl such as vinyloxycarbonyl, acetoxy, propionyloxy, benzoyloxy Group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, metoxalyl group and other acyl groups, methylsulfanyl group, tert-butylsulfanyl group and other alkylsulfanyl groups, phenylsulfanyl Arylsulfanyl groups such as p-tolylsulfanyl group, alkylamino groups such as methylamino group and cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, phenylamino group, p-tolylamino Aryl groups such as alkyl groups, alkyl groups such as methyl groups, ethyl groups, tert-butyl groups, dodecyl groups, aryl groups such as phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups Group, hydroxyl group, carboxyl group, amide group, sulfonamido group, formyl group, mercapto group, alkylthio group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano group, trifluoro group Methyl group, trichloromethyl group, Trimethylsilyl group, a phosphinico group, a phosphono group, an alkylsulfonyl group, an arylsulfonyl group, trialkylammonium group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like. These substituents may be further substituted with a halogen group.

  Among such substituents, a preferred substituent is an electron-withdrawing substituent. By substitution with an electron-attracting substituent, the ionic compound is generally easily dissociated and the antistatic ability is enhanced.

  Such electron-attracting substituents are generic names for substituents that attract electrons from the other party by resonance effects and induced effects, and many of them have a positive value for the substituent constant σ in Hammett's rule. It is. These substituents are not particularly limited, and specific examples thereof include Chemical Review Vol. 91, Nos. 165 to 195. σp described in 1991 is greater than 0. More specifically, halogen group, cyano group, carboxyl group, nitro group, nitroso group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, amide group, perfluoro Examples thereof include an alkyl group, a perfluoroalkylthio group, a perfluoroalkylcarbonyl group, a sulfonamide group, and a 4-cyanophenyl group.

R ^{1 to} R ⁴ are preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably a substituent, in view of the stability of the compound. It is an aryl group that may have. From the viewpoint of antistatic ability, the substituent is preferably a halogen group.

R ^{5 to} R ⁸ are graft-reacted with at least one resin selected from acrylic resin (A), urethane resin (B), and polyester resin (C), and therefore at least one of them is It is necessary to be an alkenyl group which may have a substituent. In order to perform the graft reaction stably, it is preferable that only one of R ^{5 to} R ⁸ is an alkenyl group. As the functional group other than the alkenyl group, an alkyl group which may have a substituent is preferable in consideration of the stability of the compound. Further, from the viewpoint of compatibility with the resin and antistatic ability, R ^{5 to} R ⁸ do not have a hydrophilic substituent such as a hydroxyl group, an alkoxy group, or an acyloxy group. In some cases, it may be preferable to have no group. When R < ⁵ > -R < ⁸ > has a substituent, a hydrophobic substituent is mentioned as a preferable example.

  Although the typical example of a compound represented by General formula [1] of this invention is specifically illustrated below as exemplary compound (1)-(6), it is not restricted to these. In addition, Me in exemplary compounds shows a methyl group.

  Compound (1)

  Compound (2)

  Compound (3)

  Compound (4)

  Compound (5)

  Compound (6)

  The ionic solid (d1) having a radical polymerizable functional group can be used alone or in combination of two or more.

  Next, a commercially available reactive surfactant can be used as the surfactant (d2) having a radical polymerizable functional group. The surfactant (d2) having a radical polymerizable functional group is roughly classified into anionic and nonionic nonionic ones. As the surfactant (d2) having a radical polymerizable functional group, one kind may be used alone, or a plurality kinds may be mixed and used.

Specific examples of the anionic reactive surfactant among the surfactant (d2) having a radical polymerizable functional group are shown below, but the surfactant that can be used in the present invention is as follows. It is not limited only to what is described. Examples of the surfactant include alkyl ethers (for example, Antox SAD and MS-2N manufactured by Nippon Emulsifier Co., Ltd., Aqualon KH-05, KH-10, and KH-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). KH-0530, KH-1025, Adeka Soap SR-10N, SR-20N manufactured by ADEKA Corporation, LATEMUL PD-104 manufactured by Kao Corporation, etc.);
Sulfosuccinic acid ester-based (for example, Latmul S-120, S-120A, S-180P, S-180A, Sanyo Chemical Co., Ltd., Elemiol JS-2, etc., manufactured by Kao Corporation);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -20, HS-30, HS-1025, BC-05, BC-10, BC-20, BC-1025, BC-2020, ADEKA Corporation ADEKA rear soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, SE-, etc.);
(Meth) acrylate sulfate ester (commercially available products such as Antox MS-60, MS-2N, Sanyo Kasei Kogyo Co., Ltd. Elminol RS-30 manufactured by Nippon Emulsifier Co., Ltd.);
Examples of the phosphoric acid ester (commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap PP-70 manufactured by ADEKA Co., Ltd.) and the like.

On the other hand, among surfactants (d2) having a radical polymerizable functional group, examples of nonionic reactive surfactants include, for example, alkyl ethers (for example, commercially available products such as Antox LMA-20 manufactured by Nippon Emulsifier Co., Ltd.). , LMA-27, EMH-20, LMH-20, SMH-20, Adeka Soap ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Corporation, LATEMUL PD-420, PD manufactured by Kao Corporation -430, PD-450, etc.);
Alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, RN-2025, ADEKA Corporation ADEKA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Rear soap NE-10, NE-20, NE-30, NE-40, etc.);
(Meth) acrylate sulfate-based (as commercial products, for example, RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Emulsifier Co., Ltd.) can be mentioned.

  Examples of the other antistatic agent (D) having a radical polymerizable functional group include polyoxyalkylene compounds having a radical polymerizable functional group, and specific examples thereof include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, propoxypolyethyleneglycol (meth) acrylate, n-butoxypolyethyleneglycol (meth) acrylate, n-pentoxypolyethyleneglycol (meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, polypropylene Glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate Rate, propoxypolypropylene glycol (meth) acrylate, n-butoxypolypropylene glycol (meth) acrylate, n-pentoxypolypropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypoly Examples include tetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, and methoxyhexaethylene glycol (meth) acrylate.

