JP2009051983A - Antistatic acrylic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic acrylic resin composition which is useable for coating, pressure-sensitive adhesive, etc., particularly a transparent antistatic acrylic resin composition suitable for formation of a pressure-sensitive agent layer for surface protective films of optical member such as a polarizing plate for large screen used for production of liquid crystal display and having little occurrence of electrostatic charge when released. <P>SOLUTION: The antistatic acrylic resin composition comprises (A) an acrylic resin having a hydroxy group and an alkylene oxide chain and not having alkanol ammonium salt part, (B) a compound having a functional group capable of reacting with the hydroxy group and (E) a boron-based antistatic property-imparting agent which is an ammonium salt or an alkali metal salt. <P>COPYRIGHT: (C)2009,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.

Therefore, an antistatic resin composition having adhesiveness for forming an adhesive layer of a protective film is required. Patent Document 3 (Japanese Patent Laid-Open No. 2006-291172) discloses an ionic liquid (room temperature molten salt). An acrylic resin-based pressure-sensitive adhesive containing a monomer having an alkylene oxide chain is disclosed as a pressure-sensitive adhesive with little contamination. The ionic liquid is excellent in ionic conductivity, but by coordinating with the ether chain of alkylene oxide, bleed is suppressed and adherend contamination is reduced. However, some ionic liquids cannot suppress bleeding with only alkylene oxide, and have a problem in adherend contamination. Further, when lithium perchlorate is used, there is a problem of corrosion, and the surface of the adherend may be altered. With the recent increase in the screen size of liquid crystal televisions, optical processing is also essential for the polarizing plate surface, and stricter quality is also required for the protective film.
JP 2003-261774 A JP 2003-41194 A JP 2006-291172 A

  The present invention is an antistatic acrylic resin composition that can be used for paints, pressure-sensitive adhesives, etc., and in particular, a pressure-sensitive adhesive for a surface protective film of an optical member such as a polarizing plate for a large screen used in the production of a liquid crystal display. It is an object of the present invention to provide a transparent antistatic acrylic resin composition that is suitable for forming an agent layer and that is transparent and generates little static electricity during peeling.

1st invention is the acrylic resin (A) which has a hydroxyl group and an alkylene oxide chain, and does not have an alkanol ammonium salt part,
As the compound (B) having a functional group capable of reacting with a hydroxyl group, and the antistatic agent (E),
The present invention relates to an antistatic acrylic resin composition comprising a compound (E1) represented by the following general formula [1] or a compound (E2) represented by the following general formula [2].

(In General Formula [1] and General Formula [2], R ¹ to R ⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, An alkynyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, wherein R ⁵ to R ⁸ are adjacent to each other You may form a ring with
In the general formula [2], A ⁺ represents an alkali metal ion. )

The second invention is based on 100 parts by weight of the acrylic resin (A).
1 to 30 parts by weight of a compound (B) having a functional group capable of reacting with a hydroxyl group and 0.001 to 20 parts by weight of an antistatic agent (E) The present invention relates to a functional acrylic resin composition.

  In the third invention, the acrylic resin (A) is a monomer having an acrylic monomer (a1) having a hydroxyl group, a radical polymerizable unsaturated double bond and an alkylene oxide chain, and no alkanol ammonium salt portion. The acrylic resin obtained by copolymerizing (a2) and a radically polymerizable unsaturated monomer (a3) essentially comprising an acrylic monomer other than the above (a1) and (a2) The present invention relates to the antistatic acrylic resin composition of the second invention.

  The fourth invention is the antistatic property of the third invention, wherein the proportion of the monomer (a2) is 0.01 to 40% by weight in a total of 100% by weight of the monomers (a1) to (a3). The present invention relates to an acrylic resin composition.

  The fifth invention further includes a surfactant (D) other than the anionic surfactant (D1-1) having an alkanol ammonium salt portion, and is characterized in that the invention according to any one of the first to fourth inventions is characterized. The present invention relates to an electrically conductive acrylic resin composition.

  6th invention contains 0.001-10 weight part of surfactant (D) with respect to 100 weight part of acrylic resin (A), Antistatic acrylic resin of 5th invention characterized by the above-mentioned Relates to the composition.

  The seventh invention is the antistatic acrylic resin composition according to any one of the first to sixth inventions, wherein the compound (B) having a functional group capable of reacting with a hydroxyl group is a trifunctional isocyanate compound. About.

  An eighth invention is an optical member comprising an adhesive layer formed from the antistatic acrylic resin composition of any one of the first to seventh inventions laminated on at least one surface of a plastic film substrate. The present invention relates to a protective film.

  According to the present invention, an antistatic acrylic resin composition that can be used for paints, pressure-sensitive adhesives, etc., particularly for forming a pressure-sensitive adhesive layer for a surface protective film of an optical member such as a polarizing plate of a large-screen liquid crystal display. A suitable antistatic acrylic resin composition with less generation of static electricity at the time of peeling can be obtained.

  An acrylic resin (A) having a hydroxyl group and an alkylene oxide chain and not having an alkanol ammonium salt part (hereinafter sometimes simply referred to as “acrylic resin (A)”) used in the present invention is: Acrylic monomer (a1) having a hydroxyl group, a monomer (a2) having a radical polymerizable unsaturated double bond and an alkylene oxide chain, and not having an alkanol ammonium salt part, can be copolymerized with these if necessary. It can be synthesized from another acrylic monomer (a3).

  Examples of the acrylic monomer (a1) having a hydroxyl group used in the present invention (hereinafter sometimes simply referred to as “monomer (a1)”) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate and the like. In the present invention, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.

