JP3466249B2 - Antistatic agent with excellent transparency and flexibility - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a material for imparting an antistatic property to a film surface, which is excellent in transparency and flexibility and has a hydrophilic surface coated with an antistatic agent. It also relates to an antistatic agent having excellent adhesiveness and durability. Furthermore, since the surface gives a film rich in hydrophilicity, an aqueous undercoat film for an aqueous coating solution,
It can be used as an easily adhesive film or an antifogging film.

[0002]

2. Description of the Related Art Conventionally, various kinds of surfactants, water-soluble polymers, conductive carbons, metal oxides, etc. have been used as antistatic agents for preventing the electrification of insulating films such as films, and these have been applied to the film surface. Various attempts have been made to prevent electrification by coating or kneading. For example,
Japanese Patent Laid-Open No. 3-229787 uses a copolymer of poly (styrene sulfonate) and N-methylol acrylamide as a water-soluble polymer, and coats this on a film to exhibit antistatic performance. Is disclosed. Alternatively, JP-A-55-84658 and 56-56.
-92535, 61-174542, 61-1
As described in Japanese Patent No. 74543, a combination of an antistatic water-soluble polymer and a curing agent is applied to the surface of a support such as a film to prepare an antistatic film having excellent durability such as water resistance. Is disclosed.

However, in the above-mentioned method, the adhesion to the surface of the support becomes a problem, and depending on the conditions of use, peeling may occur between the layer containing the antistatic agent and the support, or it may change over time. There was a problem that the antistatic performance was significantly deteriorated. Stretching processing such as biaxial stretching processing is widely performed for the purpose of increasing the strength as a film, but antistatic processing on the film surface is particularly preferably performed immediately before stretching processing, and coating and subsequent The surface of the antistatic agent is preferably fixed by stretching and heating. In this case, when the properties of the antistatic agent used are lacking in film property and flexibility, the coating film cannot follow the stretching of the film which is the support during the stretching process after coating on the film surface, and the coating layer tears. However, it has been a problem to cause problems such as peeling or whitening. Furthermore, it is often the case that another coating liquid is applied onto a layer coated with an antistatic agent for various purposes, but when the coating liquid to be coated contains water as a solvent, However, there is a problem in that the hydrophilicity is insufficient and coating unevenness occurs, or the adhesiveness between the coating layer and the antistatic layer is poor, causing film peeling.

Alternatively, although a method of coating or kneading a low-molecular-weight surfactant or the like on the surface of a support such as a film has been studied in the past, problems such as stickiness due to bleed-out from the surface, whitening, and deterioration over time, etc. Was occurring.

By using a metal oxide, an antistatic film having a surface resistance less dependent on humidity can be achieved by a coating or kneading method. In this case, the metal oxide is coated or kneaded in a finely dispersed state. However, in order to impart sufficient antistatic performance to the film, it is necessary to pack the metal oxide particles so densely that they are in contact with each other. Inevitably, there was a problem that the transparency of the film was lowered.

Further, in the case of reusing such an antistatic-treated film, when the film is heated to a melting temperature, the introduced antistatic agent is thermally decomposed, and there is a serious problem that the performance of the film is deteriorated such as coloring. Therefore, in the present situation, an antistatic agent excellent in heat resistance is also desired.

[0007]

An object of the present invention is to provide an antistatic agent which is excellent in flexibility and transparency without deterioration with time in antistatic performance by coating on the surface of a support such as a film. Another object is to find an antistatic agent that is excellent in flexibility of the coated antistatic agent itself, has a hydrophilic surface, and is excellent in adhesiveness. Further, it is an object to find an antistatic agent having excellent recyclability, which does not cause performance deterioration of a recycled film or a problem of generation of foreign matter or coloring even when a discarded film is collected and melted and reused.

[0008]

The above object can be achieved by the present invention described below. That is, as the antistatic agent, 10 parts by weight or more and 70 parts by weight or less of the monomer unit represented by the chemical formula 1 and 10 parts by weight of the monomer unit represented by the chemical formula 2 are used.
The object of the present invention is achieved by using a polymer containing at least 80 parts by weight and at least 80 parts by weight, and further containing at least 1 part by weight and not more than 50 parts by weight of the monomer unit represented by Chemical Formula 3 above.

In formula 1, X ₁ represents hydrogen or sodium, potassium or NH ₄ .

