JP2009046599A - Resin composition for forming antistatic layer and antistatic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic film having all of an antistatic performance, solvent resistance and blocking resistance and excellent transparency, and to provide a composition for forming an antistatic layer, from which the plastic film can be formed. <P>SOLUTION: The following composition for forming the antistatic layer is used. The composition comprises: (a) a quaternary ammonium salt type cationic polymer compound having active hydrogen in the molecule; (b) at least one kind selected from a group consisting of acrylic resin, polyurethane resin, polyamide resin, polyester resin and polyether resin having active hydrogen in the molecule; (c) polyisocyanate compound; and as necessary, (d) silane-modified epoxy resin; and/or (f) a compound having at least two active hydrogen atoms. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition for forming an antistatic layer and an antistatic film.

Plastic film has excellent properties such as mechanical strength, dimensional stability, flatness, heat resistance, chemical resistance, and transparency, so it can be used as a base film for magnetic recording media, film for plate making, packaging film, optical It is used for a wide range of applications, including film.

However, a common problem with plastic films is that they are easily charged by static electricity. Static electricity charged on the film may accumulate during film winding and unwinding operations, when passing through a coating device, or during film processing. There was a problem of attracting surrounding dust and causing physical defects.

Therefore, as a method of efficiently eliminating static electricity, a method of providing an antistatic layer containing a quaternary ammonium salt type cationic polymer compound in the film structure has been proposed. (See Patent Document 1)

However, when a high molecular weight quaternary ammonium salt type cationic polymer is used, the viscosity of the coating solution becomes too high, the productivity is deteriorated, and the performance of the obtained coated film may be deteriorated. Therefore, in order to solve such a problem, a method of applying a compound having a reactive group and a quaternary ammonium base in a molecule that is not a polymer to a film has been proposed. (See Patent Document 2)

According to this method, although the antistatic performance is improved, there is a problem that the antistatic layer is peeled off and the effect is lowered when it comes into contact with an organic solvent or the like during the film production process. Further, since blocking occurs during film winding or the like, further improvement has been demanded.

Japanese Patent Laid-Open No. 10-315373 JP 2004-75731 A

The present invention has been made in view of the above circumstances, and its solution is to combine antistatic performance, solvent resistance, and blocking resistance, and to provide a plastic film that is excellent in transparency and a charge that can form the plastic film. It is providing the composition for prevention layer formation.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by a combination of specific types of compounds, and have completed the present invention.

That is, the present invention includes (a) a quaternary ammonium salt type cationic polymer compound having active hydrogen in the molecule, (b) a polyurethane resin, a polyester resin, a polyamide resin, and a polyether resin having active hydrogen in the molecule. And at least one selected from the group consisting of acrylic resins, (c) a polyisocyanate compound and optionally (d) a silane-modified epoxy resin and / or (f) a compound having at least two active hydrogens Layer forming resin composition; an antistatic layer obtained by reacting the antistatic layer forming resin composition is provided on one side of the base film, and the surface resistivity of the antistatic layer is 1 × 10 ^{The present invention} relates to an antistatic film of ⁷ to 1 × 10 ¹³ Ω / □.

ADVANTAGE OF THE INVENTION According to this invention, the composition for antistatic layer formation and antistatic film which have antistatic performance, solvent resistance, and blocking resistance, and can form the plastic film excellent in transparency can be provided.

  The resin composition for forming an antistatic layer of the present invention comprises (a) a quaternary ammonium salt type cationic polymer compound having active hydrogen in the molecule (hereinafter referred to as component (a)), (b) in the molecule. At least one selected from the group consisting of an acrylic resin having active hydrogen, polyurethane resin, polyamide resin, polyester resin and polyether resin (hereinafter referred to as component (b)), (c) polyisocyanate compound (hereinafter referred to as ( c) component)) and, if necessary, (d) a silane-modified epoxy resin (hereinafter referred to as component (d)) and / or (f) a compound having at least two active hydrogens (hereinafter referred to as component (f)). .).

The component (a) used in the present invention is not particularly limited as long as it is a polymer compound having at least one active hydrogen and at least one quaternary ammonium base in one molecule, and known compounds can be used. Although it does not specifically limit as a functional group used as an active hydrogen source, For example, an amino group, a hydroxyl group, a thiol group, etc. are mentioned. From the viewpoint of versatility, a hydroxyl group is particularly preferable. Examples of the counter anion of the quaternary ammonium base include ions such as halogen, alkyl sulfate, alkyl sulfonate, and nitric acid.

