JP2007320093A - Antistatic film and coating for forming antistatic layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic film having a durable antistatic function, transparency, solvent resistance, water resistance, printability, slidability, processability, adhesion to a base film, environmental resistance, etc. <P>SOLUTION: In the antistatic film comprising the base film and an antistatic layer formed on at least one side of the base film, the antistatic layer contains a resin (A) having active hydrogen groups in a molecule, a polyurethane resin (B) having polysiloxane groups, a polyisocyanate (C), and an ionic conductive agent (D) as coat 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, a durable antistatic function, transparency, solvent resistance, water resistance, and external environment (humidity). The present invention also relates to an antistatic film having a performance that is not easily influenced by the coating material 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, when conductive metal powder is used as an antistatic agent, it is difficult to disperse the metal powder, the film appearance becomes opaque, and it is expensive depending on the amount used. Furthermore, there are problems such as detachment of the conductive metal powder from the antistatic film.

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

Moreover, an antistatic composition comprising 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 film has a surface resistance value of about 1.0 × 10 ¹² Ω / cm ² , and has a weak durable charging performance.

  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 need for an antistatic film with higher performance than before and a coating material for forming such an antistatic film.

  Therefore, the object of the present invention is to provide a durable antistatic function, 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, and printability. , Slipperiness (appropriate slipperiness is required in the case of roll-roll), processability (composite film, recoating suitability, etc.), adhesion to the substrate film, and external environment (humidity) An object is to provide an antistatic film having difficult performance and the like, and a paint for forming the film.

The above object is achieved by the present invention having the following constitution.
1. 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 (A) (hereinafter simply referred to as an active hydrogen group in the molecule). "Resin (A)"), polyurethane resin (B) containing a polysiloxane group (hereinafter sometimes simply referred to as "resin (B)"), polyisocyanate (C), and ionic conductive agent An antistatic film formed by using (D) as a film-forming component.

2. 2. The antistatic film as described in 1 above, wherein the resin (A) is a resin having at least one group selected from a hydroxyl group, a carboxyl group, an amino group, a thiol group and an epoxy group in the main chain and / or side chain.

3. The resin (B) is a polyurethane resin obtained by reacting a polysiloxane compound having at least one active hydrogen group in the molecule, a polyisocyanate, a polyol or a polyamine, and has a weight average molecular weight of 5,000 to 2. The antistatic film as described in 1 above, which is 300,000.

4). The ionic conductive agent (D) contains an organic cation component such as imidazolium ion, pyridinium ion, ammonium ion and phosphonium ion, BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ CO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N _2. The antistatic film as described in 1 above, which is a salt composed of a fluorine ion compound such as ^— and CF ₃ SO ₂ ^— or an inorganic or organic anion component such as CH ₃ CO ₂ ^— or NO ₃ ^— .

5). 2. The antistatic film as described in 1 above, wherein the antistatic layer has a surface resistance value of 10 ⁵ to 10 ¹² Ω / cm ² .

6). 2. The antistatic film as described in 1 above, wherein the antistatic layer has a haze value of 3.0% or less.

7). 2. The antistatic film as described in 1 above, wherein the antistatic layer has a dynamic friction coefficient of 0.05 to 0.30.
8). A paint for forming an antistatic layer, wherein the resin (A), the resin (B), and the ionic conductive agent (D) are dissolved or dispersed in an organic solvent.

9. Resin (A) is 15-98.9 mass% of the total amount (100 mass%) of resin (A), resin (B), and ionic conductive agent (D), and resin (B) is 55 The paint according to 8 above, which is ˜1% by mass and the ionic conductive agent (D) is 30˜0.1% by mass.

10. 9. The coating material according to 8 above, further comprising adding a polyisocyanate before use or containing a stabilized polyisocyanate.

  According to the present invention, by forming the antistatic layer from a specific material, antistatic properties, transparency, solvent resistance, water resistance, printability, slipperiness, workability, adhesion to the substrate film, and Provided is an antistatic film having a performance hardly affected by an external environment (humidity).

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

  In the present invention, when the antistatic layer is formed, the resin (A), the resin (B), and the polyisocyanate (C) are solvent resistant, moderate slippery, adhesion to the base material, water resistance and external environment. The antistatic film of the present invention has an antistatic property because the surface property of the antistatic layer is low (humidity) and the antistatic property is expressed by using the ionic conductive agent (D) as an antistatic agent. The bleed-out of the agent is small, and the antistatic property is excellent.

