JPH0978056A - Antistatic agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic agent capable of being applied on the surface of a film to impart an antistatic performance thereto and good in printability by using a polymer containing unsaturated monomer units having polyoxyalkylene groups, sulfo gropes and tertiary amino groups, respectively. SOLUTION: This antistatic agent is obtained by adding an epoxy curing agent to a polymer comprising 10-80wt.% of polyoxyalkylene group-containing monomer units of formula I (R<1> , R<2> are each H, methyl; R<3> is H, an aryl, a 1-4C alkyl; n is 1-30), 10-80wt.% of sulfo group-containing monomer units of formula II (R<4> is H, methyl; Q<1> is a divalent bonding group; g is 0, 1; M is H, Na, K, NH4 ), and further 1-50wt.% of tertiary amino group-containing monomer units of formula III (R<5> is H, methyl; Q<2> is COO, CONH; R<6> , R<7> are each methyl, ethyl; n is 1-3) or amino group-containing monomer units such as allylamine units, diallyl amine units, N-methyldiallylamine units, N,N- dimethylallylamine units or vinyl imidazole units.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a material for imparting antistatic performance to a film surface, which is excellent in transparency and flexibility, and has a surface coated with an antistatic agent which is adhesive. The present invention also relates to an antistatic agent which has excellent durability and has good adhesiveness to ink when printing with a printing ink on the surface.

[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.
These publications disclose an antistatic agent obtained by curing a conductive polymer having a carboxyl group with an aziridine curing agent. Further, JP-A-2-291552 discloses a conductive polymer having an alkylene oxide in a side chain by an aziridine. Crosslinking cured antistatic agents are 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. Further, although stretching processing such as biaxial stretching processing is widely performed for the purpose of increasing the strength as a film, it is preferable to perform the antistatic processing on the film surface immediately before the stretching processing, coating and subsequent coating. The surface of the antistatic agent is preferably fixed by stretching treatment and heat treatment, but in this case, if the property of the antistatic agent used is not filmy and lacks flexibility, it is applied to the film surface and then stretched. At times, the coating film cannot follow the stretching of the film that is the support, causing problems such as tearing, peeling or whitening of the coating layer.

Further, it is often the case that another coating liquid is applied onto a layer coated with an antistatic agent for various purposes. However, the adhesion between the coating layer and the antistatic layer is poor. Therefore, there is a problem that inconvenience such as film peeling occurs. Furthermore, even in an attempt to improve the adhesion of the antistatic layer by using a curing agent, when the above-mentioned aziridine curing agent is used, it was attempted to be carried out on an industrially large scale due to the toxicity problem of aziridine. In this case, a problem arises, and the adhesiveness has not yet been able to give sufficient performance for the purpose of the present invention.

Further, 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, the problem of stickiness due to bleed-out from the surface, the problem of whitening, and the deterioration over time have been encountered. Etc. had occurred.

By using the metal oxide, an antistatic film having a surface resistance less dependent on humidity can be obtained by a method such as coating or kneading. In this case, the metal oxide needs to be applied or kneaded in a state of being dispersed in the form of fine particles, but a step of dispersing such fine particles is required,
Further, in order to impart sufficient antistatic performance to the film, it is necessary to densely fill the metal oxide fine particles with each other so that they are in contact with each other, which inevitably causes a problem of decreasing transparency of the film.

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.

Further, in any of the above examples, when a layer containing various antistatic agents is provided on the film surface and the printing ink is used for printing, the film surface is compatible with the printing ink. However, problems such as printed characters peeling off due to friction occur, and it has been extremely difficult to find an antistatic agent that achieves both printability and antistatic performance.

[0009]

An object of the present invention is to provide an antistatic agent which is excellent in flexibility and transparency without deterioration with time of antistatic performance by coating on the surface of a support such as a film. Another object is to find an antistatic agent which is excellent in flexibility of the coated antistatic agent itself and is excellent in adhesiveness to a film support. Further, it is to find an antistatic agent having excellent recyclability, which does not cause performance deterioration of the recycled film, generation of foreign matters, and coloring problems even when the discarded film is collected and melted and reused. further,
The purpose is to find an antistatic agent that exhibits good adhesion to the ink when printing is performed on the surface coated with the antistatic agent with a printing ink.

