JP2008150544A - Antistatic acrylic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic acrylic resin composition usable for a coating, an adhesive and the like, which is transparent, shows little development of static electricity during release, does not show reduction in ionic conductivity even after crosslinked, and, in particular, is suitable as an adhesive layer for surface protective films for optical members such as polarizing plates used for manufacturing liquid crystal displays. <P>SOLUTION: The antistatic acrylic resin composition comprises an acrylic resin (A) having a hydroxy group, an isocyanurate-modified hexamethylene diisocyanate (B), a trimethylolpropane-modified diisocyanate compound (C), and an ionic compound (D). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic acrylic resin composition. More specifically, the present invention relates to an antistatic acrylic resin composition having excellent transparency used for packaging materials for electronic and optical parts.

Countermeasures against static electricity are required for packaging materials for electronic parts and optical parts typified by IC chips. Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-261774) discloses that an antistatic resin composition containing lithium bis (trifluoromethanesulfonyl) imide as an ionic compound has a high electrostatic dissipation function, sustainability, and molding processing. It is disclosed as an anti-static resin composition having excellent properties and not coloring. However, since lithium bis (trifluoromethanesulfonyl) imide is an expensive material, when the entire molded product is made of the antistatic resin composition, the cost is high, and it can be used only for special applications with high added value. .
Therefore, Patent Document 2 (Japanese Patent Application Laid-Open No. 2003-41194) discloses an antistatic coating excellent in economic efficiency in which a coating film of an antistatic resin composition is formed on the surface of a molded product.

On the other hand, tapes and films have been developed so that the form of the packaging material itself is represented by a protective film for use as a carrier tape or an optical component from a container such as a conventional container.
In particular, the protective film remarkably expands with the spread of liquid crystal displays. As an example of use, transparent films made of polyethylene, polyester, polypropylene, etc. are used for optical parts such as polarizing plates used in liquid crystal displays and laminates equivalent thereto. A film is used by being laminated via an adhesive layer.
The protective film is peeled off from the optical component after being incorporated into a liquid crystal display or the like, but there is a problem of occurrence of trouble that destroys the liquid crystal and the electronic circuit due to static electricity generated at the time of peeling. Simply applying an antistatic resin to the surface of the protective film does not provide a sufficient effect for suppressing static electricity generated during peeling.

Accordingly, an antistatic resin composition having adhesiveness for forming an adhesive layer of a protective film is required. Patent Document 3 (Japanese Patent Application Laid-Open No. 2005-206776) discloses lithium perchlorate and alkylene oxide chains. An acrylic resin-based pressure-sensitive adhesive containing a monomer having the following is disclosed. However, in order to impart releasability, the acrylic resin is cured with a crosslinking agent, thereby inhibiting the molecular motion of the alkylene oxide chain and lowering the ionic conductivity. As a result, with the recent increase in screen size of liquid crystal televisions, the protective film itself is also increased in area and the peeling speed is increased, so that the effect of preventing static electricity generated at the time of peeling is not sufficiently obtained.
JP 2003-261774 A JP 2003-41194 A Japanese Patent Application Laid-Open No. 2005-206776

  The present invention is an antistatic acrylic resin composition that can be used for paints, pressure-sensitive adhesives, and the like, and has an ionic conductivity that does not decrease even after crosslinking, and an optical member such as a polarizing plate used in the production of a liquid crystal display It aims at providing the antistatic acrylic resin composition with few generation | occurrence | production of the static electricity at the time of peeling suitable as an adhesion layer for the surface protection film for the direction.

  That is, the present invention contains an acrylic resin (A) having a hydroxyl group, an isocyanurate modified product (B) of hexamethylene diisocyanate, a trimethylolpropane modified product (C) of a diisocyanate compound, and an ionic compound (D). The present invention relates to an antistatic acrylic resin composition.

  The present invention also relates to the antistatic acrylic resin composition according to the invention, wherein the diisocyanate compound is tolylene diisocyanate.

  In addition, the present invention provides 0.05 to 5 parts by weight of an isocyanurate-modified product of hexamethylene diisocyanate (B) and 100 parts by weight of an acrylic resin (A) having a hydroxyl group, and a trimethylolpropane-modified product of a diisocyanate compound. (C) It is related with the antistatic acrylic resin composition of any one of the said invention characterized by including 0.3-15 weight part.

  The present invention also relates to the antistatic acrylic resin composition according to any one of the above inventions, wherein the ionic compound (D) is an alkali metal organic salt and / or an organic cation-anion salt.

  Moreover, this invention contains 0.01-10 weight part of ionic compound (D) with respect to 100 weight part of acrylic resin (A) which has a hydroxyl group, The antistatic property of any one of the said invention characterized by the above-mentioned. The present invention relates to an acrylic resin composition.