  The resin for pressure-sensitive adhesives of the present invention has at least an antistatic agent (D) having a radical polymerizable functional group selected from an acrylic resin (A), a urethane resin (B), and a polyester resin (C). Obtained by grafting to one resin. The graft reaction of the present invention is a compound having a radical polymerizable functional group on a acrylic resin, urethane resin or polyester resin using a peroxide-based initiator and a compound having a radical polymerizable functional group. This is a method of chemically bonding. An unsaturated double bond may or may not be contained in the skeleton of the acrylic resin, urethane resin, or polyester resin. When the skeleton does not contain an unsaturated double bond, a radical is generated due to a hydrogen abstraction reaction of the peroxide-based initiator to form a chemical bond. In the present invention, a monomer having a radical polymerizable functional group other than the antistatic agent (D) can be used in combination with the antistatic agent (D) having a radical polymerizable functional group. However, when a monomer having a radical polymerizable functional group other than the antistatic agent (D) is used in combination, the amount used is other than the antistatic agent (D) and the antistatic agent (D) in consideration of antistatic properties. It is preferable to use 50% by weight or less in a total of 100% by weight with the monomer having a radical polymerizable functional group.

  The at least 1 sort (s) of resin chosen from acrylic resin (A), urethane type resin (B), and polyester-type resin (C), and the antistatic agent (D) which has the radically polymerizable functional group used for graft reaction The weight ratio is preferably 99.5 / 0.5 to 50/50. Furthermore, it is more preferable that it is in the range of 99/1 to 70/30. When the antistatic agent (D) exceeds the above range, the adhesiveness of the resulting pressure-sensitive adhesive resin may be adversely affected. On the other hand, if the amount of the antistatic agent (D) is less than the above range, the antistatic effect may not be obtained.

  The organic solvent used in the graft reaction is not particularly limited, except for an organic solvent that inhibits the graft reaction. For example, an organic solvent such as toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, alkyl alcohol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, etc. It can be used, and if necessary, it may be added separately after the reaction.

   The peroxide initiator is not particularly limited, but benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, cumene hydroperoxide, etc. Can be mentioned.

  Moreover, as a monomer which has radically polymerizable functional groups other than antistatic agent (D), the monomer used in order to obtain acrylic resin (A) mentioned above can be used.

  The graft reaction is an antistatic agent having a radical polymerizable functional group on the aliphatic skeleton carbon atom of at least one resin selected from acrylic resin (A), urethane resin (B), and polyester resin (C). (D) grafts. By using 20 to 100 parts by weight of the peroxide-based initiator with respect to 100 parts by weight of the antistatic agent (D) having a radical polymerizable functional group, the graft reaction onto the aliphatic skeleton carbon is preferential and efficient. Done.

  As a method of the graft reaction, an acrylic resin solution, a urethane resin solution, and a polyester resin solution dissolved in an organic solvent are previously charged in a reaction layer, and an antistatic agent (D) having a radical polymerizable functional group and The peroxide initiator may be dropped in an organic solvent, or an acrylic resin solution, a urethane resin solution, a polyester resin solution and an antistatic agent (D) are charged into the reaction layer. Alternatively, only the peroxide-based initiator may be dissolved in an organic solvent and dropped. The reaction temperature is usually preferably from 60 ° C to 120 ° C, but can be appropriately selected depending on the type of the reaction solvent used and the initiator used. The dropping time is usually 30 minutes to 120 minutes. One hour after the completion of dropping, it was confirmed whether or not the anti-reactive agent (D) having an unreacted radical polymerizable functional group remained. If it remained, 1/10 amount of the used initiator was added. Then, the reaction is further performed after 1 hour, and it is confirmed that the antistatic agent (D) having an unreacted radical polymerizable functional group does not remain. If it still remains, add 1/10 of the initiator and repeat the reaction after 1 hour. Thus, by preventing the antistatic agent (D) having an unreacted radical polymerizable functional group from remaining almost completely, the contamination to the adherend is reduced and the adhesion reliability is further improved. A resin for pressure sensitive adhesives can be obtained.

  The pressure-sensitive adhesive composition of the present invention has a radical polymerizable functional group for at least one resin selected from acrylic resin (A), urethane resin (B), and polyester resin (C). The antistatic agent (D) having an antistatic property obtained by graft-reacting the antistatic agent (D) with a peroxide-based initiator, and these pressure-sensitive adhesive resins can be reacted. And a reactive compound (E) [hereinafter also referred to as “reactive compound (E)”].

  That is, the reactive compound (E) used in the present invention is a functional group capable of reacting with a hydroxyl group, a carboxyl group, an amino group, or an amide group in the pressure-sensitive adhesive resin having antistatic properties described above. It is a compound possessed inside. Examples of the reactive compound (E) include a compound (e1) having a functional group capable of reacting with a hydroxyl group in the pressure-sensitive adhesive resin [hereinafter also referred to as “compound (e1)”] and a carboxyl group. And a compound (e2) having a functional group [hereinafter also referred to as “compound (e2)”]. Examples of the compound (e1) include polyfunctional isocyanate compounds, polyfunctional silane compounds, polyfunctional acid anhydrides, N-methylol group-containing compounds, and melamine compounds. Moreover, as a compound (e2), a polyfunctional epoxy compound, a polyfunctional amine compound, a polyfunctional aziridine compound, a polyfunctional carbodiimide compound, a polyfunctional oxazoline compound, a metal chelate compound etc. are mentioned, for example. In particular, when the acid value of the pressure sensitive adhesive resin is relatively high, it is preferable to use the compound (e2), and in particular, an epoxy compound, an aziridine compound, a carbodiimide compound, an oxazoline compound, or a metal chelate compound is more preferably used. It is done. Further, when the hydroxyl value of the pressure-sensitive adhesive resin is relatively high, it is preferable to use the compound (e1), and more preferably a polyfunctional isocyanate compound or a polyfunctional silane compound. These are preferably used because they have excellent adhesion to the adherend of the pressure-sensitive adhesive layer after the crosslinking reaction and adhesion to the sheet-like substrate. Further, as a reactive compound, it is one of preferable modes to use the compound (e1) and the compound (e2) in combination.

  Examples of the polyfunctional epoxy compound include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol. Diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) And cyclohexane.

