JP2007119600A - Printing varnish composition having antistatic effect, substrate coated therewith, and processed molding of the substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing varnish composition which can form a coating film on a film to make its surface permanently antistatic without adding any antistatic agent to a film base and without any problem of antistatic bleed and is excellent in coating film properties such as water resistance and chemical resistance. <P>SOLUTION: The printing varnish composition having an antistatic effect comprises a cationic thermoplastic resin (A) comprising 10 to 60 wt.% quaternary ammonium salt-containing unsaturated monomer (a) represented by formula (1), 5 to 40 wt.% hydroxyl-containing unsaturated monomer (b), and 5 to 85 wt.% other (meth)acrylic monomers (c) and a thermoplastic resin (B) comprising 5 to 40 wt.% hydroxyl-containing unsaturated monomer (b) and 60 to 95 wt.% other (meth)acrylic monomers (c) in an (A):(B) ratio of 10:90 to 85:15 by weight. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic agent that is effective in preventing static charge on the surface of a substrate such as a film, paper, or laminated paper, or on the surface of a printing ink layer.

  Conventionally, the packaging and transport materials for products that do not like the generation of static electricity, such as powder products and electronic precision parts, and the appearance of dirt, dust, etc. due to electrostatic charge being soiled by suction or damage to the appearance. Antistatic effects have been required for materials for exterior materials for disliked building materials. Antistatic agents for film are mainly those that exhibit antistatic effects by applying a hygroscopic resin film typified by nonionic or ionic surfactants or hydrophilic polymers to the surface. there were. However, this type of film material has a problem that the antistatic agent bleed out on the surface is easily removed by washing, wiping, or the like, and the antistatic property is likely to deteriorate.

Therefore, in recent years, for the purpose of making the antistatic effect permanent, JP-A-8-127755 uses a specific anchor coating agent that can exhibit an antistatic ability regardless of bleeding on the surface of the antistatic agent. An antistatic film was disclosed. However, this anchor coat agent is inferior in water resistance, and there is a problem that the anchor coat layer part is liable to be peeled off due to moisture. There is a problem that it is difficult to use for a highly likely application. On the other hand, Japanese Patent Application Laid-Open No. 2001-341237 discloses an antistatic film comprising a crosslinkable composition of an antistatic copolymer having a quaternary ammonium base and a carboxyl in the side chain and polyglycidyl ether. However, since the copolymer resin has high polarity, the compatibility with the general-purpose resin is poor and the solution becomes white turbidly separated, which makes it difficult to improve the coating film properties.
JP-A-8-127755 JP 2001-341237 A

  The object of the present invention is to permanently impart an antistatic effect to the film surface without mixing the antistatic agent into the film base material, without considering the bleeding of the antistatic agent, and with water resistance and chemical resistance. It is providing the printing varnish composition which produces | generates the coating film excellent in coating-film physical properties, such as property.