[0010]

The above objects are achieved by the present invention described below. The first invention of the present invention comprises 10% by weight or more of the monomer unit represented by the general formula 1 above.
0% by weight or less and 10% by weight or more and 80% by weight or less of the monomer unit represented by the general formula 2, and the monomer unit represented by the general formula 3 or allylamine,
Diallylamine, N-methyldiallylamine, N, N-
The antistatic agent comprises a polymer containing at least 1% by weight and 50% by weight or less of an amino group-containing monomer unit selected from the group of dimethylallylamine and vinylimidazole.

In Formula 1, R ¹ and R ² represent hydrogen or a methyl group, R ³ represents a hydrogen or aryl group, and an alkyl group having 4 or less carbon atoms. n represents an integer of 1 to 30. Preferable examples of the monomer unit represented by the general formula 1 include the following formulas 5 to 11.

[0012]

Embedded image

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

In the chemical formula 2, R ⁴ represents hydrogen or a methyl group,
Q ¹ represents a divalent linking group, and q represents an integer of 0 or 1. M represents hydrogen or sodium, potassium or NH ₄ . Preferred examples of Q ¹ include methylene group, phenylene group, amide group and the like. Preferred examples of the monomer unit represented by the general formula 2 are sodium allyl sulfonate, sodium methallyl sulfonate, potassium allyl sulfonate, potassium methallyl sulfonate, ammonium allyl sulfonate, ammonium methallyl sulfonate, styrene sulfone. Sodium acid salt, potassium styrene sulfonate, ammonium styrene sulfonate, sodium vinyl sulfonate, 2-acrylamido-2-
Methyl propane sulfonic acid and its sodium salt, potassium salt, ammonium salt and the like can be mentioned.

In formula 3, R ⁵ represents hydrogen or a methyl group,
Q ² represents a COO or CONH group, R ⁶ and R ⁷ represent a methyl or ethyl group, and m represents an integer of 1 to 3.

Preferred examples of the monomer unit represented by the general formula 3 are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and N- (3-dimethylamino). Propyl) (meth) acrylamide and the like. Furthermore, allylamine, diallylamine, N-methyldiallylamine,
N, N-dimethylallylamine, vinylimidazole and the like are also preferable. Even if these amino group-containing monomers are neutralized with a suitable acid such as hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid or the like, the effect of introduction is not affected, and it is preferably carried out for the purpose of appropriately adjusting the pH of the polymer solution. I can.

As the ratio of these monomer units in the polymer, the monomer unit represented by the general formula 1 must be 10% by weight or more and 80% by weight or less in the polymer composition, and within this range. By introducing the monomer unit shown in Chemical formula 1, the performance as an antistatic agent having flexibility is sufficiently exhibited. That is, when an antistatic agent is applied to a support such as a film and used as an antistatic film, an external force such as bending or stretching may be applied to the film. When deformed, cracks and the like may occur due to external force of the antistatic layer on the surface, and white turbidity may occur. However, by using the antistatic agent having the repeating unit of Chemical formula 1 within the above range, the antistatic agent Good flexibility, even if the film is deformed by external force,
It is possible to exert a very preferable effect that white turbidity does not occur.

When the monomer unit of Chemical formula 1 is contained in the polymer at a ratio exceeding the above range and less than 10% by weight, the polymer itself becomes very rigid and has no flexibility, so that the film is deformed. When the addition of a polymer solution is applied to the film, or when an attempt is made to form an antistatic film integrated with the film by, for example, coating a polymer solution on the film, and immediately stretching and heat treatment, The coating film formed by the coalescence cannot follow the stretching of the film which is the support, and there arises a problem that the coating film has fine cracks and becomes opaque.

