KR102025101B1 - Antistatic surface-protective film - Google Patents

Abstract

The present invention provides a pressure-sensitive adhesive composition and an antistatic surface protective film that are less contaminated to the adherend, do not deteriorate with time, and have excellent peeling antistatic performance. (a1) At least 1 type or more of the (meth) acrylic acid ester monomer whose C1-C4 carbon number of an alkyl group, (A2) At least 1 type or more of the (meth) acrylic acid ester monomer whose C1-C18 carbon number of an alkyl group are (B) Copolymerize at least one or more types of copolymerizable monomers containing hydroxyl groups, (C) at least one or more types of copolymerizable monomers containing carboxyl groups, and (D) at least one or more types of polyalkylene glycol mono (meth) acrylic acid ester monomers (H) a ionic compound which is solid at a temperature of 25 to 50 ° C., (E) a bifunctional or higher isocyanate compound, (F) a crosslinking accelerator, and (G) a ketoenol tautomer compound It is done by

Description

Antistatic surface protection film {ANTISTATIC SURFACE-PROTECTIVE FILM}

The present invention relates to an adhesive composition and a surface protective film. More specifically, it relates to the adhesive composition for surface protection films provided with antistatic performance, and the surface protection film using the same. The present invention provides a pressure-sensitive adhesive composition having a low pollution and not deteriorating with time even when the adherend is a polarizing plate subjected to a low reflection surface treatment, and having an excellent antistatic peeling performance, and an antistatic surface protective film using the same.

When manufacturing and conveying optical films such as polarizing plates, retardation plates, lens films for displays, antireflection films, hard coat films, transparent conductive films for touch panels, and displays using the same, the surface of the optical film Bonding a surface protection film is performed to prevent the surface contamination and a flaw in a post process. The external appearance inspection of the optical film which is an optical product may be performed in the state which bonded the surface protection film to the optical film in order to reduce the effort of peeling and bonding again a surface protection film and to raise work efficiency.

Conventionally, the surface protection film which provided the adhesive layer in one side of the base film is generally used in the manufacturing process of an optical product, in order to prevent a damage | wound and adhesion of a dirt. The surface protection film is bonded to the optical film via the adhesive layer of a non-adhesive force. The non-adhesive force of the pressure-sensitive adhesive layer can be easily peeled off when the used surface protection film is peeled off and removed from the surface of the optical film, and the pressure-sensitive adhesive does not remain attached to the optical film of the product which is the adherend ( So-called pressure-sensitive adhesive residues).

In recent years, in the production process of a liquid crystal display panel, circuit components, such as a driver IC, for controlling the display screen of a liquid crystal display panel by the peeling charge voltage which arises when peeling and removing the surface protection film bonded on the optical film. The occurrence of this breakdown and the phenomenon that the orientation of the liquid crystal molecules are impaired are small but occur.

In addition, in order to reduce the power consumption of the liquid crystal display panel, the driving voltage of the liquid crystal material is lowered, and with this, the breakdown voltage of the driver IC is also lowered. For this reason, when peeling a surface protection film from the optical film which is a to-be-adhered body, in order to prevent the problem by having high peeling electrification voltage, the surface protection film using the adhesive layer containing the antistatic agent for suppressing peeling electrification voltage low. Is being proposed.

For example, Patent Document 1 includes a (meth) acrylic polymer having a (meth) acrylic acid ester monomer having an alkyl group of C 1 to C 14 as a main component, a polyether compound, and an ionic compound having a melting point of 30 ° C. or higher. A pressure-sensitive adhesive composition is described.

Further, Patent Document 2 discloses 50 to 99.9 wt% of (meth) acrylate having 0.1 to 4.9 wt% of alkylene oxide group-containing reactive monomer having an average added mole number of oxyalkylene units of 3 to 40 and an alkyl group having 1 to 14 carbon atoms. The adhesive composition which contains the (meth) acrylic-type polymer and alkali metal salt which make a monomer component are described.

In addition, Patent Document 3 describes an adhesive copolymer containing an acrylic copolymer having a hydroxyl group in a molecule, an alkali metal salt, and a dimethylpolysiloxane compound having a polyoxyalkylene group in the molecule and having an HLB value of 1 or more and 10 or less.

Japanese Unexamined Patent Publication No. 2013-163783 Japanese Unexamined Patent Publication No. 2012-237004 Japanese Unexamined Patent Publication No. 2013-163744

In the prior art, it is essential to add an antistatic agent to the pressure-sensitive adhesive layer in the surface protective film having antistatic performance. For this reason, the relationship between antistatic performance and contamination with an adherend has a trade off relationship. In recent years, however, the display panel has become increasingly high in quality and high in quality, and the criterion for evaluation of contamination resistance becomes more stringent. It is required.

This invention is made | formed in view of the said situation, and makes it a subject to provide the adhesive composition and antistatic surface protection film which have few contamination with a to-be-adhered body, and do not deteriorate with time, and have the outstanding peeling antistatic performance.

As a result of earnestly examining in order to solve the said subject, the inventors adopted the (meth) acrylic acid ester monomer group which has C1-C18 carbon number of an alkyl group as a main component of the acryl-type polymer which comprises an adhesive composition, and divides it into two monomer groups, By selecting at least one monomer from each monomer group and setting it as a specific monomer ratio, it was found that it has a specific effect of reducing the contamination to a to-be-adhered body.

In addition, by selecting an antistatic agent that does not adversely affect the contamination on the adherend and incorporating it into the pressure sensitive adhesive composition, it is possible to obtain an adhesive composition having less contamination on the adherend and not deteriorating with time and having excellent peeling antistatic performance. The problem of the present invention was solved.

That is, the present invention is an acrylic polymer constituting the pressure-sensitive adhesive composition

(A) (meth) acrylic acid ester monomer which has C1-C18 carbon number of an alkyl group,

(B) at least one or more of copolymerizable monomers containing a hydroxyl group,

(C) at least one or more of copolymerizable monomers containing a carboxyl group,

(D) It is set as the copolymer which copolymerized at least 1 sort (s) of a polyalkylene glycol mono (meth) acrylic acid ester monomer,

The (meth) acrylic acid ester monomer having a C1 to C18 carbon number of the (A) alkyl group is at least one or more of the (meth) acrylic acid ester monomer having a C1 to C4 carbon number of the (a1) alkyl group, and the carbon number of the (a2) alkyl group. The adherend of the pressure-sensitive adhesive obtained by using at least one or more of the (meth) acrylic acid ester monomers of C5 to C18 and setting the content ratio (a2 / a1) of the (a1) and the (a2) to a specific ratio range by mass ratio. It is a technical idea to reduce the pollution to the.