  Furthermore, the present invention is a protective film for optical members, characterized in that an adhesive layer formed from the antistatic acrylic resin composition of any of the above inventions is laminated on at least one surface of a plastic film substrate. About.

  According to the present invention, an antistatic acrylic resin composition that can be used for paints, pressure-sensitive adhesives, etc., and the ion conductivity does not decrease even after crosslinking with a crosslinking agent. An antistatic acrylic resin composition that is suitable as a pressure-sensitive adhesive layer for a surface protective film for optical members and generates less static electricity at the time of peeling can be obtained.

The acrylic resin (A) having a hydroxyl group used in the present invention is synthesized from an acrylic monomer (a1) having a hydroxyl group and, if necessary, other acrylic monomers (a2) copolymerizable therewith. Can do.
The purpose of using the acrylic monomer (a1) having a hydroxyl group in the present invention is to ensure releasability while ensuring adhesion to the adherend. More specifically, an isocyanurate-modified product (B) of hexamethylene diisocyanate (hereinafter referred to simply as “modified product (B)”), which will be used later when forming the adhesive layer. ] And a trimethylolpropane modified product (C) of a diisocyanate compound [hereinafter also simply referred to as “modified product (C)”. ] And a hydroxyl group in the acrylic resin (A) having a hydroxyl group (hereinafter sometimes simply referred to as “acrylic resin (A)”) to form a crosslinked structure. By controlling including the molecular weight of the copolymer (A), it is possible to balance the adhesiveness and the peelability. Therefore, when the sum total of the monomer which comprises acrylic resin (A) is 100 weight%, it is preferable that the acrylic monomer (a1) which has a hydroxyl group is 0.5-30 weight%. More preferably, it is 1 to 10% by weight.
When the acrylic monomer (a1) having a hydroxyl group is less than 0.5% by weight, the cohesive force as the adhesive layer is insufficient, and the peelability is lowered, which is not preferable. If it exceeds 30% by weight, the degree of crosslinking becomes too high, and the tackiness and antistatic property become poor, which is not preferable.

As the acrylic monomer (a1) having a hydroxyl group used in the present invention, a hydroxyalkyl (meth) acrylate having a primary hydroxyl group is preferably used, and among them, the alkyl chain has 3 to 20 carbon atoms. Preferably, it is 4-12.
When the alkyl chain of the hydroxyalkyl (meth) acrylate having a primary hydroxyl group has 2 or less carbon atoms, the modified body (B) and the modified body (C) used as a curing agent inhibit the molecular motion of the resin after crosslinking. For this reason, the antistatic property due to the ionic compound (D) is also lowered, which is not preferable. On the other hand, when it is more than 20, even if the curing agent is increased, the cohesive force as the adhesive layer is insufficient, and the peelability is lowered, which is not preferable.

Specific examples of the hydroxyalkyl (meth) acrylate having a primary hydroxyl group and an alkyl chain having 3 to 20 carbon atoms include 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 18-hydroxystearyl (meth) acrylate, etc. Can be mentioned.
Among the above-mentioned compounds, in the present invention, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (meth) 12-hydroxylauryl acrylate is preferred.
In addition, as the acrylic monomer (a1) having a hydroxyl group, a hydroxyalkyl (meth) acrylate having a secondary or tertiary hydroxyl group, or an alkyl chain having 2 or less carbon atoms within a range not impairing the effects of the present invention. More than 20 hydroxyalkyl (meth) acrylates may be used in combination.

As the monomer (a2) copolymerizable with the acrylic monomer (a1) having a hydroxyl group used in the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) ) Acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, Octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, docosyl (meth) acrylate and (meth) acrylic acid. In the present invention, it is preferable to use an alkyl (meth) acrylate having 4 to 24 carbon atoms in the alkyl chain for copolymerization from the viewpoint of ensuring the adhesiveness. More preferred are t-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
These monomers (a2) can be appropriately selected and used alone or in combination of two or more for the purpose of obtaining desirable physical properties as the antistatic acrylic resin composition. In particular, in order to impart adhesive strength, the type of monomer (a2) can be selected so that the glass transition temperature (hereinafter also referred to as “Tg”) of the resulting acrylic resin (A) is 0 ° C. or lower. preferable.

The weight average molecular weight (Mw) of the acrylic resin (A) obtained by copolymerizing the acrylic monomer (a1) having a hydroxyl group and the other monomer (a2) is preferably 200,000 to 1,000,000. More preferably, it is 300,000 to 700,000.
If it is less than 200,000, it is difficult to obtain the required releasability, and if it exceeds 1,000,000, the viscosity at the time of synthesis becomes too high, and the productivity tends to decrease, which is not preferable.

