JP2007321014A - Antistatic film, and coating for forming antistatic layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic film excellent in static prevention, transparency, solvent resistance, waterproof property, printing aptitude, sliding property, processability, close adhesion with a substrate film, etc., and coating for forming the antistatic layer. <P>SOLUTION: This antistatic film consisting of the substrate film and the antistatic layer installed on at least one of the surfaces of the substrate film is characterized in that the antistatic layer is formed by containing (A) a resin having an active hydrogen group in its molecule, (B) a resin consisting of an ion-conductive polymer and a supporting electrolytic salt and (C) a polyisocyanate as film-forming components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic film and a coating for forming an antistatic layer (hereinafter sometimes simply referred to as “paint”), and more specifically, an antistatic function, transparency, solvent resistance, water resistance, printability, moderate The present invention relates to an antistatic film excellent in slipperiness, processability, and adhesion to a substrate film, and a coating material for forming the film.

  General biaxially stretched polyester films have excellent properties such as mechanical strength, dimensional stability, uniformity, heat resistance, chemical resistance, and transparency. Therefore, packaging films, optical films, and recording media It is used in a wide range of applications including films, platemaking films, release films, agricultural films, wind films and labels. Polyolefin resin films are lightweight, have good gas barrier properties and moisture-proof properties, and are inexpensive, and are therefore used as packaging materials and films in a wide range of fields such as food, electronic parts and precision parts. In addition, resin films made of materials such as polycarbonate, polyacrylate, triacetyl cellulose, and cycloolefin plastics are also used in various fields. However, as a problem common to plastic films, it is said that they are easily charged by static electricity. A point is mentioned. For this reason, there is a problem that surrounding dust adheres to the processed film or the processed product.

For this reason, conventionally, a surface resistance value is 1.0 × 10 ¹² Ω by coating or kneading a non-ionic, anionic or cationic low molecular weight surfactant or conductive metal powder on a plastic film. The antistatic performance is imparted to the film by lowering to / cm ² or less.

  However, such a conventional technique has a problem in that the low molecular weight surfactant volatilizes or decomposes at the time of film production, so that the surfactant concentration in the film varies and the film performance is not stable. In addition, after film formation, the surfactant bleeds on the film surface over time, the surfactant bleeded on the film surface falls, and the surface resistance performance decreases over time, transparency, blocking, There is a problem that adhesiveness and printability are impaired.

  In addition, in the case of using conductive metal powder as an antistatic agent, in addition to difficulty in dispersion processing of metal powder, the film appearance becomes opaque, and depending on the amount used, it is expensive. Furthermore, there are problems such as detachment of the conductive metal powder from the antistatic film.

  There has been proposed a film characterized in that a coating solution containing an amphoteric polymer compound is applied to a film to impart antistatic properties to the film (Patent Document 1). As the amphoteric polymer compound, a compound having a carboxylate as an anionic group and a quaternary ammonium base as a cationic group has been devised. In the antistatic film obtained, a stable surface resistance value cannot be obtained when the humidity is low.

Further, an antistatic composition having a composition in which at least one of an anionic surfactant and a cationic surfactant contains at least one polyoxyalkylene group has been proposed (Patent Document 2). The antistatic film treated with this composition has a surface resistance value of about 1.0 × 10 ¹¹ Ω / cm ² and is at a practical level, but has low durability charging performance (antistatic performance decreases with time). To do).

Recently, antistatic films are required to have antistatic function, transparency, solvent resistance, water resistance and performance that is hardly affected by the external environment (humidity), and a coating material that can form such an antistatic layer is used. It has been demanded.
JP 2004-175821 A JP 7-233365 A

  However, the proposed technique does not provide an antistatic film that satisfies all the functions described above. In addition, there is a demand for an antistatic film having higher performance than before and a coating material for forming the film.

  Therefore, the object of the present invention is to provide antistatic properties, transparency, and solvent resistance (the organic solvent is used when cleaning the roll, so that it does not remain in the solvent used), water resistance (external environment ( (Humidity) is required to have a performance that is not easily affected), printability (product quality control and product processing printing is possible), slipperiness (in the case of roll-roll, moderate slipperiness is required) It is to provide an antistatic film excellent in processing suitability (composite film, repeat coat suitability, etc.) and adhesion to a substrate film, and a coating for forming the film.

  The above object is achieved by the present invention described below. That is, the present invention provides an antistatic film comprising a base film and an antistatic layer provided on at least one surface of the base film, wherein the antistatic layer is a resin having an active hydrogen group in the molecule. (A) (hereinafter sometimes referred to simply as “resin (A)”), a resin (B) composed of an ion conductive polymer and a supporting electrolytic salt (hereinafter also referred to simply as “resin (B)”) and a poly Provided is an antistatic film characterized in that it is formed using isocyanate (C) as a film-forming component.

In the present invention, the active hydrogen group in the resin (A) has at least one group selected from a hydroxyl group, amino group, carboxyl group, thiol group and / or epoxy group in the main chain and / or side chain. The ion conductive polymer of the resin (B) is a resin containing a hydrophilic segment and a siloxane segment; and the supporting electrolytic salt of the resin (B) is a salt represented by the following general formula: It is preferable.
M ⁺ X ^-
(M ⁺ is at least one selected from Li ⁺ , Na ⁺ and K ⁺ , and X ⁻ is ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , CF _3. Selected from SO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ and (C ₂ F ₅ SO ₂ ) ₃ C ⁻ At least one).