In order to solve the said subject, this invention is an adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent, Comprising: The said acrylic polymer is with respect to 100 weight part of the said acrylic polymer,

(A) 50-99.8 weight part of total sum of the (meth) acrylic acid ester monomer of C1-C18 carbon number of an alkyl group,

As a copolymerizable monomer group,

(B) 0.1-14 weight part of at least 1 sort (s) of the copolymerizable monomer containing a hydroxyl group,

0.01 to 1.0 part by weight of at least one copolymerizable monomer containing a (C) carboxyl group,

(D) more than 0 to 35 parts by weight or less of at least one or more of the polyalkylene glycol mono (meth) acrylic acid ester monomer,

It is a copolymer copolymerized without containing the nitrogen-containing vinyl monomer which does not contain a hydroxyl group, and the alkoxy-group containing alkyl (meth) acrylate monomer,

The (meth) acrylic acid ester monomer having a C1 to C18 carbon number of the (A) alkyl group is at least one or more of the (meth) acrylic acid ester monomer having a C1 to C4 carbon number of the (a1) alkyl group, and the carbon number of the (a2) alkyl group. It consists of at least 1 sort (s) or more of the (meth) acrylic acid ester monomer which is C5-C18, The content ratio (a2 / a1) of said (a1) and said (a2) is more than 1 and 50 or less by mass ratio,

The antistatic agent is an ionic compound which is a solid (H) at a melting point of 25 to 50 ° C. and a temperature of 25 ° C.,

The crosslinking agent is an (E) bifunctional or higher isocyanate compound,

The pressure-sensitive adhesive composition further comprises (F) a crosslinking accelerator and (G) a ketoenol tautomer compound.

It is preferable that the average repeating number of the alkylene oxide which the said (D) polyalkylene glycol mono (meth) acrylic acid ester monomer comprises a polyalkylene glycol chain is 3-14, and the diester content in a monomer is 0.2% or less.

Said (F) crosslinking promoter is at least 1 sort (s) or more selected from the group which consists of an aluminum chelate compound, a titanium chelate compound, and an iron chelate compound, and 0.001-0.5 weight part of said (F) crosslinking promoters with respect to 100 weight part of said acrylic polymers. And the (G) ketoenol tautomer compound in a proportion of 0.1 to 300 parts by weight, and the proportion by weight of (G) / (F) is preferably 70 to 1000.

The copolymerizable monomer containing the said (B) hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl At least one or more selected from the group consisting of (meth) acrylates, N-hydroxy (meth) acrylamides, N-hydroxymethyl (meth) acrylamides, and N-hydroxyethyl (meth) acrylamides;

The copolymerizable monomer containing the (C) carboxyl group is (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahexaphthalic acid, 2- ( Meta) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypoly It is preferable that it is at least 1 sort (s) or more chosen from the compound group which consists of caprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.

As said monomer group which can be copolymerized, the said (D) polyalkylene glycol mono (meth) acrylic acid ester whose average repeating number of the alkylene oxide which comprises the said polyalkylene glycol chain is 3-14, and the diester content in a monomer is 0.2% or less. It is preferable to contain at least 1 sort (s) chosen from polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate as a monomer.

As said (E) bifunctional or more isocyanate compound, a bifunctional isocyanate compound is a compound formed by making a diisocyanate compound and a diol compound react with a non-cyclic aliphatic isocyanate compound, As a diisocyanate compound, it is aliphatic diisocyanate, tetramethylene 1 type selected from the group consisting of diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and diol compounds include 2-methyl-1,3-propanediol, 2,2 -Dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol 1 type selected from the group consisting of 2,2-dimethyl-1,3-propanediol monohydroxy pivalate, polyethylene glycol and polypropylene glycol The trifunctional isocyanate compound is composed of isocyanurate of hexamethylene diisocyanate compound, isocyanurate of isophorone diisocyanate compound, adduct of hexamethylene diisocyanate compound, and isophorone diisocyanate compound. Adduct body, biuret body of hexamethylene diisocyanate compound, biuret body of isophorone diisocyanate compound, isocyanurate body of tolylene diisocyanate compound, isocyanurate body of xylylene diisocyanate compound, hydrogenated xylylene diisocyanate Isocyanurate compound, adduct body of tolylene diisocyanate compound, adduct body of xylylene diisocyanate compound, adduct body of hydrogenated xylylene diisocyanate compound, and with respect to 100 parts by weight of the acrylic polymer, 0 It is preferable to contain in ratio of .1-10 weight part.

It is preferable that the said adhesive composition contains the polyether modified siloxane compound of (I) HLB value 7-15 further at 0.01-1.0 weight part with respect to 100 weight part of the said acrylic polymer.

Moreover, this invention provides the antistatic surface protection film characterized by laminating | stacking the adhesive layer which bridge | crosslinked the said adhesive composition on one surface of the resin film.

In addition, the present invention is characterized in that the antistatic property when the antistatic surface protective film is peeled off after bonding the antistatic surface protective film to the polarizing plate subjected to the low reflection surface treatment at a reflectance of 2% or less via the pressure sensitive adhesive layer is good. Provide a surface protective film.

Moreover, in this invention, after peeling the said antistatic surface protection film through the said adhesive layer to the polarizing plate in which the low reflectivity surface treatment was performed at the reflectance 2% or less, the peeling electrification voltage when peeling is ± 0.8 kPa or less Moreover, the surface resistivity of the said adhesive surface is 9.0x10 <^{11> (} ohm) / square or less, The antistatic surface protection film characterized by the above-mentioned.

In addition, the present invention is a peeling band when the antistatic surface protection film is peeled off after the low reflection surface treatment is performed at a reflectance of 2% or less through the pressure sensitive adhesive layer and the paste is peeled off after bonding to a polarizing plate subjected to antiglare treatment. A voltage is ± 0.8 kPa or less, and the surface resistivity of the said adhesive surface is 9.0x10 <^{11> (} ohm) / square or less, The antistatic surface protection film is provided.

Moreover, this invention provides the adhesive film formed by forming the adhesive layer which crosslinks the said adhesive composition on one side or both sides of a resin film.

Moreover, this invention consists of the said antistatic surface protection film, and provides the antistatic surface protection film used as a use of the protective film for polarizing plates.

Moreover, this invention provides the antistatic surface protection film by which antistatic treatment and antifouling treatment are given to the surface opposite to the side in which the said adhesive layer on one side of the said resin film was formed.

ADVANTAGE OF THE INVENTION According to this invention, even if a to-be-adhered body is a polarizing plate to which the low reflection surface treatment was given, it can provide the adhesive composition and antistatic surface protection film which have little contamination with a to-be-adhered body, and do not deteriorate with time, and have the outstanding peeling antistatic performance.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on preferable embodiment.

The pressure-sensitive adhesive composition of the present invention is an pressure-sensitive adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent, wherein the acrylic polymer has a C1 to C18 carbon number of (A) alkyl group to 100 parts by weight of the acrylic polymer. As a monomer group which can copolymerize the sum total of an acrylic acid ester monomer with 50-99.8 weight part, (B) Copolymer containing 0.1-14 weight part and (C) carboxyl group at least 1 sort (s) of the copolymerizable monomer containing a hydroxyl group is possible. Nitrogen containing vinyl monomer which does not contain a hydroxyl group from 0.01-1.0 weight part of at least 1 type of monomer, and 0 to 35 weight part of at least 1 or more types of (D) polyalkylene glycol mono (meth) acrylic acid ester monomer. And a copolymer copolymerized without containing an alkoxy group-containing alkyl (meth) acrylate monomer, wherein the (A) alkyl group has 1 to 18 carbon atoms (meth) The at least 1 sort (s) of the (meth) acrylic acid ester monomer whose (a1) alkyl group has C1-C4 carbon number of a (a1) alkyl group, and the (meth) acrylic ester ester monomer whose carbon number of a (a2) alkyl group is C5-C18 The content ratio (a2 / a1) of the above-mentioned (a1) and the said (a2) is more than 1 and 50 or less by mass ratio, and the said antistatic agent is a solid at the temperature of 25-50 degreeC of (H) melting | fusing point at 25 degreeC A phosphorous ionic compound, wherein the crosslinking agent is an (E) bifunctional or higher isocyanate compound, and the pressure-sensitive adhesive composition further comprises (F) a crosslinking accelerator and a (G) ketoenol tautomer compound. Composition.