In the chemical formula 2, R1 represents hydrogen or a methyl group,
X ₂ represents hydrogen or sodium, potassium or NH ₄ .

In formula 3, R ₂ represents hydrogen or a methyl group,
R ₃ is CH ₂ CH ₂ , CH ₂ CHCH ₃ , CH ₂ CH ₂
It represents an OCH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ group, and R ₄ represents hydrogen or a methyl group.

Preferred examples of the monomer represented by the chemical formula 3 are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate and 2-methoxyethyl methacrylate. Is mentioned.

As a ratio of these monomers in the polymer, the monomer unit represented by the chemical formula 1 must be 10 parts by weight or more and 70 parts by weight or less in the polymer composition. By introducing the monomer unit represented by, the performance as an antistatic agent is sufficiently exhibited. That is, when the monomer unit of Chemical formula 1 is contained in the polymer in a ratio exceeding the above range and exceeding 70 parts by weight, the polymer itself becomes extremely rigid and inflexible. When an attempt is made to form an antistatic film integrated with the film by applying the coating to the above, and then immediately stretching and heating the coating, the coating film formed by the above polymer can follow the stretching of the film which is the support. No
There is a problem that the coating film has fine cracks and becomes opaque. On the other hand, if it is less than the above range and less than 10 parts by weight, the humidity dependence of the antistatic performance becomes remarkable when used as an antistatic agent, and the antistatic performance is remarkably deteriorated particularly under low humidity, and it cannot withstand actual use. The problem occurs.

Further, the monomer unit represented by the chemical formula 2 must be in the range of 10 parts by weight or more and 80 parts by weight or less in the polymer, and the molecular weight of the polymer as an antistatic agent obtained in this range is appropriate. It also serves to adjust the range to various ranges and makes the antistatic performance of the polymer more excellent and imparts flexibility to the polymer. Even when the polymer solution is applied to the film surface and stretched, a film is formed. It has the excellent property of not impairing the transparency. When the monomer unit of the chemical formula 2 is introduced into the polymer in a ratio exceeding the above range and exceeding 80 parts by weight, the antistatic performance of the polymer is deteriorated under low humidity, and a polymer having an appropriate degree of polymerization is obtained. It is difficult to reduce the molecular weight to about several thousand, which causes problems such as a decrease in water resistance and a decrease in film strength. Alternatively, when the amount is less than the above range and less than 10 parts by weight is introduced into the polymer, the flexibility of the polymer is inferior, and when the coated film is stretched, there is a problem that the coating becomes opaque. In order to achieve both the performance as an antistatic agent and the transparency of the film, it is very important that the monomer units of Chemical formula 1 and Chemical formula 2 are simultaneously contained in the polymer in a ratio within the above range, The object of the present invention cannot be achieved at all by using each monomer unit alone.

Further, in addition to the monomer units represented by the chemical formulas 1 and 2, the monomer units represented by the chemical formula 3 are introduced into the polymer at a ratio of 1 part by weight or more and 50 parts by weight or less,
The flexibility is further improved without impairing the antistatic performance of the resulting antistatic coating formed from the polymer, and the adhesion to the film support and the coating properties of other coatings on the antistatic layer and It has been found that the adhesion with this is significantly improved. That is, when the monomer unit represented by the chemical formula 3 is introduced into the polymer only at a ratio of less than 1 part by weight, the adhesiveness to the film support is lowered, and the antistatic layer can be easily formed by means such as friction on the surface. This causes the inconvenience of peeling. If the monomer unit represented by the formula (3) is used in an amount exceeding 50 parts by weight, the function as an antistatic agent is remarkably deteriorated, and the surface resistance value becomes a high value of 10 ¹³ ohms or more particularly under low humidity, which is a practical problem. Become.

The object of the present invention is basically achieved by a polymer obtained by using the above-mentioned monomer within the specified range, but by using such a polymer alone and coating it on the film surface, antistatic property can be obtained. Although a functional coating is formed, it is also preferable to use various additives in combination for the purpose of further improving the abrasion resistance, blocking resistance, water resistance and the like of the coating. Examples of such additives include polymer emulsions such as styrene-butadiene latex, styrene-acrylic latex, various acrylic emulsions, vinyl acetate latex, polyurethane emulsion, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxy. Various cellulose derivatives such as methyl cellulose, various water-soluble polymers such as starch, gelatin, polyvinylpyrrolidone and chitosan, or inorganic particles such as silica, colloidal silica, titanium oxide and zinc oxide, polystyrene particles, polymethylmethacrylate particles, silicone particles The above object can be preferably achieved by adding organic polymer particles such as When such an additive is used, the ratio of the two in the combination with the above antistatic agent becomes a problem, but the antistatic agent for the entire coating layer in the coating layer for forming the antistatic layer is used. The proportion is preferably 10 parts by weight or more, and if it is less than this, the antistatic performance may be insufficient.