For example, in the case where the surface of the biaxially stretched film is subjected to antistatic treatment, the antistatic film is obtained by further applying a coating liquid containing the antistatic agent of the present invention onto the film formed after the biaxial stretching. It is also possible to obtain, for example, in the actual processing in the case of a polyester film, melted polyester is extruded from a die slit to form an amorphous polyester film on a cooling roll, and then this film is longitudinally formed. Forming an antistatic layer firmly adhered on a polyester film by applying a coating liquid containing the antistatic agent of the present invention after stretching and subsequently continuously stretching in the transverse direction under heating and applying heat treatment. Can be obtained and gives extremely favorable results in terms of production process and durability of antistatic performance. When the antistatic agent is used in such a method, the transparency of the film is deteriorated due to the breakage of the antistatic layer when the film is stretched after applying the antistatic agent. Although the flexibility of the agent itself is important, it has been found that in this sense, it is very effective to introduce the monomer unit shown in Chemical formula 1 into the polymer.

Further, the monomer unit shown in Chemical formula 1 is
When the obtained antistatic agent is applied on a film to form an antistatic layer and printing is performed on this surface with a printing ink, the affinity between the printing ink and the antistatic layer is improved and the antistatic property is improved. It was found that the layer surface does not repel the printing ink and does not peel off even when the printed part is rubbed, etc.

On the other hand, when the monomer unit represented by Chemical formula 1 exceeds the above range in the polymer composition and exceeds 80% by weight, the hygroscopicity is high and stickiness occurs,
When it is applied to the film surface, blocking occurs remarkably, so that it cannot be used practically.

The monomer unit represented by the general formula 2 must be in the range of 10% by weight or more and 80% by weight or less in the polymer, and the resistance value of the polymer itself formed in this range is to prevent the static electricity. It can exert the effect of lowering it to the extent necessary for the purpose. If the content exceeds the above range and exceeds 80% by weight, the flexibility of the antistatic agent decreases, and when an external force such as stretching or bending is applied to the film coated with the antistatic agent, the film becomes cloudy. This is not preferable because it causes problems. On the other hand, if it is less than 10% by weight, the resistance value of the surface does not become a sufficiently low value, so that the effect as an antistatic agent is not sufficiently exhibited.

Further, in addition to the monomer units represented by the general formulas 1 and 2, from the group of monomer units represented by the general formula 3 or allylamine, diallylamine, N-methyldiallylamine, N, N-dimethylallylamine, vinylimidazole. By introducing the selected amino group-containing monomer unit into the polymer composition in a proportion of 1% by weight or more and 50% by weight or less, the flexibility is maintained without impairing the antistatic performance of the antistatic film formed from the antistatic agent. Alternatively, it has been found that the flexibility is further improved, and the adhesiveness to the film support and the coatability of another film on the antistatic layer and the adhesiveness thereof are remarkably improved.

That is, when the monomer unit represented by the chemical formula 3 is introduced into the polymer composition only at a ratio of less than 1% by weight, the adhesiveness to the film support is lowered and the surface is rubbed. There is a disadvantage that the antistatic layer is easily peeled off. When the monomer unit represented by Chemical formula 3 is used in an amount exceeding 50% by weight, the function as an antistatic agent is remarkably deteriorated, and the surface resistance value is 10 ¹³ especially in low humidity.
This is a practical problem because the value is higher than ohms.

Preferred examples of the monomer represented by the general formula 3 are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and N- (3-dimethylaminopropyl). (Meth) acrylamide etc. are mentioned. Furthermore, allylamine, diallylamine, N-methyldiallylamine, N,
N-dimethylallylamine, vinylimidazole and the like are also preferable. By introducing such an amino group-containing monomer unit into the polymer at a ratio of 50% by weight or less, a polar group is further added to the obtained polymer, and the interaction between this and other polymers is increased. Therefore, it is recognized that the adhesiveness between the layers is further improved not only between the film and the antistatic agent layer but also when various other polymers are further coated on the antistatic layer.

When the layer containing the antistatic agent of the present invention is formed as a coating layer on a film support, a further characteristic is that the surface has a good affinity for water and a solvent. When the antistatic agent according to the present invention is not applied to the surface of the film using the base film as a support, the aqueous coating liquid is repelled by the surface and it is practically impossible to apply it to the surface of the film. On the contrary, if a 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 water-based coating liquid becomes very good, and 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 is also very good. It can be something. Similarly, it is also one of the features that the solvent-based coating liquid containing a solvent can be applied favorably and printing with a printing ink can be performed well.