  Examples of the polyfunctional aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropane-tri -Β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane Tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) buty Rate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2′-bis Hydroxymethylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N′-ethyleneurea, 1,6-hexa And methylenebis-N, N′-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, and the like. It is done.

  As the polyfunctional carbodiimide compound, for example, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide can be used.

  Moreover, as a polyfunctional carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used. Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.

  As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  Examples of such polyfunctional carbodiimide compounds include the Carbodilite series manufactured by Nisshinbo Industries, Ltd. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

  As the polyfunctional oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′-ethylenebis (2-oxazoline) is used. 2,2′-ethylenebis (4-methyl-2-oxazoline), 2,2′-propylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′- Hexamethylene bis (2-oxazoline), 2,2′-octamethylene bis (2-oxazoline), 2,2′-p-phenylene bis (2-oxazoline), 2,2′-p-phenylene bis (4 4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4-phenyl) Lu-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2′-o-phenylenebis (2-oxazoline), 2, 2'-o-phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'- Bis (4-ethyl-2-oxazoline), 2,2′-bis (4-phenyl-2-oxazoline) and the like can be mentioned. Or copolymerization of vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline with other monomers copolymerizable with these vinyl monomers It may be combined.

  Examples of the polyfunctional isocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', Examples thereof include 4 "-triphenylmethane triisocyanate.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

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

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane. Diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like can be mentioned.

  Moreover, the trimethylol propane adduct body of the said polyisocyanate, the trimer which has an isocyanurate ring, etc. can be used. Furthermore, polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and polyisocyanate-modified products thereof 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 selected from isocyanurate groups, or a modified product having two or more of these groups can be used. . A reaction product of polyol and diisocyanate can also be used as the polyfunctional isocyanate compound.

  Among these polyfunctional isocyanate compounds, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), xylylene diisocyanate, 4,4 ′ Use of a non-yellowing or hard-yellowing polyisocyanate compound such as methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI) is particularly preferred from the viewpoint of weather resistance, heat resistance, and moist heat resistance.

  When a polyfunctional isocyanate compound is used as the reactive compound (E), a known catalyst can be used as necessary to accelerate the reaction. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use a single compound or plural compounds.

  Examples of the metal chelate compound include compounds in which a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium is coordinated to acetylacetone or ethyl acetoacetate. Can be mentioned.

Examples of the polyfunctional silane compound include a silane coupling agent. Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyl. A silane compound having two methacryloxy groups such as methyldiethoxysilane, an alkyl group and an alkoxy group;
a silane compound having two acryloxy groups, an alkyl group and an alkoxy group, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-acryloxypropylmethyldimethoxysilane;
Silane compounds having three (meth) acryloxyalkyl groups and three alkoxy groups such as γ-methacryloxymethyltrimethoxysilane and γ-acryloxymethyltrimethoxysilane;
Alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane;
Alkoxysilanes having an alkyl group 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.

  Examples of the N-methylol group-containing compound include amino resins and phenol resins, and examples thereof include addition compounds of partial compounds such as urea, melamine, benzoguanamine, phenol, cresols, bisphenols and formaldehyde, or partial condensates thereof.

  The polyfunctional acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but includes tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, And maleic anhydride copolymer resin. In addition, polycarboxylic acids, polycarboxylic acid esters, polycarboxylic acid half esters, and the like that can be converted into anhydrides through a dehydration reaction during the reaction are included in the polyfunctional acid anhydrides referred to in the present invention.

  More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-" manufactured by Shin Nippon Chemical Co., Ltd. 10 ”,“ Licacid MTA-15 ”,“ Licacid TMEG series ”,“ Licacid TDA ”, and the like.

  These reactive compounds may be used alone or in combination.

  The pressure-sensitive adhesive composition of the present invention preferably contains 0.001 to 20 parts by weight of the reactive compound (E) with respect to 100 parts by weight of the pressure-sensitive adhesive resin having antistatic properties. It is more preferable to contain 0.01-10 weight part. When the amount of the reactive compound (E) used exceeds 20 parts by weight, the adhesiveness of the resulting pressure-sensitive adhesive composition tends to decrease, the cohesive strength of the resin layer is low, and stability and durability during repeated use. It is inferior in property and is not preferable. On the other hand, when the amount is less than 0.001 part by weight, a sufficient cross-linked structure cannot be obtained, so that the cohesive force tends to be reduced, and the heat resistance and heat-and-moisture resistance tend to be reduced. The resin composition is three-dimensionally cross-linked by the reaction between the hydroxyl group or carboxyl group in the pressure-sensitive adhesive resin having antistatic properties and the reactive functional group in the reactive compound. Not only can the adhesiveness be ensured, but also heat resistance and heat-and-moisture resistance under conditions that are harsher than conventional ones can be improved, so that it can be preferably used for optical members.

  In the pressure-sensitive adhesive composition of the present invention, various resins, coupling agents, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weathering stabilizers, as long as the effects of the present invention are not impaired. , Tackifier, plasticizer, filler, anti-aging agent and the like may be blended.

  By using the pressure-sensitive adhesive composition of the present invention, a laminated product (hereinafter referred to as “adhesive sheet”) composed of an adhesive layer and a sheet-like substrate can be obtained. For example, an adhesive sheet can be obtained by coating, drying and curing the pressure-sensitive adhesive composition of the present invention on various sheet-like substrates.

  When applying a pressure-sensitive adhesive composition, an appropriate liquid medium, for example, a hydrocarbon solvent such as toluene, xylene, hexane or heptane; an ester solvent such as ethyl acetate or butyl acetate; a ketone such as acetone or methyl ethyl ketone Viscosity can be adjusted by adding organic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as diethyl ether, methoxytoluene and dioxane, and other hydrocarbon solvents. In addition, the pressure-sensitive adhesive composition can be heated to reduce the viscosity. However, when a polyfunctional isocyanate compound is used as the reactive compound (E), it is not preferable to use a solvent containing a hydroxyl group.

  Examples of the sheet-like base material include cellophane, various plastic sheets, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood and the like in a flat shape. Various base materials can be used alone or in a multi-layered state in which a plurality of base materials are laminated. Further, the surface can be peeled off.