A further feature is that when the layer containing the above-mentioned polymer is formed as a coating layer on a film support, the surface has a good affinity for water. Normally, the contact angle to water is 50 degrees. It is characterized by the following good wettability and particularly good coating suitability when coating is further performed using an aqueous coating liquid. For example, in a state where the polyester film is used as a support and the antistatic agent according to the present invention is not applied to the film surface, the water-based coating liquid is repelled by the surface and it is practically impossible to apply it to the film surface. On the contrary, if the film coated with the antistatic agent according to the present invention alone or in combination with the above-mentioned additives is used, the wettability of the film surface with respect to the aqueous coating solution is very good. Next to
Various water-based coating liquids can be applied to the surface in a uniform state, and the adhesion between the formed coating film and the film can be made extremely excellent.

The adhesion of the film containing the antistatic agent is not limited to the above-mentioned water-based coating liquid, but also shows good adhesion to a coating liquid containing a solvent-based binder containing no water or a printing ink. However, for the purpose of further improving the surface adhesiveness, an amino group-containing monomer unit as shown in the above chemical formula 4 or a component of the above polymer or acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc. It is preferable to introduce the carboxyl group-containing monomer unit as a copolymerization component into the polymer at a ratio of 20 parts by weight or less. As a preferable example of the monomer represented by Chemical formula 4, N, N-dimethylaminoethyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Acrylate, dimethylaminopropyl acrylamide, etc. are mentioned, and in addition to these, diallylamine, allylamine, N-methyldiallylamine, N, N-dimethylallylamine, vinylimidazole, etc. are particularly preferable, and these amino group-containing monomers are hydrochloric acid, sulfuric acid, acetic acid. ,
Even if neutralized with a suitable acid such as phosphoric acid, the effect of introduction is not affected and it can be preferably carried out for the purpose of appropriately adjusting the pH of the polymer solution.

[0019]

[Chemical 4] In Chemical formula 4, R ₅ represents hydrogen or a methyl group, and R ₆ is CH.
₂ CH ₂ or CH ₂ CH ₂ CH ₂ group, R ₇ , R ₈
Represents a methyl group or an ethyl group. The linking group Q is C
Represents an OO or CONH group.

When such an amino group- or carboxyl group-containing monomer unit is introduced into a polymer, the antistatic layer obtained by using the polymer obtained by introducing it in a proportion of more than 20 parts by weight has a particularly poor water resistance. Even when the above-mentioned various additives are added to the polymer to form a film, the water resistance of the film is lowered, and a durable antistatic film cannot be obtained. Alternatively, in such a case, when it is attempted to apply an aqueous coating liquid on the antistatic layer, the lower antistatic layer is dissolved in the stage until the aqueous coating liquid is dried, resulting in uniform coating. May not be performed, or the adhesiveness may be significantly poor. By introducing the amino group-containing monomer represented by Chemical formula 4 or the monomer unit containing a carboxyl group into the polymer at a ratio of 20 parts by weight or less, a polar group is further added to the obtained polymer. Since the interaction between this and other polymers is increased, it is recognized as an effect that the adhesion between the layers is improved when various other polymers are coated on the antistatic layer.

Another object of the present invention is to provide an antistatic agent having excellent recyclability. For example, there are various quaternary ammonium salt type antistatic agents obtained by quaternizing poly (chloromethylstyrene) with triethylamine, and various other quaternary salt type antistatic agents, which have good antistatic performance. Pyrolysis due to heating is significant as a serious drawback, however, for example, when an antistatic film discarded when used for a polyester film is melted by heating to form a pellet again and the pellet is reused. Had a serious problem such as being markedly colored. The antistatic agent obtained in the present invention can be film-processed again even when the film is reused by such a method, since no coloring or foreign matter is observed in the pellets regenerated by heating and melting. It is characterized by showing good recyclability.