In the present invention, the surface resistance value of the antistatic layer is 10 ⁵ to 10 ¹² Ω / cm ² ; the haze value of the antistatic layer is 3.0% or less; and the antistatic layer The dynamic friction coefficient is preferably 0.05 to 0.30.

  Moreover, this invention provides the coating material formed by melt | dissolving or disperse | distributing the said resin (A) and the said resin (B) in the organic solvent.

  In the coating material of the present invention, the resin (A) is 5 to 95% by mass of the total amount (100% by mass) of the resin (A) and the resin (B), and the resin (B) is 95 to 95%. It is preferable that the polyisocyanate is added immediately before use, or a stabilized polyisocyanate is contained.

  As a result of intensive studies to solve the above problems, the present inventors have made the antistatic layer of the antistatic film as a film-forming component using the resin (A), the resin (B), and the polyisocyanate (C). It has been found that an antistatic film having an excellent function can be obtained by forming.

  In the present invention, an ethylene oxide unit in which the resin (A) and the polyisocyanate (C) bring out surface properties such as solvent resistance of the antistatic layer and adhesion to the substrate, and the resin (B) is a hydrophilic segment. Oxygen atoms of these ions undergo ion dissociation, and ions of the supporting dissociation salt move due to the movement of the polymer chain, thereby exhibiting antistatic properties in the antistatic layer. At that time, if the resin (B) has a siloxane segment, the resin (B) is oriented toward the surface side of the antistatic layer by tilted orientation, and the effect of antistatic properties is enhanced.

  Therefore, according to the present invention, an antistatic film excellent in antistatic properties, transparency, solvent resistance, water resistance, printability, slipperiness, suitability for processing, adhesion to a base film, and the like are formed. A paint is provided for.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The antistatic film of the present invention comprises a base film and an antistatic layer provided on at least one surface of the base film.

  Next, the antistatic layer characterizing the present invention will be described in more detail. The antistatic layer is formed using the resin (A), the resin (B), and the polyisocyanate (C) as a film-forming component, and these are dissolved in a solvent or the like to form a paint without solvent. It is preferably formed by applying and drying on a material film. The coating material in this case is a composition comprising resin (A), resin (B), and polyisocyanate (C).

  The active hydrogen group in the resin (A) is, for example, a hydroxyl group, an amino group, a carboxyl group, a thiol group and / or an epoxy group. Among these, a hydroxyl group is preferably used. When the resin (A) has an active hydrogen group in its molecule, it can be used as it is as the resin (A), but the resin (A) has an active hydrogen group in its molecule. If not, it can be used as the resin (A) by applying a treatment such as modification to give an active hydrogen group.

  Examples of the resin (A) include polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, Ethylene-vinyl alcohol-vinyl acetate copolymer resin, acrylic resin, epoxy resin, modified epoxy resin, phenoxy resin, modified phenoxy resin, phenoxy ether resin, phenoxy ester resin, fluorine resin, melamine resin, alkyd resin, phenol Examples include resins, polyethers, polyesters, celluloses, chitosan, and urethane resins.

  Among the resins (A), ethylene-vinyl alcohol copolymer, partially saponified polyvinyl alcohol, and phenoxy resin are particularly preferable. Furthermore, a resin obtained by modifying an acrylic resin, polyvinyl alcohol, butyral group-modified polyvinyl alcohol or the like with a fluorine-modified silicone group or a long-chain alkyl group can also be used.

  The resins (A) listed above are preferred resins used in the present invention, but the present invention is not limited to these exemplified resins. Accordingly, not only the above-exemplified resins but also other resins (A) that are currently commercially available and can be easily obtained from the market can be preferably used in the present invention.

  One example of the ion conductive polymer in the resin (B) used in the present invention is a polyurethane resin containing a hydrophilic segment and a polysiloxane segment therein. The polysiloxane segment is contained in the main chain of the polyurethane resin or contained in a branched state. That is, if the polysiloxane segment-containing compound that is the raw material of the polyurethane resin is a double-end reactive type, the polysiloxane segment-containing compound is at one end or a branched reactive type at the trunk portion that is the main chain of the polyurethane resin. And contained in a state branched from the main chain of the polyurethane resin.

  The polyurethane resin as described above is obtained by reacting a hydrophilic polyol and / or polyamine, an organic polyisocyanate, and a polysiloxane compound having at least one active hydrogen group in the absence or presence of a chain extender. . The content of the hydrophilic segment composed of the hydrophilic polyol and / or polyamine in the polyurethane resin is preferably an amount occupying 20 to 90% by mass in the whole resin, and the content of the polysiloxane segment is The amount of the resin is preferably from 0.01 to 30% by mass, and the weight average molecular weight of the resin is preferably from 3,000 to 500,000.