  In the present invention, the purpose of using the acrylic monomer (a1) having a hydroxyl group is to ensure the removability while ensuring the adhesive force to the adherend. More specifically, a crosslinked structure is formed by utilizing the reaction between a hydroxyl group and a compound (B) having a functional group capable of reacting with a hydroxyl group, which will be described later, which is used when forming the pressure-sensitive adhesive layer. Thus, by controlling the molecular weight of the acrylic resin (A), it is possible to balance the adhesive force and the removability.

When the total of the monomers constituting the acrylic resin (A) is 100% by weight, the proportion of the acrylic monomer (a1) having a hydroxyl group is preferably 1 to 30% by weight. More preferably, it is 3 to 10% by weight. When the acrylic monomer (a1) having a hydroxyl group is less than 1% by weight, the degree of crosslinking and cohesion as the pressure-sensitive adhesive layer are insufficient, and the pressure-sensitive adhesive strength becomes excessively large or adhesive residue is liable to occur. If it exceeds 30% by weight, the degree of crosslinking becomes too high and the tackiness becomes poor.
In the present invention, the monomer having an alkylene oxide chain whose terminal is a hydroxyl group is classified into the monomer (a2) described later.

  In the present invention, the purpose of using the monomer (a2) having a radical polymerizable unsaturated double bond and an alkylene oxide chain and not having an alkanol ammonium salt portion (hereinafter also simply referred to as “monomer (a2)”) is as follows. This is because the compound (E1) and the compound (E2), which will be described later, coordinate to the alkylene oxide chain in the monomer (a2), thereby suppressing their migration to the surface and reducing contamination of the adherend. .

When the total amount of monomers constituting the acrylic resin (A) is 100% by weight, the proportion of the monomer (a2) is preferably 0.01 to 40% by weight, more preferably 0.01 to 20% by weight, and 0 More preferably, the content is 0.01 to 1% by weight.
When the monomer (a2) is less than 0.01% by weight, the effect of reducing the contamination on the adherend cannot be expected. On the other hand, when it exceeds 40% by weight, gelation may occur during polymerization due to the influence of a bifunctional monomer that may be contained as an impurity in the monomer (a2). Moreover, a monomer (a2) may be used independently and may be used in mixture of 2 or more types.

  In the present invention, the monomer (a2) having a radically polymerizable unsaturated double bond and an alkylene oxide chain and not having an alkanol ammonium salt portion includes, for example, (meth) acrylic acid alkylene oxide adduct, And reactive surfactants having reactive substituents such as acryloyl, methacryloyl and allyl groups.

  Specific examples of the (meth) acrylic acid alkylene oxide adduct in the present invention include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol. (Meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauro Xylethylene glycol (meth) acrylate, stearoxy polyethylene Glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxypolyethylene glycol - polypropylene glycol (meth) acrylate.

  Specific examples of the reactive surfactant having an alkylene oxide group include, for example, an anionic reactive surfactant having a (meth) acryloyl group or an allyl group, a nonionic reactive surfactant, and a cationic reactive agent. Surfactant etc. are mention | raise | lifted.

  Examples of the anionic reactive surfactant include those represented by formulas (A1) to (A10).

[R ₁ in Formula (A1) represents hydrogen or a methyl group, R ₂ represents a hydrocarbon group having 1 to 30 carbon atoms or an acyl group, X represents an anionic hydrophilic group, R ₃ and R ₄ are The alkylene groups having 1 to 6 carbon atoms are the same or different, and the average added mole number m and n are 0 to 40, where (m + n) represents 3 to 40. ].

[R ₁ in Formula (A2) represents hydrogen or a methyl group, R ₂ and R ₇ are the same or different, represent an alkylene group having 1 to 6 carbon atoms, and R ₃ and R ₅ are the same or different, Represents hydrogen or an alkyl group, R ₄ and R ₆ are the same or different and represent hydrogen, an alkyl group, a benzyl group or a styrene group, X represents an anionic hydrophilic group, and the average number of added moles m and n are 0 to 40, where (m + n) represents a number from 3 to 40. ].

[R ₁ in Formula (A3) represents hydrogen or a methyl group, R ₂ represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average number of added moles n is 3 to 40 Represents a number. "

[R ₁ in Formula (A4) represents hydrogen or a methyl group, R ₂ represents a hydrocarbon group or acyl group having 1 to 30 carbon atoms, and R ₃ and R ₄ may be the same or different, and 6 represents an alkylene group, X represents an anionic hydrophilic group, the average added mole number m and n are 0 to 40, and (m + n) represents a number of 3 to 40. ].

[R ₁ in Formula (A5) represents a hydrocarbon group, an amino group, or a carboxylic acid residue, R ₂ represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and average added mole The number n represents an integer of 3 to 40. ].

[In Formula (A6), R ₁ represents a hydrocarbon group having 1 to 30 carbon atoms, R ₂ represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, R ₃ represents hydrogen or a propenyl group, and R ₄ represents An alkylene group having 1 to 6 carbon atoms is represented, X represents an anionic hydrophilic group, and the average added mole number n represents a number of 3 to 40. ].

[R ₁ in Formula (A7) represents hydrogen or a methyl group, R ₂ and R ₄ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and R ₃ represents a hydrocarbon having 1 to 30 carbon atoms. Represents a group, M represents a hydrogen, alkali metal, or ammonium group, the average number of added moles m and n is 0 to 40, where (m + n) represents a number of 3 to 40. ].

[And _{R 1} and _{R 5} in the formula (A8) the same or different, represent a hydrogen or a methyl group, _{R 2} and _{R 4} are the same or different and each represents an alkylene group having a carbon number of 1 to 6, _{R 3} is A hydrocarbon group having 1 to 30 carbon atoms is represented, M represents hydrogen, an alkali metal, or an ammonium group, and the average number of added moles m and n is 0 to 40, where (m + n) represents a number of 3 to 40. ].