(A) In the (meth) acrylic acid ester monomer whose C1-C18 carbon number of an alkyl group, (a1) At least 1 sort (s) of the (meth) acrylic acid ester monomer whose C1-C4 carbon number of an alkyl group is butyl (meth) acrylate and iso Butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate.

Moreover, as a (meth) acrylic acid ester monomer whose C5-C18 carbon number of the (a2) alkyl group is pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and iso Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl ( Meta) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) Acrylate, octadecyl (meth) acrylate, myristyl (meth) acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, isocetyl (meth) acrylate, stearyl (meth) acrylate Isostea (Meth) acrylate.

(A) 1-100 of at least 1 sort (s) of the (meth) acrylic acid ester monomer which has C1-C4 carbon number of an alkyl group with respect to a total of 100 weight part of the C1-C18 (meth) acrylic acid ester monomers. It is preferable that a weight part and (a2) contain at least 1 sort (s) of the (meth) acrylic acid ester monomer whose C2-C18 carbon number is C50-99 weight part, and at least 1 sort (s) of said (a1) is 3- It is more preferable that 45 weight part and at least 1 type of said (a2) are contained by the ratio of 55-97 weight part, 5 to 45 weight part and at least 1 of said (a2) at least 1 type of said (a1). It is particularly preferable to contain the species in the proportion of 55 to 95 parts by weight, at least one of the above (a1) is contained 8 to 40 parts by weight, and at least one of the above (a2) at a ratio of 60 to 92 parts by weight Most preferably.

That is, with respect to 100 parts by weight of the acrylic polymer,

(1) The (meth) acrylic acid ester monomer whose C1-C18 carbon number of (A) alkyl group is contained in the ratio of 50-99.8 weight part, and the carbon number of said (a1) alkyl group is C1-C4 It is preferable that the content ratio (a2 / a1) of the at least 1 sort (s) or more of (a2) and the (meth) acrylic acid ester monomer whose C3-C18 carbon number of the said (a2) alkyl group is more than 1 and 50 or less by mass ratio.

(2) The (meth) acrylic acid ester monomer whose carbon number of (A) alkyl group is C1-C18 (meth) acrylic acid ester monomer in 62-99.5 weight part, and the carbon number of said (a1) alkyl group is C1-C4 It is more preferable that the content ratio (a2 / a1) of at least 1 or more types of and the (meth) acrylic acid ester monomer whose C1-C18 carbon number of the said (a2) alkyl group is 1.2-33 by mass ratio.

(3) The (meth) acrylic acid ester monomer whose C1-C18 carbon number of (A) alkyl group is contained in the ratio of 66-96.0 weight part, and the C1-C4 carbon number of the said (a1) alkyl group is contained. It is especially preferable that the content ratio (a2 / a1) of at least 1 sort (s) or more of (a2) and the (meth) acrylic acid ester monomer whose carbon number of said (a2) alkyl group is C5-C18 is 1.5-19 by mass ratio.

(4) (A) The (meth) acrylic acid ester monomer whose C1-C18 carbon number of an alkyl group is contained in the ratio of 70-93.0 weight part, and the C1-C4 carbon number of the said (a1) alkyl group is contained. It is most preferable that the content ratio (a2 / a1) of at least 1 sort (s) or more of (a2) and the (meth) acrylic acid ester monomer whose C1-C18 carbon number of the said (a2) alkyl group is more than 1.5 in mass ratio.

(B) The copolymerizable monomer containing a hydroxyl group includes hydroxyalkyl (meth) acrylates, hydroxyl group-containing (meth) acrylamides, and the like. Specific examples thereof include 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N It is preferable that it is at least 1 sort (s) or more chosen from the compound group which consists of -hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide. The copolymerizable monomer containing these (B) hydroxyl groups does not have a polyalkylene glycol chain unlike the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer mentioned later.

It is preferable to contain the sum total of at least 1 sort (s) or more of the copolymerizable monomer containing a hydroxyl group (B) with respect to 100 weight part of the said acrylic polymer in 0.1-14 weight part ratio, and the ratio of 0.5-12 weight part is more preferable The ratio of 2.0-10.0 weight part is especially preferable, and the ratio of 2.5-10.0 weight part is the most preferable.

Examples of the copolymerizable monomer containing a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahexaphthalic acid, and 2- ( Meta) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypoly It is preferable that it is at least 1 sort (s) or more chosen from the compound group which consists of caprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.

It is preferable to contain the sum total of at least 1 or more types of copolymerizable monomers containing (C) carboxyl group in the ratio of 0.01-1.0 weight part with respect to 100 weight part of the said acrylic polymer, and the ratio of 0.02-1.0 weight part is more preferable , And a ratio of 0.03 to 0.8 parts by weight is particularly preferable, and a ratio of 0.05 to 0.8 parts by weight is most preferred.

As a (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, what is necessary is just the compound in which one hydroxyl group was esterified as (meth) acrylic acid ester among the several hydroxyl groups which polyalkylene glycol has. Since a (meth) acrylic acid ester group becomes a polymeric group, it can copolymerize to the said acrylic polymer. Other hydroxyl groups may be OH, or may be alkyl ethers such as methyl ether or ethyl ether, or saturated carboxylic acid esters such as acetate ester.

Although the ethylene group, the propylene group, butylene group etc. are mentioned as an alkylene group which polyalkylene glycol has, It is not limited to these. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol. Examples of the copolymer of polyalkylene glycol include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, polyethylene glycol-polypropylene glycol-polybutylene glycol, and the like. The copolymer may be a block copolymer or a random copolymer.

(D) It is preferable that the average repeating number of the alkylene oxide which a polyalkylene glycol mono (meth) acrylic acid ester monomer comprises a polyalkylene glycol chain is 3-14. "Average repeating number of alkylene oxide" is a part of the "polyalkylene glycol chain" contained in the molecular structure of the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, and an alkylene oxide unit repeats Average number.

(D) Polyalkylene glycol mono (meth) acrylic acid ester monomer WHEREIN: It is preferable that the diester content in a monomer is 0.2% or less. A "diester powder in a monomer" is content rate (weight%) of the polyalkylene glycol di (meth) acrylic acid ester contained in the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer.

(D) As polyalkylene glycol mono (meth) acrylic acid ester monomer, polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate It is preferable that it is at least 1 sort (s) or more selected from among.