  The hydrophilic polyol or polyamine used for introducing the hydrophilic segment into the polyurethane resin is preferably a compound having a hydroxyl group, an amino group, a carboxyl group and the like and having a weight average molecular weight in the range of 400 to 8,000. Examples of those having a terminal hydroxyl group and hydrophilicity include polyethylene glycol, polyethylene glycol / polytetramethylene glycol copolymer polyol, polyethylene glycol / polypropylene glycol copolymer polyol, polyethylene glycol adipate, polyethylene glycol carbonate, polyethylene glycol / poly- Examples include ε-lactone copolymer polyols, block or random copolymers such as polyethylene glycol / poly-valerolactone copolymer polyols, and derivatives formed by reacting methoxypolyethylene glycol monool with isocyanate via urethane bonds.

  Examples of those having an amino group at the end and having hydrophilicity include polyethylene oxide diamine, polyethylene oxide propylene oxide diamine, polyethylene oxide triamine, polyethylene oxide propylene oxide triamine, and other ethylene oxide adducts having a carboxyl group or a vinyl group. Etc.

  In the present invention, it is also possible to copolymerize other polyols, polyamines, polycarboxylic acids and the like that do not have a hydrophilic chain in order to impart other performance. The compounds having an active hydrogen group listed above are preferable compounds used in the present invention, but the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be preferably used in the present invention.

  The raw material component used as the said polysiloxane segment used by this invention is demonstrated. As the polysiloxane compound having at least one active hydrogen group used in the present invention, for example, the following compounds are preferably used (in this, an epoxy-modified polysiloxane modified by using active hydrogen groups). A siloxane compound is also included, but it is included because it reacts with an isocyanate group and is contained in a polyurethane resin).

(1) Amino-modified polysiloxane compound

(2) Epoxy-modified polysiloxane compound

(3) Alcohol-modified polysiloxane compound

(4) Mercapto-modified polysiloxane compound

  In addition to the above, a polylactone (polyester) -polysiloxane compound obtained by modifying a polysiloxane compound with a lactone such as a polyethylene oxide polysiloxane compound modified with ethylene oxide or propylene oxide or a polypropylene oxide polysiloxane compound is preferably used. Particularly preferred are polyether-polysiloxane compounds obtained by ether-modifying a polysiloxane compound having one or more active hydrogen groups in the molecule with ethylene oxide, propylene oxide or the like. Specific examples of alkylene oxides for obtaining the molecular chain of the preferred oxyalkylene polymer used herein include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, and styrene oxide. , Α-methylstyrene oxide and the like, and can be obtained by ring-opening polymerization in the presence of various catalysts.

  The polysiloxane compounds having active hydrogen groups listed above are preferred compounds used in the present invention, but the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be preferably used in the present invention. Particularly preferred compounds in the present invention are polysiloxane compounds having two hydroxyl groups or amino groups.

  As other polyols that can be used for the production of the polyurethane resin, preferably known ones such as short-chain diols, polyhydric alcohols, and polymer polyols conventionally used for the production of polyurethane are also used as polyamines. The short-chain diamine conventionally used for the production of polyurethane can be used.

  Examples of the short-chain diol include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, and neopentyl glycol. And its alkylene oxide low mole adduct (number average molecular weight less than 500), alicyclic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol, and its alkylene oxide low mole Adducts (number average molecular weight less than 500), aromatic glycols such as xylylene glycol and their alkylene oxide low molar adducts (number average molecular weight less than 500), bisphenol A, thiobisphenol and sulfone bisphenol Phenols and alkylene oxide low mol adduct (number average molecular weight of less than 500), and the like.

  Examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, and 1,1,1- Examples include trimethylolpropane. Furthermore, as a compound having both at least one active hydrogen-containing group and a hydrophilic group other than a hydroxyl group in the same molecule, compounds such as sulfonic acid, carboxylic acid, phosphoric acid, and amine can be used.

  For example, examples of the sulfonic acid compound include N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid. In addition, as carboxylic acid compounds, dimethylolpropanoic acid, dimethylolbutanoic acid and their alkylene oxide low-mole adducts (number average molecular weight less than 500) and γ-caprolactone low-mole adducts (number average molecular weight less than 500), Examples thereof include half esters derived from an acid anhydride and glycerin, and compounds derived from a monomer containing a hydroxyl group and an unsaturated group and a monomer containing a carboxyl group and an unsaturated group by a free radical reaction. If it is an amine system, compounds, such as alkyl dialkanolamines, such as C1-C18 alkyl diethanolamine, are mentioned. These can be used alone or in combination of two or more.

Examples of the polymer polyol include the following.
(1) Polyether polyols such as those obtained by polymerizing or copolymerizing alkylene oxides (propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.), specifically polypropylene Glycol, polytetramethylene ether glycol and polyhexamethylene glycol, etc.

(2) Polyester polyols such as aliphatic dicarboxylic acids (eg succinic acid, adipic acid, sebacic acid, glutaric acid and azelaic acid) and / or aromatic dicarboxylic acids (eg isophthalic acid and terephthalic acid) And low molecular weight glycols (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol and 1,4-bishydroxy For example, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butyle. Adipate diol, polyneopentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, and polybutylene isophthalate diol, etc.,

(3) Polylactone polyols such as polycaprolactone diol or polycaprolactone triol and poly-3-methylvalerolactone diol,
(4) Polycarbonate diol, such as polyhexamethylene carbonate diol,
(5) Polyolefin polyol, such as polybutadiene glycol and polyisoprene glycol, or a hydride thereof,
(6) Polymethacrylate diols such as α, ω-polymethylmethacrylate diol and α, ω-polybutylmethacrylate diol are exemplified.