By the way, some optical members are very thin and fragile, while others are relatively strong. Depending on what kind of adherend the protective film is to be attached to, it is required for the protective film and adhesive layer. The magnitude of the peel force applied is different.
That is, when the fragile optical member is used as an adherend, the peeling force is preferably 200 g / 25 mm or less so as not to damage the adherend when the protective film is peeled off after sticking. More preferably, it is 100 g / 25 mm or less.
On the other hand, when a relatively strong optical member is used as the adherend, the peel force can be allowed to be about 1000 g / 25 mm. In addition, when the peeling force is too low, it may be peeled off from the adherend when not required, which is inconvenient. Specifically, the peel force is preferably 4 g / 25 mm or more.
Further, it is always required that the antistatic acrylic resin composition does not remain on the adherend when it is peeled off, regardless of the adherend.

Next, the isocyanurate modified body (B) of hexamethylene diisocyanate and the trimethylolpropane modified body (C) of the diisocyanate compound used in the present invention will be described.
The isocyanurate-modified product (B) of hexamethylene diisocyanate is a trifunctional isocyanate curing agent formed by trimerizing hexamethylene diisocyanate to form an isocyanurate ring.
The modified trimethylolpropane (C) of a diisocyanate compound is an adduct composed of one molecule of a diisocyanate compound and three molecules of trimethylolpropane, and is a trifunctional isocyanate curing agent.
Examples of the diisocyanate compound constituting the modified product (C) include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylyl Diisocyanate, 1,3-tetramethylxylylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 1,4-bis (Isocyanate methyl) cyclohexane and the like can be mentioned, among which tolylene diisocyanate is preferably used.

The purpose of using the modified body (B) and the modified body (C) in the present invention is to obtain an appropriate adhesive strength as a protective film without impairing the antistatic property.
When only the modified material (B) is used as the curing agent when forming the adhesive layer, a protective film with good antistatic properties can be obtained, but there is a disadvantage that the peel force becomes too low, and it is deposited when not required. Since it will peel off from a body, it is not preferable.
On the other hand, when only the modified body (C) is used as the curing agent, an adequate peeling force may be obtained, but sufficient antistatic properties may not be obtained.
Therefore, in order to overcome the above disadvantages, in the present invention, it is important to use both the modified body (B) and the modified body (C) as a curing agent.

The peeling force of the protective film using the antistatic acrylic resin composition is the cohesive strength of the main component itself constituting the acrylic resin, the main component, the modified body (B) that functions as a curing agent, and the modified material. It is greatly influenced by the situation of crosslinking with the body (C).
Generally, the peeling force can be reduced by using a large amount of a curing agent with respect to the main component. In general, the cohesive force of the main component itself can be increased by increasing the molecular weight of the main component. In the present invention, when a low peeling force of 200 g / 25 mm or less, preferably 100 g / 25 mm or less is required at the time of peeling, a modified product (B) with respect to 100 parts by weight of the main component, that is, the acrylic resin (A). ) 0.05-5 parts by weight and modified body (C) 0.3-15 parts by weight are preferably used, 0.05-4 parts by weight of modified body (B) and modified body (C) 0 More preferably, it is used in an amount of 7 to 10.0 parts by weight.
When the amount of the modified body (B) and the modified body (C) is too small, the effect of crosslinking is hardly exhibited.
On the other hand, when the amount of both is too large, the crosslinking becomes excessive, and the peeling force tends to further decrease, and when it is not necessary, it tends to peel off from the adherend.
Furthermore, since the molecular motion of the resin component of the cured coating film is inhibited and the antistatic effect by the ionic compound (D) described later is lowered, it is not preferable.

Next, the ionic compound (D) will be described.
As an ionic compound (D) used for this invention, the organic salt and / or organic cation-anion salt of an alkali metal can be used preferably. These can be used alone or in combination. Furthermore, examples of the ionic compound (D) include inorganic salts such as lithium perchlorate, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, lithium iodide, and ammonium sulfate. These can be used alone or in combination.
The “organic cation-anion salt” as used in the present invention refers to an organic salt whose cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. May be.
Examples of the alkali metal constituting the organic salt of the alkali metal used in the present invention include lithium, sodium and potassium.
Specific examples of the alkali metal organic salt include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) IN, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) IN, Li (CF ₃ SO ₂ ) ₃ C, KO ₃ S (CF ₂ ) ₃ SO ₃ K, LiO _{3 S (CF 2) 3 SO 3} K , and the like, among these _{LiCF 3 SO 3, Li (CF} 3 SO 2) 2 N, Li (CF 3 SO 2) iN, Li (C 2 F 5 SO 2) _{2 N, Li (C 2 F} 5 SO 2) IN, Li (CF 3 SO 2) 3 C and the like are _{preferable, Li (CF 3 SO 2)} 2 N, Li (CF 3 SO 2) IN, Li (C _{F 5 SO 2) 2 N,} Li (C 2 F 5 SO 2) fluorine-containing lithium imide salt is more preferred, such as IN, in particular (perfluoroalkyl sulfonyl) imide lithium salts are preferred.