More specifically, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylic Elate, polyethyleneglycol polybutylene glycol mono (meth) acrylate, polypropylene glycol polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylic Rate; Methoxypolyethylene glycol- (meth) acrylate, methoxy polypropylene glycol- (meth) acrylate, methoxypolybutylene glycol- (meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol- (meth) acrylic Latex, methoxy- polyethyleneglycol- polybutylene glycol- (meth) acrylate, methoxy- polypropylene glycol- polybutylene glycol- (meth) acrylate, methoxy- polyethyleneglycol- polypropylene glycol- polybutylene Glycol- (meth) acrylates; Ethoxy Polyethylene Glycol- (meth) acrylate, Ethoxy Polypropylene Glycol- (meth) acrylate, Ethoxy Polybutylene Glycol- (meth) acrylate, Ethoxy Polyethylene Glycol-Polypropylene Glycol- (meth) acrylic Ethoxy Polyethylene Glycol Polybutylene Glycol (meth) acrylate Ethoxy Polypropylene Glycol Polybutylene Glycol (meth) acrylate Ethoxy Polyethylene Glycol Polypropylene Glycol Polybutylene Glycol- (meth) acrylate, and the like.

It is preferable to contain the sum total of at least 1 or more types of (D) polyalkylene glycol mono (meth) acrylic acid ester monomer in the ratio of more than 0 to 35 weight part with respect to 100 weight part of the said acrylic polymer, and it is more than 0 and 25 weight It is more preferable to contain in the ratio of parts or less, It is especially preferable to set it as the ratio of 2.0-23.0 weight part, It is most preferable to set it as the ratio of 4.0-20.0 weight part.

As the (E) bifunctional or higher isocyanate compound, at least one or two or more selected from polyisocyanate compounds having at least two or more isocyanate (NCO) groups in one molecule may be used. Although there exist classifications, such as aliphatic isocyanate, aromatic isocyanate, acyclic isocyanate, alicyclic isocyanate, etc. in a polyisocyanate compound, Any may be sufficient as it. Specific examples of the polyisocyanate compound include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and trimethylhexamethylene diisocyanate (TMDI), diphenylmethane diisocyanate (MDI) and xyl. And aromatic isocyanate compounds such as reylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), dimethyldiphenylene diisocyanate (TOID), and tolylene diisocyanate (TDI).

Examples of the trifunctional or higher isocyanate compound include trivalent or higher polyols (one molecule) such as a biuret modified product of a bifunctional isocyanate compound (a compound having two NCO groups in one molecule), an isocyanurate modified product, trimethylolpropane (TMP), and glycerin And adducts (polyol modified substances) with at least three or more OH groups).

It is also possible to use only (E-1) trifunctional isocyanate compound or (E-2) difunctional isocyanate compound as (E) bifunctional or more isocyanate compound. Moreover, it is also possible to use together the (E-1) trifunctional isocyanate compound and (E-2) difunctional isocyanate compound.

Moreover, as (E-1) trifunctional isocyanate compound used for this invention, the isocyanurate body of the hexamethylene diisocyanate compound, the isocyanurate body of the isophorone diisocyanate compound, and the hexamethylene diisocyanate compound, At least 1 sort (s) chosen from the group of (E-1-1) 1st aliphatic isocyanate compounds which consist of a duct body, an adduct body of an isophorone diisocyanate compound, the burette body of a hexamethylene diisocyanate compound, and the burette body of an isophorone diisocyanate compound. The above isocyanurate body of tolylene diisocyanate compound, isocyanurate body of xylylene diisocyanate compound, isocyanurate body of hydrogenated xylylene diisocyanate compound, adduct body of tolylene diisocyanate compound, xylyl Adduct, Number of Rendiisocyanate Compounds Xylyl preferably comprises a diisocyanate compound in the air duct body comprising (E-1-2) a second aromatic diisocyanate, at least one or more kinds selected from the compound group. It is preferable to use together the (E-1-1) 1st aliphatic isocyanate compound group and (E-1-2) 2nd aromatic type isocyanate compound group. In the present invention, at least one or more selected from the (E-1-1) first aliphatic isocyanate compound group as the (E-1) trifunctional isocyanate compound, and from the (E-1-2) second aromatic isocyanate compound group By using together at least 1 sort (s) or more selected, the balance of the adhesive force of a low speed peeling area and a high speed peeling area | region can further be improved.

In addition, the (E-1) trifunctional isocyanate compound is at least one or more selected from the above-mentioned (E-1-1) first aliphatic isocyanate compound group, and the (E-1-2) second aromatic isocyanate compound group. It is preferable that it contains at least 1 sort (s) or more selected from among 0.5-5 weight part in total with respect to 100 weight part of said acrylic polymers. Further, the mixing ratio of at least one selected from the group of (E-1-1) first aliphatic isocyanate compounds and at least one type selected from the group of (E-1-2) second aromatic isocyanate compounds is (E-1-1). It is preferable that 1-1) :( E-1-2) exists in the range of 10%: 90%-90%: 10% by weight ratio.

Moreover, as (E-2) difunctional isocyanate compound used for this invention, it is a non-cyclic aliphatic isocyanate compound, It is preferable that it is a compound produced by making a diisocyanate compound and a diol compound react.

For example, a diisocyanate compound is represented by the general formula "O = C = NXN = C = O" (wherein X is divalent) and a diol compound is represented by the formula "HO-Y-OH" (where Y is divalent). When it shows, as a compound produced by making a diisocyanate compound and a diol compound react, the compound represented by following formula (Z) is mentioned, for example.

[Formula Z]

O = C = NX- (NH-CO-OYO-CO-NH-X) _n -N = C = O

N is an integer of 0 or more. In the case where n is 0, the chemical formula Z represents "O = C = N-X-N = C = O". As the bifunctional acyclic aliphatic isocyanate compound, in the general formula (Z), a compound in which n is 0 (unreacted diisocyanate compound relative to the diol compound) may be included, but it is preferable to include a compound in which n is an integer of 1 or more as an essential component. . The bifunctional acyclic aliphatic isocyanate compound may be a mixture composed of a plurality of compounds in which n in the general formula Z is different.

The diisocyanate compound represented by general formula "O = C = N-X-N = C = O" is an aliphatic diisocyanate. X is acyclic and preferably an aliphatic divalent group. As said aliphatic diisocyanate, it is preferable that it consists of 1 type, or 2 or more types chosen from the compound group which consists of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.

The diol compound represented by general formula "HO-Y-OH" is an aliphatic diol. Y is acyclic and preferably an aliphatic divalent group. The diol compound is 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-2- Selected from the group consisting of butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol monohydroxypivalate, polyethylene glycol and polypropylene glycol It is preferable to consist of 1 type, or 2 or more types.

It is preferable that the weight ratio (E-1 / E-2) of the said (E-1) trifunctional isocyanate compound and (E-2) difunctional isocyanate compound is 1-90. It is preferable that the ratio of said (E) bifunctional or more isocyanate compound is 0.1-10 weight part with respect to 100 weight part of the said acrylic polymer.

(F) The crosslinking accelerator may be a substance which functions as a catalyst for the reaction (crosslinking reaction) of the acrylic polymer and the crosslinking agent when the polyisocyanate compound is used as a crosslinking agent, and includes amine compounds such as tertiary amines, metal chelate compounds, Organic metal compounds, such as an organotin compound, an organic lead compound, and an organozinc compound, etc. are mentioned. In this invention, a metal chelate compound and an organic tin compound are preferable as a crosslinking promoter.