  Various plastic sheets are also called various plastic films, such as polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, polyolefin resin film such as 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 film, etc. And the like.

  When the pressure-sensitive adhesive composition contains a liquid medium such as an organic solvent or water after the pressure-sensitive adhesive composition is applied to the sheet-like base material by an appropriate method according to a conventional method, the liquid medium If the pressure-sensitive adhesive composition does not contain a liquid medium that should be volatilized, the adhesive layer in the molten state is cooled and solidified, and pressure-sensitive adhesive is applied to the sheet-like substrate. An agent layer can be formed. The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 1 μm to 100 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 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 coater, Various coating methods such as a knife coater, a reverse coater, and a spin coater can be used. There is no particular limitation on the drying method, and examples include those using hot air drying, infrared rays or a reduced pressure method. 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 surface protective film of the present invention is a film for mechanically or electrically protecting the surface of an adherend for a predetermined period, and is used for optical components such as liquid crystal panels, plasma displays, polarizing plates, and CRTs (CRTs). Used to temporarily protect the surface. The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention is laminated on the surface of a plastic film substrate such as polyethylene or polypropylene. On the other surface of the pressure-sensitive adhesive layer, a sheet-like base material subjected to a release treatment can be laminated.

  The laminate of the present invention is a so-called sheet (also referred to as “film” as described above) optical member having various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film. And a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention. 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) the 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 applied to the surface of the pressure-sensitive adhesive layer. Or (i) coating a sheet-like optical member with a pressure-sensitive adhesive composition, drying, and laminating the release-treated surface of the sheet-like substrate that has been peel-treated on the surface of the pressure-sensitive adhesive layer Can be obtained.

  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 / glass member for liquid crystal cell” can be obtained.

  The pressure-sensitive adhesive composition using the antistatic pressure-sensitive adhesive resin of the present invention is different from the conventional pressure-sensitive adhesive composition having antistatic properties in which an antistatic agent is blended in the resin. Since the resin and the antistatic agent are chemically bonded by the graft reaction, the antistatic agent bleeds or contaminates the adherend under the passage of time, heat, or moist heat after forming the adhesive layer. And the adhesive strength does not decrease.

  The resin for pressure-sensitive adhesives of the present invention is suitable for use as an optical member, and in addition to general labels and seals, paints, elastic wall materials, coating waterproofing materials, flooring materials, tackifiers, adhesives, laminates Structural adhesives, sealing agents, molding materials, surface modification coating agents, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foam (Hard, semi-rigid, soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent Resin for artificial marble, impact modifier for artificial marble, resin for ink, film (laminate adhesive, protective film) Etc.), laminated glass resin, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

[Synthesis of acrylic resin]
(Synthesis Example 1)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and reflux condenser, 200 parts of butyl acrylate, 8 parts of 2-hydroxyethyl acrylate, 625 parts of ethyl acetate, 2,2′-azo as a polymerization initiator 0.3 parts of bisisobutyronitrile was charged, and gently stirred while introducing nitrogen gas, and the temperature in the flask was raised to 65 ° C. While maintaining the temperature at 65 ° C., a polymerization reaction was performed for about 6 hours to obtain an acrylic resin solution A-1. The acrylic resin A-1 had a weight average molecular weight of 900,000, a glass transition temperature of −54 ° C., and a solid content of 25%.

(Synthesis Example 2)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and reflux condenser, 55 parts of butyl acrylate, 25 parts of 2-ethylhexyl acrylate, 5 parts of 2-hydroxyethyl acrylate, 10 parts of 2-methoxyethyl acrylate, Charge 75 parts of ethyl acetate, 15 parts of acetone, and 0.2 part of 2,2′-azobisisobutyronitrile as a polymerization initiator, and gently stir while introducing nitrogen gas to adjust the temperature in the flask to that of the solvent. Raised to reflux temperature. While maintaining the reflux temperature, the polymerization reaction was carried out for about 7 hours. After completion of the reaction, it was diluted with ethyl acetate to obtain an acrylic resin solution A-2. The acrylic resin A-2 had a weight average molecular weight of 540,000, a glass transition temperature of −60 ° C., and a solid content of 25%.

(Synthesis Example 3)
As a polymerization initiator, 79 parts of butyl acrylate, 20 parts of methoxyethyl acrylate, 1 part of 4-hydroxybutyl acrylate, 100 parts of ethyl acetate, a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and reflux condenser. 0.22 parts of 2,2′-azobisisobutyronitrile was charged, and the temperature in the flask was raised to 60 ° C. by gently stirring while introducing nitrogen gas. The polymerization reaction was carried out for about 6 hours while maintaining 60 ° C. After completion of the reaction, it was diluted with ethyl acetate to obtain an acrylic resin solution A-3. The acrylic resin A-3 had a weight average molecular weight of 1,400,000, a glass transition temperature of −50 ° C., and a solid content of 25%.

[Synthesis of urethane resin]
(Synthesis Example 4)
To a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel, polyester polyol P-1010 (bifunctional polyester polyol, OH value 112 mgKOH / g, number average molecular weight 1,000, Kuraray) 68 parts, polyether polyol G-3000B (trifunctional polyether polyol, PO chain 100% by weight, OH value 56 mgKOH / g, number average molecular weight 3,000, manufactured by ADEKA) 265 parts, toluene 125 parts, catalyst As described above, 0.03 part of iron 2-ethylhexanoate and 0.04 part of lead naphthenate are charged and stirred. After the solution was sufficiently uniform, 24 parts of hexamethylene diisocyanate (manufactured by Sumitomo Bayer) was dropped from the dropping funnel over 1 hour, and a polymerization reaction was further performed at 90 ° C. for 3 hours. After confirming the disappearance of the isocyanate group with an infrared spectrophotometer, the mixture was cooled and 115 parts of toluene was added to obtain a urethane resin solution B-1. This urethane resin solution B-1 was colorless and transparent, the weight average molecular weight was 50,000, the glass transition temperature was -62 ° C, and the solid content was 60%.