［式中、Ｒ¹ は水素原子またはメチル基を、Ｒ³ ，Ｒ⁴ ，Ｒ⁵ は各々独立に水素原子またはアルキル基を、Ｒ² はアルキレン基またはオキシアルキレン基を、Ｘ^- はハロゲンイオン、Ｒ⁶ ＳＯ₃ ^- （Ｒ⁶ はアルキル基置換芳香族基、若しくはアルコキシ基を示す）または（Ｒ⁷ ０）₂ Ｐ０₂ ^- （Ｒ⁷ はアルキル基を示す）を示す。］
請求項２に記載した発明は、請求項１に記載した発明にイソシアネート系架橋剤(C)を混合した帯電防止効果を有する印刷ワニス組成物である。
請求項３に記載した発明は、カチオン系熱可塑性樹脂(A)、熱可塑性樹脂(B)及びイソシアネート系架橋剤(C)の混合物１００重量％に対し、４級アンモニウム塩を有する不飽和単量体(a)の含有量が５〜５０重量％であることを特徴とする帯電防止効果を有する印刷ワニス組成物である。
請求項４に記載した発明は、請求項１〜３いずれか１項に記載の帯電防止効果を有する印刷ワニス組成物を塗工してなる帯電防止フィルム基材被覆物である。
請求項５に記載した発明は、請求項４に記載した帯電防止フィルム基材被覆物の基材加工成型物である。 The invention described in claim 1 is an unsaturated monomer (a) having a quaternary ammonium salt represented by the following general formula (a) in the varnish composition, and an unsaturated monomer having a hydroxy group. A cationic thermoplastic resin (A) comprising 5 to 40% by weight of the body (b) and other (meth) acrylic monomer (c) and 5 to 85% by weight, and an unsaturated monomer having a hydroxy group ( b) A thermoplastic resin (B) comprising 5 to 40% by weight and other (meth) acrylic monomer (c) 60 to 95% by weight, and (A) :( B) = 10: 90 to 85 : A printing varnish composition having an antistatic effect, characterized in that it is contained at a weight ratio of 15.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group, R ² represents an alkylene group or an oxyalkylene group, X ⁻ represents a halogen ion, R ⁶ SO ₃ ⁻ (R ⁶ represents an alkyl group-substituted aromatic group or alkoxy group) or (R ⁷⁰ ) ₂ P0 ₂ ⁻ (R ⁷ represents an alkyl group). ]
The invention described in claim 2 is a printing varnish composition having an antistatic effect obtained by mixing the isocyanate crosslinking agent (C) with the invention described in claim 1.
The invention described in claim 3 is an unsaturated monomer having a quaternary ammonium salt with respect to 100% by weight of a mixture of the cationic thermoplastic resin (A), the thermoplastic resin (B) and the isocyanate crosslinking agent (C). A printing varnish composition having an antistatic effect, wherein the content of the body (a) is 5 to 50% by weight.
Invention of Claim 4 is an antistatic film base-material coating formed by coating the printing varnish composition which has the antistatic effect of any one of Claims 1-3.
The invention described in claim 5 is a base material processed molded article of the antistatic film base material coating described in claim 4.

  The printing varnish composition having the antistatic effect of the present invention produces a coating film with excellent coating properties such as water resistance and chemical resistance, and is excellent on the outer surface of the base film due to its electrostatic induction prevention performance. An antistatic effect can be imparted. These effects are obtained by the crosslinking polymer of the cationic isocyanate resin (A) having a quaternary ammonium base of the present invention and the hydroxyl group in the thermoplastic resin (B) and the crosslinking reaction of the organic isocyanate mixed composition according to claim 2. This is due to characteristics such as water resistance and chemical resistance. Further, the quaternary ammonium base in the side chain of this copolymer imparts electrostatic induction prevention performance. Due to its conductivity and dielectric effect, the coating layer of this printing varnish composition has a rapid dielectric polarization relaxation behavior. It acts as an antistatic effect on the film surface by attenuating the interface and surface band charges of the plastic film in contact with the layer.

［式中、Ｒ¹ は水素原子またはメチル基を、Ｒ³ ，Ｒ⁴ ，Ｒ⁵ は各々独立に水素原子またはアルキル基を、Ｒ² はアルキレン基またはオキシアルキレン基を、Ｘ^- はハロゲンイオン、Ｒ⁶ ＳＯ₃ ^- （Ｒ⁶ はアルキル基置換芳香族基、若しくはアルコキシ基）または（Ｒ⁷ ０）₂ Ｐ０₂ ^- （Ｒ⁷ はアルキル基）を示す］ In the present invention, the cationic thermoplastic resin (A) containing an unsaturated monomer having a quaternary ammonium base is a component that exhibits a basic antistatic effect. The cationic thermoplastic resin (A) includes an unsaturated monomer (a) having a quaternary ammonium salt represented by the following general formula (a), an unsaturated monomer (b) having a hydroxy group, and other (meta ) A resin obtained by copolymerizing an acrylic monomer (c).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group, R ² represents an alkylene group or an oxyalkylene group, X ⁻ represents a halogen ion, R ⁶ SO ₃ ⁻ (R ⁶ is an alkyl group-substituted aromatic group or alkoxy group) or (R ⁷⁰ ) ₂ P0 ₂ ⁻ (R ⁷ is an alkyl group)]