The metal chelate compound is a compound in which at least one polydentate ligand L is bonded to the central metal atom M. The metal chelate compound may or may not have one or more single-site ligands X bonded to the metal atom M. For example, when the chemical formula of a metal chelate compound having one metal atom M is represented by M (L) _m (X) _n , m ≧ 1 and _n ≧ 0. When m is 2 or more, m pieces of L may be the same ligand or may be different ligands. When n is two or more, n pieces of X may be the same ligand or different ligands.

Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn and the like.

As the polydentate ligand L, β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, acetoacetic acid oleyl, acetoacetic acid lauryl, acetoacetate acetate, acetylacetone (nickname 2,4-pentanedione), (Beta) -diketone, such as 2, 4- hexanedione and benzoyl acetone, is mentioned. These are ketoenol tautomer compounds, and in the multidentate ligand L, the enolate in which the enol is deprotoned (for example, acetylacetonate) may be used.

As the single ligand, X, alkoxy groups such as halogen atoms such as chlorine atom and bromine atom, pentanoyl group, hexanoyl group, 2-ethylhexanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group and octadecanoyl group And alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, butoxy group and the like.

Specific examples of the metal chelate compound include tris (2,4-pentanedionate) iron (III), iron trisacetylacetonate, titanium trisacetylacetonate, ruthenium trisacetylacetonate, zinc bisacetylacetonate, aluminum trisacetyl Acetonate, zirconium tetrakisacetylacetonate, tris (2,4-hexanedionate) iron (III), bis (2,4-hexanedionate) zinc, tris (2,4-hexanedionate) titanium, tris (2,4-hexane dionate) aluminum, tetrakis (2, 4- hexane dionate) zirconium, etc. are mentioned.

Examples of the organic tin compound include dialkyl tin oxide, fatty acid salts of dialkyl tin, fatty acid salts of first tin, and the like. Conventionally, many dibutyltin compounds have been used, but in recent years, the problem of toxicity of organotin compounds has been pointed out, and tributyltin (TBT) contained in the dibutyltin compound is particularly concerned as an endocrine disrupting substance. From the viewpoint of safety, long chain alkyl tin compounds such as dioctyl tin compounds are preferred. Dioctyl tin oxide, dioctyl tin dilaurate, etc. are mentioned as a specific organic tin compound. Although it is possible to use Sn compounds temporarily, it is preferable to use metal chelate compounds such as Al, Ti, and Fe, which are more safe than Sn, in view of the trend of using more safe materials in the future. Do.

It is preferable that it is at least 1 sort (s) chosen from the group which consists of an aluminum chelate compound, a titanium chelate compound, and an iron chelate compound as (F) crosslinking promoter in the adhesive composition which concerns on this invention.

(F) It is preferable to contain 0.001-0.5 weight part with respect to 100 weight part of said acrylic polymers.

(G) Ketoenol tautomer compounds include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, acetoacetate, octyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate, acetylacetone, 2, (Beta) -diketone, such as 4-hexanedione and benzoyl acetone, is mentioned. In the adhesive composition which uses a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group which a crosslinking agent has, the excess viscosity rise and gelation of the adhesive composition after mix | blending of a crosslinking agent can be suppressed, and the pot life of an adhesive composition can be extended.

(G) It is preferable that a ketoenol tautomer compound is contained 0.1-300 weight part with respect to 100 weight part of the said acrylic polymer.

The (G) ketoenol tautomer compound has the effect of inhibiting crosslinking as opposed to the (F) crosslinking accelerator, and thus the ratio of the (G) ketoenol tautomer compound to the (F) crosslinking accelerator is appropriately set. It is desirable to. In order to lengthen the pot life of an adhesive composition and to improve storage stability, it is preferable that the weight part ratio of (G) / (F) is 70-1000, It is more preferable that it is 70-700, It is especially 80-600 desirable.

Moreover, the adhesive composition which concerns on this invention contains the ionic compound which is solid at 25 degreeC of (H) melting | fusing point as a antistatic agent at the temperature of 25-50 degreeC. Since these antistatic agents have low melting | fusing point and long alkyl group, it is estimated that affinity with an acrylic polymer is high.

(H) An ionic compound having a melting point of 25 to 50 ° C. and a solid at 25 ° C. is an ionic compound having a cation and an anion. The cation is pyridinium cation, imidazolium cation, pyrimidinium cation, pyrazolium cation, pyrrolidin pyridinium cation, ammonium cationic nitrogen-containing onium, such as on-cation or phosphonium cation, alcohol or the like phosphonium cation, the anion is hexafluorophosphate phosphate (PF ₆ ^-), thiocyanate (SCN ^-), alkyl benzene sulfonate (RC ₆ H ₄ SO ₃ ^-), perchlorate (ClO ₄ ^-), 4 fluoride borate (BF ₄ ^-), bis (sulfonyl fluorophenyl) already deuyeom (FSI), bis (tri And compounds that are inorganic or organic anions such as fluoromethanesulfonyl) imide salt (TFSI) and trifluoromethanesulfonate salt (TF). It is preferable that it is solid at normal temperature (for example, 25 degreeC), and it can obtain that melting | fusing point is 25-50 degreeC by selection of the chain length of an alkyl group, the position, the number of substituents, etc. The cation is preferably quaternary nitrogen-onium cation, and quaternary pyridinium cations such as 1-alkylpyridinium (carbon atoms at 2 to 6 positions may have a substituent or may be unsubstituted). Quaternary amidazolium cations such as 3-dialkylimidazolium (carbon atoms in the 2, 4 and 5 positions may have a substituent or may be unsubstituted), quaternary ammonium cations such as tetraalkylammonium, and the like Can be mentioned.

It is preferable that (H) melting | fusing point contains the sum total of at least 1 or more types of ionic compound which is solid at the temperature of 25-50 degreeC with respect to 100 weight part of the said acrylic polymer in the ratio of 0.01-5.0 weight part.

(H) As a specific example of the ionic compound which is solid at 25 degreeC of melting | fusing point 25 degreeC, for example, 1-octylpyridinium hexafluorophosphate, 1-nonylpyridinium hexafluorophosphate, 2-methyl- 1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecylpyridinium thiocyanate, 1-dodecylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octyl Pyridinium hexafluorophosphate etc. are mentioned.

The pressure-sensitive adhesive composition may optionally contain a polyether modified siloxane compound having a (I) HLB value of 7 to 15. The polyether modified siloxane compound is a siloxane compound having a polyether group, and in addition to the usual siloxane unit [-SiR ¹ ₂ -O-], a siloxane unit having a polyether group [-SiR ¹ (R ² O (R ³ O) _n R ⁴ ) -O-]. Wherein R ¹ is one or two or more alkyl groups or aryl groups, R ² and R ³ are one or two or more alkylene groups, and R ⁴ is one or two or more alkyl groups or acyl groups (terminal groups) Indicates. Polyether groups include a polyoxyethylene group [(C ₂ H ₄ O) _n] and a polyoxypropylene group [(C ₃ H ₆ O) _n], such as a polyoxyalkylene group of the.

A polyether modified siloxane compound can be obtained by grafting the organic compound which has an unsaturated bond and a polyoxyalkylene group with the hydrosilylation reaction, for example with respect to the polyorganosiloxane main chain which has a silicon hydride group. Specifically, dimethylsiloxane methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane methyl (polyoxyethylene) siloxane methyl (polyoxypropylene) siloxane copolymer, dimethyl siloxane methyl (polyoxypropylene) siloxane polymer, etc. Can be mentioned. The HLB value of a polyether modified siloxane compound can be adjusted by selecting the ratio of a polyether group and a siloxane group.