(Synthesis Example 5)
To a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel, polyester polyol P-1010 (bifunctional polyester polyol, OH value 112 mgKOH / g, number average molecular weight 1,000, Kuraray) 68 parts, polyether polyol GL-3000 (trifunctional polyether polyol, EO / PO = 20/80% by weight, OH value 56 mgKOH / g, number average molecular weight 3,000, manufactured by ADEKA) 265 parts, toluene 125 parts, 0.09 part dibutyltin dilaurate and 0.04 part tin 2-ethylhexanoate as a catalyst are charged and stirred. After the solution was sufficiently uniform, 24 parts of hexamethylene diisocyanate (manufactured by Sumitomo Bayer) was dropped from the dropping funnel over 1 hour, and a polymerization reaction was further performed at 90 ° C. for 2 hours. After confirming the disappearance of the isocyanate group with an infrared spectrophotometer, the mixture was cooled and 115 parts of toluene was added to obtain a urethane resin solution B-2. The urethane resin solution B-2 was colorless and transparent, had a weight average molecular weight of 70,000, a glass transition temperature of −56 ° C., and a solid content of 60%.

(Synthesis Example 6)
To a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel, polyester polyol P-1010 (bifunctional polyester polyol, OH value 112 mgKOH / g, number average molecular weight 1,000, Kuraray) 68 parts), 20 parts of dimethyl polyethylene glycol, 50 parts of toluene, and 0.1 part of dioctyltin dilaurate as a catalyst are charged and stirred. After the solution became sufficiently uniform, 9 parts of hexamethylene diisocyanate (manufactured by Sumitomo Bayer) was dropped from the dropping funnel over 1 hour, and a polymerization reaction was further performed at 90 ° C. for 2 hours. After confirming disappearance of the isocyanate group with an infrared spectrophotometer, the mixture was cooled and 15 parts of toluene was added to obtain a urethane resin solution B-3. This urethane resin solution B-3 was colorless and transparent, the weight average molecular weight was 120,000, the glass transition temperature was -64 ° C, and the solid content was 60%.

[Synthesis of polyester resin]
(Synthesis Example 7)
A four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a water separator was charged with a polyvalent carboxylic acid component and a polyhydric alcohol component at the following ratios, respectively.

[Polymerization tank]
Sebacic acid 232.76 parts Isophthalic acid 215.70 parts 1,4-butanediol 53.40 parts 1,6-hexanediol 70.65 parts 2-methyl-1,3-propanediol 77.67 parts 2-butyl- 2-ethyl-1,3-propanediol 96.22 parts trimethylolpropane 3.61 parts

  After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 160 ° C. in a nitrogen atmosphere while stirring. After confirming dehydration at 160 ° C., the temperature was gradually raised to 240 ° C. over about 8 hours to conduct dehydration reaction. Next, when the acid value became 15 mgKOH / g or less, the temperature was lowered to 150 ° C., 0.1 part of tetrabutyl titanate was added as a catalyst, and the pressure was gradually reduced while raising the temperature. The reaction was carried out at 5 ° C. for 5 hours, and when the molecular weight was reached, the reaction was terminated by dissolving in a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to obtain a polyester resin solution C-1. This polyester resin solution C-1 was light yellow and transparent, and had a weight average molecular weight (Mw) of 120,000, Mw / Mn = 2.96, a glass transition temperature of -35 ° C., and a solid content of 50%.

(Synthesis Example 8)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and water separator, 19.8 parts of sebacic acid as the polyvalent carboxylic acid component, polycarbonate diol (Daicel) as the polyhydric alcohol component 200.0 parts by chemical industry, PLACEL CD220PL, OH value: 55.1 mg KOH / g) 0.1 parts of tetra-n-butyl titanate were charged as a catalyst. After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 160 ° C. in a nitrogen atmosphere while stirring. After confirming dehydration at 160 ° C., the temperature was gradually raised to 240 ° C. over about 8 hours to conduct dehydration reaction. Next, when the acid value became 15 mgKOH / g or less, the temperature was lowered to 150 ° C., 0.1 part of tetrabutyl titanate was added as a catalyst, and the pressure was gradually reduced while raising the temperature. The reaction was carried out at 5 ° C. for 5 hours. When the molecular weight was reached, the reaction was terminated by dissolving in a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to obtain a polyester resin solution C-2. This polyester resin solution C-2 was light yellow and transparent, and had a weight average molecular weight (Mw) of 80,000, Mw / Mn = 1.96, a glass transition temperature of −46 ° C., and a solid content of 50%.

(Synthesis Example 9)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and water separator, 55.4 parts of sebacic acid as the polyvalent carboxylic acid component, polycarbonate diol (Kuraray) as the polyhydric alcohol component PNOC-2000, OH number: 53.7 mgKOH / g) 140 parts, Daomer diol (Uniquema, PRIPOL-2033) 60 parts, trimethylolpropane 9.8 parts, tetra-n-butyl as catalyst 0.1 part of titanate was charged. After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 160 ° C. in a nitrogen atmosphere while stirring. After confirming dehydration at 160 ° C., the temperature was gradually raised to 240 ° C. over about 8 hours to conduct dehydration reaction. Next, when the acid value became 15 mgKOH / g or less, the temperature was lowered to 150 ° C., 0.1 part of tetrabutyl titanate was added as a catalyst, and the pressure was gradually reduced while raising the temperature. The reaction was carried out at 5 ° C. for 5 hours. When the molecular weight was reached, the reaction was terminated by dissolving in a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to obtain a polyester resin solution C-3. This polyester resin solution C-3 was light yellow and transparent, and had a weight average molecular weight (Mw) of 150,000, Mw / Mn = 3.8, a glass transition temperature of −41 ° C., and a solid content of 50%.

[Synthesis of ionic solid having radical polymerizability]
(Synthesis Example 10) Synthesis of Compound (1) 342 parts of sodium tetraphenylborate was dissolved in 1 L of ion-exchanged water to obtain an aqueous solution of sodium tetraphenylborate. To this aqueous solution, an aqueous solution of trimethylvinyloxycarbonylmethylammonium chloride obtained by dissolving 210 parts of trimethylvinyloxycarbonylmethylammonium chloride in 1 L of ion-exchanged water was gradually added. Compound (1) was obtained by filtering the precipitate. Elemental analysis [MT-5, manufactured by Yanagimoto Seisakusho Co., Ltd., the same applies below] (Composition formula: C ₃₁ H ₃₄ BNO ₂ calculated value (%): C, 80.34; H, 7.40; N, 3.02) Value (%): C, 80.41; H, 7.33; N, 2.98).