  The structure and molecular weight of these polyols are not particularly limited, but they can be used in combination with the hydrophilic polyol and / or polyamine.

  Preferred polyamines as the polyamine include, for example, short chain diamines, aliphatic, aromatic diamines, long chain diamines and hydrazines. Examples of the short-chain diamine include aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine and octamethylene diamine, phenylene diamine, 3,3′-dichloro-4,4′-diaminodiphenyl methane, 4 , 4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether and aromatic diamine compounds such as 4,4′-diaminodiphenylsulfone, cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, And alicyclic diamine compounds such as 4-diaminocyclohexane and isophoronediamine.

  Examples of the long-chain diamine include those obtained by polymerization or copolymerization of alkylene oxide (such as propylene oxide and butylene oxide), and specific examples include polypropylene diamine. Further, hydrazines such as hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and phthalic acid dihydrazide can be mentioned. These can be used alone or in combination of two or more. As the polyol and the polyamine, the diol compound and the diamine compound that can be used in combination with the hydrophilic polyol and / or the polyamine are preferably polyethers.

  As the polyisocyanate compound used for the synthesis of the polyurethane resin used in the present invention, any of those conventionally used for producing polyurethane can be used and is not particularly limited. Preferred examples of the polyisocyanate compound include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, and 4-chloro-1,3-phenylene diisocyanate. 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), jurylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1, Aromatic diisocyanates such as 5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate and 4,4′-diisocyanate dibenzyl, methyl Diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate and other aliphatic diisocyanates, 1,4-cyclohexylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI and hydrogenated XDI, etc., or these diisocyanate compounds and low molecular weight polyols or polyamines are reacted so as to be isocyanates. Naturally, the obtained polyurethane prepolymer can also be used.

  A method for producing a polyurethane resin using the above raw materials is not particularly limited, and a conventionally known method for producing polyurethane can be used. For example, a compound in which a hydrophilic polyol and / or polyamine, at least one active hydrogen group, and a polysiloxane segment coexist in the same molecule in the presence or absence of an organic solvent that does not contain active hydrogen in the molecule. , Polyol and / or polyamine, polyisocyanate, and optionally a low molecular diol or low molecular diamine as a chain extender, and the equivalent ratio of isocyanate group to active hydrogen-containing functional group is usually 1.0. By blending, a polyurethane resin can be obtained by reacting at 20 to 150 ° C., preferably 30 to 110 ° C. until there is almost no isocyanate group, by a one-shot method or a multistage method.

  The polyurethane resin may be synthesized without a solvent or may be synthesized using an organic solvent. Preferable organic solvents include, for example, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate and cyclohexanone. Further, acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate and N-methyl-2- Pyrrolidone and the like can also be used.

In the case of producing a polyurethane resin, the hydrophilic polyol and / or polyamine is 20 to 95% by mass, preferably 30 to 80% by mass, and a polysiloxane compound having at least one active hydrogen group in the same molecule. The compound is contained in 0.01 to 30% by mass, preferably 0.1 to 20% by mass, the chain extender is 0 to 50% by mass, preferably 0 to 40% by mass (the total of these components is 100% by mass). The resin (B) is synthesized with a polyisocyanate ratio of NCO / OH (NH ₂ ) = 1.0.

  In the above reaction component, if the amount of the hydrophilic polyol and / or polyamine is large (exceeding 95% by mass), the antistatic film in the antistatic film is not preferable because the water resistance of the antistatic layer is lowered and humidity control of the outside air is impossible. . On the other hand, when the amount of the hydrophilic polyol and / or polyamine is small (less than 20% by mass), the antistatic performance of the antistatic film is deteriorated, which is not preferable (the antistatic mechanism is a hydrophilic segment (ion dissociation polymer)). For ion-conducting polymer consisting of a supporting electrolyte salt).

  Further, in the above reaction component, when the amount of the polysiloxane compound is large (exceeding 30% by mass), the antistatic films on which the antistatic layer is formed slip too much to cause a problem. Also, if there is residual unreacted polysiloxane component, the ink / paint used for product stains (contaminants such as hand oil adhere to the siloxane component), printing and overcoating should be selected. It is not preferable because a repelling phenomenon occurs. On the other hand, when the amount of the polysiloxane compound is small (less than 0.01% by mass), it is not preferable because slippage between the antistatic films formed with the antistatic layer is insufficient and humidity control of the outside air is impossible.

  The molecular weight of the polyurethane resin used in the present invention is preferably in the range of 5,000 to 500,000 in terms of weight average molecular weight (measured by GPC, converted to standard polystyrene).

  Another example of the ion conductive polymer in the resin (B) is a siloxane-modified polyalkylene oxide resin obtained by reacting a compound having at least one active hydrogen group and a siloxane segment with an ethylene oxide and / or propylene oxide compound. Useful. The resin will be described below.