  On the other hand, an antistatic film obtained by using a quaternary cationic polymer that exhibits ionic conductivity, lithium ions, or a conductive polymer that exhibits electronic conductivity, which has been used as an antistatic agent, has a surface of acetic acid. If it is wiped off with a solvent such as ethyl, the antistatic performance of that part may be reduced. In addition, an antistatic film formed using a conductive filler exhibiting electronic conductivity is opaque and has a problem of toxicity, and an antistatic film using conductive carbon such as ketjen black (carbon black) is conductive. Although there is a problem that carbon is desorbed and contaminates the surroundings, the present invention solves such a problem.

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 structure of the antistatic layer will be described in more detail. The antistatic layer is formed using resin (A), resin (B), polyisocyanate (C), and ionic conductive agent (D) as a film forming component. The antistatic layer is preferably formed by dissolving and dispersing each of the above components in a solvent or the like, or by applying and drying the paint on a base film as a paint without a solvent. The paint in this case contains the resin (A), the resin (B) and the ionic conductive agent (D). When the paint is used, the polyisocyanate (C) is added or the stabilized polyisocyanate. When (C) is used, the stabilized polyisocyanate (C) may be added to the paint in advance.

  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. Furthermore, at least one selected from these is preferably used. Of these, ethylene-vinyl alcohol copolymer, partially saponified polyvinyl alcohol and phenoxy resin are particularly preferable. Furthermore, resins obtained by modifying acrylic resins, phenoxy resins, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, butyral group-modified polyvinyl alcohols with fluorine-modified silicone groups or long-chain alkyl groups can also be used.

Examples of the active hydrogen group in the resin (A) include a hydroxyl group (—OH), a carboxyl group (—COOH), an amino group (—NR (R: hydrocarbon group) H, —NH ₂ etc.), a thiol group ( -SH) and an epoxy group (glycidyl group), among which a hydroxyl group is preferably used. When the resin has an active hydrogen group in the molecule, it can be used as it is as the resin (A), but when the resin does not have an active hydrogen group in the molecule, a treatment such as modification is performed. To give an active hydrogen group.

  The resins (A) listed above are preferable 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.

  The resin (B) will be described below. The polysiloxane group in the resin (B) is contained as a polysiloxane segment in the resin (B), and is contained in the main chain of the polyurethane resin or in a branched state. That is, if the polysiloxane used as a raw material is a double-end reactive type, it is branched to the trunk portion of the main chain of the polyurethane resin. If the polysiloxane used as a raw material is a single-end or branched reaction type, it is branched from the main chain of the polyurethane resin. It will be contained in the state.

  The resin (B) is a resin (B) obtained by reacting a polysiloxane compound having at least one active hydrogen group in the molecule, a polyisocyanate, and a polyol or polyamine, and its preferred weight average molecular weight. Is 5,000 to 300,000.

The raw material component used as the said polysiloxane group 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

上記のエポキシ化合物はポリオール、ポリアミド、ポリカルボン酸などと反応させ末端活性水素を有するようにして使用することができる。

The above epoxy compounds can be used by reacting with polyols, polyamides, polycarboxylic acids and the like to have terminal active hydrogen.

(3) Alcohol-modified polysiloxane compound

(4) Mercapto-modified polysiloxane compound

  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.

  In addition to these, a polylactone (polyester) -polysiloxane compound obtained by modifying a polysiloxane compound with a lactone, a polyethylene oxide-polysiloxane compound modified with ethylene oxide or propylene oxide, a polypropylene oxide-polysiloxane compound, and the like are also preferably used. Particularly preferably, a polylactone-polysiloxane compound obtained by modifying a polysiloxane compound having one or more active hydrogen groups in the molecule with a lactone and a polysiloxane compound having one or more active hydrogen groups in the molecule are used as ethylene oxide or propylene oxide. A polyether-polysiloxane compound modified with ether.

  Preferred lactones used here are β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octanolide, γ-valerolactone, γ-caprolactone and δ-caprolactone. .

  Further, as the alkylene oxides for obtaining the molecular chain of the oxyalkylene polymer, specifically, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α -Methylstyrene oxide etc. are mentioned, and it is obtained by carrying out ring-opening polymerization in the presence of various catalysts.

  In the present invention, the polylactone-polysiloxane compound, that is, the polylactone-polysiloxane compound obtained by modifying a polysiloxane compound having at least one active hydrogen group in the molecule with a lactone is one or more in the molecule. A siloxane compound having an active hydrogen group, such as an amino group, a hydroxyl group or a carboxyl group, is obtained by subjecting the lactone to ring-opening polymerization with the active hydrogen atom group and then subjecting it to a reduced pressure treatment.