Component (a) is, for example, a method in which a polymer prepared in advance is modified to introduce an active hydrogen group and a quaternary ammonium base, or a polymerization component containing a monomer having an active hydrogen group and a monomer having a tertiary amino group Can be prepared by a method such as quaternization of a tertiary amino group, but (a1) a monomer having an active hydrogen group (hereinafter referred to as component (a1)) and (a2) a tertiary amino group A method such as quaternization of a tertiary amino group after copolymerization of a monomer having a monomer (hereinafter referred to as component (a2)) is preferred because the operation is simple. Examples of the component (a1) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples of the component (a2) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide. These may be used alone or in combination of two or more. In addition, you may use other polymerization components other than (a1) component and (a2) component as needed. Examples of the polymerization component other than the component (a1) and the component (a2) include, for example, anionic monomers (for example, monocarboxylic acids such as (meth) acrylic acid and crotonic acid; maleic acid, fumaric acid, itaconic acid, muconic acid Dicarboxylic acids such as vinyl sulfonic acid, styrene sulfonic acid, organic sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid; or alkali metal salts such as sodium salt and potassium salt of these various organic acids, ammonium salts, etc.) In addition, known monomers such as alkyl esters of anionic vinyl monomers (alkyl group having 1 to 8 carbon atoms), acrylonitrile, styrenes, vinyl acetate, and methyl vinyl ether can be used. These may be used alone or in combination of two or more.

Although the usage-amount of (a1) component and (a2) component is not specifically limited, Usually, it is preferable to use about 1-40 mol% of (a1) component and about 1-40 mol% of (a2) component.

The copolymerization of the polymerization component containing the component (a1) and the component (a2) may be performed by a known radical polymerization method. The component (a) can be obtained by reacting the obtained copolymer with a quaternizing agent such as methyl chloride, benzyl chloride, dimethyl sulfate or epichlorohydrin.

The molecular weight of the component (a) is not particularly limited, but the weight average molecular weight is preferably about 500 to 500,000 from the viewpoint of film forming property and solvent resistance, and particularly preferably 2000 to 100,000. As (a) component which satisfy | fills such conditions, you may use commercial items, such as Elecondo SGM-001 and 002 by Soken Chemical Co., Ltd., for example.

The component (b) used in the present invention is an acrylic resin, polyurethane resin, polyamide resin, polyether resin and polyester resin having active hydrogen in the molecule other than the component (a). Other than the component (a) If it is, it will not specifically limit, A well-known thing can be used. The active hydrogen is preferably an amino group, a hydroxyl group and a thiol group. Among these, acrylic resins, polyurethane resins, and polyamide resins are particularly preferable from the viewpoints of adhesion to the base material and film forming properties of the coating layer.

The acrylic resin used as the component (b) is a polymer of a monomer having a (meth) acrylic acid ester monomer as a main component (at least 50% by weight or more) as typified by an acrylic or methacrylic monomer. It may be a polymer of a polymerizable monomer having a carbon-carbon double bond other than the (meth) acrylic acid ester monomer. These may be either homopolymers or copolymers. Further, it may be copolymerized with unsaturated polyester or polyurethane into which a double bond is introduced. Specifically, a block copolymer, a graft copolymer, etc. are mentioned, for example. Further, it may be a graft polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond using a peroxide or the like in a polyester solution or a polyester dispersion. Similarly, it may be a polymer (possibly a mixture of polymers) obtained by graft polymerization of a polymerizable monomer having a carbon-carbon double bond using a peroxide or the like in a polyurethane solution or polyurethane dispersion. Furthermore, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond using a peroxide or the like in another polymer solution or dispersion is also included.

Examples of (meth) acrylic acid ester monomers include hydroxyl group-containing acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; Examples include (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and various (meth) acrylic acid alkyl ester monomers such as lauryl (meth) acrylate. A seed may be used independently or 2 or more types may be used together. Moreover, it does not specifically limit as a polymerizable monomer which has a carbon-carbon double bond, For example, it is as follows. (Meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, (anhydrous) maleic acid, various carboxyl group-containing monomers such as citraconic acid, and salts thereof; monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate Various hydroxyl group-containing monomers such as (meth) acrylimide, diacetoneacrylamide, N-methylolacrylamide, various nitrogen-containing vinyl monomers such as (meth) acrylonitrile, etc .; styrene, α-methylstyrene, divinyl Various styrene derivatives such as benzene and vinyltoluene, various vinyl esters such as vinyl acetate and vinyl propionate; γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, “Silaplane FM-” manufactured by Chisso Corporation 07 "(Meta Various silicon-containing polymerizable monomers such as acryloyl silicon macromer); phosphorus-containing vinyl monomers; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, chlorotri Examples include various vinyl halides such as fluoroethylene and hexafluoropropylene; and various conjugated dienes such as butadiene. These may be used alone or in combination of two or more.

As a polyurethane resin, what is obtained by making a polyol and polyisocyanate react can be used, for example.