(I) By mix | blending the polyether modified siloxane compound whose HLB value is 7-15 with an adhesive composition, the adhesive force and stainability of an adhesive can be improved. When an adhesive composition does not contain a polyether modified siloxane compound, it becomes low cost.

It is preferable that a polyether modified siloxane compound is a polyether modified siloxane compound whose HLB value is 7-15. HLB is a hydrophilic lipophilic balance (hydrophilic lipophilic ratio) prescribed | regulated to JISK3211 (surfactant term) etc., for example.

Moreover, it is preferable to contain the polyether modified siloxane compound of (I) HLB value 7-15 with a ratio of 0.01-1.0 weight part with respect to 100 weight part of the said acrylic polymer, and the ratio of 0.05-0.8 weight part is more preferable. The ratio of 0.1-0.5 weight part is especially preferable.

The acrylic polymer used for the adhesive composition of this invention is a (meth) acrylic acid ester monomer whose carbon number of (A) alkyl group is C1-C18, and (a1) at least 1 of the (meth) acrylic acid ester monomer whose carbon number of an alkyl group is C1-C4. At least one or more of (a) a copolymerizable monomer group containing at least one of the (meth) acrylic acid ester monomer having a C5 to C18 carbon number of the alkyl group (a2) and at least one or more of the copolymerizable monomers containing a hydroxyl group (B); And (C) It can synthesize | combine by copolymerizing at least 1 sort (s) or more of the copolymerizable monomer containing a carboxyl group, and at least 1 sort (s) or more of (D) polyalkylene glycol mono (meth) acrylic acid ester monomer. The polymerization method of an acrylic polymer is not specifically limited, Suitable polymerization methods, such as solution polymerization and emulsion polymerization, can be used.

At the time of preparation of the copolymer which is a subject, in order to reduce mixing of water with respect to an adhesive composition, it is preferable to perform a polymerization reaction on anhydrous conditions, such as solution polymerization using anhydrous organic solvent. In particular, since the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer has high hydrophilicity, it is preferable to use a thing with low water content.

In order to avoid the viscosity rise of an adhesive composition, each monomer used for manufacture of the copolymer which is a subject is preferable to reduce as much as possible the quantity of the polyfunctional (bifunctional or more) monomer which can function as a crosslinking agent. In particular, since the corresponding diester powder is the di (meth) acrylic acid ester of a bifunctional monomer, the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is preferable to use a thing with few diester components.

The pressure-sensitive adhesive composition of the present invention comprises (E) a bifunctional or higher isocyanate compound, (F) crosslinking accelerator, (G) ketoenol tautomer compound, and (H) a melting point of 25 to 50 ° C. in the acrylic polymer. It can manufacture by mix | blending suitably the ionic compound which is solid at degreeC, and arbitrary additives further.

The adhesive composition of this invention is a copolymer in which the said acrylic polymer copolymerized without containing the nitrogen-containing vinyl monomer and the alkoxy group containing alkyl (meth) acrylate monomer which do not contain a hydroxyl group.

Here, as a nitrogen-containing vinyl monomer which does not contain the said hydroxyl group, For example, Acrylic monomer containing a N, N-dialkyl substituted amino group or N, N-dialkyl substituted amide group; N-vinyl substituted lactams, such as N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and N-vinyl-2- piperidone; N- (meth) acryloyl substituted cyclic amines, such as N- (meth) acryloyl morpholine and N- (meth) acryloyl pyrrolidine; Acrylo di-containing ionic compounds, such as an acryloyl group containing ammonium salt, etc. are mentioned.

Specific examples of the acryloyl group-containing ionic compound include dimethylaminomethyl (meth) acrylate methyl fluorophosphate [(CH ₃ ) ₃ N ⁺ CH ₂ OCOCQ = CH ₂ · PF ₆ ⁻ , provided that Q = H Or CH ₃ ] and dimethylaminoethyl (meth) acrylate bis (trifluoromethanesulfonyl) imidemethyl salt [(CH ₃ ) ₃ N ⁺ (CH ₂ ) ₂ OCOCQ = CH ₂ · (CF ₃ SO ₂ ) ₂ N ⁻ , provided that Q = H or CH ₃ ], dimethylaminomethylmethacrylate bis (fluorosulfonyl) imidemethyl salt [(CH ₃ ) ₃ N ⁺ CH ₂ OCOCQ = CH ₂ · (FSO ₂ ) ₂ N ⁻ , provided that Q = H or CH ₃ ].

Moreover, as said alkoxy group containing alkyl (meth) acrylate monomer, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acryl, for example. Late, 2-isopropoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-prop Foxypropyl (meth) acrylate, 2-isopropoxypropyl (meth) acrylate, 2-butoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) Acrylate, 3-propoxypropyl (meth) acrylate, 3-isopropoxypropyl (meth) acrylate, 3-butoxypropyl (meth) acrylate, 4-methoxy butyl (meth) acrylate, 4- Ethoxybutyl (meth) acrylate, 4-propoxybutyl (meth) acrylate, 4-isopropoxy Butyl (meth) acrylate, 4-butoxy-butyl (meth) acrylate.

These alkoxy group containing alkyl (meth) acrylate monomers have the structure where the atom of the alkyl group in alkyl (meth) acrylate was substituted by the alkoxy group. Since the alkoxy group-containing alkyl (meth) acrylate monomer does not have a polyalkylene glycol structure, the alkoxy group-containing (D) polyalkylene glycol mono (meth) acrylic acid ester monomer is an alkoxy group-containing alkyl (meth) acrylate monomer. This does not apply.

According to the present invention, even when the acrylic polymer included in the pressure-sensitive adhesive composition does not contain a nitrogen-containing vinyl monomer and an alkoxy group-containing alkyl (meth) acrylate monomer that do not contain a hydroxyl group, the contamination on the adherend is small, and it does not deteriorate with time and is excellent. It has the characteristics to solve the subject of providing the adhesive composition which has peeling antistatic performance, and an antistatic surface protection film.

As an optional additive component, well-known additives, such as surfactant, a hardening accelerator, a plasticizer, a filler, a hardening retarder, a processing aid, an antioxidant, and antioxidant, can be mix | blended suitably with the adhesive composition which concerns on this invention. These may be used alone or in combination of two or more.

It is preferable that the adhesive force in the low speed peeling speed 0.3m / min of the adhesive layer formed by crosslinking the said adhesive composition is 0.05-0.1N / 25mm, and the adhesive force in the high speed peeling speed 30m / min is 1.0N / 25mm or less. Thereby, performance with little change also in adhesive force by peeling speed can be obtained, and it becomes possible to peel quickly also by high speed peeling. In addition, in order to reattach, excessive force is not required even when peeling off an antistatic surface protection film once, and it is easy to peel from an adherend.

It is preferable that the gel fraction of the adhesive layer (pressure-sensitive adhesive after crosslinking) which crosslinks the adhesive composition of this invention is 95 to 100%. In this way, the gel fraction is high, the adhesive force does not become excessive at a low peeling speed, the elution of the unpolymerized monomer or oligomer from the acrylic polymer is reduced, the contamination, the durability at high temperature and high humidity are improved, and the adherend Contamination can be suppressed.