The unsaturated monomer (a) having a quaternary ammonium salt used as a monomer of the cationic thermoplastic resin (A) is represented by the above general formula (a), and an acrylate or methacrylate having an amino group is represented by 4 Obtained by grading. Examples of the dialkylamino group-containing unsaturated monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like. The quaternary ammonium salt is a counter ion such as a halogen ion such as Cl ⁻ , Br ⁻ , or I ⁻ , or R ⁶ SO ₃ ⁻ (where R ⁶ is an alkyl group-substituted aromatic group or alkoxy group) or (R ⁷ 0) ₂ P0 ₂ ⁻ (R ⁷ represents an alkyl group)]. Further, as quaternary ammonium salts of other dialkylamino group-containing unsaturated monomers, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (Meth) acrylamidopropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride and the like. R ¹ is —H or —CH ₃ , R ² is —CH ₂ —, —C ₂ H ₄ — or —C ₃ H ₆ —, and R ³ , R ⁴ , R ⁵ are —CH ₃ or —C ₂ H ₅ is preferred. X is a halogen such as chlorine or bromine, with chlorine being preferred. A representative compound of (meth) acrylate chloride containing a quaternary ammonium salt in the molecule is commercially available as Kyoeisha Chemical Co., Ltd. methacryloyloxyethyltrimethylammonium chloride trade name: Light Ester DQ-100). . The unsaturated monomer (a) having the quaternary ammonium salt may be used alone or in combination of two or more.

  The unsaturated monomer (b) having a hydroxy group is preferably an alcoholic hydroxy group-containing (meth) acrylic monomer, specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate , Poly (meth) acrylates of polyhydric alcohols such as ditrimethylolpropane tri (meth) acrylate, polypropylene glycol mono (meth) acrylate, or residual hydroxyl group poly (meth) acrylates (Meth) acrylic acid ester monomers and N-methylolacrylamide are exemplified. The unsaturated monomer (b) having a hydroxy group may be used alone or in combination of two or more. Of these, (meth) acryloyl group-containing (meth) acrylic acid alkyl ester monomers having one (meth) acryloyl group in the molecule are preferred, and hydroxyethyl (meth) acrylate is more preferred.

Examples of other (meth) acrylic monomers (c) include alkyl (meth) acrylates and alkylene glycol (meth) acrylates, and these monomers have functional groups such as alkoxy groups and amide groups. Or a halogen atom or the like.
Moreover, you may use a carboxyl group-containing (meth) acrylic-type monomer to such an extent that the effect of this invention is not inhibited. In particular, acrylic acid and methacrylic acid are preferably used.
When the alkyl (meth) acrylate (c) having 10 or less carbon atoms, more preferably 4 or less, described below is used as the other (meth) acrylic monomer, the resulting cationic thermoplastic resin (A) Not only is water resistance improved, but a synergistic effect with the thermoplastic resin (B) is easily obtained, which is preferable. The other (meth) acrylic monomers (c) can be used alone or in combination of two or more.

  The copolymer composition of the unsaturated monomer (a) having a quaternary ammonium salt, the unsaturated monomer (b) having a hydroxy group, and another (meth) acrylic monomer (c) 10 to 60% by weight, preferably 15 to 50% by weight of the unsaturated monomer (a) having a quaternary ammonium salt, and 5% of the unsaturated monomer (b) having a hydroxy group, based on the total amount of the body -40% by weight, preferably 5-30% by weight, and other (meth) acrylic monomers (c) are composed of 5-85% by weight, preferably 10-80% by weight. If the copolymerization ratio of the unsaturated monomer (a) having a quaternary ammonium salt is less than 10% by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 60% by weight, the polarity increases and the thermoplastic resin (B ), The water resistance and chemical resistance of the resulting printing varnish composition are inferior. If the copolymerization ratio of the unsaturated monomer (b) having a hydroxy group is less than 5% by weight, the compatibility with the thermoplastic resin (B) is lowered, and if it exceeds 40% by weight, the crosslinking density becomes high and sufficient. The antistatic effect cannot be obtained.

  In the present invention, the thermoplastic resin (B) comprising 5 to 40% by weight of the hydroxy group-containing unsaturated monomer (b) and 60 to 95% by weight of the other (meth) acrylic monomer (c) It plays a role as a compatibilizing agent for improving the antistatic effect of the cationic thermoplastic resin (A), improving the adhesion of the base material, improving water resistance and chemical resistance. The copolymer composition of the unsaturated monomer (b) having a hydroxy group and the other (meth) acrylic monomer (c) is such that the unsaturated monomer (b) having a hydroxy group is 5 to 5. It consists of 40% by weight, preferably 5-30% by weight, and other (meth) acrylic monomers (c) 60-95% by weight, preferably 70-90% by weight. If the copolymerization ratio of the unsaturated monomer (b) having a hydroxy group is less than 5% by weight, the compatibility with the cationic thermoplastic resin (A) decreases, and if it exceeds 40% by weight, the crosslinking density is high. Therefore, a sufficient antistatic effect cannot be obtained.