The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is composed of an organic substance.
As the cation component, specifically, pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, Examples thereof include a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation.
Examples of the anion component include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , _{^{(CN) 2 N -, C}} 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, CF 3 SO - 2 CF 3 CO) N -, - O 3 S (CF ₂ ) ₃ SO ₃ ^— or the like is used. Among these, an anion component containing a fluorine atom is particularly preferably used because an ionic compound having good ion dissociation properties can be obtained.

As specific examples of the organic cation-anion salt used in the present invention, a compound comprising a combination of the above cation component and anion component is appropriately selected and used. For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium Hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3- Methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindoletetraph Oroborate, 1,2-dimethylindoletetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3- Methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl -3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroe Sulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1- Butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1 -Hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium Tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) Imido, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammoni Mutetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2- Methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium Bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltri Tylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (Trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (trifluoromethanesulfonyl) ) Trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoro Acetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium Bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) ) Imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluorometa) Sulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl -N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylammonium bi (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethyl Heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethane) Sulfonyl) imide, N, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (tri Fluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N -Ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl- -Methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N -Methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butyl-3methylpyridine-1-ium trifluoromethanesulfonate and the like.
As these commercially available products, for example, “CIL-314” (manufactured by Nippon Carlit Co., Ltd.), “ILA2-1” (manufactured by Koei Chemical Co., Ltd.) and the like can be used.

In the present invention, a surfactant can also be used as the ionic compound (D).
Examples of the surfactant that can be used as the ionic compound (D) include a cationic surfactant and an anionic surfactant.
As the cationic surfactant, for example, it has a quaternary ammonium group such as alkyltrimethylammonium salt, acyloylamidopropyltrimethylammonium methosulfate, alkylbenzylmethylammonium salt, acylcholine chloride, and dimethylaminoethyl methacrylate quaternized product. Examples thereof include (meth) acrylate copolymers, styrene copolymers having a quaternary ammonium group such as polyvinylbenzyltrimethylammonium chloride, and diallylamine copolymers having a quaternary ammonium group such as polydiallyldimethylammonium chloride. These compounds may be used alone or in combination of two or more.
Examples of the anionic surfactant include alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ethoxy sulfate ester salt, alkyl phosphate ester salt, sulfonic acid group-containing styrene copolymer, and the like. These compounds may be used alone or in combination of two or more.
As these commercial products, for example, “KS-1158” (manufactured by Kao Corporation) can be used.

  Moreover, it is preferable that content of an ionic compound (D) is 0.01-10 weight part with respect to 100 weight part of acrylic resin (A). More preferably, it is 0.05-5 weight part. If the amount is less than 0.01 part by weight, sufficient ionic conductivity cannot be obtained, and even if the amount of the ionic compound (D) is more than 10 parts by weight, the effect of improving the conductivity can hardly be expected, and the adhesiveness is further reduced. It is not preferable.

The antistatic acrylic resin composition of the present invention can also contain a compound having an alkylene oxide chain. As a compound which has an alkylene oxide chain, it is preferable that the content rate of the alkylene oxide chain which occupies in the compound which has an alkylene oxide chain is 10 to 80 weight%, and it is more preferable that it is 20 to 50 weight%.
Moreover, it is preferable that the weight average molecular weights of the compound which has the said alkylene oxide chain are 1000-10000, and it is more preferable that it is 1000-5000.
As the compound having an alkylene oxide chain, for example, a compound having an ethylene oxide chain and / or a propylene oxide chain in the molecule can be used. Specifically, for example, trade names Epan 420, 450, 750 (first Kogyo Seiyaku Co., Ltd.) can be used.

In addition, when the content of the alkylene oxide chain in the compound having an alkylene oxide chain is less than 10% by weight, sufficient ionic conductivity is difficult to obtain, and when the content exceeds 80% by weight or the weight average molecular weight exceeds 10,000, Since the crystallinity is increased, the ionic conductivity is lowered, which is not preferable.
A weight average molecular weight of less than 1000 is not preferable because it tends to bleed on the surface of the adhesive layer and easily contaminates the adherend surface.
The compound having an alkylene oxide chain is blended in an amount of 1 to 40 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the acrylic resin (A). If the compounding amount of the compound having an alkylene oxide chain is less than 1 part by weight, sufficient antistatic properties may be difficult to obtain. On the other hand, if it exceeds 40 parts by weight, the tackiness is remarkably lowered, which is not preferable.

  In the antistatic acrylic resin composition of the present invention, if necessary, other resins such as acrylic resin, polyester resin, amino resin, epoxy resin, and polyurethane resin can be used in combination. Also, depending on the use, additives such as tackifiers, fillers such as talc, calcium carbonate, titanium oxide, colorants, ultraviolet absorbers, antifoaming agents, light stabilizers, antioxidants may be blended. good.

A pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer formed using the antistatic acrylic resin composition of the present invention and a base material such as a plastic film, paper, cloth, or foam are laminated can be obtained, and the surface of the pressure-sensitive adhesive layer Can be covered with a release sheet.
The pressure-sensitive adhesive sheet can be obtained by applying or impregnating an antistatic acrylic resin composition to various base materials, and drying and curing it. Alternatively, the antistatic acrylic resin composition is applied on the release sheet, dried, and various substrates are laminated on the surface of the adhesive layer that is being formed, and the hydroxyl group in the acrylic resin (A) and the modified body It can also be obtained by advancing the reaction with the isocyanate group in (B) and the modified product (C).

By applying the antistatic acrylic resin composition of the present invention to a transparent plastic film, preferably as a substrate, a surface protective adhesive film for an optical member can be suitably obtained.
Examples of the plastic film include polyvinyl chloride film, polyethylene film, polyethylene terephthalate (PET) film, polyurethane film, nylon film, treated polyolefin film, untreated polyolefin film, and the like.
The antistatic acrylic resin composition of the present invention is preferably applied to a substrate or the like so as to have a thickness of about 2 to 200 μm when dried and cured. If it is less than 2 μm, the ionic conductivity becomes poor, and if it exceeds 200 μm, the production and handling of the pressure-sensitive adhesive sheet becomes difficult.

Using the antistatic acrylic resin composition of the present invention, antistatic pressure-sensitive adhesive films of various aspects can be obtained in consideration of its use, required performance and the like.
For example, an antistatic adhesive film for a protective film for a polarizing plate will be described with reference to the drawings.
FIG. 1 shows a state in which an antistatic adhesive film according to the present invention comprising a PET (polyethylene terephthalate) film substrate 1 and an adhesive layer 2 supported on one surface thereof is attached to a polarizing plate 3 by the adhesive layer 2. It is a typical sectional view shown.
FIG. 2 is a schematic cross-sectional view showing a state in which an antistatic adhesive film according to the present invention in which an adhesive layer 2 is provided on both surfaces of a PET film substrate 1 is attached to a polarizing plate 3 by one adhesive layer 2.
FIG. 3 shows an antistatic adhesive film according to the present invention in which an antistatic coating agent layer 4 is provided on one surface of a PET film substrate 1 and an adhesive layer 2 is further supported on the surface. FIG. 4 is a schematic cross-sectional view showing a state of being attached to a plate 3.
FIG. 4 shows an antistatic adhesive film according to the present invention in which an adhesive layer 2 is provided on one surface of a PET film substrate 1 and an antistatic coating agent layer 4 is provided on the opposite surface. FIG. 4 is a schematic cross-sectional view showing a state of being attached to a plate 3.

When the resin composition of the present invention is used for a film for protecting the surface of an optical member or an electronic member, an antistatic coating agent layer is provided as shown in FIGS. 3 and 4 in order to further reduce the peel charge amount. Is also possible. Further, in applications where the functionality of the plastic film is imparted, as shown in FIG. 2, an adhesive layer is provided on both sides of the base film, and a functional film (for example, a retardation film, an optical film) is provided on one adhesive layer. Compensation film, light diffusion film, electromagnetic wave shielding film, etc.) can be further bonded together. In consideration of workability and production cost, the embodiment of FIG. 1 is most preferable.
As shown in FIG. 3 and FIG. 4, when an antistatic coating agent layer having no adhesiveness is provided between the adhesive layer and the plastic film substrate or on the opposite side of the plastic film substrate that is not the adhesive layer side, A filler, a quaternary ammonium salt derivative, a surfactant, a conductive resin, or the like can be used.
Examples of the metal filler include metal oxides such as tin oxide, zinc oxide, iron oxide and antimony oxide, and metals such as carbon, silver and copper. In consideration of the transparency of the coating film, tin oxide, antimony oxide and the like are preferable.
As the quaternary ammonium salt derivative, a polymer of a (meth) acrylate monomer having a quaternary ammonium group or a copolymer with another (meth) acrylate monomer can be used. Moreover, it is also possible to use for an antistatic coating agent layer by adjusting Tg of the antistatic acrylic resin composition of this invention.
The antistatic coating agent layer preferably has a thickness of 0.01 μm to 10 μm, more preferably 0.1 μm to 5 μm, as a coating film. If it is less than 0.01 μm, the effect of preventing static electricity cannot be sufficiently exhibited, and if it exceeds 5 μm, there are problems in cost, coatability, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “part” means “part by weight”, and “%” means “% by weight”.
(Synthesis Example 1)
An acrylic resin composed of monomers having the composition ratio (weight ratio) shown in Table 1 was obtained as follows.
That is, using a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 50% by weight of 2EHA in the reaction kettle [50% of “73”% by weight described in Table 1] Meaning of% by weight; the same applies hereinafter), 50% by weight of BA, 50% by weight of 4HBA, ethyl acetate as solvent, azobisisobutyronitrile as initiator,
A solution prepared by adding appropriate amounts of ethyl acetate and azobisisobutyronitrile to the total amount of the remaining monomers was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, it was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 41%, a viscosity of 1700 mPa · s, and Mw (weight average molecular weight) of 390,000.