  The polyol used for the production of the resin (B) is preferably a conventionally known one such as a short-chain diol, a polyhydric alcohol compound and a polymer polyol conventionally used for the production of polyurethane, or a polyamine. For example, a short-chain diamine conventionally used in the production of polyurethane can be used, but these are not particularly limited. Each compound used below is described.

  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), 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol and other alicyclic glycols and alkylene oxide low mole thereof 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. Of bisphenols and alkylene oxide low-mol adduct (number average molecular weight of less than 500), and compounds such as alkyl dialkanolamines, such as alkyl diethanolamine of C1~C18 thereof. Examples of the polyhydric alcohol compound include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, and 1,1, Examples thereof include 1-trimethylolpropane. 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 (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.) are specifically exemplified. Are polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol and polyhexamethylene glycol,

(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.

  Although the structure and molecular weight of these polyols are not particularly limited, polyether polyols such as ethylene oxide and propylene oxide are usually preferred with a number average molecular weight of about 500 to 4,000. Moreover, these polyols can be used individually or in combination of 2 or more types.

  Examples of preferred polyamines as the polyamine include short chain diamines, aliphatic diamines, aromatic diamines, long chain diamines, and hydrazines. Examples of the short-chain diamine include aliphatic diamine compounds such as ethylene diamine, trimethylene diamine, hexamethylene diamine and octamethylene diamine, phenylene diamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, and 4,4 ′. -Aromatic diamine compounds such as methylene bis (phenylamine), 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl sulfone, cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diamino And alicyclic diamine compounds such as cyclohexane and isophorone diamine. As long chain diamine, what is obtained by superposing | polymerizing or copolymerizing alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) is illustrated, Specifically, polyethylenediamine, polypropylenediamine, etc. are mentioned. 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 polyamine, polyether-based diol compounds and diamine compounds such as ethylene oxide and propylene oxide are preferable.

  As a polyisocyanate compound used for the synthesis | combination of the said resin (B), what is conventionally used for manufacture of a polyurethane can be used and it does not specifically limit. 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, or these diisocyanate compounds and low molecular weight polyols or polyamines are reacted so that the terminal is isocyanate. Naturally, the obtained polyurethane prepolymer can also be used.

  The production method of the resin (B) using the above raw materials is not particularly limited, and a conventionally known polyurethane production method can be used. For example, a compound in which at least one active hydrogen group and a polysiloxane segment coexist in the same molecule in the presence or absence of an organic solvent containing no active hydrogen in the molecule, a polyol and / or a polyamine, A 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, a one-shot method, or The resin (B) can be obtained by reacting at a temperature of 20 to 150 ° C., preferably 30 to 110 ° C. until the isocyanate group is almost eliminated by a multistage method.

  In addition, about resin (B), you may synthesize | combine without a solvent or may synthesize | combine 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 the resin (B), 0.01 to 90% by mass, preferably 0.1 to 70% by mass of a polysiloxane compound containing at least one active hydrogen group in the same molecule, The polyol and / or polyamine is 0 to 90% by mass, preferably 0 to 80% by mass, the chain extender is 40 to 0% by mass, preferably 30 to 0% by mass (the total of these components is 100% by mass). The resin (B) is synthesized with a polyisocyanate ratio of NCO / OH≈1.0. If there are many polysiloxane compounds (over 90% by mass), antistatic films will slip too much, unreacted polysiloxane components will cause printing failure (a phenomenon that repels ink), and sufficient surface resistance performance will be exhibited. Not. On the other hand, when the amount of the polysiloxane compound is small (less than 0.01% by mass), slippage between the antistatic films (defects such as curling) is unfavorable, and solvent resistance and humidity control of the outside air become impossible.

  The molecular weight of the resin (B) used in the present invention is preferably in the range of 5,000 to 300,000 in terms of weight average molecular weight (measured by GPC, converted to standard polystyrene).

  In the present invention, as the polyisocyanate (C) used for forming the antistatic layer, a conventionally known polyisocyanate (C) can be used and is 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 and polyisocyanate prepolymers such as isocyanate, fatty acid-modified polyfunctional aliphatic isocyanate, and blocked polyfunctional aliphatic isocyanate.