(Synthesis Example 11) Synthesis of Compound (2) 194 parts of sodium tetrakis (pentafluorophenyl) borate was dissolved in 1 L of ion-exchanged water to obtain an aqueous solution of sodium tetrakis (pentafluorophenyl) borate. [2- (Methacryloyloxy) ethyl] trimethylammonium chloride aqueous solution obtained by dissolving 63 parts of [2- (methacryloyloxy) ethyl] trimethylammonium chloride in 1 L of ion-exchanged water was gradually added to this aqueous solution. The precipitate was filtered to obtain compound (2). Elemental analysis (composition formula: C ₃₁ H ₃₄ BNO ₂ calculated value (%): C, 46.56; H, 2.13; N, 1.65 Actual value (%): C, 46.62; H, 2 .03; N, 1.79).

(Synthesis Example 12) Synthesis of Compound (3) Compound (3) was obtained in the same manner as in Synthesis Example 10 except that allyltrimethylammonium bromide was used instead of trimethylvinyloxycarbonylmethylammonium chloride. Elemental analysis (composition formula: C ₃₀ H ₃₄ BN calculated value (%): C, 85.91; H, 8.17; N, 3.34 measured value (%): C, 85.81; H, 8. 25; N, 3.33).

(Synthesis Example 13) Synthesis of Compound (4) Compound (4) was obtained in the same manner as in Synthesis Example 12, except that sodium tetrakis (pentafluorophenyl) borate was used instead of sodium tetraphenylborate. Elemental analysis (composition formula: C ₃₀ H ₁₄ BF ₂₀ N calculated value (%): C, 46.24; H, 1.81; N, 1.80 actual value (%): C, 46.18; H, 1.74; N, 1.89).

  The raw materials were purchased from reagent manufacturers such as Aldrich, Tokyo Kasei, Nacalai Tesque and Merck.

  As for borates which are difficult to obtain, JP-A-62-213293, JP-A-62-277307, JP-A-6-247980, JP-A-6-247981, JP-A-8-311074. JP-A-10-330281, JP-A-10-310589, JP-A-11-292893, JP-A-2000-143671, JP-A-2003-238572, JP-A-2003-335786, JP-A-2004-43435, U.S. Pat. No. 398236, U.S. Pat. No. 5,473,036, Journal of Organometallic Chemistry, Vol. 1964, Vol. 245, Journal of Organic Chemistry, 1967. Synthesis was carried out with reference to Volume 8, Page 411 and the like.

[Grafting reaction of radical polymerizable antistatic agent]
(Synthesis Example 14)
A four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel was charged with 200 parts of the polyester-based resin solution C-1 (solid content 50%) obtained in Synthesis Example 3 and stirred. The temperature inside the flask was raised to 80 ° C. To the dropping funnel, 10 parts of the radically polymerizable antistatic agent of compound (1) obtained in Synthesis Example 10, 34 parts of ethyl acetate, and 2.2 parts of tertiary butyl peroxy-2-ethylhexanoate as an initiator were added. The mixture was added and added dropwise over 30 minutes. After completion of the dropwise addition, 0.2 part of tertiary butyl peroxy-2-ethylhexanoate was added twice every 1 hour, and the reaction was performed after 1 hour to obtain a resin solution CG-1 for pressure-sensitive adhesive. The solid content of this resin was 45%.

(Synthesis Examples 15 to 34)
In the same manner as in Synthesis Example 14, a graft reaction was performed according to the formulation in Table 1 to obtain pressure-sensitive adhesive resins (CG-2 to CG-21).

Aqualon BC-10, Aqualon BC-20: Aqualon BC-05: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether anionic surfactant Aqualon RN-10: Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether Nonionic surfactant Aqualon KH-10: Daiichi Kogyo Seiyaku Co., Ltd., reactive alkyl ether anionic surfactant Antox SAD: Nihon Emulsifier Co., Ltd., reactive alkyl ester anionic surfactant

(Synthesis Examples 35-55)
In the same manner as in Synthesis Example 14, a graft reaction was performed according to the formulation in Table-2 to obtain pressure-sensitive adhesive resins (AG-1 to AG-21).

Aqualon BC-10, Aqualon BC-20: Aqualon BC-05: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether anionic surfactant Aqualon RN-10: Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether Nonionic surfactant Aqualon KH-10: Daiichi Kogyo Seiyaku Co., Ltd., reactive alkyl ether anionic surfactant Antox SAD: Nihon Emulsifier Co., Ltd., reactive alkyl ester anionic surfactant

(Synthesis Examples 56 to 76)
In the same manner as in Synthesis Example 14, a graft reaction was performed according to the formulation shown in Table-3 to obtain pressure-sensitive adhesive resins (BG-1 to BG-21).

Aqualon BC-10, Aqualon BC-20: Aqualon BC-05: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether anionic surfactant Aqualon RN-10: Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether Nonionic surfactant Aqualon KH-10: Daiichi Kogyo Seiyaku Co., Ltd., reactive alkyl ether anionic surfactant Antox SAD: Nihon Emulsifier Co., Ltd., reactive alkyl ester anionic surfactant

[Copolymerization of antistatic agent having radical polymerizable functional group and acrylic monomer]
(Synthesis Example 77)
In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser, and dropping funnel, 80 parts of ethyl acetate was charged, and the temperature in the flask was raised to 77 ° C. while stirring. Next, in the dropping funnel, 30 parts of antistatic agent Aqualon BC-05 (reactive alkylphenyl ether anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) having a radical polymerizable functional group, 30 parts of butyl acrylate, tertiary butyl 0.3 parts of peroxy-2-ethylhexanoate and 60 parts of ethyl acetate were mixed and added dropwise over 1 hour while maintaining a temperature of 77 ° C. After completion of the dropwise addition, 0.03 part of tertiary butyl peroxy-2-ethylhexanoate was added twice every 1 hour, and a reaction was performed after 1 hour to obtain a copolymer resin D. The polymer had a broad molecular weight distribution with a number average molecular weight of 514 and a weight average molecular weight of 3420. The solid content was 27%.