The polyisocyanate is not particularly limited as long as it is a compound having at least two isocyanate groups, and known ones can be used. Specifically, for example, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), XDI (xylylene diisocyanate), NDI (naphthylene 1,5-diisocyanate), TMXDI (tetramethylene xylylene diisocyanate) Aromatic isocyanates such as IPDI (isophorone diisocyanate), H12MDI (hydrogenated MDI, dicyclohexylmethane diisocyanate), H6XDI (hydrogenated XDI), and the like, HDI (hexamethylene diisocyanate), DDI There are aliphatic isocyanates such as (dimer acid diisocyanate) and NBDI (norbornene diisocyanate). These may be used alone or in combination of two or more.

Polyols include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol; polyester polyols such as polyethylene adipate, polyethylene-butylene adipate, and polycaprolactone; acrylic polyols, polycarbonates Examples thereof include polyols, polydimethylsiloxane-ethylene oxide adducts, polydimethylsiloxane-propylene oxide adducts, and castor oil. Usually, a polyol having a molecular weight of 300 to 2000 is used. These may be used alone or in combination of two or more.

In addition, a chain extender or a crosslinking agent can be used as necessary. Examples of the chain extender or crosslinking agent include ethylene glycol, propylene glycol, butanediol, diethylene glycol, trimethylolpropane, hydrazine, ethylenediamine, diethylenetriamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodicyclohexylmethane, Water etc. can be mentioned. These may be used alone or in combination of two or more. In order to react these, for example, Japanese Patent Publication No. 42-24194, Japanese Patent Publication No. 46-7720, Japanese Patent Publication No. 46-10193, Japanese Patent Publication No. 49-37839, Japanese Patent Publication No. 50-123197, The methods disclosed in JP-A-53-126058, JP-A-54-138098 and the like can be used.

As the polyamide resin, known resins can be used without any particular limitation. Specific examples include those obtained by polymerizing oligoamines or polyamines with dicarboxylic acids. In particular, a polyamide resin containing at least one —NH— group in the main chain is preferable from the viewpoints of adhesion to the substrate, film-forming properties of the coating layer, film properties, and the like.

Examples of the oligoamine for synthesizing a polyamide resin having at least one -NH- group in the main chain include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 2-methyl-1, 4,7-triazaheptane, 3-n-butyl-1,4,7-triazaheptane, 2,3-dimethyl-1,4,7-triazaheptane, 2-methyl-1,4,7, 10-tetraazadecane, 3-ethyl-1,4,7,10-tetraazadecane, 5-methyl-1,4,7,10-tetraazadecane, 5-benzyl-1,4,7,10- Tetraazadecane, 2,3-diethyl-1,4,7,10-tetraazadecane, 2,5-dimethyl-1,4,7,10-tetraazadecane, 5,6-diethyl-3-me Ru-4-benzyl-1,4,7,10-tetraazadecane, 2,5,8-trimethyl-1,4,7,10-tetraazadecane, 2,7-dimethyl-1,4,7, 10,13-pentaazatridecane, 2,5,8,11-tetramethyl-1,4,7,10,13-pentaazatridecane, 7- (N′-phenyl) thiocarbamoyl-1,4 7,10,13-pentaazatridecane, 7-phenyl-1,4,7,10,13-pentaazatridecane, 7- (2'-cyanoethyl) -2,5,8,11-tetramethyl- Examples thereof include 1,4,7,10,13-pentaazatridecane, 2,5,8,11,14-pentamethyl-1,4,7,10,13,16-hexaazahexadecane and the like. These may be used alone or in combination of two or more.

Such oligoamines may be used alone or in combination of two or more thereof, and these and other polymerizable diamines may be used in combination.

As the dicarboxylic acid component which is the other monomer component for forming the polyamide, a well-known polymerizable dicarboxylic acid component can be appropriately used.

Specific examples of dicarboxylic acid components are known for the production of general polyesters and polyamides such as adipic acid, succinic acid dimethyl ester, adipic acid dichloride, terephthalic acid dibromide, isophthalic acid dichloride, naphthalene dicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride. And derivatives of dicarboxylic acids. These may be used alone or in combination of two or more.

For these reactions, an ordinary polyamide polymerization reaction may be employed. Specifically, for example, known polyamides disclosed in JP-A-61-152900, JP-A-63-277237, JP-B-07-025879, or polyamides based thereon are used. Can do.

The degree of polymerization of the polyamide is not particularly limited, but is usually 100 or more, preferably 300 to 40,000. When the degree of polymerization is 100 or less, the water resistance of the coating layer tends to decrease.