(Synthesis Example 2)
An acrylic resin composed of monomers having the composition ratio (weight ratio) shown in Table 1 was obtained as follows.
That is, a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 50% by weight of 2EHA, 50% by weight of BA, 50% by weight of 2HEA, A suitable amount of ethyl acetate and azobisisobutyronitrile as an initiator is charged.
A solution prepared by adding appropriate amounts of ethyl acetate and azobisisobutyronitrile to the total amount of the remaining monomers was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, it was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 41%, a viscosity of 1700 mPa · s, and Mw (weight average molecular weight) of 400,000.

(Synthesis Example 3)
An acrylic resin composed of monomers having the composition ratio (weight ratio) shown in Table 1 was obtained as follows.
That is, a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was used. The reaction kettle was 50% by weight of 2EHA, 50% by weight of BA, and 75 of 6-hydroxyhexyl acrylate. % By weight, ethyl acetate as solvent, azobisisobutyronitrile as initiator,
A solution prepared by adding appropriate amounts of ethyl acetate and azobisisobutyronitrile to the total amount of the remaining monomers was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, it was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 41%, a viscosity of 1700 mPa · s, and Mw (weight average molecular weight) of 390,000.

(Synthesis Example 4)
An acrylic resin composed of monomers having the composition ratio (weight ratio) shown in Table 1 was obtained as follows.
That is, using a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, the reaction kettle was 50% by weight of 2EHA, 50% by weight of BA, and the total amount of 12-hydroxylauryl acrylate. , Ethyl acetate as the solvent, azobisisobutyronitrile as the initiator,
A solution prepared by adding appropriate amounts of ethyl acetate and azobisisobutyronitrile to the total amount of the remaining monomers was added dropwise over about 1 hour and polymerized at about 80 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, it was cooled and diluted with ethyl acetate. This reaction solution had a solid content of 41%, a viscosity of 1700 mPa · s, and Mw (weight average molecular weight) of 370,000.

[Example 1]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, hexamethylene diisocyanate modified isocyanurate modified 37% ethyl acetate solution 0.6 part, tolylene diisocyanate modified trimethylolpropane 9.0 parts of a 37% ethyl acetate solution was blended to obtain an adhesive.
The obtained pressure-sensitive adhesive was coated on a release paper so that the thickness of the dry coating film was 20 μm, dried at 100 ° C. for 2 minutes, and then a polyethylene terephthalate film (thickness: 38 μm) on the pressure-sensitive adhesive layer being formed. ) Were laminated for 2 days at room temperature in this state to obtain a test pressure-sensitive adhesive sheet.
Using the pressure-sensitive adhesive sheet, the adhesive strength and peeling charge were evaluated according to the following methods.

<Adhesive strength>
The test adhesive tape is cut to a width of 25 mm, the release paper is peeled off, and the exposed adhesive layer is attached to a glass plate with a thickness of 2 mm at 23 ° C.-50% RH, and roll pressure bonding is performed according to JIS Z-0237. did. Peel strength (180 degree peel, pulling speed 300 mm / min, unit: g / 25 mm) was measured with a shopper type peel tester after 24 hours from the press bonding.

<Peeling electrification>
The release paper of the A4 size test pressure-sensitive adhesive sheet was peeled off, and the exposed pressure-sensitive adhesive layer was attached to a polarizing plate at 23 ° C.-50% RH and pressure-bonded with a hand roll. 24 hours after pressing, the test adhesive sheet was peeled off from the polarizing plate on the glass plate, and the static electricity on the polarizing plate surface was measured at 10 locations using a static electricity meter ("STATION DZ3" manufactured by Sisid Electrostatic Co., Ltd.). The value having the maximum absolute value was defined as peeling charge.