<Measurement of solid content>
About 1 g of each resin solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated to obtain the solid content (unit:%).

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined in terms of polystyrene. .

<Measurement of glass transition temperature (Tg)>
The measurement was performed by connecting a “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) to a robot DSC (differential scanning calorimeter) “RDC220” (manufactured by Seiko Instruments Inc.). About 10 mg of sample was weighed in an aluminum pan and set in a DSC apparatus (reference: the same type of aluminum pan without sample). After heating at 300 ° C. for 5 minutes, using liquid nitrogen − Rapid cooling was performed to 120 ° C. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg) was calculated from the obtained DSC chart (unit: ° C.).

[Adjustment of pressure-sensitive adhesive composition]
Example 1
The pressure-sensitive adhesive resin solution (CG-1) obtained in Synthesis Example 14 (solid content 45%) was diluted with toluene to a solid content of 40%, and trimethylol was added as a reactive compound to 250 parts by weight of the resin solution. Propane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) 5.5 parts by weight and, as a catalyst, 3.0 parts by weight of dibutyltin dilaurate (1% by weight ethyl acetate solution) were added and stirred well. Thus, a pressure-sensitive adhesive composition (CK-1) of the present invention was obtained.

(Examples 2 to 21)
Using the pressure-sensitive adhesive resin solutions (CG-2 to CG-21) obtained in Synthesis Examples 15 to 34, pressure-sensitive adhesive compositions (CK-2 to CK- 21) Obtained.

(Example 22)
The pressure-sensitive adhesive resin solution (AG-1) obtained in Synthesis Example 35 (solid content: 22%) was diluted with toluene to a solid content of 20%, and trimethylol was added as a reactive compound to 500 parts by weight of this resin solution. Propane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) 1.0 part by weight and dibutyltin dilaurate (1% by weight ethyl acetate solution) 0.5 part by weight as a catalyst were added and stirred well. Thus, a pressure-sensitive adhesive composition (AK-1) of the present invention was obtained.

(Examples 23 to 42)
Using the pressure-sensitive adhesive resin solutions (AG-2 to AG-21) obtained in Synthesis Examples 36 to 55, pressure-sensitive adhesive compositions (AK-2 to AK-) were prepared in the same manner as in Example 22. 21) Obtained.

(Example 43)
The pressure-sensitive adhesive resin solution (BG-1) obtained in Synthesis Example 56 (solid content 55%) was diluted with toluene to a solid content of 50%, and trimethylol was added as a reactive compound to 200 parts by weight of the resin solution. Propane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) 2.5 parts by weight and 1.5 parts by weight of dibutyltin dilaurate (1% by weight ethyl acetate solution) as a catalyst were added and stirred well. Thus, a pressure-sensitive adhesive composition (BK-1) of the present invention was obtained.

(Examples 44 to 63)
Using the pressure-sensitive adhesive resin solutions (BG-2 to BG-21) obtained in Synthesis Examples 57 to 76, the pressure-sensitive adhesive composition (BK-2 to BK-) was prepared in the same manner as in Example 43. 21) Obtained.

[Formation of pressure-sensitive adhesive layer]
The pressure sensitive adhesive composition (CK-1 to 21, AK-1 to 21, BK-1 to 21) obtained in Examples 1 to 63 was applied to the release surface of the release paper, and the thickness of the dry coating film was Coating was performed to 25 μm, and drying was performed at 100 ° C. for 2 minutes. A 25 μm-thick polyethylene terephthalate film was laminated on the formed pressure-sensitive adhesive layer, and aged for one week at a temperature of 23 ° C. in this state to obtain a test pressure-sensitive adhesive sheet. Using this test adhesive sheet, the surface resistance value, adhesive force (remaining trace), holding power, and transparency were evaluated by the methods shown below. The results are shown in Tables 4, 5, and 6.

TMP / TDI: Trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L)
DBTDLA: Dibutyltin dilaurate

TMP / TDI: Trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L)
DBTDLA: Dibutyltin dilaurate

TMP / TDI: Trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L)
DBTDLA: Dibutyltin dilaurate

[Adjustment of pressure-sensitive adhesive composition]
(Comparative Example 1)
Polyester resin solution C-1 (solid content 50%) obtained in Synthesis Example 7 was diluted with toluene to a solid content of 40%, and trimethylolpropane / tolylene diisocyanate as a reactive compound in 250 parts by weight of this resin solution. Trimer adduct (Nihon Polyurethane Kogyo Co., Ltd., Coronate L) 5.5 parts by weight and 3.0 parts by weight of dibutyltin dilaurate (1% by weight ethyl acetate solution) as a catalyst were added and stirred well. An adhesive composition was obtained.

(Comparative Example 2)
Polyester resin solution C-1 (solid content 50%) obtained in Synthesis Example 7 was diluted with toluene to a solid content of 40%, and trimethylolpropane / tolylene diisocyanate as a reactive compound in 250 parts by weight of this resin solution. Obtained in 5.5 parts by weight of a trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L), 3.0 parts by weight of dibutyltin dilaurate (1% by weight ethyl acetate solution) as a catalyst, and obtained in Synthesis Example 10 as an antistatic agent 2.0 parts of the obtained compound (1) was added and stirred well to obtain a pressure-sensitive adhesive composition.

(Comparative Examples 3 to 21)
Polyester resin solution C-1 obtained in Synthesis Example 7 (solid content 50%), acrylic resin solution A-1 obtained in Synthesis Example 1 (solid content 25%), urethane obtained in Synthesis Example 4 Using each of the resin resin solutions B-1 (solid content 60%), a pressure-sensitive adhesive composition was obtained in the same manner as in Comparative Example 1 according to the formulation in Table-7. The polyester resin solution C-1 was diluted with toluene to a solid content of 40%, the acrylic resin solution A-1 was diluted with toluene to a solid content of 20%, and the urethane resin solution B-1 was Diluted with toluene to a solid content of 50% was used.