  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 these polyisocyanates (C) used is 5 to 80 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of the resin (A), resin (B) and ionic conductive agent (D). 60 parts by mass. If it exceeds 80 parts by mass, it is not preferable because the working life of the paint is lowered, and if it is less than 5 parts by mass, the crosslinking density of the antistatic layer is reduced, and the solvent resistance of the antistatic layer cannot be exhibited.

  A preferred ionic conductive agent (D) used in the present invention will be described. Examples of the cation component constituting the ionic conductive agent include alkyl imidazolium cations represented by 1-ethyl-3-methylimidazolium (EMI), alkyl pyridinium cations, alkyl ammonium cations, alkyl phosphonium cations, and alkyl sulfonium cations. Compounds can be used.

Examples of the anionic component constituting the ionic conductive agent include fluorine-based ionic compounds such as BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ CO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and CF ₃ SO ₂ ⁻ , and CH _3. CO ₂ ^- and NO ₃ ^- inorganic or organic anion compounds can be mentioned, such as to form an ion conductive agent using these anionic compounds. The ionic conductive agent used in the present invention is not particularly limited, and any known ionic conductive agent may be used. However, since it is usually difficult to purify impurities by complicated synthesis, either an anionic compound or a cationic compound is used. It is desirable to select organic ones.

Specific examples of the ionic conductive agent used as an antistatic agent in the present invention are shown below.
(1) <Alkylimidazolium cationic compound>

(2) <Aliphatic alkylammonium cation compound>

(3) <Alicyclic alkyl ammonium cation compound>

(4) <Alkylpyridinium cationic compound>

(5) <Alkylsulfonium cation compound>

（式中のＲ₁〜Ｒ₄は同一または異なる基であり、水素原子または置換基を有してもよい炭素数が１〜１０のアルキル基（該基中にＯ、Ｓ、またはＮの原子を有してもよい）である。Ｘ^-はアニオン成分；例えば、ＡｌＣｌ₄ ^-アニオン、含フッ素アニオン（例えば、Ｎ（ＣＦ₃ＳＯ₂）₂ ^-、ＣＦ₃ＳＯ₃ ^-、ＢＦ₄ ^-、ＰＦ₆ ^-）および硝酸アニオンや酢酸アニオンである。） (6) <Alkylphosphonium cationic compound>

(In the formula, R _{1 to} R ₄ are the same or different groups, and may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent (the atoms of O, S, or N in the group) X ⁻ represents an anionic component; for example, AlCl ₄ ⁻ anion, fluorine-containing anion (for example, N (CF ₃ SO ₂ ) ₂ ⁻ , CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ^-) and nitrate anion and acetate anion).

  Preferable organic cation components include alkyl imidazolium cations, alkyl pyridinium cations, alkyl ammonium cations, alkyl phosphonium cations, and alkyl sulfonium cations.

  Specific examples of the ammonium cation include triethylmethylammonium cation, tetraethylammonium cation, ammonium cation, trimethylammonium cation, ethyldimethylammonium cation, diethylmethylammonium cation, triethylammonium cation and tetramethylammonium cation.

  Specific examples of the alkyl imidazolium cation include 1-methyl-3-methyl imidazolium cation, 1-methyl-3-ethyl imidazolium cation and 1-methyl-3-propyl imidazolium cation.

  Examples of phosphonium cations include chain phosphonium cations such as tetraethylphosphonium and cyclic phosphonium cations. Examples of the sulfonium cation include chain sulfonium cations such as triethylsulfonium and cyclic sulfonium cations.

Examples of the anionic component to be salted with the above cation component include AlCl ₄ ⁻ , NO ₃ ⁻ , NO ₂ ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , CH ₃ CO ₂ ⁻ , CF ₃ CO ₂ ⁻ , CH ₃ SO ₂ ⁻ , CF ₃ SO ₂ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₃ F ₇ CO ₂ ⁻ , C ₄ F _{9 ^{sO 3 -, (CF 3 sO}} 2) 2 N -, (C 2 F 5 sO 2) 2 N - and _{(C 2 F 5 sO 2)} (CF 3 CO) N - Although the like, typically BF ₄ ⁻ , PF ₆ ⁻ and (CF ₃ SO ₂ ) ₂ N ⁻ are preferably used. The present invention is not limited to these anion components, and other commercially available amide anion compounds, methide anion compounds, borate anion compounds, phosphate anion compounds, sulfonate anion compounds and carboxylate anion compounds can also be used.