As described above, the object of the present invention is to use a polymer which simultaneously contains three kinds of repeating units of the amino group-containing monomer unit represented by the above general formulas 1, 2, and 3. This is achieved for the first time, and if any one of these is lacking, the object of the present invention cannot be achieved at all.

The second invention of the present invention is such that the monomer unit represented by the general formula 2 is 10% by weight or more and 80% by weight or less, and the monomer unit represented by the general formula 4 is 1% by weight or less.
It is an antistatic agent composed of a polymer containing at least 0% by weight and 90% by weight or less.

In the general formula 4, R ⁸ , R ⁹ and R ¹⁰ represent hydrogen or a methyl group, and R ¹¹ and R ¹² represent hydrogen or an alkyl group having 10 or less carbon atoms, which may be the same or different. R ¹¹ and R ¹² may form a ring via a methylene group. Q ³ is COO group or CO
Represents an NH group, and p represents an integer of 1 to 30.

Preferred examples of the monomer unit represented by the general formula 4 include those represented by the following chemical formulas 12 to 16. The monomer unit represented by Chemical formula 4 has the properties of the monomer unit represented by Chemical formula 1 and the properties of the amino group-containing monomer unit represented by Chemical formula 3,
By introducing the monomer unit shown in Chemical formula 4, both effects are satisfied at the same time, which is extremely preferable. Furthermore, the introduction of repeating units of alkylene oxide may usually cause a problem that blocking of the surface coated with the obtained polymer is likely to occur, but by introducing an amino group at the terminal of alkylene oxide, It is extremely preferable because it shows an effect of reducing the degree of occurrence of blocking.

The monomer unit represented by the general formula 2 must be in the range of 10% by weight or more and 80% by weight or less in the polymer, and the resistance value of the polymer itself formed in this range is antistatic. The effect of lowering it to the extent required for use for the purpose can be exhibited.

The monomer unit represented by the general formula 4 must be in the range of 10% by weight to 90% by weight in the polymer. The chemical formula 4 has the functions of the monomer units represented by the general formulas 1 and 3 at the same time. By introducing the monomer unit represented by the chemical formula 4 in the above range, the chemical formula 4 is represented by the chemical formulas 1 and 3. The effect of the monomer unit is exerted. In other words, the flexibility is good without impairing the antistatic performance, the adhesion to the film support is improved, and the coatability of other films on the antistatic layer and the adhesion with it are outstanding. Improve to.

The ratio of the chemical formula 4 in the polymer is 90% by weight.
If it is more than 10% by weight, the surface becomes sticky again. If it is less than 10% by weight,
The effect of the introduction is not recognized, which is not preferable. Further, in addition to the monomer units shown in Chemical formulas 2 and 4,
A monomer unit represented by the general formula 3 used in the first invention, or allylamine, diallylamine, N-methyldiallylamine, N, N-dimethylallylamine,
By further introducing an amino group-containing monomer unit such as vinylimidazole, as described above, the effect of improving the adhesiveness by introducing the amino group can be further enhanced, which is preferable. In this case, the amount of the amino group-containing monomer unit introduced is preferably 50% by weight or less, and if it exceeds this amount, the resistance value of the antistatic agent itself becomes high and the effect cannot be recognized, which is not preferable.

[0039]

[Chemical 12]

[0040]

Embedded image

[0041]

Embedded image

[0042]

[Chemical 15]

[0043]

Embedded image

The molecular weight of the antistatic polymer of the present invention is
The weight average molecular weight is preferably in the range of 10,000 to 5,000,000, and the best effect can be obtained when the weight average molecular weight is 50,000 or more and 2,000,000 or less. That is, when the weight average molecular weight is less than 10,000, the adhesion between the antistatic agent layer and the film support, which is one of the objects, or the layer formed on the antistatic layer or the ink to be printed If the weight average molecular weight is further 50,000 or more, no problem will occur in order to exhibit a sufficiently good adhesive property, which is not preferable because the adhesive property becomes very weak. Also, the weight average molecular weight is 5
If it exceeds, 000,000, it is not preferable because the viscosity of the antistatic agent solution becomes high and the coating is hindered.
When it is at most, 000,000, it is preferable because the viscosity range at the time of applying the antistatic agent solution can be suppressed to an appropriate range.