As a polyester resin, a well-known thing can be used without being specifically limited. Specifically, it can be obtained by condensation reaction of a dicarboxylic acid component and a diol component or ring-opening polymerization of a lactone. The acid component is not particularly limited, and known dicarboxylic acids or alkyl esters thereof can be used. Specifically, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, etc. or their dialkyl esters, diaryls Aromatic dicarboxylic acids such as esters, cyclohexane dicarboxylic acid, dimer acid, tetrahydrophthalic acid, etc., or alicyclic dicarboxylic acids such as dialkyl esters and diaryl esters, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, alkenyl Examples thereof include succinic anhydride and the like, and aliphatic dicarboxylic acids such as dialkyl esters and diaryl esters thereof. These may be used alone or in combination of two or more.

Specific examples of the glycol component include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-bis (4-hydroxycyclohexyl) propane, Cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane-ethylene oxide adduct, 2,2-bis (4-hydroxyphenyl) propane-propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethyleneglycol -Long chain glycols having a molecular weight of 400 to 6000, such as polydimethylsiloxane-ethylene oxide adduct, polydimethylsiloxane-propylene oxide adduct, and mixtures thereof. These may be used alone or in combination of two or more. Examples of lactones include ε-caprolactone.

As a polyether resin, a well-known thing can be used without being specifically limited. Specific examples include those obtained by addition polymerization of a divalent alcohol compound and a bifunctional epoxy resin. In particular, a polyether resin containing at least one active hydrogen group in the main chain is preferable from the viewpoints of adhesion to the substrate, film-forming properties of the coating layer, film properties, and the like. Specifically, for example, known polyether resins disclosed in Japanese Patent Laid-Open Nos. 61-16919, 2007-177054, and 2619639 or polyether resins based thereon are used. Can do.

The component (c) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule and is other than the component (a) and the component (b). Can be used. Specifically, for example, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), XDI (xylylene diisocyanate), NDI (naphthylene 1,5-diisocyanate), TMXDI (tetramethylene xylylene diisocyanate) Aromatic isocyanates such as IPDI (isophorone diisocyanate), H12MDI (hydrogenated MDI, dicyclohexylmethane diisocyanate), H6XDI (hydrogenated XDI), and the like, HDI (hexamethylene diisocyanate), DDI (Dimer acid diisocyanate) type, NBDI (norbornene diisocyanate) type and the like. These may be used alone or in combination of two or more. As the component (c), IPDI-based and HDI-based alicyclic isocyanates and aliphatic isocyanates are preferable because yellowing hardly occurs. Also, blocked isocyanate (reacted with a hydroxyl group-containing compound (blocking agent) such as methanol, isopropanol, ε-caprolactam and polyisocyanate, which decomposes upon heating to produce an isocyanate group) Since reaction is suppressed, handling property, storage stability, etc. can be improved, which is particularly preferable. Among the above-mentioned blocked isocyanates, aliphatic blocked isocyanates are preferable because they do not yellow, and the minimum curing temperature (the temperature at which the blocking agent's protective action decreases and functions effectively as a curing agent) is 130 ° C. or less, particularly 100 The thing below ℃ is preferred. When the minimum curing temperature exceeds 130 ° C., there are cases where the choices of usable substrates are narrowed. For example, when polyethylene terephthalate (PET) is used as the substrate, the temperature that can be applied to PET is 150 ° C., preferably 130 ° C. or less. Examples of the curing agent that satisfies such conditions include Duranate MF-K60X (HDI-based blocked isocyanate, minimum curing temperature 90 ° C.) manufactured by Asahi Kasei Corporation.

Here, the ratio (molar ratio) of the active hydrogen groups (—OH, —SH and —NH—) contained in the component (a) and the component (b) to the isocyanate group (—NCO) of the polyisocyanate is the ratio of the crosslinked resin. In consideration of characteristics such as solvent resistance, blocking resistance and strength, NCO / OH is preferably in the range of 0.05 to 1, and particularly preferably in the range of 0.1 to 0.5.

Moreover, the existing curing catalyst (dibutyltin dilaurate etc.) can also be used together with (c) component as needed. Depending on the type of curing agent, the curing rate of the crosslinkable resin can be significantly increased by using a curing catalyst in combination.

Furthermore, in addition to the components (a) to (c), the component (d) can be used in combination as necessary. The component (d) is not particularly limited as long as it is a silane-modified epoxy resin other than the components (a) to (c), and a known component can be used. Specific examples include those having at least two epoxy groups in the molecule and one or more hydrolyzable alkoxysilyl groups. Examples of the component (d) include Composeran E-102 and 103 manufactured by Arakawa Chemical Industries, Ltd.