The object of the present invention can be sufficiently achieved by using a polymer having the above-mentioned constitution as an antistatic agent. Further, various monomers other than the monomer units shown in Chemical formulas 1 to 4 can be used. It is also possible to introduce various copolymerizable monomer components for the purpose. As such a monomer, styrene, (meth) acrylic acid alkyl ester,
Various monomers such as (meth) acrylamide, N-methylol acrylamide and vinyl acetate can be introduced. However, the introduction of such a component is required to be introduced within a range that does not impair the antistatic performance. If so, it does not particularly affect the antistatic performance.

The antistatic film obtained by adding various epoxy curing agents to the antistatic agent obtained in the present invention and three-dimensionally cross-linking the antistatic film further enhances the durability of the antistatic performance. Is preferably done. Compounds represented by Chemical formulas 5 to 13 are particularly preferable examples of the epoxy-based curing agent used for such a purpose. However, as long as the compound has at least two or more reactive epoxy groups in the molecule, these compounds can be used. It is possible to use other than the example. It is particularly effective to introduce the above-mentioned amino group- or carboxyl group-containing monomer unit into the polymer in order to rapidly cure at low temperature by the reaction with such an epoxy compound. By being contained in itself, the reaction with various epoxy curing agents allows the crosslinking reaction to proceed rapidly within a few hours even under relatively low temperature conditions of 100 ° C or less. It is particularly preferable for production.

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

In Chemical formula 7, n represents an integer of 2 or 3.

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

In Chemical Formula 12, m represents an integer of 1 to 22.

[0034]

[Chemical 13]

In Chemical formula 13, q represents an integer of 1 to 11.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples in addition to the effects. Parts in the examples indicate parts by weight.

Synthesis Example 1 40 parts of sodium p-styrene sulfonate, 30 parts of sodium allyl sulfonate and 30 parts of 2-hydroxyethyl methacrylate were dissolved in 200 parts of distilled water and 50 parts of ethanol, and a stirrer, a thermometer, V-50 (2,2'-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator while stirring at 4O 0 C in a 4-necked flask equipped with a nitrogen inlet tube and a reflux condenser tube while stirring. (Koujunyaku)
Polymerization was started by adding 1 part of Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution having a weight average molecular weight of about 70,000.

Synthesis Examples 2 to 13 Polymerization was carried out in the same manner as in Synthesis Example 1 with the compositions shown in Table 1 to obtain polymers.

[0039]

[Table 1]

In Table 1, SSS = sodium p-styrene sulfonate, AS = sodium allyl sulfonate, MAS = sodium methallyl sulfonate, HEMA = 2-hydroxyethyl methacrylate, HEA = 2-hydroxyethyl acrylate, HPA = 2 -Hydroxypropyl acrylate, HPMA
= 2-hydroxypropyl methacrylate, MAA = methacrylic acid, DMAEMA = N, N-dimethylaminoethyl methacrylate.