[Example 2]
“CIL-314” (manufactured by Nippon Carlit Co., Ltd .: 1-butyl-3methylpyridine-1-ium trifluoromethanesulfonate) with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1. 0 parts, “Epan 750” (made by Daiichi Kogyo Co., Ltd .: weight average molecular weight 4000, ethylene oxide chain content 50%) as a compound having an ethylene oxide chain 4.0 parts, isocyanurate modified of hexamethylene diisocyanate A pressure-sensitive adhesive was obtained by blending 2.0 parts of a 37% ethyl acetate solution and 3.0 parts of a 37% ethyl acetate solution of a modified trimethylolpropane of tolylene diisocyanate.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 3]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, hexamethylene diisocyanate modified isocyanurate modified 37% ethyl acetate solution 4.0 parts, tolylene diisocyanate trimethylolpropane modified A 37% ethyl acetate solution (1.0 part) was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 4]
For 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 2, 1.0 part of “ILA2-1” (manufactured by Koei Chemical Co., Ltd .: aliphatic amine-based solid ionic compound), ethylene oxide chain As a compound having “Epan 750” (Daiichi Kogyo Co., Ltd .: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 37% ethyl acetate solution of hexamethylene diisocyanate modified isocyanurate 0 part and 10.5 parts of 37% ethyl acetate solution of a trimethylolpropane modified product of tolylene diisocyanate were blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 5]
As a compound having 0.5 parts of lithium bis (pentafluoroethanesulfonyl) imide and an ethylene oxide chain with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 2, “Epan 750” (Daiichi Kogyo) Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, hexamethylene diisocyanate modified isocyanurate modified 37% ethyl acetate solution 2.5 parts, tolylene diisocyanate modified trimethylolpropane A 37% ethyl acetate solution (2.5 parts) was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 6]
As a compound having 0.5 parts of lithium bis (pentafluoroethanesulfonyl) imide and an ethylene oxide chain with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 3, “Epan 750” (manufactured by Daiichi Kogyo) Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, hexamethylene diisocyanate modified isocyanurate modified 37% ethyl acetate solution 1.0 part, hexamethylene diisocyanate modified trimethylolpropane A 37% ethyl acetate solution (3.5 parts) was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 7]
As a compound having 0.5 parts of lithium bis (pentafluoroethanesulfonyl) imide and an ethylene oxide chain with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 3, “Epan 750” (manufactured by Daiichi Kogyo) Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, hexamethylene diisocyanate modified isocyanurate modified 37% ethyl acetate solution 3.0 parts, tolylene diisocyanate modified trimethylolpropane A 37% ethyl acetate solution (2.0 parts) was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 8]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 4, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, hexamethylene diisocyanate modified isocyanurate modified 37% ethyl acetate solution 0.6 part, tolylene diisocyanate modified trimethylolpropane 10.5 parts of a 37% ethyl acetate solution was added to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 9]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 4, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain Company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate 4.0 parts, trimethylolpropane modified form of xylylene diisocyanate A 37% ethyl acetate solution (0.8 part) was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 10]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 1.0 part of lithium perchlorate and “Epan 750” (made by Daiichi Kogyo Co., Ltd .: weight average) as a compound having an ethylene oxide chain 4.0 parts molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate 1.0 part, 37% ethyl acetate of trimethylolpropane modified form of tolylene diisocyanate 9.0 parts of the solution was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 11]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 2, 1.0 part of lithium perchlorate and “Epan 750” (made by Daiichi Kogyo Co., Ltd .: weight average) as a compound having an ethylene oxide chain 4.0 parts molecular weight, ethylene oxide chain content 50%) 4.0 parts, 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate 2.5 parts, 37% ethyl acetate of trimethylolpropane modified form of tolylene diisocyanate The adhesive was obtained by blending 1.5 parts of the solution.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 12]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 1.0 part of “KS-1158” (manufactured by Kao Corporation: phosphate ester potassium salt) and “Epane as a compound having an ethylene oxide chain” 750 "(Daiichi Kogyo Co., Ltd .: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 1.0 part of a 37% ethyl acetate solution of a modified isocyanurate of hexamethylene diisocyanate, tolylene diene 9.0 parts of a 37% ethyl acetate solution of a modified trimethylolpropane of isocyanate was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Example 13]
As a compound having 1.0 part of “KS-1158” (manufactured by Kao Corporation: phosphoric acid ester potassium salt) and 40 parts of ethylene oxide chain, “Epan” with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 2 750 "(Daiichi Kogyo Co., Ltd .: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 3.0 parts of 37% ethyl acetate solution of isocyanurate modified of hexamethylene diisocyanate, tolylene 1.0 part of 37% ethyl acetate solution of a modified trimethylolpropane of isocyanate was blended to obtain a pressure-sensitive adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Comparative Example 1]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain (Made by company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 4.0 parts of 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate was obtained to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Comparative Example 2]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 1, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain (Made by company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 10.0 parts of xylylene diisocyanate trimethylolpropane 37% ethyl acetate solution was blended to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
[Comparative Example 3]
As a compound having 0.5 parts of lithium bis (pentafluoroethanesulfonyl) imide and an ethylene oxide chain with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 2, “Epan 750” (Daiichi Kogyo) (Made by company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 4.0 parts of 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate was obtained to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Comparative Example 4]
As a compound having 0.5 parts of lithium bis (pentafluoroethanesulfonyl) imide and an ethylene oxide chain with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 2, “Epan 750” (Daiichi Kogyo) Co., Ltd .: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 15.0 parts of 37% ethyl acetate solution of trimethylolpropane modified xylylene diisocyanate was obtained to obtain a pressure-sensitive adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Comparative Example 5]
As a compound having 0.5 parts of lithium bis (pentafluoroethanesulfonyl) imide and an ethylene oxide chain with respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 3, “Epan 750” (manufactured by Daiichi Kogyo) (Made by company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 4.0 parts of 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate was obtained to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