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. In addition to the monomer units represented by the general formulas (1) to (4), It is also possible to introduce various copolymerizable monomer components for various purposes. Various monomers such as styrene, (meth) acrylic acid alkyl ester, (meth) acrylamide, N-methylol acrylamide, and vinyl acetate can be introduced as such a monomer, but the introduction of such components does not impair the antistatic performance. Since it is necessary to introduce it within the range, if it is at most 20% by weight, it does not particularly affect the antistatic performance.

The object of the present invention is basically achieved by the antistatic agent polymer of the present invention, and an antistatic film is formed by coating the film surface with the polymer alone. 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 object of the present invention can be preferably achieved by adding organic polymer fine particles such as When such an additive is used, the ratio of the two in the combination with the antistatic agent of the present invention becomes a problem, but the antistatic agent for the entire coating layer in the coating layer for forming the antistatic layer is used. Is preferably 10% by weight or more, and if it is less than this, the antistatic performance may be insufficient.

The antistatic film obtained by adding various epoxy curing agents to the antistatic agent of the present invention and three-dimensionally crosslinking the antistatic film can further enhance the durability of the antistatic performance. It is preferably carried out. Particularly preferable examples of the epoxy-based curing agent used for such a purpose include the compounds represented by the following chemical formulas 17 to 25, but if 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-containing monomer unit into the polymer in order to rapidly perform the curing by the reaction with such an epoxy compound at a low temperature, and by including such an amino group in the polymer itself, Since the cross-linking reaction progresses rapidly within a few hours even under relatively low temperature conditions of 100 ° C or less, the reaction with various epoxy curing agents is particularly useful for easily producing an antistatic film having excellent durability. preferable.

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

In Chemical Formula 19, x represents an integer of 2 or 3.

[0053]

Embedded image

[0054]

[Chemical 21]

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

In formula 24, y represents an integer of 1 to 22.

[0059]

Embedded image

In Chemical Formula 25, z represents an integer of 1 to 11.

[0061]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as well as the effects. Parts in Examples are parts by weight.

Synthesis Example 1 20 parts of sodium p-styrenesulfonate, 70 parts of the monomer represented by Chemical formula 5 and 10 parts of N, N-dimethylaminoethyl methacrylate were dissolved in 900 parts of distilled water, and the pH was adjusted to 7 with 1N hydrochloric acid. Adjusted to. 1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride 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 tube. Polymerization was initiated by the addition. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Synthesis Examples 2 to 14 Polymerization was carried out in the same manner as in Synthesis Example 1 with the compositions shown in Table 1 to obtain polymers.

[0064]

[Table 1]

In Table 1, SSS = p-sodium styrenesulfonate, AS = sodium allylsulfonate, DMAEMA = N, N-dimethylaminoethyl methacrylate, DMAPAA = N-
Represents (3-dimethylaminopropyl) acrylamide.