Synthesis Example 14 40 parts of ammonium p-styrene sulfonate, 35 parts of ammonium methallyl sulfonate, 20 parts of 2-hydroxyethyl acrylate and 5 parts of diallylamine were dissolved in 200 parts of distilled water and 50 parts of ethanol, and the pH was adjusted with an aqueous hydrochloric acid solution. Was adjusted to 7, and V-50 (2,2) was used as a polymerization initiator while heating and stirring at 60 ° C. in a 4-necked flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser.
Polymerization was initiated by adding 1 part of 2'-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Synthesis Example 15 20 parts of potassium p-styrene sulfonate, 45 parts of sodium allyl sulfonate, 30 parts of 2-hydroxypropyl methacrylate and 5 parts of crotonic acid were dissolved in 200 parts of distilled water and 50 parts of ethanol and stirred. Machine, thermometer,
6 in a 4-necked flask equipped with a nitrogen inlet tube and a reflux condenser
V-50 as a polymerization initiator while heating and stirring at 0 ° C.
Polymerization was started by adding 1 part of (2,2′-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.). Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Synthesis Example 16 35 parts of sodium p-styrenesulfonate, 45 parts of sodium methallylsulfonate, 20 parts of 2-methoxyethyl methacrylate and 10 parts of vinylimidazole were dissolved in 200 parts of distilled water and 50 parts of ethanol and stirred. V-50 (2,2'-azobis (2-amidinopropane) as a polymerization initiator while heating and stirring at 60 ° C in a 4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser tube. Polymerization was started by adding 1 part of dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.). Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 1 85 parts of sodium p-styrene sulfonate, 5 parts of sodium methallyl sulfonate and 0.5 part of 2-hydroxyethyl methacrylate were dissolved in 200 parts of distilled water and 50 parts of ethanol and stirred. V-50 (2,2'-azobis (2-amidinopropane) 2 as a polymerization initiator while stirring at 4O 0 C in a 4-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux condenser tube while stirring. Polymerization was started by adding 1 part of hydrochloride, manufactured by Wako Pure Chemical Industries, Ltd. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 2 85 parts of sodium p-styrenesulfonate and 15 parts of 2-hydroxyethyl methacrylate were dissolved in 200 parts of distilled water and 50 parts of ethanol, and a stirrer, a thermometer,
6 in a 4-necked flask equipped with a nitrogen inlet tube and a reflux condenser
V-50 as a polymerization initiator while heating and stirring at 0 ° C.
Polymerization was started by adding 1 part of (2,2′-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.). Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 3 5 parts of sodium p-styrene sulfonate and 95 parts of sodium allyl sulfonate were dissolved in 200 parts of distilled water and 50 parts of ethanol, and a stirrer, a thermometer, a nitrogen introduction tube, and a reflux cooling tube were used. V-50 (2,2'-azobis (2-amidinopropane) dihydrochloride, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator while heating and stirring at 60 ° C in a 4-necked flask equipped with
Polymerization was started by adding 1 part of Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthetic Example 4 100 parts of p-vinylbenzyltrimethylammonium chloride was dissolved in 200 parts of distilled water, and the mixture was stirred in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser tube. V-5 as a polymerization initiator while heating and stirring at ℃
Polymerization was initiated by adding 1 part of 0 (2,2'-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.). Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 5 100 parts of a quaternary product of methyl chloride of dimethylaminoethyl methacrylate was dissolved in 300 parts of distilled water,
4 equipped with a stirrer, thermometer, nitrogen inlet pipe, reflux condenser
By adding 1 part of V-50 (2,2'-azobis (2-amidinopropane) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator while heating and stirring at 60 ° C in a two-necked flask. Polymerization started. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Example 1 Polyethylene terephthalate (PET) chips were melted, extruded through a die slit to form a film, and rapidly cooled with a cooling roller to form an amorphous PET film, which was then heated and stretched in the longitudinal direction to form a single surface. A wire bar was used to apply the polymer solutions (antistatic agent solutions) obtained in Synthetic Examples 1 to 16 and Comparative Synthetic Examples 1 to 5 to a coating amount of 0.1 g / m ^2, and then continuously. Then, both ends of the film were held by tenter clips and heated while being transversely stretched. A sample was taken after cooling through a heating chamber at 200 ° C. The coating amount of the antistatic agent after transverse stretching was about 0.03 g / m ² . Obtained antistatic PE
The physical properties of the T film are shown in Tables 2 and 3.

[0050]

[Table 2]

In Table 2, the surface resistance value is measured by using a high resistance resistivity meter Hiresta IP manufactured by Mitsubishi Yuka Co., Ltd. after conditioning the sample for 12 hours in a temperature / humidity atmosphere of 20 ° C. and 65%. did. The contact angle was measured using an automatic contact angle measuring instrument manufactured by Kyowa Interface Science Co., Ltd., and the contact angle of the coated film surface with respect to pure water at 20 ° C. and 65% temperature and humidity was measured. Adhesiveness was evaluated by scratching the conductive surface in a grid pattern of a 5 mm image with a cutter knife, adhering the adhesive surface of the cellophane tape, and then peeling at a stretch to determine whether or not a peeled portion would occur. . The evaluation was carried out by a three-level evaluation of ◯ (no peeling at all), Δ (partially peeling off), and x (peeling off over half the area of the adhesive surface of the cellophane tape).

[0052]

[Table 3]

In Table 3, the evaluation of transparency is P after coating.
The ET film was evaluated by the haze value and the degree of coloring. ◎ (haze value less than 2%), ○ (haze value 2 or more 10
%), Δ (haze value 10 or more and less than 20%), × (haze value 20% or more). Evaluation of surface blocking property is 3
Under conditions of 0 ° C. and 80% temperature and humidity, the coated surfaces were overlapped and allowed to stand for 5 hours. ◎ (less than 20 g), ○ (20 g or more and less than 60 g), Δ (60 g or more and less than 100 g), × (1
00g or more). To evaluate the recyclability, a PET film coated with an antistatic agent was melted and heated, and the degree of coloring in the regenerated PET was visually evaluated. The case where coloration was observed was marked with x, and the other cases were marked with o.