  The siloxane-modified polyalkylene oxide resin uses the siloxane compound exemplified above as at least one active hydrogen group-containing siloxane compound, and ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, It can be obtained by ring-opening polymerization of cyclohexene oxide, styrene oxide, α-methylstyrene oxide or the like in the presence of various catalysts. Examples of the polymerization catalyst include alkali catalysts such as KOH and NaOH. Particularly preferred polyalkylene oxide compounds here are ethylene oxide and propylene oxide, and particularly preferred is ethylene oxide. Further, the terminal group (hydroxyl group) of the resin obtained by the reaction is preferably bifunctional or more in order to cause polyisocyanate reaction when forming the antistatic layer of the antistatic film (solvent resistance and bleed out are low). ). Examples of resins (compounds) obtained by reacting polysiloxane with ethylene oxide are shown below.

As other siloxane-modified polyalkylene oxide resins,
(1) methyl hydrogen polysiloxane compound (SiH) and polyoxyethylene allyl ether compound _{(CH 2 = CH-CH 2} O~) and polyether siloxane co obtainable by hydrosilylation reaction using a platinum catalyst to heavy Coalescence,
(2) A polyether siloxane copolymer obtained by polycondensation reaction between a siloxane compound containing both terminal ester groups and polyethylene glycol using a tetrabutyl titanate ester catalyst, and (3) a polysiloxane having an active hydrogen group Examples thereof include polyether siloxane copolymers obtained by reacting a compound and methoxypolyethylene glycol with diisocyanate (via a urethane bond).

  Another example of the ion conductive polymer in the resin (B) is a polysiloxane / alkylene-modified acrylic using a siloxane macromonomer ((meth) acrylic group-containing siloxane macromer) and methoxypolyethylene oxide methacrylate or methoxypolyethylene oxide acrylate. Resin. The resin will be described. Examples of the polysiloxane compound having at least one (meth) acryl group in the molecule used for the production of the resin include the following compounds.

  Examples of the hydrophilic compound having at least one (meth) acrylic group and / or acrylic group in the molecule used for the production of the resin include the following compounds.

  Examples of acrylic monomer compounds that may be copolymerized with the siloxane macromonomer include, for example, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, benzyl methacrylate, trimethylsilylpropyl methacrylate, and the like. Methacrylic acid and ester monomers thereof, alkyl acrylates having 1 to 12 carbon atoms in alkyl groups such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, Examples thereof include aromatic vinyl monomers such as styrene and α-methylstyrene, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more. The polymerization method for copolymerizing the siloxane macromonomer or the like with an acrylic monomer is not particularly limited, and a method similar to a conventionally known polymerization method for an acrylic monomer can be used.

Examples of the supporting electrolytic salt used in the present invention include salts represented by the following general formula.
M ⁺ X ^-
(M ⁺ is one selected from Li ⁺ , Na ⁺ and K ⁺ , and X ⁻ is ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , CF ₃ SO _{1 selected from 2} ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ and (C ₂ F ₅ SO ₂ ) ₃ C ⁻ Seeds.)

  Specific examples of the supporting electrolyte salt include, for example, lithium perchlorate, lithium bistrifluoromethanesulfonimide, lithium borofluoride, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium pentafluoroethanesulfonate, lithium bispenta Examples thereof include fluoroethanesulfonimide, tetraethylammonium borofluoride, tetraethylammonium hexafluorophosphate, and potassium bistrifluoromethanesulfonimide.

  The amount of the supporting electrolytic salt used with respect to the ion conductive polymer is preferably 1 to 30 parts by mass per 100 parts by mass of the ion conductive polymer. When the amount of the supporting electrolyte salt used is less than 1 part by mass, the antistatic property of the formed antistatic layer is insufficient. On the other hand, even when the amount of the supporting electrolyte salt used exceeds 30 parts by mass, it is particularly advantageous. There is no.

  The resin (A) and the resin (B) are used in an amount of 5 to 95% by mass of the resin (A) in the total amount (100% by mass) of the resin (A) and the resin (B). (B) is 95-5 mass%. If the amount of the resin (A) used exceeds 95% by mass, the pot life of the paint used in the present invention (pot life) and the adhesion of the antistatic layer to the substrate film are unfavorable, When the amount of the resin (A) used is less than 5% by mass, the crosslink density and solvent resistance of the antistatic layer to be formed are lowered, which is not preferable. On the other hand, if the amount of the resin (B) used exceeds 95% by mass, the water resistance and solvent resistance of the formed antistatic layer may be lowered, which is not preferable. On the other hand, the amount of the resin (B) used is not preferable. If it is less than 5% by mass, the antistatic effect of the antistatic layer becomes diluted, which is not preferable.

  As the polyisocyanate (C) used in the present invention, known ones used conventionally can be used and are not particularly limited. For example, dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanatephenyl) thiophosphite, polyfunctional aromatic isocyanate, polyfunctional aromatic aliphatic isocyanate, polyfunctional aliphatic Examples thereof include blocked polyisocyanates such as isocyanate, fatty acid-modified polyfunctional aliphatic isocyanate, and blocked polyfunctional aliphatic isocyanate, and polyisocyanate prepolymers. Of these, it is possible to use either aromatic or aliphatic, preferably modified compounds such as diphenylmethane diisocyanate and tolylene diisocyanate for aromatic systems, hexamethylene diisocyanate and isophorone diisocyanate for aliphatic systems, and molecules. A urethane prepolymer obtained by reacting a polyisocyanate multimer or an adduct with another compound, or a low molecular weight polyol or polyamine so as to be a terminal isocyanate is preferable. Etc. are also preferably used. These are exemplified below with structural formulas, but are not limited thereto.