  The other (meth) acrylic monomer (c) is used for the purpose of imparting film-forming properties to the antistatic agent, and is an alkyl acrylate having 10 or less carbon atoms, particularly 4 or less carbon atoms, or the corresponding one. Methacrylate is preferred. The alkyl group may have a linear structure or a branched structure. As the alkyl (meth) acrylate (c), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are particularly preferable.

The isocyanate-based crosslinking agent (C) used in the present invention is the number of moles of isocyanate groups in the isocyanate-based crosslinking agent (C) with respect to the number of moles of hydroxy groups in the cationic thermoplastic resin (A) and / or thermoplastic resin (B). The ratio is preferably 0.6 to 2.5, more preferably 0.9 to 1.3. If the molar ratio is less than 0.6, the curability of the coating film may not be sufficient. On the other hand, when the molar ratio exceeds 2.5, the appearance of the coating film may be slightly deteriorated.
As the isocyanate-based crosslinking agent (C), various known aromatic, aliphatic or alicyclic diisocyanates can be used. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, Typical examples include dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimerisocyanate in which the carboxyl group of dimer acid is converted to an isocyanate group. As mentioned. Preferred suitable cross-linking agents include polyisocyanates known in paint chemistry, which include urethane groups, uretdione groups, allophanate groups, biuret groups, iminooxadiazinedione groups and / or isocyanurate groups. included. If desired, this type of polyisocyanate may be in a form in which (—NCO group) is completely or partially blocked. In particular, a trimethylolpropane adduct of hexamethylene diisocyanate, which is an aliphatic isocyanate having good weather resistance, a biuret body, an isocyanurate body, a mixture thereof or a condensate thereof can be used particularly well.

  The method for polymerizing the cationic thermoplastic resin (A) and the thermoplastic resin (B) in the present invention is not particularly limited. Usually, a method such as solution polymerization or bulk polymerization is used in the presence of a radical initiator and a chain transfer agent. I can do it. It is also advantageous to perform drop polymerization in order to facilitate the copolymerization.

  As the solvent, a ketone solvent such as acetone or methyl ethyl ketone, an alcohol solvent such as methanol, ethanol or isopropyl alcohol, an ether solvent such as propylene glycol monomethyl ether, an ester solvent such as ethyl acetate, or the above-mentioned solvent was mixed. A solvent or the like can be used.

  Examples of the radical polymerization initiator include peroxide initiators such as benzoyl peroxide, t-butyl peroxide, cumene hydroxy peroxide, lauroyl peroxide, and azo such as azobisisobutyronitrile and azobiscyclohexanenitrile. System initiators, persulfuric acid initiators such as potassium persulfate and ammonium persulfate can be used. The amount of the radical polymerization initiator used is preferably 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, based on the total amount of monomers.

  The printing varnish composition having an antistatic effect of the present invention comprises a cationic thermoplastic resin (A) and a thermoplastic resin (B) (A) :( B) = 10: 90 to 85:15, preferably 15: In a weight ratio of 85-80: 20. Without the thermoplastic resin (B), sufficient film performance cannot be obtained, and without the cationic thermoplastic resin (A), it is difficult to obtain an antistatic effect.

  The printing varnish composition having the antistatic effect of the present invention is obtained by mixing and dissolving the above thermoplastic resin in an organic solvent, and for adjusting the viscosity and resin concentration necessary for the printing varnish and for imparting printability and physical properties of the varnish film. It can be produced by blending other compounds such as the above thermoplastic resin and / or other resins compatible with the resin, waxes, leveling agents, antifoaming agents, thickeners, light stabilizers and UV absorbers. . Other compatible resins include, for example, acrylic resins other than the present invention, urethane resins, polyester resins, and the like, and within a range that does not interfere with the object of the present invention, a single or a mixture of two or more types can be used as a printing varnish. Can be added to impart the necessary properties.

  On the other hand, as the wax, various known waxes such as polyolefin wax, paraffin wax and fatty acid amide wax can be used.