Comparative Synthesis Example 1 20 parts of sodium p-styrenesulfonate and 80 parts of the monomer shown in Chemical formula 6 were dissolved in 900 parts of distilled water, and the pH was adjusted to 7 with 1N hydrochloric acid. 1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride 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 tube. Polymerization was initiated by the addition. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 2 20 parts of sodium p-styrenesulfonate, 70 parts of the monomer shown in Chemical formula 7 and 10 parts of methacrylic acid were added to 90 parts of distilled water.
Dissolve in 0 parts and p with 1N sodium hydroxide solution
The H was adjusted to 7. 1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride 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 tube. Polymerization was initiated by the addition. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 3 80 parts of sodium p-styrenesulfonate, 10 parts of the monomer shown in Chemical formula 6 and 10 parts of methacrylic acid were mixed with 90 parts of distilled water.
Dissolve in 0 parts and p with 1N sodium hydroxide solution
The H was adjusted to 7. 1 part of 2,2′-azobis (2-amidinopropane) dihydrochloride 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 tube. Polymerization was initiated by the addition. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 4 85 parts of sodium p-styrenesulfonate and 15 parts of methacrylic acid were dissolved in 900 parts of distilled water, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. Stirrer,
As a polymerization initiator while heating and stirring at 60 ° C. in a 4-necked flask equipped with a thermometer, a nitrogen inlet tube, and a reflux condenser tube,
Add 2'-azobis (2-amidinopropane) dihydrochloride to 1
Polymerization was started by adding a part. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Comparative Synthesis Example 5 80 parts of sodium p-styrenesulfonate, 5 parts of the monomer shown in Chemical formula 7 and 15 parts of N, N-dimethylaminoethyl methacrylate were dissolved in 900 parts of distilled water, and the pH was adjusted with 1N hydrochloric acid. Adjusted to 7. Stirrer, thermometer, nitrogen inlet tube,
While heating and stirring at 60 ° C. in a four-necked flask equipped with a reflux condenser, 2,2′-azobis (2-
Polymerization was initiated by the addition of 1 part amidinopropane) dihydrochloride. Polymerization was carried out at this temperature for 5 hours to obtain a polymer solution.

Example 1 In the polymer solutions obtained in Synthesis Examples 1 to 14 and Comparative Synthesis Examples 1 to 5, the epoxy curing agent represented by Chemical formula 17 was added in an amount of 1% by weight of the polymer.
The solution added so as to be 0% by weight was applied on a polyethylene terephthalate (PET) film by a wire bar so that the dry weight was 1 g / m ^2, and heated in a dryer adjusted to 50 ° C. for 5 hours. The evaluation results of the obtained antistatic film are summarized in Tables 2 and 3.

[0072]

[Table 2]

In Table 2, the surface resistance was 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 and humidity atmosphere of 20 ° C. and 65%. did. The water resistance was evaluated by washing the coated surface of the antistatic agent with running water for 5 minutes, and then measuring the surface resistance value in the same manner as described above. When the change was a change, it was marked with ◯, and when the change in the surface resistance value after cleaning showed a two-digit or more increase, it was marked with a mark.

The adhesion was evaluated by checking whether the conductive treated surface was scratched in a grid pattern of 5 mm with a cutter knife and the adhesive surface of the cellophane tape was brought into close contact, and then peeled off at once when peeled off at once. I went. 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).

To evaluate the adhesiveness with the solvent coating layer, a methyl ethyl ketone solution of Diabeam UR-4310 (manufactured by Mitsubishi Rayon Co., Ltd.) was coated on the antistatic agent coated surface with a wire bar so that the dry weight was 2 g / m ^2. After preliminarily drying at 80 ° C., the high pressure mercury lamp was irradiated for 1 minute to cure the solvent coating layer. The evaluation of the adhesiveness between the antistatic layer and the solvent coating layer was performed in the same manner as the evaluation of the adhesiveness.

[0076]

[Table 3]

In Table 3, the evaluation of transparency is performed by applying P after coating.
The haze value of the ET film was evaluated. ◎ (haze value 2% or less), ○ (haze value 2% or more and less than 10%), △
(Haze value 10% or more and less than 20%), × (haze value 20
% Or more).

The surface blocking property was evaluated at 20 ° C., 5
Under the condition of 0% temperature and humidity, the coated surfaces were overlapped and allowed to stand for 5 hours to evaluate the degree of adhesion due to the stickiness of the surfaces, and the load required to separate the film coated surfaces was evaluated. ⊚ (20 g or less), ◯ (20 g or more and less than 60 g), Δ (60 g or more and less than 100 g), × (100 g or more).

The printability was evaluated by using Dainippon Ink Floss Black B as a printing ink, printing on the antistatic surface, drying at 50 ° C. for 20 minutes, and then rubbing the printed area to change the printed area. The case where no image was observed was marked with ◯, and the case where the printed portion was peeled off was marked with x.