In the present invention, a lubricant having a functional group capable of reacting with at least one of the components (e) (a) to (c) (hereinafter referred to as the component (e)) can also be used. The component (e) is not particularly limited as long as it has one or more active hydrogens in the molecule other than the components (a) to (d), and known components can be used. These may be used alone or in combination of two or more. Specifically, for example, BYK-370, 375 and 377 (manufactured by BYK Chemie), Silaplane FM-3311, 3321 and 3325, FM-4411, 4421 and 4425, FM-DA11, DA21 and DA26 (Chisso ( Etc.). From the viewpoint of compatibility with the paint and versatility, BYK-375 and Silaplane FM-3311 are most preferable.

In the present invention, the component (f) can be used as necessary. The component (f) is not particularly limited as long as it is a compound having at least two active hydrogens in one molecule other than the components (a) to (e), and known compounds can be used. Specifically, for example, dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, trimethylolpropane tris (3-mercaptopropioate) ), And polythiols such as tetraethylene glycol bis (3-mercaptopropionate), polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine, and polyols such as ethylene glycol, diethylene glycol, and glycerin. Etc. These may be used alone or in combination of two or more. Of these, dipentaerythritol hexakis (3-mercaptopropionate) is preferable because of its high crosslink density.

The resin composition for forming an antistatic layer of the present invention is at least one selected from the group consisting of the components (a) to (c) and, if necessary, the component (d), the component (e) and the component (e). Containing. Although these usage-amounts are not specifically limited, Usually, about (b) component 90-10 weight part and (c) component about 10-50 weight part with respect to (a) component 10-90 weight part. When the component (d) and the component (e) are contained, the component (d) is usually about 10 to 40 parts by weight, the component (e) is about 5 to 10 parts by weight, and the component (f) is about 5 to 20 parts by weight. It is. The resin composition for forming an antistatic layer of the present invention further comprises a surfactant, an antifoaming agent, a coating property improver, a thickener, an antistatic agent, an organic lubricant, organic particles, inorganic particles, oxidation You may contain well-known additives, such as an inhibitor, a ultraviolet absorber, a foaming agent, dye, and a pigment. These additives may be used alone or in combination of two or more as necessary.

In the antistatic film of the present invention, an antistatic layer obtained by reacting a resin composition for forming an antistatic layer is provided on one side of a base film, and the surface resistivity of the antistatic layer is 1 × 10. ^{It is 7} to 1 × 10 ¹³ Ω / □. The antistatic film of this invention is obtained by apply | coating the resin composition for antistatic layer formation on a base film, and making each component react. The resin composition for forming an antistatic layer may be applied as it is, or may be applied as a coating solution using an organic solvent or the like as a solution. Although there is no restriction | limiting in particular in the solid content density | concentration of a coating liquid, Usually, about 0.3 to 65 weight%, Preferably it is 0.5 to 30 weight%, More preferably, it is 1 to 10 weight%. When the concentration is too high or too low than these ranges, it may be difficult to provide a coating layer having a thickness necessary for sufficiently expressing the function.

The thickness of a coating layer is the thickness after drying, and is about 0.003-1.5 micrometers normally, Preferably it is 0.01-0.5 micrometer. If the thickness of the coating layer is less than 0.003 μm, sufficient performance may not be obtained, and if it exceeds 1.5 μm, blocking between films tends to occur.

As a method for applying the coating solution to the polyester film, for example, a coating technique as shown in “Coating system” published by Yuji Harasaki, Tsuji Shoten, published in 1979 can be used. Specifically, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater, Techniques such as an extrusion coater and a bar coater can be mentioned.

Various known films can be used as the base film of the antistatic film of the present invention. Specifically, a polyester film, triacetyl cellulose (TAC), an acrylic film, a cycloolefin polymer (COP) (example), etc. are mentioned. Among these, a polyester film is preferable in terms of versatility, transparency, and easy handling, and polyethylene terephthalate, polyethylene-2,6-naphthalate, and poly-1,4-cyclohexanedimethylene terephthalate are particularly preferable. These films may be polyesters copolymerized with other acid components and glycol components to the extent that they do not affect the effects of the present invention, and contain other components and additives as necessary. Also good.

The polyester film in the present invention may contain particles for the purpose of imparting slipperiness for easy handling. Examples of such particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. Further, organic particles such as crosslinked polymer particles and calcium oxalate, and precipitated particles during the polyester production process can be used.

The particle size and content of the particles to be used are selected according to the use and purpose of the film, but the average particle size is usually in the range of 0.005 to 5.0 μm, preferably 0.01 to 3.0 μm. It is. When the average particle diameter exceeds 5.0 μm, the film surface roughness tends to be too rough, or the particles tend to fall off from the film surface. If the average particle size is less than 0.005 μm, the surface roughness is too small and sufficient slipperiness may not be obtained. About particle content, it is about 0.001 to 30.0 weight% normally in a film, Preferably it is 0.01 to 10.0 weight%. When the amount of particles increases, the mechanical properties and transparency of the film tend to be impaired, and when the amount is small, the slipperiness tends to deteriorate.