  The amount of the resin (A), the resin (B) and the ionic conductive agent (D) used is (A) of the total amount (100% by mass) of (A), (B) and (D). Is 15 to 98.9 mass%, (B) is 55 to 1 mass%, and (D) is 30 to 0.1 mass%. If the amount of use of (A) exceeds 98.9% by mass, it is not preferable because the working life of the paint and the adhesion to the substrate film are lowered. Since the crosslinking density and solvent resistance of a prevention layer fall, it is unpreferable. If the amount of (B) used exceeds 55% by mass, the antistatic films are too slippery, resulting in poor ink suitability and a decrease in solvent resistance, and less than 1% by mass is susceptible to environmental humidity. Therefore, it is not preferable. On the other hand, if the amount of (D) used exceeds 30% by mass, the solvent resistance and scratch resistance of the antistatic layer will decrease, and the paint used will be unstable. Is unfavorable because it decreases.

  In addition, in order to form the antistatic layer of this invention, the coating material containing said resin (A), resin (B), and an ionic conductive agent (D) 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. Further, acetone, cyclohexane, tetrahydrofuran, N-methyl-2-pyrrolidone, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, and the like can be given. 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.

  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 film 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). Siloxane etc.), various waxes, acrylic polymers, long chain alkyl modified polymers, fluorine modified polymers and siloxane modified polymers.

  Furthermore, other antistatic agents can be used in combination. Other antistatic agents include, for example, polyvinyl alcohol, cation-modified polyvinyl alcohol, alkali metal salt-containing polyether, alkali metal salt-containing siloxane-modified polyether, alkali metal salt-containing ether polyurethane, polyamine, and quaternary cation salt-containing acrylic. Resin, specially modified polyester, special cationic resin, cellulose derivative, polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline and sulfonated polyaniline, etc., organic conductive materials, carbon nanotubes, carbon black, tin oxide, zinc oxide and oxidation Additives such as metal oxides such as titanium and various metal alkoxides and conductive filler-containing polymers such as ITO powder can be added.

  Among the compounds, alkali metal salt-containing polyether, alkali metal salt-containing siloxane-modified polyether and alkali metal salt in the alkali metal salt-containing ether polyurethane, for example, lithium perchlorate, lithium bistrifluoromethanesulfonimide, Lithium borofluoride, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium pentafluoroethanesulfonate, lithium bispentafluoroethanesulfonimide, tetraethylammonium borofluoride, tetraethylammonium hexafluorophosphate and potassium bistrifluoromethanesulfone An imide etc. can be mentioned.

  As a base film used by this invention, the film which uses polyester, a polycarbonate, polyacrylate, a cycloolefin, a polyimide, polyethylene, a polypropylene etc. as a component is mentioned, for example. Particularly preferred is a biaxially stretched polyethylene terephthalate film, which is suitable for the antistatic film and has the required strength. 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 the said coating material, and manufacturing method itself is not specifically limited. Moreover, as for materials other than the material for forming an antistatic layer such as a base film, any known material can be used, 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.

  The antistatic layer thus obtained is a base film because the active hydrogen group of the resin (A) is hydrophilic due to the difference in surface energy between the resin (A) and the polysiloxane group in the resin (B). Oriented on the surface to improve the adhesion of the antistatic layer to the substrate film. On the other hand, the component (B) containing a polysiloxane group having a low surface energy is oriented on the opposite side (air side) of the base film, thereby imparting water resistance and appropriate slipperiness.

  Since the polyisocyanate (C) forming the antistatic layer crosslinks the components in the film forming material, the solvent resistance and scratch resistance (up the surface hardness) of the antistatic layer can be further improved. About the antistatic function, the function is maintained by containing an ionic conductive agent (D) in a coating material.

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 3]
A reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser was replaced with nitrogen gas, and then the lactone compound and siloxane compound shown in Table 1 were charged to a predetermined concentration and 100 ° C. under a nitrogen stream. The mixture was stirred until uniform. Subsequently, predetermined tetra-n-butyl titanate was added and reacted for 10 hours at a temperature of 180 ° C. under a nitrogen stream. As the reaction proceeds, the viscosity of the reactant increases. Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction, and the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound were completely removed. Table 1 shows the composition and properties of the obtained polycaprolactone-modified polysiloxane compound.

The siloxane compound (a) in Table 1 has the following structure.

[Synthesis Examples 4 to 7]
After replacing the reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole with nitrogen gas, the polycaprolactone-modified polysiloxane compound having a hydroxyl group obtained in the above synthesis example (or polyethylene oxide-modified polysiloxane) Siloxane compound: a-4), a polyol compound, a chain extender compound, and a solvent were added in predetermined amounts and uniformly dissolved, and the 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 2 shows the raw material composition, properties and physical properties of the resulting siloxane-containing polyurethane resin.