Example 2 The polymer solutions obtained in Synthesis Examples 1 to 16 were mixed with a solid content concentration of 10
To give a coating solution by diluting with pure water so that the content of the compound becomes 5%, and further adding the compound represented by Chemical formula 5 as an epoxy curing agent to 20% by weight with respect to the polymer solid content. The pH of the coating liquid was adjusted to pH 7.5 using a 1N hydrochloric acid aqueous solution or a 1N sodium hydroxide aqueous solution. The coating solution thus prepared was applied onto a PET film which had been subjected to an aqueous undercoating treatment with gelatin and dried at 80 ° C. for 4 hours to obtain an antistatic film. Table 4 shows the physical properties of the obtained antistatic film.
And summarized in Table 5.

[0055]

[Table 4]

In Table 4, the measurement after washing with water in the measurement of the surface resistance value was carried out by washing the sample with warm water of 40 ° C. for 1 minute, followed by drying and conditioning at 20 ° C. and a humidity of 65% for 12 hours. After that, the surface resistance value was measured in the same manner as in the previous case. The adhesiveness was evaluated here by further applying an aqueous gelatin solution containing a curing agent on the coated surface and drying the coated gelatin film.
Heat at 0 ℃ for 1 day to fully cure, then 4
The surface coated with gelatin was washed with warm water of 0 ° C. while rubbing, and the case where the surface was partially peeled off was evaluated as x, and the case where the gelatin film was completely left was evaluated as o.

[0057]

[Table 5]

[0058]

EFFECTS OF THE INVENTION The film formed according to the present invention provides a water-resistant antistatic film having excellent antistatic performance and excellent transparency without deterioration over time. Further, it can be used as a film having a high hydrophilicity on the surface and subjected to an aqueous undercoating process or an easy-adhesion process, and can also be used as an anti-fog film.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09K 3/16 108 C09K 3/16 108

Claims (4)

(57) [Claims] 1. A monomer unit represented by Chemical formula 1 is 10 parts by weight or more and 70 parts by weight or less, a monomer unit represented by Chemical formula 2 is 10 parts by weight or more and 80 parts by weight or less, and a monomer unit represented by Chemical formula 3 is 1 part by weight. An antistatic agent, which is a polymer containing at least 50 parts by weight but not more than 50 parts by weight. [Chemical 1] (Where X ₁ is hydrogen or sodium, potassium, NH
Represents ₄ . ) [Chemical 2] (In Chemical Formula 2, R ₁ represents hydrogen or a methyl group, and X ₂ represents hydrogen, or sodium, potassium, or NH _4. ) (In the chemical formula 3, R ₂ represents hydrogen or a methyl group, and R ₃ is CH.
₂ CH ₂ , CH ₂ CHCH ₃ , CH ₂ CH ₂ OCH ₂ C
H ₂ and CH ₂ CH ₂ CH ₂ groups are represented, and R ₄ represents hydrogen or a methyl group. ) 2. In addition to the monomer unit shown in claim 1, a monomer unit shown in Chemical formula 4 or an amino group selected from allylamine, diallylamine, N-methyldiallylamine, N, N-dimethylallylamine, and vinylimidazole. An antistatic agent, which is a polymer containing a content of monomer units in an amount of 20 parts by weight or less as a copolymerization component. [Chemical 4] (In Chemical Formula 4, R ₅ represents hydrogen or a methyl group, and R ₆ represents C
Represents a H ₂ CH ₂ or CH ₂ CH ₂ CH ₂ group, R ₇ ,
R ₈ represents a methyl group or an ethyl group. The linking group Q represents a COO or CONH group. ) 3. A copolymerization component in which, in addition to the monomer units shown in claim 1, a carboxyl group-containing monomer unit selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid in a proportion of 20 parts by weight or less. An antistatic agent, which is a polymer containing as. 4. An antistatic agent according to claim 2 or 3, wherein the polymer is three-dimensionally crosslinked with an epoxy curing agent.