  Next, as a solvent used in the varnish composition having an antistatic effect of the present invention, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mainly used. Ketone organic solvents, ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, n-octane, and cyclohexane, methylcyclohexane , Alicyclic hydrocarbon organic solvents such as ethylcyclohexane, cycloheptane, cyclooctane, aromatic hydrocarbon organic solvents such as toluene, ether solvents such as propylene glycol monomethyl ether, and binder resin dissolution Sex Etc. in consideration of 燥性, it is preferable to use by mixing.

The printing varnish composition obtained from the above materials and production method is diluted with an organic solvent until an appropriate viscosity is obtained at the time of printing, and various coating methods such as gravure printing and flexographic printing are used to cover various plastic films and the like. The antistatic film base material coating of the present invention can be obtained by printing on the adherend. For example, it can be provided on a substrate such as paper, plastic film, various non-woven fabrics, synthetic paper, metal foil, or a composite sheet combining these, metal, wood, glass, and the like. Moreover, the printing ink layer may be provided by offset ink, gravure ink, flexo ink, etc. on these base materials.
However, the surface free energy of the substrate surface is desirably in the range of 20 to 60 mN / m, and the surface of the substrate is excellent in corona treatment, plasma treatment, or adhesion to the substrate in order to improve adhesion. It is safe to coat the resin.

  Plastic films include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polyvinyl fluoride, polyvinylidene fluoride, rigid polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polystyrene, polyvinyl alcohol, and ethylene / vinyl alcohol copolymer. , Polycarbonate, polyacrylonitrile, polybutene, soft polyvinyl chloride, polyvinylidene fluoride, polyethylene, polypropylene, polyurethane, ethylene vinyl acetate copolymer, polyvinyl acetate, and the like.

Furthermore, a base-material processed molded product can be obtained by post-processing the antistatic film base material covering of this invention. For example, it can be laminated on another adherend (backing material).
As the adherend, plate materials such as flat plates and curved plates of various materials, sheets (or films), and various three-dimensional articles (molded products) are targeted. Examples of the method of laminating on various adherends include, for example, a method of laminating by pressing with a pressure roller on a plate-like substrate with an adhesive layer interposed therebetween, a simultaneous injection molding laminating method, a vacuum press laminating method, and a lapping process. And a V-cut or U-cut processing method. Also, lamination methods used when manufacturing ordinary packaging materials, for example, wet lamination method, dry lamination method, solventless lamination method, extrusion lamination method, co-extrusion lamination method The laminate can also be produced by other methods. The base material processed molded product can be applied to various materials such as architecture, building materials, home appliances, information home appliances such as mobile phones and personal computers, and packaging materials.

The surface resistance of the antistatic film substrate coating obtained in the present invention is less than 10 ¹⁴ Ω / □, more preferably less than 10 ¹³ Ω / □. Those having a resistance of 10 ¹⁴ Ω / □ or more are ineffective from the viewpoint of the antistatic effect.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to this. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

(Synthesis Example 1)
Stirrer, reflux condenser, nitrogen inlet tube, thermometer, 4-neck flask equipped with dropping funnel and dropping funnel, methyl methacrylate (MMA) 50 parts, butyl methacrylate (BMA) 20 parts, hydroxyethyl methacrylate (2HEMA ) 10 parts, dimethylaminoethyl methacrylate chloride salt (DQ-100) 20 parts, methyl ethyl ketone (MEK) 90 parts, isopropyl alcohol (IPA) 40 parts, azobisisobutyronitrile (AIBN) 2 parts, After stirring for 10 minutes at room temperature and confirming that the system was uniform, the temperature was increased and stirred. When the temperature in the reaction system reached 70 ° C., the amount charged in the dropping funnel was added over 1 hour. After completion of the dropwise addition, the mixture was further reacted for 4 hours under reflux, and 0.4 parts of AIBN was further added and reacted for 1 hour to obtain a cationic thermoplastic resin solution (A) having a solid content of 40%.

(Synthesis Example 2)
Stirrer, reflux condenser, nitrogen inlet tube, thermometer, 4-neck flask equipped with dropping funnel and dropping funnel, 80 parts methyl methacrylate (MMA), 20 parts hydroxyethyl methacrylate (2HEMA), methyl ethyl ketone (MEK) 90 parts, 60 parts of isopropyl alcohol (IPA) and 2 parts of azobisisobutyronitrile (AIBN) were added, stirred at room temperature for 10 minutes, and after confirming that the system was uniform, the temperature was increased and stirred. . When the temperature in the reaction system reached 70 ° C., the amount charged in the dropping funnel was added over 1 hour. After completion of the dropwise addition, the mixture was further reacted for 4 hours under reflux, and further 0.4 part of AIBN was added and reacted for 1 hour to obtain a thermoplastic resin solution (B) having a solid content of 40%.