The antistatic surface protection film of this invention forms the adhesive layer which crosslinks an adhesive composition on one side or both sides of a resin film. Since the antistatic surface protection film of this invention is formed by the adhesive layer which bridge | crosslinked the adhesive composition in which each component of said (A)-(H) was balanced, it is equipped with the outstanding antistatic performance, and it is a low peeling speed And at a high peeling speed, it is excellent in the balance of adhesive force, and also excellent in durability performance and contamination. For this reason, since it can use suitably as a use of the surface protection film of a polarizing plate, industrial use value is high.

As a polarizing plate which is a to-be-adhered body, a polarizing plate (LR polarizing plate) with low reflection surface treatment performed with a reflectance of 2% or less, a low reflecting surface treatment with a reflectance of 2% or less, and a polarizing plate (AG-LR polarizing plate) further subjected to anti-glare treatment Can be mentioned.

It is preferable that the surface resistivity of the adhesive layer which crosslinks the said adhesive composition is 9.0 * 10 <^{11> (} ohm) / square or less. Moreover, after bonding the said antistatic surface protection film to the said polarizing plate through the said adhesive layer, it is preferable that the peeling electrification voltage at the time of peeling is "± 0.8 kPa or less". In the present invention, "± 0.8 Hz or less" means 0 to -0.8 Hz and 0 to +0.8 Hz, that is, -0.8 to +0.8 Hz. When surface resistivity is large, when peeling an antistatic surface protection film from a to-be-adhered body, the performance which will let | release the static electricity generated by charging will fall. For this reason, by making surface resistivity small enough, the peeling electrification voltage generate | occur | produced with the static electricity which arises when a to-be-adhered body peels an adhesive layer can be reduced, and it can suppress that it affects the electrical control circuit of a to-be-adhered body, etc ..

Resin films, such as a polyester film, etc. can be used as a base film of an adhesive layer, and the peeling film (separator) which protects an adhesive surface.

The base film can be subjected to antistatic treatment by antifouling treatment with a silicone-based, fluorine-based release agent or coating agent, silica fine particles or the like, application or mixing of an antistatic agent, and the like on the opposite side to the side where the pressure-sensitive adhesive layer of the resin film is formed.

The release film is subjected to a release film by a silicone-based, fluorine-based release agent or the like on the side of the side of the release film that is joined to the adhesive face of the pressure-sensitive adhesive layer.

Example

Next, an Example demonstrates this invention in detail.

<Production of Adhesive Composition>

Example 1

Nitrogen gas was introduce | transduced into the reaction apparatus provided with the stirrer, the thermometer, the reflux cooler, and the nitrogen inlet tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, 15 parts by weight of methyl acrylate, 85 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 8-hydroxyoctyl acrylate, 0.1 part by weight of acrylic acid, and polypropylene glycol monoacrylate (n = 12) were added to the reaction apparatus. 60 weight part of solvents (ethyl acetate) were added with 10 weight part. Then, 0.1 weight part of azobisisobutyronitrile was dripped over 2 hours as a polymerization initiator, it was made to react at 65 degreeC for 6 hours, and the acrylic polymer solution used for Example 1 of 500,000 of weight average molecular weights was obtained. To this acrylic polymer solution, 9.0 parts by weight of acetylacetone was added and stirred, followed by 2.0 parts by weight of coronate HX (isocyanurate of hexamethylene diisocyanate compound), 0.1 part by weight of titanium trisacetylacetonate, and 1- 1.0 weight part of nonylpyridinium hexafluorophosphates and 0.1 weight part of polyether modified siloxane compounds (HLB = 7) were added, and it stirred and mixed, and obtained the adhesive composition of Example 1.

[Examples 2 to 6 and Comparative Examples 1 to 3]

Except having made the composition of the adhesive composition of Example 1 as described in Table 1 and Table 2, respectively, it carried out similarly to Example 1, and obtained the adhesive composition of Examples 2-6 and Comparative Examples 1-3.

Both Table 1 and Table 2 show the numerical values in parts by weight of the sum of the groups (a1) and (a2) as 100 parts by weight in parentheses. In addition, the compound name of the symbol of each component used for Table 1 and Table 2 is shown in Table 3 and Table 4. Here, Coronate (trademark) HX, HL, and L are brand names of Toso Corporation, and Takenate (trademark) D-140N, D-127N, and D-110N are brand names of Mitsui Chemicals Corporation.

Regarding the group (D) in Table 3, the numerical value of "n" is the average repeating number of the alkylene oxide constituting the polyalkylene glycol chain. In the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer (D-1 to D-5) used in Examples 1-6, the average repeating number of the alkylene oxide which comprises a polyalkylene glycol chain is 3-14. And diester content in a monomer is 0.2% or less.

<Synthesis of Bifunctional Isocyanate Compound>

The bifunctional isocyanate compound of the synthesis examples 1 and 2 was synthesize | combined by the following method. As shown in Table 5 and Table 6, the diisocyanate and the diol compound were mixed at a molar ratio of NCO / OH = 16, reacted at 120 ° C for 3 hours, and then unreacted under reduced pressure using a thin film evaporator. Diisocyanate was removed and the desired bifunctional isocyanate compound was obtained.

<Production of an antistatic surface protection film>

Example 1

The pressure-sensitive adhesive composition of Example 1 prepared as described above was applied onto a release film made of a polyethylene resin coated polyethylene terephthalate (PET) film, and then dried at 90 ° C. to remove the solvent, and the pressure-sensitive adhesive layer had a thickness of 25 μm. A sheet was obtained. After that, the pressure-sensitive adhesive sheet was transferred to a surface opposite to the antistatic and antifouling surface of the antistatic and antifouling polyethylene terephthalate (PET) film on one surface thereof, and thus the "antistatic and antifouling PET film / The antistatic surface protection film of Example 1 which has the laminated constitution of "A pressure sensitive adhesive layer / peeling film (silicone resin coat PET film)" was obtained.

[Examples 2 to 6 and Comparative Examples 1 to 3]

It carried out similarly to the antistatic surface protection film of the said Example 1, and obtained the antistatic surface protection film of Examples 2-6 and Comparative Examples 1-3.

<Test method and evaluation>

After aging the antistatic surface protection film in Examples 1-6 and Comparative Examples 1-3 for 7 days in 23 degreeC and 50% RH atmosphere, the peeling film (silicone resin-coated PET film) was peeled off and an adhesive What expressed the layer was made into the measurement sample of surface resistivity.

Moreover, after pasting the antistatic surface protection film which expressed this adhesive layer on the surface of a polarizing plate through an adhesive layer, and leaving it to stand for 1 day, it autoclave-processes 50 degreeC, 5 atmospheres, and 20 minutes, and again at room temperature for 12 hours. What was left to stand was made into the measurement sample of adhesive force, peeling electrification voltage, and contamination. The polarizing plate of the adherend is an LR polarizing plate or an AG-LR polarizing plate.

<Adhesive force>

Low-speed peeling speed (0.3 m /) using the tensile tester to measure the measurement sample obtained by attaching the antistatic surface protection film of 25 mm width to the surface of the polarizing plate which performed LR process or AG-LR process in 180 degree direction obtained above min) and at a high peel rate (30 m / min), and the measured peel strength was regarded as adhesive force (N / 25 mm).