Moreover, you may add an additive other than said particle | grain as needed. Examples of such additives include an antistatic agent, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, an antioxidant, a dye, a pigment, a light blocking agent, and an ultraviolet absorber.

The antistatic film of the present invention may have a multilayer structure as long as it satisfies the requirements of the present invention. In addition, the coating layer is naturally included in the concept of the present invention, whether it is provided on only one side of the film or on both sides.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. “Part” or “%” is based on weight unless otherwise specified. The hydroxyl value and the weight average molecular weight were measured by the following methods.

Hydroxyl value: Measured according to JIS K1557.
Weight average molecular weight: Measured by gel permeation chromatography (trade name “HLC-8220”, manufactured by Tosoh Corporation), column: product name “TSKguardcolumnSperHZ-L” manufactured by Tosoh Corporation.
Moreover, the evaluation method in an Example and a comparative example is as follows.
(1) Surface resistivity value Measured according to JIS K 6911 with an applied voltage of 500 volts using a ring electrode (URTRAMEGOHMMETER SM-8210, SME-883, manufactured by Toa Denpa Kogyo Co., Ltd.).
○: Good. The surface resistivity is 1 × 10 ¹² Ω / □ or less.
Δ: Normal. The surface resistivity is 1 × 10 ¹⁴ Ω / □ or less and higher than 1 × 10 ¹² Ω / □.
X: Defect. The surface resistivity is higher than 1 × 10 ¹⁴ Ω / □.
(2) The coating surface is superimposed on the easy-adhesion surface of the blocking-resistant easy-adhesion PET film (Cosmo Shine A-4100 manufactured by Toyobo Co., Ltd.), and a load of 500 g / cm ² is applied to the film. Visual inspection of blocking resistance after time.
○: Good. No or little blocking.
X: Defect. Block.
(3) A rubbing test with a solvent-resistant MEK-impregnated cotton swab of the antistatic layer is conducted, and the number of rubbing times until the coating film dissolves and peels is inspected. The number of times until the coating film dissolves and peels is described.
(4) Coating Appearance The appearance of the coating layer of the sample film was visually inspected, and coating unevenness and whitening that resulted in poor appearance were evaluated according to the following criteria.
○: There is no coating unevenness and it is clear.
Δ: There is some uneven coating. Or the coating film is slightly whitened.
X: There is uneven coating. Or the coating is whitened.

Production Example 1 (Synthesis of hydroxyl group-containing acrylic resin (1))
In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 75 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 175 parts of methyl methacrylate (hereinafter referred to as MMA), 1.3 lauryl mercaptan 1.3 , 1500 parts of methyl isobutyl ketone and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN), and the system temperature was about 85 ° C. over about 1 hour under a nitrogen stream. The temperature was raised to 0, and the temperature was kept for 1 hour. Next, the mixture was dropped into the system in about 2 hours under a nitrogen stream from a dropping funnel previously charged with a mixture consisting of 225 parts of HEMA, 525 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN. After keeping the same temperature for 3 hours, 10 parts of AIBN was charged and kept warm for 1 hour. Then, it heated up at 130 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., 1.3 parts of methoquinone was charged and cooled, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40%. The hydroxyl value was 127 mgKOH / g, and the weight average molecular weight was 13,250 (based on styrene conversion by GPC).

Production Example 2 (Synthesis of hydroxyl group-containing acrylic resin (2))
In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 175 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 75 parts of methyl methacrylate (hereinafter referred to as MMA), 1.3 parts of lauryl mercaptan 1.3 1 part, 1000 parts of methyl isobutyl ketone, 500 parts of propylene glycol monomethyl ether and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) were added for about 1 hour under a nitrogen stream. The temperature was raised until the system temperature reached about 85 ° C., and the temperature was kept for 1 hour. Next, the mixture is dropped into the system in about 2 hours under a nitrogen stream from a dropping funnel previously charged with a mixture consisting of 525 parts of HEMA, 225 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN. After keeping the same temperature for 3 hours, 10 parts of AIBN was charged and kept warm for 1 hour. Then, it heated up at 130 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., 1.3 parts of methoquinone was charged and cooled, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40%. The hydroxyl value was 297 mgKOH / g, and the weight average molecular weight (based on styrene conversion by GPC) was 14,600.

Production Example 3 (Synthesis of amino group-containing polyamide resin (PAM-200))
A reactor equipped with a stirrer, a condenser, a dropping funnel and a water separator was charged with 87.6 parts of adipic acid and 30 parts of water, and 61.8 parts of diethylenetriamine was added dropwise with stirring. Next, the internal temperature of the reaction system was gradually raised and kept at 180 ° C. for 4 hours to carry out a dehydration condensation reaction. Thereafter, 127.8 parts of water was gradually added to obtain a polyamide polyamine resin solution having a concentration of 50%.