[R ₁ in Formula (A9) represents an alkylene group having 1 to 6 carbon atoms, R ₂ represents a hydrocarbon group having 1 to 30 carbon atoms, M represents hydrogen, an alkali metal, or an ammonium group. The added mole number n represents a number of 3 to 40. ].

[R ₁ , R ₂ and R _{3 in} Formula (A10) are the same or different and represent hydrogen or a methyl group, and R ₄ represents a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, R ₄ R ₅ and R ₆ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and average added mole numbers m and n are 0 to 40, where (m + n) represents a number from 3 to 40. ].

  X in the above formulas (A1) to (A6) and (A10) represents an anionic hydrophilic group. Examples of the anionic hydrophilic group include those represented by the following formulas (A11) to (A12).

(A11)
-SO ₃ M ₁

[M ₁ in Formula (A11) represents hydrogen, an alkali metal, or an ammonium group. ].

(A12)

[The _{M 2} and _{M 3} in the formula (A12) the same or different and each represents hydrogen, an alkali metal or an ammonium group. ].
Examples of nonionic reactive surfactants include those represented by formulas (N1) to (N6).

[R ₁ in Formula (N1) represents hydrogen or a methyl group, R ₂ represents a hydrocarbon group or an acyl group having 1 to 30 carbon atoms, and R ₃ and R ₄ may be the same or different, and 6 represents an alkylene group, and average addition mole numbers m and n are 0 to 40, where (m + n) represents a number of 3 to 40. ].

[R ₁ in Formula (N2) represents hydrogen or a methyl group, R ₂ , R ₃ , and R ₄ are the same or different and represent an alkylene group having 1 to 6 carbon atoms, and the average number of added moles n, m , And l are 0 to 40, and (n + m + 1) represents a number from 3 to 40. ].

[R ₁ in Formula (N3) represents hydrogen or a methyl group, R ₂ and R ₃ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and R ₄ represents a hydrocarbon having 1 to 30 carbon atoms. A group or an acyl group, the average number of added moles m and n is 0 to 40, where (m + n) represents a number of 3 to 40. ].

[R ₁ and R _{2 in} formula (N4) are the same or different and each represents a hydrocarbon group having 1 to 30 carbon atoms, R ₃ represents hydrogen or a propenyl group, and R ₄ represents an alkylene having 1 to 6 carbon atoms Represents the group, and the average addition mole number n represents a number of 3 to 40. ].

[In formula (N5), R ₁ and R ₃ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ₂ and R ₄ are the same or different and represent hydrogen or a hydrocarbon having 1 to 30 carbon atoms; A group or an acyl group, and the average addition mole numbers m and n are 0 to 40, where (m + n) represents a number of 3 to 40. ].

[R ₁ , R ₂ and R _{3 in} Formula (N6) are the same or different and represent hydrogen or a methyl group, and R ₄ represents a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, R ₄ R ₅ and R ₆ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and the average added mole numbers m and n are 0 to 40, provided that (m + n) is 3 to 3. The number of 40 is represented. ].

  Moreover, as a commercial item of monomer (a2), specifically, for example, NK ester M90G (manufactured by Shin-Nakamura Chemical Co., Ltd.), Blemmer PME-400, Blemmer PME-1000, Blemmer 50POEP-800B (all above, (Manufactured by Nippon Oil & Fats Co., Ltd.), Latemu PD-104, Latemu PD-420, Latemu PD-430 (all of which are manufactured by Kao Corporation), Adeka Soap ER-10, Adeka Soap NE-10, Adeka Soap SR- 10S (all of which are manufactured by Asahi Denka Kogyo Co., Ltd.).

The radical-polymerizable unsaturated monomer (a3) [hereinafter also simply referred to as “monomer (a3)]”, which essentially contains an acrylic monomer other than the above (a1) and (a2), is used for the monomer (a1). ), A monomer copolymerizable with the monomer (a2).
Specific examples of the monomer used as the monomer (a3) include 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 (a3) can be appropriately selected and used alone or in combination of two or more for the purpose of obtaining desirable physical properties as an antistatic acrylic resin composition. In particular, the type of monomer (a3) may 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 in order to impart adhesive strength. preferable.

The weight average molecular weight (Mw) of the acrylic resin (A) obtained by copolymerizing the monomer (a1), the monomer (a2) and the other monomer (a3) 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.
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 adhered to, it is required for the adhesive layer of the protective film. 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, it is always required that the antistatic acrylic resin composition does not remain on the adherend at the time of peeling regardless of the adherend.
The peel strength of the protective film using the antistatic acrylic resin composition can react with the cohesive strength of the main component acrylic resin itself and the main component and a hydroxyl group that functions as a curing agent described later. It is greatly influenced by the situation of crosslinking with the compound (B) having a functional group. 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 is required at the time of peeling, the curing agent is added in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the main component, that is, the acrylic resin (A). It is preferably used, more preferably 2 to 20 parts by weight, and even more preferably 3 to 15 parts by weight.
In addition, it is preferable that there are many hardening | curing agents from a viewpoint of low peeling force expression. However, if the amount is too large, crosslinking is excessive and the antistatic property is lowered, which is not preferable.

Next, the antistatic agent (E) used in the present invention will be described.
The antistatic imparting agent (E) used in the present invention is a boron-based antistatic agent, and is an ammonium salt compound (E1) represented by the following general formula [1], or the following general formula [2]. This is a represented alkali metal salt compound (E2).