[Comparative Example 6]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 4, 0.5 part of lithium bis (pentafluoroethanesulfonyl) imide and “Epan 750” (Daiichi Kogyo) as a compound having an ethylene oxide chain (Made by company: weight average molecular weight 4000, ethylene oxide chain content 50%) 4.0 parts, 4.0 parts of 37% ethyl acetate solution of isocyanurate modified form of hexamethylene diisocyanate was obtained to obtain an adhesive.
Using the obtained adhesive, an adhesive sheet was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
The above evaluation results are shown in Table 2.

The abbreviations of ionic compounds in Table 2 are as follows.
CIL-314: 1-butyl-3methylpyridine-1-ium trifluoromethanesulfonate (manufactured by Nippon Carlit)
ILA2-1: aliphatic amine-based solid ionic compound (manufactured by Guangei Chemical Co., Ltd.)
KS-1158: Phosphate ester potassium salt (manufactured by Kao Corporation)

As described above, when the antistatic acrylic resin composition of the present invention is used as an adhesive layer for a surface protective film for an optical member such as a polarizing plate used in a liquid crystal display, the generation of static electricity at the time of peeling is small. In addition, it can be seen that moderate adhesive strength can be obtained.
On the other hand, the acrylic resin compositions shown in Comparative Examples 1, 3, 5 and 6 use only the isocyanurate-modified product of hexamethylene diisocyanate as a curing agent, and generation of static electricity at the time of peeling is Although it can be reduced, the adhesive strength is too low, so there is a risk of peeling from the adherend.
In addition, the acrylic resin compositions shown in Comparative Examples 2 and 4 are obtained by using only a trimethylolpropane modified product of a diisocyanate compound as a curing agent, and can obtain an appropriate adhesive force. The generation of static electricity cannot be suppressed.

  The antistatic acrylic resin composition of the present invention is an antistatic acrylic resin composition that can be used for paints, pressure-sensitive adhesives, etc., and the ion conductivity does not decrease even after crosslinking with a crosslinking agent. Suitable as a surface protective film for mechanically and electrically protecting the surface of the adherend for a predetermined period. For example, adhesive for surface protection of optical components such as liquid crystal panels, plasma displays, polarizing plates, CRTs (CRTs) It is suitably used for film formation.

It is typical sectional drawing which shows the state which affixed the antistatic adhesive film by this invention which consists of a PET film base material and the adhesion layer carry | supported on the one surface to the polarizing plate by the adhesion layer. It is typical sectional drawing which shows the state which affixed the antistatic adhesive film by this invention which provides an adhesive layer on both surfaces of a PET film base material to a polarizing plate by one adhesive layer. Schematic showing a state in which an antistatic coating film according to the present invention, in which an antistatic coating agent layer is provided on one surface of a PET film substrate, and further an adhesive layer is supported thereon, is attached to a polarizing plate by the adhesive layer. FIG. Schematic showing a state in which an antistatic adhesive film according to the present invention in which an adhesive layer is provided on one surface of a PET film substrate and an antistatic coating agent layer is provided on the opposite surface is attached to a polarizing plate by the adhesive layer. FIG.

Explanation of symbols

1: PET film base material 2: Adhesive layer 3: Polarizing plate 4: Antistatic coating agent layer

Claims (6)

  It contains an acrylic resin (A) having a hydroxyl group, an isocyanurate-modified product (B) of hexamethylene diisocyanate, a trimethylolpropane-modified product (C) of a diisocyanate compound, and an ionic compound (D). Acrylic resin composition.   2. The antistatic acrylic resin composition according to claim 1, wherein the diisocyanate compound is tolylene diisocyanate.   0.05 to 5 parts by weight of an isocyanurate modified form of hexamethylene diisocyanate (B) and a trimethylolpropane modified form of diisocyanate compound (C) 0.3 per 100 parts by weight of acrylic resin (A) having a hydroxyl group The antistatic acrylic resin composition according to claim 1, comprising ˜15 parts by weight.   4. The antistatic acrylic resin composition according to claim 1, wherein the ionic compound (D) is an alkali metal organic salt and / or an organic cation-anion salt.   The antistatic acrylic system according to any one of claims 1 to 4, comprising 0.01 to 10 parts by weight of the ionic compound (D) with respect to 100 parts by weight of the acrylic resin (A) having a hydroxyl group. Resin composition.   A protective film for an optical member, wherein an adhesive layer formed from the antistatic acrylic resin composition according to any one of claims 1 to 5 is laminated on at least one surface of a plastic film substrate.

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