  The amount of the polyisocyanate (C) used in the paint of the present invention is 5 to 80 parts by mass, preferably 5 to 60 parts by mass with respect to 100 parts by mass of the resin (A) and the resin (B). Part. If the amount of the polyisocyanate (C) used exceeds 80 parts by mass, it is not preferable because the working time of the paint used is shortened. On the other hand, if the amount of the polyisocyanate (C) used is less than 5 parts by mass, formation occurs. This is not preferable because the crosslink density of the antistatic layer is lowered.

  In the coating material, a curing catalyst, a reaction inhibitor, and other additives can be appropriately used as necessary. Examples of the curing catalyst include dibutyltin laurate, dioctyltin laurate, stannous octoate, lead octylate, tetra-n-butyl titanate, and salts of organic or inorganic acids and organometallic derivatives such as triethylamine. And organic amines such as diazabicycloundecene catalysts. Examples of the reaction inhibitor include phosphoric acid, acetic acid, tartaric acid, phthalic acid, and formic acid ester.

  Further, for the purpose of imparting slipperiness to the antistatic layer and water resistance, for example, silicone oil and / or modified silicone oil (for example, polydimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane and aralkyl-modified polydimethyl) are used. Siloxane etc.), various waxes, acrylic polymers, long chain alkyl modified polymers, fluorine modified polymers and siloxane modified polymers.

  Furthermore, in the coating material of this invention, in addition to the said supporting electrolytic salt, another antistatic agent can be used together. Examples of these antistatic agents include polyvinyl alcohol, cation-modified polyvinyl alcohol, alkali metal salt-containing polyether, alkali metal salt-containing ether polyurethane, polyamine, quaternary cation salt-containing acrylic resin, specially modified polyester, and special cation. Resin, cellulose derivatives, polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline, sulfonated polyaniline and other organic conductive materials, carbon nanotubes, carbon black, tin oxide, zinc oxide, titanium oxide, and other metal oxides and various metals Additives such as conductive filler-containing polymers such as alkoxides and ITO powders can be added.

  In addition, in order to form an antistatic layer in this invention, the coating material containing the said resin (A), resin (B), and polyisocyanate (C) is used. When using this paint, it is preferable to add the above-mentioned polyisocyanate before use or to add a stabilized polyisocyanate in advance. The paint may be prepared without a solvent or may be prepared using an organic solvent. Preferable examples of the organic solvent include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate and butyl acetate. Acetone, cyclohexane, tetrahydrofuran, N-methyl-2-pyrrolidone, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve and cellosolve acetate can also be used. Although the solid content of the coating material prepared using the organic solvent is not particularly limited, it is preferably about 3 to 95% by mass.

  As the base film, for example, a film containing polyester, polyimide, polyethylene, polypropylene, polycarbonate, polyacrylate, triacetyl cellulose, cycloolefin plastic, or the like as a component is used. Particularly preferred is a biaxially stretched polyethylene terephthalate film, which has an appropriate and necessary strength suitable for an antistatic film. The film thickness of the base film is preferably 4 to 300 μm, more preferably 10 to 200 μm. These base films may be subjected to corona treatment, antistatic treatment or easy adhesion treatment as necessary.

  The antistatic film of this invention can be manufactured by a conventionally well-known method using said coating material, and manufacturing method itself is not specifically limited. In addition, any material other than the antistatic layer forming material can be a known material, and is not particularly limited. In forming the antistatic layer of the antistatic film of the present invention, the coating material of the present invention is dried on the surface (and / or both surfaces) of the base film by a conventionally known method with a dry thickness of about 0.01 to 1 μm. The film is formed by coating.

  In the antistatic layer thus obtained, the resin (A) and the polyisocyanate (C) crosslink the components in the antistatic layer forming material, so that the solvent resistance and scratch resistance ( The surface hardness can be further improved. Further, in the resin (B), the oxygen atom of the ethylene oxide unit undergoes ion dissociation, and the ions of the supporting electrolyte salt move due to the polymer chain movement, thereby exhibiting antistatic properties. In that case, when it has a siloxane segment, the resin (B) is oriented to the surface side of the antistatic layer by being inclined and the effect of antistatic properties is imparted.

In the antistatic film of the present invention as described above, the surface resistance value of the antistatic layer is preferably from 10 ⁵ to 10 ¹² Ω / cm ² . When the surface resistance value exceeds the above range, the antistatic property is insufficient. On the other hand, even if the surface resistance value is less than the above range, there is no particular advantage.

  The haze value of the antistatic layer is preferably 3.0% or less. When the haze value exceeds 3.0%, transparency may be insufficient when the antistatic film of the present invention is used as a substrate for an optical film. If the usage is other usage, there is no problem even if the haze value exceeds 3.0%.

  The dynamic friction coefficient of the antistatic layer is preferably 0.05 to 0.30. When the coefficient of dynamic friction is less than 0.05, the resulting antistatic film is too slippery, and curling occurs when the film is processed, or the silicone component is backed out or processed over time (molding, overprinting, On the other hand, if the coefficient of dynamic friction exceeds 0.30, the coating speed of the antistatic film does not increase and the post-processability tends to deteriorate. .