(In General Formula [1] and General Formula [2], R ¹ to R ⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, An alkynyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, wherein R ⁵ to R ⁸ are adjacent to each other You may form a ring with
In the general formula [2], A ⁺ represents an alkali metal ion. )

In the ammonium salt compound (E1), the cation part is N ⁺ R ⁵ R ⁶ R ⁷ R ⁸ , and all the constituent parts including the anion part are organic, so that the acrylic resin (A) and the solvent are used. It is characterized by high compatibility. Further, when the ammonium salt compound (E1) is used, the antistatic performance is hardly affected by the environmental humidity, and the contamination to the adherend is small for a long time even in a high temperature and high humidity environment.
Further, the compound (E2) has a feature that since the cation portion is an alkali metal ion, the production process can be shortened and can be produced at low cost.
However, when an alkali metal salt compound (E2) is used, there is a possibility that electronic components such as internal circuits, transistors, ICs, and CPUs may be contaminated. The Further, when the alkali metal salt compound (E2) is used, the antistatic performance is easily affected by the environmental humidity, and the adherend may be contaminated in a high temperature and high humidity environment.
Therefore, in this invention, it is preferable to use the ammonium salt type compound (E1) represented by General formula [1] as an antistatic provision agent (E).

In R ^{1 to} R ⁸ in the general formula [1] and the general formula [2],
As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophena Examples include a syl group.

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

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

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

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

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

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, vinyloxycarbonyl group, alkoxycarbonyl group such as aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group An arylsulfuric group such as an acyl group such as an isobutyryl group, an acryloyl group, a methacryloyl group or a methoxalyl group, an alkylsulfanyl group such as a methylsulfanyl group or a tert-butylsulfanyl group, a phenylsulfanyl group or a p-tolylsulfanyl group Nyl group, alkylamino group such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group Alkyl group such as ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and other aryl groups, hydroxyl group, carboxyl Group, sulfonamido group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, nitroso group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group , Phosphono group, alkylsulfonyl group, aryl Examples include a sulfonyl group, a trialkylammonium group, a dimethylsulfonyl group, and a triphenylphenacylphosphoniumyl group.

  Among such substituents, a preferred substituent is an electron-withdrawing substituent. When the electron-withdrawing substituent is substituted, the ionic compound is generally easily dissociated and the antistatic ability is enhanced.

  Such electron-attracting substituents are generic names for substituents that attract electrons from the other party due to resonance effects and induced effects, and many of them have a positive substituent constant σ on the Hammett side. It is. These substituents are not particularly limited, and specific examples thereof include Chemical Review Vol. 91, Nos. 165 to 195 σp described in 1991 is greater than 0, and more specifically, halogen group, cyano group, carboxyl group, nitro group, nitroso group, acyl group, alkyloxycarbonyl Group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, amide group, perfluoroalkyl group, perfluoroalkylthio group, perfluoroalkylcarbonyl group, sulfonamide group, 4-cyanophenyl group and the like.

R ¹ to R ⁴ are preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably a substituent, in view of the stability of the compound. It is an aryl group that may have.

R ⁵ to R ⁸ are preferably an alkyl group which may have a substituent in consideration of the stability of the compound.

Representative examples of the boron-based ammonium salt compound (E1) represented by the general formula [1] used as the antistatic agent (E) in the present invention are exemplified compounds (E1-1) to (E1-15). ) As representative compounds of the boron-based alkali metal salt compound (E2) represented by the general formula [2] as exemplified compounds (E2-1) to (E2-4) These are specifically exemplified in Table 2 below, but are not limited thereto.
In the exemplified compounds, Me represents a methyl group, Et represents an ethyl group, Bu represents a normal butyl group, c-Hex represents a cyclohexyl group, and Ph represents a phenyl group.

  As addition amount of antistatic provision agent (E), 0.001-20 weight part is preferable with respect to 100 weight part of acrylic resin (A), and 0.01-10 weight part is more preferable. If it is less than 0.001 part by weight, an antistatic function cannot be expected. If it exceeds 20 parts by weight, the physical properties of the adhesive may deteriorate. Further, the antistatic agent (E) can be used alone or in combination.

Furthermore, the antistatic acrylic resin composition of the present invention comprises a surfactant (D) other than the anionic surfactant (D1-1) having an alkanol ammonium salt portion (hereinafter simply referred to as “surfactant (D)”). It is preferable that it is also expressed. As the usage-amount, it is preferable to contain 0.001-10 weight part with respect to 100 weight part of acrylic resin (A), and it is still more preferable to contain 0.01-5 weight part. If it is less than 0.001 part by weight, the antistatic effect cannot be improved. On the other hand, if the amount exceeds 10 parts by weight, contamination of the adherend increases, which is not preferable.
Examples of the surfactant (D) include cationic surfactants, nonionic surfactants, zwitterionic surfactants, and anionic surfactants.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, cationic surfactants having an alkylene oxide group, acyloylamidopropyltrimethylammonium methosulfate, alkylbenzylmethylammonium salts, acylcholine chloride, dimethylaminoethyl methacrylate A (meth) acrylate copolymer having a quaternary ammonium group such as a quaternized product, a styrene copolymer having a quaternary ammonium group such as polyvinylbenzyltrimethylammonium chloride, or a quaternary ammonium group such as polydiallyldimethylammonium chloride. Examples thereof include diallylamine copolymers. For example, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and distearyl trimethyl ammonium chloride are preferable. Moreover, these compounds may be used independently and may be used in combination of 2 or more type.

  Specific examples of commercially available cationic surfactants include Elegan 264WAX and Elegan LD-204 (all of which are manufactured by NOF Corporation).

Nonionic surfactants include, for example, fatty acid alkylolamide, di (2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester , Polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyethylene glycol, polyoxyethylene diamine, copolymer of polyether, polyester and polyamide, methoxy polyethylene glycol (meth) acrylate, polyoxyalkylene fatty acid esters, polyoxy Alkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene Alkyl ethers, polyoxyalkylene alkyl allyl er chill, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene derivatives, polyoxyalkylene alkylamines, polyoxyalkylene alkylamines fatty acid esters and the like. These compounds may be used alone or in combination of two or more.