Example 1
In a glass bottle, 337.5 parts of Eleconde SGM-002 (manufactured by Soken Chemical Co., Ltd.), 1195 parts of methyl cellosolve, 30 parts of PAM-200 prepared in Production Example 3, 25 parts of Duranate MF-K60X (manufactured by Asahi Kasei Chemicals Corporation) , BYK-375 (manufactured by BYK Chemie) 3.0 parts, formate TK-1 (manufactured by Mitsui Takeda Chemical Co., Ltd.) 0.06 parts, methyl ethyl ketone 62.5 parts, and an antistatic layer forming resin composition solution Got.

Example 2
262.5 parts of Elecondo SGM-002 in a glass bottle, 1077.5 parts of methyl cellosolve, 30 parts of Composelan E-102, 30 parts of PAM-200 prepared in Production Example 3, 37.5 parts of Duranate MF-K60X, BYK-375 3 0.0 part, Formate TK-1 0.06 part, Gaskamine 1.2 part, and methyl ethyl ketone 62.5 part were added, and the resin composition solution for antistatic layer formation was obtained.

Example 3
337.5 parts of Elecondo SGM-002 in a glass bottle, 1187.5 parts of methyl cellosolve, 37.5 parts of hydroxyl-containing acrylic resin (2) prepared in Production Example 2, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375 Then, 0.06 part of formate TK-1 and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Example 4
In a glass bottle, 337.5 parts of Elecondo SGM-002, 1210 parts of methyl cellosolve, 15 parts of Gaskamine 240 (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, Formate TK-1 0 0.06 part and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Example 5
In a glass bottle, 337.5 parts of Elecondo SGM-002, 1210 parts of methyl cellosolve, 15 parts of dipentaerythritol hexakis (3-mercaptopropionate) (hereinafter DPMP, manufactured by Sakai Chemical Industry Co., Ltd.), 25 parts of Duranate MF-K60X 3.0 parts of BYK-375, 0.06 parts of formate TK-1 and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Example 6
SGM-002 / PAM-200 / Silaplane FM-3311 / MF-K60X
In a glass bottle, 337.5 parts of Eleconde SGM-002 (manufactured by Soken Chemical Co., Ltd.), 1360 parts of methyl cellosolve, 30 parts of PAM-200, 25 parts of Duranate MF-K60X (manufactured by Asahi Kasei Chemicals Corporation), BYK-375 (BYK) Chemie) 3.0 parts, Formate TK-1 (manufactured by Mitsui Takeda Chemical Co., Ltd.) 0.06 parts, methyl ethyl ketone 62.5 parts, Silaplane FM-3311 (manufactured by Chisso Corporation) 18.3 parts In addition, an antistatic layer forming resin composition solution was obtained.

Example 7
337.5 parts of Elecondo SGM-002, 1330 parts of methyl cellosolve, 30 parts of PAM-200, 15 parts of DPMP, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, 0.06 parts of Formate TK-1 Then, 62.5 parts of methyl ethyl ketone was added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 1
270 parts of Elecondo QO-101 (manufactured by Soken Chemical Co., Ltd.) having no active hydrogen in the glass bottle, 1268.7 parts of methyl cellosolve, 30 parts of PAM-200, 2700 of Coronate (manufactured by Nippon Polyurethane Industry Co., Ltd.) 18 8 parts, 3.0 parts of BYK-375, 0.06 parts of formate TK-1 and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 2
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1261.2 parts of methyl cellosolve, 37.5 parts of hydroxyl group-containing acrylic resin (1) prepared in Production Example 1, 18.8 parts of Coronate 2507, BYK 3.0 parts of -375, 0.06 parts of formate TK-1, and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 3
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1261.2 parts of methyl cellosolve, 37.5 parts of hydroxyl group-containing acrylic resin (2) prepared in Production Example 2, 18.8 parts of Coronate 2507, BYK 3.0 parts of -375, 0.06 parts of formate TK-1, and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 4
270 parts of Elecondo QO-101 having no active hydrogen in the glass bottle, 1283.7 parts of methyl cellosolve, 15 parts of Gaskamine 240, 18.8 parts of Coronate 2507, 3.0 parts of BYK-375, Formate TK-1 06 parts and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 5
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1283.7 parts of methyl cellosolve, 15 parts of DPMP, 18.8 parts of Coronate 2507, 3.0 parts of BYK-375, Formate TK-1 06 parts and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 6
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1262.5 parts of methyl cellosolve, 30 parts of PAM-200, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, Formate TK-1 0.06 part and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 7
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1255 parts of methyl cellosolve, 37.5 parts of the hydroxyl group-containing acrylic resin (1) prepared in Production Example 1, 25 parts of Duranate MF-K60X, BYK-375 3.0 parts, 0.06 parts of formate TK-1 and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 8
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in a glass bottle, 1255 parts of methyl cellosolve, 37.5 parts of hydroxyl group-containing acrylic resin (2) prepared in Production Example 2, 25 parts of Duranate MF-K60X, BYK-375 3.0 parts, 0.06 parts of formate TK-1 and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 9
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1277.5 parts of methyl cellosolve, 15 parts of Gascamine 240, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, Formate TK-1 06 parts and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 10
270 parts of Elecondo QO-101 having no active hydrogen in the molecule in the glass bottle, 1277.5 parts of methyl cellosolve, 15 parts of DPMP, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, Formate TK-1 06 parts and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 11
337.5 parts of Elecondo SGM-002 in a glass bottle, 1201.2 parts of methyl cellosolve, 30 parts of Composelan E-102 (manufactured by Arakawa Chemical Co., Ltd.), 18.8 parts of Coronate 2507, 3.0 parts of BYK-375, Four Mate TK-1 0.06 part, Gaskamine 1.2 part, methyl ethyl ketone 62.5 parts were added, and the resin composition solution for antistatic layer formation was obtained.