  The above-described antistatic film of the present invention includes, for example, a base film of an optical protective film, a light diffusing film, a reflective film, an antireflection film, a light guide plate (backlight member), a carrier tape and a cover tape (for transporting electronic components) ), Background tape, dicing tape, antistatic imparting release film, OHP sheet, photographic film, flexible printed wiring board and other antistatic imparting protective films, triacetylcellulose protective film, touch panel, various packaging materials and bags, displays, belts In addition to the production of the above-mentioned various articles, the coating of the present invention is useful for surface treatment agents such as optical materials such as optical lenses and optical disk substrates, fiber coating agents, and antifouling ( It is also useful as an antistatic coating.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited thereto. Moreover, in the following sentence, “part” indicates mass part, and “%” indicates mass%.

[Synthesis Examples 1 to 4]
After replacing the reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole with nitrogen gas, add a predetermined amount of polyether-modified polysiloxane compound having a hydroxyl group, polyol compound, chain extender compound and solvent. The solution was uniformly dissolved and the final solution concentration was adjusted to 30%. Subsequently, a predetermined amount of diisocyanate compound (equal mole to 1 mole of active hydrogen groups) is added and the reaction is carried out at 80 ° C., and the reaction is continued until no absorption due to 2,270 cm ⁻¹ free isocyanate groups is observed in the infrared absorption spectrum. Went. Table 1 shows the raw material composition, properties and physical properties of the obtained siloxane-containing polyurethane resin.

・ (A-1)

・ＰＥＧ：ポリエチレンオキシドジオール
（東邦化学工業社製、商品名ＰＥＧ−２０００、平均分子量２，０００）
・１，３−ＢＤ：１，３−ブタンジオール
・ＤＢＡ：Ｎ，Ｎ−ジヒドロキシエチル−ｎ−ブチルアミン
・ＴＥＧ：トリエチレングリコール
・ＨＤＩ：ヘキサメチレンジイソシアネート
・ＭＥＫ：メチルエチルケトン ・ (A-2)

PEG: polyethylene oxide diol (manufactured by Toho Chemical Industry Co., Ltd., trade name PEG-2000, average molecular weight 2,000)
-1,3-BD: 1,3-butanediol-DBA: N, N-dihydroxyethyl-n-butylamine-TEG: triethylene glycol-HDI: hexamethylene diisocyanate-MEK: methyl ethyl ketone

[Synthesis Example 5]
After replacing the reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube and a manhole with nitrogen gas, 100 g (0.1 mol) of a siloxane compound containing both ester groups of the following formula (a-3): After heating 220 g (0.22 mol) of polyethylene oxide diol (manufactured by Toho Chemical Industry Co., Ltd., trade name PEG-1000, average molecular weight 1,000) to 150 ° C., 1 g of tetrabutyl titanate was added and normal pressure was added. For 1 hour followed by 4 hours at 180 ° C./10 mmHg to obtain a polyether-modified polysiloxane compound having a hydroxyl value of 37.

(A-3) Siloxane compound

[Synthesis Example 6]
After replacing the reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole with nitrogen gas, 30 g of methyl methacrylate, 2 g of 2-hydroxyethyl methacrylate, 18 g of n-butyl acrylate and siloxane macromonomer ((Meth) acrylic group-containing siloxane macromer) (a-4) (10 g) and methoxypolyethylene glycol methacrylate (b-1) (40 g) were added, and a mixed solvent of toluene / methyl ethyl ketone = 1/1 was added so that the nonvolatile content was 30%. Then, 1.0 g of azobisisobutyronitrile was added as an initiator, and the mixture was heated to 70 ° C. and stirred for 8 hours while bubbling nitrogen to synthesize a siloxane-modified acrylic resin.

・ (A-4)

(B-1)

[Examples 1-7, Comparative Examples 1-2]
The paints of Examples and Comparative Examples (solid content 5%) were prepared according to the compositions shown in Tables 2 and 3.

Aging condition: 40 ° C., 2 days EVOH; ethylene vinyl alcohol, trade name: DC4212 (ethylene copolymerization ratio = 32 mol%, glass transition temperature = 61 ° C., manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
-PVA; partially saponified polyvinyl alcohol, trade name: PVA-217 (degree of saponification = 87-89, degree of polymerization = 1,700, manufactured by Kuraray Co., Ltd.)
YP-50S; phenoxy resin, trade name: phenototo YP-50S, weight average molecular weight = 40,000, manufactured by Toto Kasei Kogyo Co., Ltd.)
BL-S; butyral group / acetyl group-containing polyvinyl alcohol copolymer, trade name: BL-S, hydroxyl group = 22 mol%, acetyl group = 3 to 5 mol%, butyral degree = 70 mol% or less, Sekisui Chemical Co., Ltd. ) Made)
・ PHDI; HDI biuret type, trade name: Duranate 24A-100, manufactured by Asahi Kasei Chemicals Corporation)
C-1; alkylene-modified polysiloxane / lithium compound, trade name: PC-3600, manufactured by Maruhishi Oil Chemical Co., Ltd.)
DMF; dimethylformamide anone; cyclohexanone

[Supported electrolytic salt]
L-1: lithium perchlorate L-2: lithium bistrifluoromethanesulfonimide

  The paint used for the production of the antistatic film of the present invention was prepared by dissolving or dispersing an ion conductive polymer and a resin (B) comprising a supporting electrolytic salt in an organic solvent, and then mixing the resin (A). Any known method may be used as a method for dissolving or dispersing each of the above components, and is not particularly limited.