Moreover, as a commercial item of a nonionic surfactant, specifically, for example, Newcol 1008 (polyoxyethylene 2-ethylhexyl ether, ethylene oxide (hereinafter also referred to as “EO”) added mole number 8), New Coal 2303 (Polyoxyethylene C _12-13 alkyl ether EO addition mole number 3), New Coal 2308 (Polyoxyethylene C _12-13 alkyl ether EO addition mole number 8), New Coal 2320 (Polyoxyethylene C _{12- 13} alkyl ether EO addition mole number 20), New Coal 2360 (polyoxyethylene C _12-13 alkyl ether EO addition mole number 60), New Coal 1807 (Polyoxyethylene stearyl ether EO addition mole number 7 (all are Japan) Emulsifier Co., Ltd.) etc. Among them, New Coal 1008, New Coal 2303, New Coal 2308, and New Coal 2320 having 8 to 13 carbon atoms in the alkyl chain of the ethylene oxide-added alkyl alcohol and 3 to 20 moles of ethylene oxide added are preferable. When the chain has less than 8 carbon atoms, the adherend tends to be contaminated. When the chain is larger than 13, the compatibility with the acrylic resin is lowered. When the added mole number of ethylene oxide is larger than 20 moles, the crystallinity is low. In any case, the antistatic effect decreases.

  As an anionic surfactant, for example, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ethoxy sulfate ester salt, alkyl phosphate ester salt, sulfonic acid group-containing styrene copolymer, polyoxyalkylene alkyl ether Examples thereof include sulfuric acid ester salts, polyoxyalkylene alkyl ether phosphoric acid ester salts, polyoxyalkylene alkyl phenyl ether sulfuric acid ester salts, polyoxyalkylene alkyl phenyl ether phosphoric acid ester salts, and the like. Among these, it is preferable that it is C8-C13 of the alkyl chain of alkyl alcohol and ethylene oxide addition alkyl alcohol, and is ethylene oxide addition mole number 0-20. These compounds may be used alone or in combination of two or more (salts excluding alkanol ammonium salts).

  The anionic surfactant has an anionic hydrophilic group, and examples of the anionic hydrophilic group include those represented by the following formulas (D1) and (D2).

(D1)
-SO ₃ M ₁

[M ₁ in Formula (D1) represents hydrogen, an alkali metal, or an ammonium group. ]

(D2)

[M ₂ and M _{3 in} Formula (D2) are the same or different and each represents hydrogen, an alkali metal, or an ammonium group. ]

Incidentally, the formula (D1), as the alkali metal used in _M 1 ~M ₃ in (D2), Li, Na, K are preferable. The same applies to the monomer (a2) having a radical polymerizable unsaturated double bond and an alkylene oxide chain and not having an alkanol ammonium salt portion.
The alkali metal of the anionic hydrophilic group in the monomer (a2) and the surfactant (D) has a low dissociation property, and in this respect, it is clear from the alkali metal salt compound (E2) which is a compound having a high ion dissociation property. Are distinguished.
Since the anionic hydrophilic group alkali metal in the monomer (a2) and the surfactant (D) has a low dissociation property, it hardly contributes to ionic conductivity, but has a feature that the adherend is hardly contaminated. . As the alkali metal used for M _{1 to} M ₃ , Na and K are preferable. More preferably, an ammonium group other than K and an alkali metal with no concern about adherend contamination is used.

Specific examples of the anionic surfactant include Newcol 1008SF (polyoxyethylene 2-ethylhexyl ether sulfate ammonium salt EO addition mole number 8), Newcol 2303SF (Polyoxyethylene C _12-13 alkyl ether). Sulfate ammonium salt EO addition mole number 3), New Coal 2308SF (polyoxyethylene C _12-13 alkyl ether sulfate sodium salt EO addition mole number 8), New Coal 2308SN (Polyoxyethylene C _12-13 alkyl ether sulfate ester) Ammonium salt EO addition mole number 8), New Coal 2320SF (polyoxyethylene C _12-13 alkyl ether sulfate ammonium salt EO addition mole number 20), FDI-01402K (lauryl phosphate ester carbonate) (Lium salt) (all of which are manufactured by Nippon Emulsifier Co., Ltd.), electro stripper F (polyoxyethylene lauryl ether potassium potassium salt manufactured by Kao Corporation), and the like.

Examples of zwitterionic surfactants include alkyl betaines, alkyl imidazolium betaines, carbobetaine graft copolymers, and the like. These compounds may be used alone or in combination of two or more.
Further, the antistatic effect by the surfactant (D) is the best for the cationic surfactant, and then the order of the anionic surfactant, the zwitterionic surfactant, and the nonionic surfactant. An anionic surfactant having no coloring problem is more preferably used.

In the antistatic acrylic resin composition of the present invention, a compound (B) having a functional group capable of reacting with a hydroxyl group as a curing agent (hereinafter simply referred to as “compound (B)” is used as a curing agent in order to increase the cohesive strength and the degree of crosslinking. It is important to use “.
The compound (B) used in the present invention preferably has two or more functional groups that can react with the hydroxyl group contained in the acrylic resin (A) in one molecule. For example, a known trifunctional isocyanate compound or a known polyfunctional epoxy compound can be suitably used. These can also be used in combination.

The known trifunctional isocyanate compound includes a so-called adduct obtained by modifying a known diisocyanate compound with a trifunctional polyol component, a burette obtained by reacting the diisocyanate compound with water, and a 3 amount having an isocyanurate ring formed from three molecules of the diisocyanate compound. The body (isocyanurate body) can be used.
Known diisocyanate compounds include aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and the like.
As aromatic diisocyanates, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Examples thereof include isocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.
Aliphatic diisocyanates include trimethylene diisocyanate, 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 and the like.
Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.
Examples of alicyclic diisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4- Examples include cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, and the like. .
Examples of the diisocyanate compound forming the trifunctional isocyanate compound used in the present invention include 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also referred to as “isophorone diisocyanate”). ) Is preferably used.
About the above-mentioned compound (B), it can be used individually or in combination of 2 or more types. In the case of using in an application in which flexibility is important, it is preferable to use a trifunctional isocyanate compound.