・ＰＥＧ：ポリエチレンオキサイドジオール
（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
・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

PEG: polyethylene oxide diol (manufactured by Toho Chemical Co., Ltd., trade name PEG-2000, average molecular weight 2,000)
・ 1,3-BD: 1,3-butanediol ・ HDI: Hexamethylene diisocyanate ・ MEK: Methyl ethyl ketone

[Examples 1-4, Comparative Examples 1-4]
The paints of Examples and Comparative Examples (solid content 5%) were prepared according to the compositions shown in Tables 3 and 4.

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
(Saponification degree = 87-89, polymerization degree = 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 = 3-5 mol%, butyral degree = 70 mol% or less, manufactured by Sekisui Chemical Co., Ltd.)
-PHDI; HDI biuret type, trade name: Duranate 24A-100
(Asahi Kasei Chemicals Corporation)
・ Ionic conductive agent; IL
(Cation component; N, N-diethyl-N-methyl-N- (2-metaoxyethylene) ammonium, anion component; (CF ₃ SO ₂ ) ₂ N ⁻ )
・ L: Lithium perchlorate ・ Anone: Cyclohexanone

  The paint used for the production of the antistatic film of the present invention was prepared by dissolving or dispersing the resin (B) and the ionic conductive agent (D) in an organic solvent and then mixing with the resin (A). Any known method may be used as a method for dissolving or dispersing each component, and is not particularly limited.

  After applying each paint obtained in each Example and Comparative Example, by gravure printing, on the surface of a polyethylene terephthalate film having a thickness of 38 μm (manufactured by Toray) so that the thickness after drying becomes 0.5 μm, The solvent was dried in the dryer under the conditions described in the above table. When the paints of Examples 1 to 4 and Comparative Examples 1, 2, and 4 were used, after application and drying, they were aged in an oven at 40 ° C. for 48 hours to form an antistatic layer. In Comparative Example 3, since no PHDI was used, the solvent was dried without aging. The following tests were conducted on these antistatic films.

[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 5 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 ¹⁰ 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 .
○: There is no change in the coating film appearance of the antistatic layer. Δ: The coating film appearance of the antistatic layer is slightly changed. 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 more and less than 5 scratches that can be confirmed Δ: 5 or more and less than 10 scratches that can be confirmed ×: 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 desirably in the range of 0.05 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 status of the magic ink is good. △: There is a slight ink repellency, but there is no problem. ×: The ink cannot be repelled and written.

As described above, according to the present invention, the antistatic function, transparency, solvent resistance, water resistance, printability, slipperiness, processability, adhesion to the substrate film, and external environment (humidity) are also affected. An antistatic film having performance that is difficult to achieve and a paint useful for producing the film are 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 comprises a resin (A) having an active hydrogen group in the molecule and polysiloxane An antistatic film comprising a polyurethane resin (B) containing a group, a polyisocyanate (C), and an ionic conductive agent (D) as a film-forming component.   The antistatic film according to claim 1, wherein the resin (A) is a resin having at least one group selected from a hydroxyl group, a carboxyl group, an amino group, a thiol group, and an epoxy group in the main chain and / or the side chain.   The resin (B) is a polyurethane resin obtained by reacting a polysiloxane compound having at least one active hydrogen group in the molecule, a polyisocyanate, a polyol or a polyamine, and has a weight average molecular weight of 5,000 to The antistatic film according to claim 1, which is 300,000. The ionic conductive agent (D) contains an organic cation component such as imidazolium ion, pyridinium ion, ammonium ion and phosphonium ion, BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ CO ₂ ⁻ , (CF ₃ SO ₂ ) ₂ N ^- and CF ₃ SO ₂ ^- fluorinated ion compounds such as and CH ₃ CO ₂ ^- and NO ₃ ^- antistatic film according to claim 1 which is composed of an inorganic or organic anion component salt such. 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), the resin (B), and the ionic conductive agent (D) are dissolved or dispersed in an organic solvent.   Resin (A) is 15-98.9 mass% of the total amount (100 mass%) of resin (A), resin (B), and ionic conductive agent (D), and resin (B) is 55 The coating material according to claim 8, which is ˜1% by mass and the ionic conductive agent (D) is 30 to 0.1% by mass. The paint according to claim 8, further comprising adding a polyisocyanate before use or containing a stabilized polyisocyanate.