(Synthesis Examples 3 to 9)
Table 1 shows an unsaturated monomer (a) having a quaternary ammonium salt, an unsaturated monomer (b) having a hydroxy group, and other (meth) acrylic monomers (c). A cationic thermoplastic resin (A) and a thermoplastic resin (B) were obtained by the same method as in Synthesis Examples 1 and 2 except that the monomer composition was used.

Table 1 shows the monomer compositions of the cationic resins and copolymers obtained in Synthesis Examples 1-9.

(Examples 1-6 and Comparative Examples 1-6)
The cationic thermoplastic resin solution and the thermoplastic resin solution obtained in Synthesis Examples 1 to 9 and a polyisocyanate crosslinking agent (“Desmodur N3200” manufactured by Sumika Bayer Urethane Co., Ltd.) are blended and mixed in the amounts shown in Table 2. The obtained antistatic agent was coated on the following substrate using a bar coater so that the dry film thickness was about 3 μm, and dried at 60 ° C. for 30 seconds. Further, after aging at 40 ° C. for 3 days and sufficiently curing, the obtained coated product was evaluated for surface resistance, substrate adhesion, printed surface adhesion, and water resistance by the following methods. In the table, “aE + b” means “a × 10 ^b ”.

(Type of base material)
PP: Polypropylene film (film thickness 20μm)
PET: Polyethylene terephthalate (film thickness 12μm)

(Evaluation method)
<Surface resistance value>
After the coating was aged at 40 ° C. for 3 days to sufficiently cure the coating film, and after storing for 2 weeks at room temperature, the surface resistance value of the coated material was measured using 4329AHIRESISTANCE METER (manufactured by HEWLET PACKARD). .
<Adhesion test>
A cellophane tape peel test was performed according to JIS5400. In addition, about the adhesiveness with a base material, the cellophane tape was affixed on the antistatic agent layer of the coating material obtained by apply | coating an antistatic agent on a base material, and 5 points | pieces evaluated adhesiveness.
5: peeling area 0%
4: Peel area less than 10% 3: Peel area 10% or more and less than 30% 2: Peel area 30% or more and less than 70% 1: Peel area 70% or more <Water resistance test>
The coated material was immersed in water at 40 ° C. for 1 hour, then pulled up to wipe off the water, and the appearance of the surface coated with the antistatic agent was visually observed.

As shown in Table 2, according to the present invention, a permanent antistatic effect excellent in coating film properties such as water resistance and chemical resistance can be imparted to the film surface.

Claims (5)

10 to 60% by weight of unsaturated monomer (a) having a quaternary ammonium salt represented by the following general formula (a) in the varnish composition, 5 to 40% by weight of unsaturated monomer (b) having a hydroxy group And other (meth) acrylic monomer (c) 5 to 85% by weight of cationic thermoplastic resin (A), hydroxy group-containing unsaturated monomer (b) 5 to 40% by weight and others (A) :( B) = 10: 90 to 85:15 in a weight ratio of (meth) acrylic monomer (c) of 60 to 95% by weight of thermoplastic resin (B). A printing varnish composition having a characteristic antistatic effect.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group, R ² represents an alkylene group or an oxyalkylene group, X ⁻ represents a halogen ion, R ⁶ SO ₃ ⁻ (R ⁶ represents an alkyl group-substituted aromatic group or alkoxy group) or (R ⁷⁰ ) ₂ P0 ₂ ⁻ (R ⁷ represents an alkyl group). ]   Furthermore, the printing varnish composition which has the antistatic effect of Claim 1 which mixed the isocyanate type crosslinking agent (C).   The content of the unsaturated monomer (a) having a quaternary ammonium salt is 5 with respect to 100% by weight of the mixture of the cationic thermoplastic resin (A), the thermoplastic resin (B) and the isocyanate crosslinking agent (C). The printing varnish composition having an antistatic effect according to claim 2, which is ˜50 wt%.   The antistatic film base material coating which coats the printing varnish composition which has the antistatic effect of any one of Claims 1-3. A base material processed molded article of the antistatic film base material coating according to claim 4.