  As described above, when a low peeling force of 200 g / 25 mm or less, preferably 100 g / 25 mm or less is required, 1 to 30 parts by weight of compound (B) is used with respect to 100 parts by weight of acrylic resin (A). Is preferably used, more preferably 2 to 20 parts by weight, and even more preferably 3 to 15 parts by weight.

The antistatic acrylic resin composition of the present invention may contain a compound (E) having an alkylene oxide chain other than the surfactant (D). As the compound (E) having an alkylene oxide chain, the content of the alkylene oxide chain in the compound having an alkylene oxide chain is preferably 10 to 80% by weight, and more preferably 20 to 50% by weight. .
Moreover, it is preferable that the weight average molecular weights of the said compound (E) which has an alkylene oxide chain are 1000-10000, and it is more preferable that it is 1000-5000.
As the compound (E) 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, and specifically, for example, trade names Epan 420, 450, 750 (Daiichi Kogyo Seiyaku Co., Ltd.) can be used.

In addition, when the content of the alkylene oxide chain in the compound (E) having an alkylene oxide chain is less than 10% by weight, sufficient ionic conductivity is difficult to obtain, and it becomes larger than 80% by weight or the weight average molecular weight is 10,000. If it exceeds the upper limit, the crystallinity becomes high and 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 (E) having an alkylene oxide chain is blended in an amount of 1 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the acrylic resin (A). When the compounding amount of the compound (E) having an alkylene oxide chain is less than 1 part by weight, sufficient antistatic properties may not be obtained, while when it exceeds 40 parts by weight, the adhesiveness is remarkably lowered. It is not preferable.

Furthermore, a silicone surfactant can be blended with the antistatic acrylic resin composition of the present invention for the purpose of further improving antistatic properties. Among these, a branched structure silicone-based surfactant having a polyoxyalkylene group or a polyglycerin group as a hydrophilic group is preferable. As these commercially available products, for example, “KF-6028”, “KF-6100” (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be used.
A silicone type surfactant mix | blends 0.001-10 weight part with respect to 100 weight part of acrylic resin (A), Preferably 0.1-10 weight part is mix | blended. When the amount of the silicone surfactant is less than 0.001 part by weight, no further improvement in antistatic property can be expected. On the other hand, when it exceeds 10 parts by weight, the adhesive physical properties are remarkably lowered, which is not preferable.

  In the antistatic acrylic resin composition of the present invention, other resins such as an acrylic resin, a polyester resin, an amino resin, an epoxy resin, and a polyurethane resin can be used in combination as necessary. 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 obtained by laminating 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 can be obtained. The surface of the layer can be coated with a release sheet.
The pressure-sensitive adhesive sheet can be obtained by applying or impregnating an antistatic acrylic resin composition to various substrates, and drying and curing it. Alternatively, the antistatic acrylic resin composition is applied onto the release sheet, dried, and various substrates are laminated on the surface of the pressure-sensitive adhesive layer being formed, and the hydroxyl group in the acrylic resin (A), It can also be obtained by advancing the reaction with a functional group capable of reacting with a hydroxyl group in the compound (B).
In addition, the adhesive layer may be laminated | stacked only on one side of the plastic film base material, and may be laminated | stacked on both surfaces.

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, that is, a protective 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 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, and is attached to a polarizing plate 3 by the adhesive layer 2. It is typical sectional drawing which shows a state.
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. is there.
FIG. 3 shows an antistatic pressure-sensitive 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 a pressure-sensitive adhesive layer 2 is further supported thereon. It is typical sectional drawing which shows the state stuck on the polarizing plate 3 by.
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. It is typical sectional drawing which shows the state stuck on the polarizing plate 3 by.

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. In applications where the plastic film has functionality, 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) is provided on one adhesive layer. Further, an optical compensation film, a light diffusion film, an electromagnetic wave shielding film, etc.) can be further bonded. 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 , Metal fillers, quaternary ammonium salt derivatives, surfactants, conductive resins and 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 a composition ratio (weight ratio) shown in Table 3 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, the reaction kettle was 50% by weight of 2EHA [50 of 69% by weight of “69” described in Table 3]. Meaning of% by weight; the same applies hereinafter), 50% by weight of BA, 50% by weight of 2HEA, ethyl acetate as a solvent, azobisisobutyronitrile as an 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% and a resin Mw (weight average molecular weight) of 400,000.

(Synthesis Example 2)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 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% and a resin Mw (weight average molecular weight) of 450,000.

(Synthesis Example 3)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 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% and a resin Mw (weight average molecular weight) of 430,000.

(Synthesis Example 4)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 was obtained as follows.
That is, a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was used. The reaction kettle was 50% by weight of 2EHA, 50% by weight of BA, 50% by weight of 4HBA, and as a solvent. 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% and a resin Mw (weight average molecular weight) of 380,000.

(Synthesis Example 5)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 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 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% and a resin Mw (weight average molecular weight) of 390,000.

(Synthesis Example 6)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 was obtained as follows.
That is, a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was used. The reaction kettle was 50% by weight of 2EHA, 50% by weight of BA, 50% by weight of 4HBA, and as a solvent. 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% and a resin Mw (weight average molecular weight) of 400,000.

(Synthesis Example 7)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 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 2HEA, ethyl acetate as the solvent, and as the initiator An appropriate amount of azobisisobutyronitrile 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% and a resin Mw (weight average molecular weight) of 750,000.