[Formation of pressure-sensitive adhesive layer]
Comparative Examples 1-21 A pressure-sensitive adhesive sheet for testing was obtained in the same manner as in Example 1 using the obtained pressure-sensitive adhesive composition. Using this test adhesive sheet, the surface resistance value, adhesive force (remaining trace), holding power, and transparency were evaluated by the methods shown below. The results are shown in Table-7.

Aqualon BC-05: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., reactive alkylphenyl ether anionic surfactant IL-A2: manufactured by Guangei Chemical Co., Ltd., aliphatic amine ionic liquid Esocard C / 12: manufactured by Lion Co., alkylbis chloride (2-hydroxyethyl) methylammonium, cationic surfactant:
TMP / TDI: Trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L)
DBTDLA: Dibutyltin dilaurate

<Measurement method of surface resistance value>
The release paper of the pressure-sensitive adhesive sheet for test was peeled off, and the surface resistance value of the exposed pressure-sensitive adhesive layer surface was measured using a surface resistance measurement device (AD83ANTU, R8340U ULTRA HIGH RESISTANCE METER). The measurement conditions are: temperature: 23 ° C., humidity: 50% RH, generated voltage: 500 V, charge time: 60 seconds, discharge time: 10 seconds. Unit: Ω / □. The surface resistance value is set to a practical level of 1 × 10 ¹² or less.

<Measurement method of adhesive strength>
The release paper of the test adhesive sheet cut to 20 mm × 100 mm was peeled off, and the exposed surface of the pressure-sensitive adhesive layer was attached to a glass plate having a thickness of 0.4 mm and roll-bonded according to the JIS method. This sample was allowed to stand for 24 hours in a constant temperature and humidity room at 23 ° C.-65% RH, and then the 180 ° peel strength was measured with a tensile tester. The measurement conditions were a pulling speed: 300 mm / min. Unit: gf / 25 mm. Adhesive strength: 1700 gf / 25 mm or more is a practical level.

<Contamination evaluation method>
The surface of the glass after measuring the adhesive force was observed, and the state of contamination of the glass surface with the pressure-sensitive adhesive was visually evaluated. The evaluation criteria are shown below. In addition, (circle) shall be a practical use level and (triangle | delta) and x shall be unpractical.
○: “There is no adhesion or contamination from the pressure-sensitive adhesive on the glass surface.”
Δ: “A thin spider is formed on the glass surface.”
×: “A part of the pressure-sensitive adhesive remains as a residue on the glass surface.”

<Measurement method of holding power>
Remove the release paper of the test adhesive sheet cut to 20mm x 100mm, and stick the exposed 20mm x 20mm part of the pressure-sensitive adhesive layer to a 1mm thick stainless steel plate whose surface is polished with water-resistant sandpaper. Then, roll pressure bonding was performed according to the JIS method. This sample was held for 70,000 seconds under conditions of temperature: 40 ° C., load: 1 kg with a constant temperature and humidity shear tester manufactured by Tester Sangyo Co., Ltd. Was measured. Evaluation was performed as follows. Those that fall off in less than 70,000 seconds are not practical, and those that do not fall off are not practical if the deviation is 0.5 mm or more.
NC: “No dropout or misalignment”
There was no dropout, but the one with a deviation showed the length of the deviation. (Unit: mm)
Those that dropped out indicated the time when they dropped out. (Unit: seconds)

<Transparency evaluation method>
The release paper of the pressure-sensitive adhesive sheet for test was peeled off, and the exposed pressure-sensitive adhesive layer surface was attached to the glass surface, followed by roll pressure bonding according to the JIS method. This sample was allowed to stand in a constant temperature and humidity room at 60 ° C.-95% RH for 1 week, and then visually evaluated from the glass surface. The evaluation criteria are shown below. In addition, (circle) shall be a practical use level and (triangle | delta) and x shall be unpractical.
○: “Colorless and transparent.”
Δ: “There are very few spiders.”
X: “White turbidity and aggregates are observed.”

  As described above, the pressure-sensitive adhesive composition using the pressure-sensitive adhesive resin obtained by graft-reacting the antistatic agent having the radical polymerizable functional group of the present invention to the resin has a low surface resistance value and an antistatic property. It was found to be excellent and excellent in adhesive strength, stain resistance, holding power and transparency. On the other hand, the pressure-sensitive adhesive composition of the comparative example to which an antistatic agent is added may exhibit antistatic ability, but satisfies all of adhesive strength, stain resistance, holding power, and transparency. Was not obtained.

Claims (10)

  Peroxidizing the antistatic agent (D) having a radical polymerizable functional group with respect to at least one resin selected from the acrylic resin (A), the urethane resin (B), and the polyester resin (C). A pressure-sensitive adhesive resin having a glass transition temperature of −80 to 0 ° C., which is obtained by a graft reaction using a physical initiator.   The antistatic agent (D) having a radical polymerizable functional group is at least selected from the group consisting of an ionic solid (d1) having a radical polymerizable functional group and a surfactant (d2) having a radical polymerizable functional group. The pressure-sensitive adhesive resin according to claim 1, wherein the resin is one type.   The pressure-sensitive adhesive resin according to claim 1 or 2, wherein the acrylic resin (A) has a weight average molecular weight of 500,000 to 1,500,000.   The pressure-sensitive adhesive resin according to claim 1 or 2, wherein the urethane resin (B) has a weight average molecular weight of 30,000 to 500,000.   The pressure-sensitive adhesive resin according to claim 1 or 2, wherein the polyester resin (C) has a weight average molecular weight of 30,000 to 500,000.   A pressure-sensitive adhesive composition comprising the pressure-sensitive adhesive resin according to claim 1 and a reactive compound (E) capable of reacting with the pressure-sensitive adhesive resin.   The reactive compound (E) is at least one selected from the group consisting of a polyfunctional epoxy compound, a polyfunctional aziridine compound, a polyfunctional carbodiimide compound, a polyfunctional oxazoline compound, a polyfunctional isocyanate compound, and a metal chelate compound. The pressure-sensitive adhesive composition according to claim 6.   A surface protective film comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to claim 6 or 7 on the surface of a plastic film substrate.   A laminate in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to claim 6 or 7 is laminated on an optical member.   A liquid crystal cell member comprising a liquid crystal cell glass member, a pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition according to claim 6, and an optical member.