<Surface resistivity>

After aging, before bonding to a polarizing plate, the peeling film (silicone resin-coated PET film) was peeled off and the adhesive layer was exposed, and the adhesive layer was used using the resistivity meter Hirestar UP-HT450 (manufactured by Mitsubishi Chemical Analyzer). Surface resistivity (ohm / square) was measured.

<Peeling large voltage>

The high-precision electrostatic sensor SK-035, SK- which generate | occur | produces the voltage (large voltage) which the polarizing plate which performed LR process or AG-LR process charges when the measurement sample obtained above is 180 degree peeled at 30 m / min of tensile speed. It measured using 200 (made by Keyence Corporation), and made the maximum value of the measured value into peeling electrification voltage.

<Pollutant>

On one side of a glass plate, the polarizing plate was bonded together through adhesive layers, such as a double-sided adhesive tape, using a bonding machine. Then, the adhesive layer of an antistatic surface protection film is bonded together using a bonding machine on the surface of the polarizing plate which performed LR process or AG-LR process. After storing for 3 days and 30 days in 23 degreeC and 50% RH environment, the antistatic surface protection film was peeled off and the contamination state of the surface of a polarizing plate was visually observed.

Surface contamination is the case where there is no contamination in any of the storage for 3 days and the storage for 30 days with respect to the surface of the polarizing plate. And the case of contamination were evaluated as "x".

Table 7 shows the results of the evaluation. Here, the surface resistivity was described by the method of making "m * 10 ^{+ n} " into "mE + n" (m is arbitrary real value and n is a positive integer).

The antistatic surface protective films of Examples 1 to 6 had an adhesive force of 0.05 to 0.1 N / 25 mm at a low peel speed of 0.3 m / min with respect to the adherend of the polarizing plate subjected to the LR treatment or the AG-LR treatment. The adhesive force at the speed of 30 m / min is 1.0 N / 25 mm or less, the surface resistivity is 9.0 × 10 ^{+ 11} Ω / □ or less, the peeling electrification voltage is ± 0 to 0.8 kPa, and for three days storage and 30 days storage, The contamination was also excellent.

Moreover, the antistatic surface protection film of the comparative example 1 in which the acryl-type polymer does not contain the (meth) acrylic acid ester monomer whose C1-C4 carbon number of the (a1) alkyl group has high peeling electrification voltage, and was slightly inferior to contamination.

Moreover, 80 weight of the (meth) acrylic acid ester monomers of C1-C4 carbon number of an alkyl group with respect to a total of 100 weight part of the (meth) acrylic acid ester monomers whose C1-C18 carbon number of the (A) alkyl group is the acrylic polymer. The antistatic surface protective film of Comparative Example 2, which contained at a negative proportion and contained more than 20 parts by weight of the (meth) acrylic acid ester monomer having C5 to C18 carbon atoms of the (a2) alkyl group, had excessive adhesive force, high surface resistivity, and The peeling electrification voltage was high and the contamination was inferior.

In addition, the antistatic surface protective film of Comparative Example 3 in which the acrylic polymer did not contain the (D) polyalkylene glycol mono (meth) acrylic acid ester monomer had high surface resistivity, high peeling electrification voltage, and poor contamination. .

As described above, the antistatic surface protective films of Comparative Examples 1 to 3 were not compatible with the suppression of contamination on the adherend and the excellent antistatic peeling performance.

Claims (9)

As an antistatic surface protection film by which the adhesive layer which crosslinks an acrylic polymer, an antistatic agent, and the adhesive composition containing a crosslinking agent is laminated | stacked on one side of a base film,
The acrylic polymer is based on 100 parts by weight of the acrylic polymer,
(A) 50-99.8 weight part of total (meth) acrylic acid ester monomers of C1-C18 carbon number of an alkyl group,
As a copolymerizable monomer group,
(B) 0.1-14 weight part of at least 1 type or more of the copolymerizable monomer containing a hydroxyl group,
(C) 0.01-1.0 weight part of at least 1 type or more of the copolymerizable monomer containing a carboxyl group,
(D) more than 0 to 35 parts by weight or less of at least one or more of the polyalkylene glycol mono (meth) acrylic acid ester monomer,
It is a copolymer copolymerized without containing the nitrogen-containing vinyl monomer which does not contain a hydroxyl group, and the alkoxy-group containing alkyl (meth) acrylate monomer,
The (meth) acrylic acid ester monomer having a C1 to C18 carbon number of the (A) alkyl group is at least one or more of the (meth) acrylic acid ester monomer having a C1 to C4 carbon number of the (a1) alkyl group, and the carbon number of the (a2) alkyl group. It consists of at least 1 sort (s) or more of the (meth) acrylic acid ester monomer which is C5-C18, The content ratio (a2 / a1) of said (a1) and said (a2) is more than 1 and 50 or less by mass ratio,
The antistatic agent is an ionic compound which is a solid (H) at a melting point of 25 to 50 ° C. and a temperature of 25 ° C.,
The crosslinking agent is an (E) bifunctional or higher isocyanate compound,
The pressure-sensitive adhesive composition further comprises (F) a crosslinking accelerator and (G) a ketoenol tautomer compound,
The (H) the ionic compound is a nitrogen-containing onium cation, phosphonium cation, sulfonium cation, hexafluorophosphate phosphates one kind of cations and selected from on (PF ₆ ^-), thiocyanate (SCN ^-), an alkyl benzene sulfonate ^{_{(RC 6 H 4 SO 3 -}} ), perchlorate (ClO ₄ ^-), ₄ fluoride borate (BF ₄ ^-), bis (sulfonyl fluorophenyl) already deuyeom (FSI), bis (trifluoromethanesulfonyloxy An antistatic surface protective film, characterized in that it is an ionic compound having at least one anion selected from an imide salt (TFSI) and a trifluoromethanesulfonate salt (TF). The method of claim 1,
As said (D) polyalkylene glycol mono (meth) acrylic acid ester monomer, polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate At least one selected from
The (D) polyalkylene glycol mono (meth) acrylic acid ester monomer has an average repeating number of 3 to 14 alkylene oxides constituting the polyalkylene glycol chain, and the diester content in the monomer is 0.2% or less. Surface protection film. The method according to claim 1 or 2,
The crosslinking accelerator (F) is at least one or more selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds,
It is contained in the ratio of 0.001-0.5 weight part of said (F) crosslinking promoters, and 0.1-300 weight part of said (G) ketoenol tautomer compounds with respect to 100 weight part of said acrylic polymers, Said (G) / The weight part ratio of said (F) is 70-1000, The antistatic surface protection film characterized by the above-mentioned. The method according to claim 1 or 2,
The copolymerizable monomer containing the said (B) hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl At least one or more selected from the group consisting of (meth) acrylates, N-hydroxy (meth) acrylamides, N-hydroxymethyl (meth) acrylamides, and N-hydroxyethyl (meth) acrylamides;
The copolymerizable monomer containing the (C) carboxyl group is (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahexaphthalic acid, 2- ( Meta) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypoly It is at least 1 sort (s) or more selected from the group which consists of a caprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, The antistatic surface protective film characterized by the above-mentioned. delete delete delete delete The method according to claim 1 or 2,
The antistatic surface protective film used as a use of the protective film for polarizing plates.