(Synthesis Example 8)
An acrylic resin composed of monomers having a composition ratio (weight ratio) shown in Table 3 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 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% and a resin Mw (weight average molecular weight) of 390,000.

(Synthesis Example 9)
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 199 parts by weight of 2-ethylhexyl acrylate, alkylene oxide group-containing reactive surfactant Latemul PD-420 (manufactured by Kao Corporation) 1 part by weight, 8 parts by weight of 2-hydroxyethyl acrylate, 0.4 part by weight of 2,2′-azobisisobutyronitrile and 312 parts by weight of ethyl acetate as a polymerization initiator were charged, and nitrogen gas was added while gently stirring. The polymerization reaction was carried out for 5 hours while maintaining the liquid temperature in the flask at around 60 ° C. This reaction solution had a solid content of 40% and a resin Mw (weight average molecular weight) of 560,000.

<Manufacture of boron antistatic agent (E)>
<Synthesis Example 10> Synthesis of ammonium salt compound (E1-1) 342 g of sodium tetraphenylborate was dissolved in 5 L of ion-exchanged water. To this, 322 g of tetrabutylammonium bromide dissolved in 5 L of ion exchange water was gradually added. After stirring for 5 hours, the precipitate was collected by filtration to obtain 373 g of a compound (E1-1) represented by the following formula. Elemental analysis (Composition formula: C ₄₀ H ₅₆ BN Calculated value (%): C, 85.53; H, 10.05; N, 2.49 Actual value (%): C, 85.55; H, 10. 52; N, 2.66).

<Synthesis Examples 11-23>
Compound (E1-2) and Compound (E1) were prepared in the same manner as in Synthesis Example 10 except that the borate shown in Table 4 was used instead of sodium tetraphenylborate and the ammonium salt shown in Table 4 was used instead of tetrabutylammonium bromide. -4) to compound (E1-15) were synthesized. Table 5 shows the results of elemental analysis.

  Compound (E3-1) was synthesized according to the description in JP-A No. 2000-169832.

[Example 1]
Compound (E1-1) 0.4 part and hexamethylene diisocyanate isocyanurate 5.0% 37% ethyl acetate solution are blended with 40 parts solid content of the acrylic resin solution obtained in Synthesis Example 1. A pressure sensitive adhesive was obtained.
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 7 days at room temperature in this state to obtain a test pressure-sensitive adhesive sheet.
Using the pressure-sensitive adhesive sheet, the adhesive strength, peeling charge, wet heat contamination, and aluminum corrosion 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. After 24 hours from the press bonding, the test adhesive sheet was peeled off from the polarizing plate on a Teflon (registered trademark) plate, and the static electricity on the polarizing plate surface was measured with an electrostatic meter (“STATION DZ3” manufactured by Sisid Electric Co., Ltd.). The spot measurement was performed and the value having the maximum absolute value was defined as peeling charge.

<Heat and heat contamination>
After peeling the release paper of the test adhesive tape and sticking the exposed adhesive layer to a glass plate, it was left for 1000 hours under conditions of 60 ° C.-95% RH and cooled to 23 ° C.-50% RH. After peeling off from the glass plate, the contamination of the glass plate was visually evaluated. Specifically, the state after peeling was evaluated in the following three stages.
No contamination ○
Very slightly contaminated △
Contaminated items ×

<Aluminum corrosive>
After peeling the release paper of the test adhesive tape and sticking the exposed adhesive layer to the aluminum plate, it was left for 100 hours under conditions of 60 ° C-95% RH and cooled to 23 ° C-50% RH After peeling off from the aluminum plate, the surface of the aluminum plate was visually evaluated. Specifically, the state after peeling was evaluated in the following three stages.
No corrosion ○
Very slightly corrosive △
Those with corrosion ×

[Example 2] to [Example 7]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the acrylic resin solutions obtained in Synthesis Examples 2, 3, 4, 5, 6, and 7 were used, and evaluated in the same manner as in Example 1.

[Example 8]
A pressure-sensitive adhesive was obtained and evaluated in the same manner as in Example 1 except that 0.02 part of the compound (E1-1) was used using the acrylic resin solution obtained in Synthesis Example 5.

[Example 9] to [Example 22]
Using the acrylic resin solution obtained in Synthesis Example 5, instead of 0.4 part of the compound (E1-1), the compound (E1-4) to the compound (E1-15), the compound (E2-1), and (E2- A pressure-sensitive adhesive was obtained and evaluated in the same manner as in Example 1 except that 0.4 part of 4) was used.

[Example 23]
Compound (E1-1) 0.1 part, New Coal 2308 (polyoxyethylene C _12-13 alkyl ether EO addition mole number 8) with respect to 40 parts of solid content of the acrylic resin solution obtained in Synthesis Example 5 0.4 part and 5.0 parts of 37% ethyl acetate solution of hexamethylene diisocyanate isocyanurate were mixed 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 the pressure-sensitive adhesive layer being formed had a polyethylene terephthalate film thickness of 38 μm) Was laminated for 7 days at room temperature to obtain a test pressure-sensitive adhesive sheet, which was evaluated in the same manner as in Example 1.

[Example 24]
Implemented except that 0.4 part of New Coal 2303SF (polyoxyethylene C _12-13 alkyl ether sulfate ammonium salt EO addition mole number 3 made by Nippon Emulsifier Co., Ltd.) was used instead of 0.4 part of New Coal 2308 An adhesive was obtained and evaluated in the same manner as in Example 23.

[Example 25]
A pressure-sensitive adhesive was obtained in the same manner as in Example 23 except that 0.4 part of electrostripper F (polyoxyethylene lauryl ether phosphate potassium salt manufactured by Kao Corporation) was used instead of 0.4 part of New Coal 2308. And evaluated.