The flexibility was evaluated by coating the solution of the antistatic agent on the amorphous PET film, drying it, and then stretching it about 2 times in the coating direction. When the increase in the haze value of the film was less than 2%, it was evaluated as ◯. If the haze value rises above%,
And

The recyclability was evaluated by melting a PET film coated with an antistatic agent and evaluating the degree of coloring and the presence of foreign matter in the regenerated PET.
The case where it was not colored and the mixture of foreign matter was not recognized was marked with ◯, and the other cases were marked with x.

Example 2 In the polymer solutions obtained in Synthetic Examples 1 to 14 and Comparative Synthetic Examples 1 to 5, the compound represented by Chemical formula 17 was added as an epoxy curing agent in an amount of 20% by weight based on the solid content of the polymer. A coating liquid was added. 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 to a PET film surface which had been subjected to an aqueous undercoating treatment with gelatin so that the dry weight was 0.2 g / m ² , and dried at 80 ° C. for 4 hours to give an antistatic film. Got The physical properties of the obtained antistatic film are summarized in Table 4.

[0083]

[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, drying and then conditioning the humidity for 12 hours at 20 ° C. in a temperature and humidity atmosphere of 65%. After that, the surface resistance value was measured in the same manner as in Example 1.

The adhesiveness was evaluated by coating the coated surface with an aqueous gelatin solution containing 4,6-dichloro-1,3,5-triazine-2-oleate sodium as a hardening agent, followed by drying. After heating for 1 day at 40 ° C to fully harden it, wash it with warm water at 40 ° C while rubbing the gelatin coated surface. If the coated surface is partially peeled off, mark x and leave the gelatin film completely. The case was marked as ○.

[0086]

The film formed from the antistatic agent of the present invention provides a water-resistant antistatic film which is excellent in antistatic performance and excellent in transparency without deterioration over time. Further, even when the film coated with the present antistatic agent is reused, coloring and the like due to heating and melting of the film do not occur, and thus an antistatic agent excellent in recyclability is provided. The antistatic layer has excellent adhesion to the film support, and even when various coating layers are formed on the antistatic layer or when printing with printing ink, the adhesion to the coating layer and printing ink An excellent antistatic layer is formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 299/02 MRS C08F 299/02 MRS C08G 65/32 NQH C08G 65/32 NQH

Claims (3)

[Claims] 1. A monomer unit represented by the following general formula 1 is 10% by weight or more and 80% by weight or less, and the following general formula 2
10% by weight to 80% by weight, further selected from the group consisting of allylamine, diallylamine, N-methyldiallylamine, N, N-dimethylallylamine and vinylimidazole. An antistatic agent comprising a polymer containing at least 1% by weight and 50% by weight or less of an amino group-containing monomer unit. Embedded image (In Chemical Formula 1, R ¹ and R ² represent hydrogen or a methyl group, R ³ represents a hydrogen or aryl group, an alkyl group having 4 or less carbon atoms, and n represents an integer of 1 to 30.) ] (In Chemical Formula 2, R ⁴ represents hydrogen or a methyl group, Q ¹ represents a divalent linking group, q represents an integer of 0 or 1, and M represents hydrogen or sodium, potassium, or NH _4. ) [Chemical 3] (In Chemical Formula 3, R ⁵ represents hydrogen or a methyl group, and Q ² represents CO.
Represents an O or CONH group, R ⁶ and R ⁷ represent a methyl group or an ethyl group, and m represents an integer of 1 to 3. ) 2. The monomer unit represented by the general formula 2 is 10% by weight or more and 80% by weight or less, and the monomer unit represented by the following general formula 4 is 10% by weight or more and 90% by weight or less.
An antistatic agent comprising a polymer containing at least the following range. Embedded image (In the formula 4, R ⁸ , R ⁹ _and R ¹⁰ represent hydrogen or a methyl group, and R ¹¹ and R ¹² represent hydrogen or an alkyl group having 10 or less carbon atoms, which may be the same or different, Also R
¹¹ and R ¹² may form a ring via a methylene group. Q ³ represents a COO or CONH group. p is 1 to 3
Represents an integer of 0. 3. The antistatic agent according to claim 1 or 2, which is three-dimensionally crosslinked by adding an epoxy curing agent to the antistatic agent.