Comparative Example 12
Elecondo SGM-002 337.5 parts in a glass bottle, methyl cellosolve 1201.2 parts, (b) component which does not have active hydrogen in the molecule 15 parts of Proof G-0130S (manufactured by NOF Corporation), Coronate 2507 18.8 parts, 3.0 parts of BYK-375, 0.06 parts of formate TK-1, 1.2 parts of Gaskamine, and 77.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 13
337.5 parts of Eleconde SGM-002, 1195 parts of methyl cellosolve, 30 parts of Composelan E-102, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, 0.06 parts of Formate TK-1 and Gaskamine 1 2 parts and 62.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

Comparative Example 14
337.5 parts of Elecondo SGM-002, 1195 parts of methyl cellosolve, 15 parts of Marproof G-0130S, 25 parts of Duranate MF-K60X, 3.0 parts of BYK-375, 0.06 parts of Formate TK-1 and Gaskamine 1.2 parts and 77.5 parts of methyl ethyl ketone were added to obtain a resin composition solution for forming an antistatic layer.

(Creation of specimen)
Each antistatic layer forming resin composition solution obtained in the above examples and comparative examples is obtained by diluting with a mixed solvent of methyl ethyl ketone / methyl cellosolve = 50/50 to a concentration of 5% and curing. A cured film was prepared and performance was evaluated for the items listed in the table below.

The antistatic layer forming resin composition solution shown in the table was applied onto a polyethylene terephthalate (PET) film with a # 8 bar coater (calculated value: film thickness 0.3 μm), dried and cured at 150 ° C. for 5 minutes. I let you. The performance evaluation results are shown in Table 1.

Claims (7)

(A) Quaternary ammonium salt type cationic polymer compound having active hydrogen in molecule, (b) Group consisting of acrylic resin, polyurethane resin, polyamide resin, polyester resin and polyether resin having active hydrogen in molecule A resin composition for forming an antistatic layer, comprising at least one selected from (c) a polyisocyanate compound and optionally (d) a silane-modified epoxy resin and / or (f) a compound having at least two active hydrogens . (A) The resin composition for forming an antistatic layer according to claim 1, wherein the quaternary ammonium salt type cationic polymer compound having active hydrogen in the molecule has a weight average molecular weight of 500 to 500,000. (A) a quaternary ammonium salt type cationic polymer compound having active hydrogen in the molecule, and (b) a group consisting of an acrylic resin, polyurethane resin, polyamide resin, polyether resin and polyester resin having active hydrogen in the molecule. 3. The resin composition for forming an antistatic layer according to claim 2, wherein the active hydrogen in at least one selected from is derived from at least one selected from the group consisting of an amino group, a hydroxyl group and a thiol group. The resin composition for forming an antistatic layer according to any one of claims 1 to 3, further comprising a lubricant having a functional group capable of reacting with at least one of the components (e) (a) to (c). (F) The resin composition for forming an antistatic layer according to any one of claims 1 to 4, wherein the compound having at least two active hydrogens is dipentaerythritol hexakis (3-mercaptopropionate). An antistatic layer obtained by reacting the resin composition for forming an antistatic layer according to any one of claims 1 to 5 is provided on one side of the base film, and the surface resistivity of the antistatic layer is 1. An antistatic film that is 1 × 10 ⁷ to 1 × 10 ¹³ Ω / □. The antistatic film according to claim 6, wherein the base film is selected from the group consisting of polyethylene terephthalate, polyethylene-2,6-naphthalate, polytrimethylene terephthalate, polybutylene naphthalate, and polybutylene terephthalate.