[Example 26]
Example 23, except that 4.0 parts of Epan 750 (manufactured by Daiichi Kogyo Co., Ltd .: weight average molecular weight 4000, ethylene oxide chain content 50%) was used instead of 0.4 parts of New Coal 2308. Similarly, an adhesive was obtained and evaluated.

[Example 27]
A pressure sensitive adhesive was obtained and evaluated in the same manner as in Example 23 except that 0.4 part of KF-6100 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 0.4 part of New Coal 2308.

[Example 28]
A pressure-sensitive adhesive was obtained and evaluated in the same manner as in Example 23 except that 0.4 part of Elegan LD204 (manufactured by NOF Corporation) was used instead of 0.4 part of New Coal 2308.

[Comparative Example 1]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the acrylic resin solution obtained in Synthesis Example 8 was used, and evaluated in the same manner as in Example 1.

[Comparative Example 2]
A pressure-sensitive adhesive as in Example 1, except that the acrylic resin solution obtained in Synthesis Example 5 was used and 0.4 part of lithium perchlorate was used instead of 0.4 part of Compound (E1-1). Obtained and evaluated.

[Comparative Example 3]
Using the acrylic resin solution obtained in Synthesis Example 5 and using 0.4 part of the compound (E3-1) instead of 0.4 part of the compound (E1-1), the same as in Example 1 An adhesive was obtained and evaluated.

[Comparative Example 4]
With respect to 40 parts of the solid content of the acrylic resin solution obtained in Synthesis Example 9, an aliphatic amine ionic liquid (IL-A1, manufactured by Kouei Chemical Co., Ltd.), 37% ethyl acetate of hexamethylene diisocyanate isocyanurate 1.6 parts of the solution was blended to obtain an adhesive.
The obtained pressure-sensitive adhesive was applied to an untreated surface of a polyethylene terephthalate film (thickness 38 μm) antistatic coated with antimony oxide so as to have a dry coating film of 20 μm, and dried at 100 ° C. for 2 minutes, A release paper was laminated on the pressure-sensitive adhesive layer that was being formed, and in this state, 7 days were allowed to elapse at room temperature to obtain a test pressure-sensitive adhesive sheet, which was evaluated in the same manner as Example 1.

[Comparative Example 5]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 0.4 part of compound (E1-1) was not used, and evaluated in the same manner as in Example 1.

  The above evaluation results are shown in Table 6.

As described above, when the antistatic acrylic resin composition of the present invention is used as a pressure-sensitive adhesive layer for a surface protective film of an optical member such as a polarizing plate of a liquid crystal display, the generation of static electricity at the time of peeling is small, and wet heat It turns out that it is excellent in pollution.
On the other hand, the acrylic resin composition used in Comparative Example 1 has poor wet heat contamination because the acrylic resin does not have an alkylene oxide chain. Comparative Examples 2, 3, and 4 have poor contamination or aluminum corrosivity. Moreover, since Comparative Example 5 does not contain an antistatic imparting agent, the peeling charge is poor.

  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, and Since it is excellent in transparency, it is suitable as a surface protective film for mechanically and electrically protecting the adherend surface for a predetermined period. For example, a liquid crystal panel, a plasma display, a polarizing plate, a CRT (CRT), etc. It is suitably used for forming an adhesive film for surface protection of optical parts.

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 adhesive layer carry | supported on the one surface to the polarizing plate by the adhesive 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. An antistatic adhesive 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. It is a typical sectional view shown. 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 of the PET film substrate is attached to a polarizing plate by the adhesive layer. It is a typical sectional view shown.

Explanation of symbols

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

Claims (8)

An acrylic resin (A) having a hydroxyl group and an alkylene oxide chain and having no alkanolammonium salt moiety,
As the compound (B) having a functional group capable of reacting with a hydroxyl group, and the antistatic agent (E),
An antistatic acrylic resin composition comprising a compound (E1) represented by the following general formula [1] or a compound (E2) represented by the following general formula [2].

(In General Formula [1] and General Formula [2], R ¹ to R ⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, An alkynyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, wherein R ⁵ to R ⁸ are adjacent to each other You may form a ring with
In the general formula [2], A ⁺ represents an alkali metal ion. ) For 100 parts by weight of acrylic resin (A),
The antistatic material according to claim 1, comprising 1 to 30 parts by weight of the compound (B) having a functional group capable of reacting with a hydroxyl group, and 0.001 to 20 parts by weight of the antistatic agent (E). Acrylic resin composition.   The acrylic resin (A) has an acrylic monomer (a1) having a hydroxyl group, a monomer (a2) having a radical polymerizable unsaturated double bond and an alkylene oxide chain, and having no alkanolammonium salt moiety; The antistatic material according to claim 1 or 2, which is an acrylic resin obtained by copolymerizing a radically polymerizable unsaturated monomer (a3) essentially comprising an acrylic monomer other than (a1) and (a2). Acrylic resin composition.   The antistatic acrylic resin composition according to claim 3, wherein the proportion of the monomer (a2) is 0.01 to 40% by weight in a total of 100% by weight of the monomers (a1) to (a3).   The antistatic acrylic resin composition according to any one of claims 1 to 4, further comprising a surfactant (D) other than the anionic surfactant (D1-1) having an alkanol ammonium salt portion. .   The antistatic acrylic resin composition according to claim 5, wherein 0.001 to 10 parts by weight of the surfactant (D) is contained with respect to 100 parts by weight of the acrylic resin (A).   The antistatic acrylic resin composition according to any one of claims 1 to 6, wherein the compound (B) having a functional group capable of reacting with a hydroxyl group is a trifunctional isocyanate compound.   The protective film for optical members in which the adhesive layer formed from the antistatic acrylic resin composition in any one of Claims 1 thru | or 7 is laminated | stacked on the at least one surface of a plastic film base material.

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