  After applying each paint described in Tables 2 and 3 to the surface of a 38 μm thick polyethylene terephthalate (PET) film (manufactured by Toray) by gravure printing so that the thickness after drying is 0.5 μm. The solvent was dried in a dryer under the conditions described in the above table. After drying, an antistatic layer was formed by aging in an oven at 40 ° C. for 48 hours.

[Test example]
The performance of the antistatic layer coating film and antistatic film obtained in the above examples and comparative examples was tested for the following items, and the results shown in Table 4 were obtained.

<Surface resistance value>
The antistatic property of the antistatic film is measured using MCP-HT450 manufactured by Mitsubishi Chemical Corporation. The measurement conditions were as follows: temperature 23 ° C., humidity 65% RH, applied voltage 100 V, 30 seconds. In order to exhibit the antistatic effect, the surface resistance value is desirably 1 × 10 ¹² Ω / cm ² or less.

<Transparency>
Using a direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., the haze value of the antistatic film was measured.
Haze value = Measured value−Haze value of base material If the haze value is less than 1.0%, the transparency is high and it is suitable for an antistatic film.

<Solvent resistance>
1 g of ethyl acetate was dropped on the surface of the antistatic film, and the appearance of the coating film of the antistatic layer was observed when rubbed with a load of 50 g / cm ² .
○: No change in coating film appearance of the antistatic layer.
(Triangle | delta): The coating-film external appearance of an antistatic layer has changed a little.
X: The coating film appearance of the antistatic layer is changed.

<Scratch resistance>
The coating film of the antistatic layer of the antistatic film was rubbed with Scotch Bright (manufactured by Sumitomo 3M Co., Ltd.) under a load of about 10 g / cm ² , and surface damage was visually confirmed.
○: 0 or less and less than 5 scratches that can be confirmed.
Δ: There are 5 or more and less than 10 scratches that can be confirmed.
X: 10 or more scratches that can be confirmed.

<Adhesion>
The adhesion between the coating film of the antistatic layer of the antistatic film and the substrate PET film was measured by a cross cut test (cellophane tape peeling cross-cut method).

<Slipperiness>
The dynamic friction coefficient of the antistatic film is measured using HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd. The measurement conditions were a temperature of 23 ° C., a humidity of 65% RH, and an average value of 5 measurements. The dynamic friction coefficient is preferably in the range of 0.18 to 0.30.

<Printability>
Magic Ink No. manufactured by Teranishi Chemical Industry Co., Ltd. 500 was written on the coating surface of the antistatic layer, and the writing state of the ink was observed.
○: The writing situation of magic ink is good.
Δ: Slight ink repellency but no problem.
X: Ink cannot be repelled and written.

As described above, according to the present invention, an antistatic film excellent in antistatic properties, transparency, solvent resistance, water resistance, printability, slipperiness, processability, adhesion to a substrate film, and the like, and A paint is provided.

Claims (10)

  An antistatic film comprising a base film and an antistatic layer provided on at least one surface of the base film, wherein the antistatic layer is ionically conductive with a resin (A) having an active hydrogen group in the molecule. An antistatic film comprising a resin (B) comprising a polymer and a supporting electrolyte salt and a polyisocyanate (C) as a film-forming component.   The active hydrogen group in the resin (A) is a resin having at least one group selected from a hydroxyl group, an amino group, a carboxyl group, a thiol group and / or an epoxy group in a main chain and / or a side chain. The antistatic film as described.   The antistatic film according to claim 1, wherein the ion conductive polymer of the resin (B) is a resin containing a hydrophilic segment and a siloxane segment. The antistatic film according to claim 1, wherein the supporting electrolytic salt of the resin (B) is a salt represented by the following general formula.
M ⁺ X ^-
(M ⁺ is at least one selected from Li ⁺ , Na ⁺ and K ⁺ , and X ⁻ is ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , CF _3. Selected from SO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ and (C ₂ F ₅ SO ₂ ) ₃ C ⁻ At least one). The antistatic film according to claim 1, wherein the antistatic layer has a surface resistance value of 10 ⁵ to 10 ¹² Ω / cm ² .   The antistatic film according to claim 1, wherein the antistatic layer has a haze value of 3.0% or less.   The antistatic film according to claim 1, wherein the antistatic layer has a dynamic friction coefficient of 0.05 to 0.30.   A paint for forming an antistatic layer, wherein the resin (A) and the resin (B) are dissolved or dispersed in an organic solvent.   The resin (A) is 5 to 95 mass% of the total amount (100 mass%) of the resin (A) and the resin (B), and the resin (B) is 95 to 5 mass%. The paint described in 1. Furthermore, the polyisocyanate is added just before use, or the coating material of Claim 8 containing the stabilized polyisocyanate.