JPH06313010A - High molecular compound and antistatic agent - Google Patents

Abstract

PURPOSE:To obtain a polymer containing a specific structural unit, having excellent antistatic properties and heat resistance and excellent in flexibility. CONSTITUTION:This high polymeric compound contains, as an essential unit, at least one kind of structural units A expressed by formula I [R1 is H or methyl; R2 is formula II; (1) and (m) are 0 or >=1; (n) is 0 or 1; 1<=1+m+n<=10; M1 and M2 are alkali metal of formula III; R3 to R5 are H, 1-18C alkyl or 1-2C hydroxyalkyl] and structural unit B expressed by formula IV [R is H or methyl; R is single bond, methyl, phenylene, COOCH2CH2, CONHC(CH3)2; M3 is alkali metal, etc.]. Further, optionally, the high polymeric compound is compounded with a water soluble melamine resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer compound useful as an antistatic agent for molded products of synthetic resins (for example, polyester, polyvinyl chloride, polycarbonate, polyacrylate, polyethylene, etc.), particularly polyester molded products, And an antistatic agent using the same.

[0002]

2. Description of the Related Art Molded articles of synthetic resins (for example, polyester, polyvinyl chloride, polycarbonate, polyacrylate, polyethylene, etc.) are used in all fields. However, in these synthetic resin molded products, for example, polyester films, the surface specific resistance value is 10 ¹⁴ to 10 ¹⁷ Ω / □, and they are generally very easily charged. Therefore, when it is used as a material for a magnetic recording medium or an electronic material, there is a problem that a problem of attracting foreign matter is likely to occur.

Therefore, as methods for imparting antistatic properties to synthetic resin moldings, conventionally known are methods of applying an antistatic coating and kneading an antistatic agent into a base polymer.

However, when a low molecular weight surfactant is used as the antistatic agent, bleeding of the antistatic agent on the surface of the molded article or drop of the antistatic agent due to abrasion or the like may cause deterioration of the antistatic property. . Further, when used for a polyester film, there is a problem of thermal decomposition and volatilization of the antistatic agent due to the high temperature treatment step at 220 ° C. or higher.

As a conventional polymer type antistatic agent, there is a cation type as seen in JP-A-3-188148, etc., but this has a problem that it is inferior in heat resistance and easily discolors. Further, in the polyalkylene glycol copolymer type as found in JP-A-3-84056 and the like, when formed into a thin film, the surface specific resistance value becomes 10 ¹¹ to 10 ¹² Ω / □ under low humidity, which is sufficient. Antistatic property cannot be obtained.

Therefore, in order to solve the problem of heat resistance and the like, it is considered to use an anion type antistatic agent, but a carboxylate cannot provide sufficient antistatic property. Further, although a conventionally known sulfonate, for example, a copolymer containing p-sodium styrene sulfonate as a main component, can provide sufficient antistatic property and heat resistance, but the resin itself is very rigid, Strain may occur during heat treatment, peeling from the substrate, followability may not be obtained in the stretching process of the polyester film, and whitening and cracks may occur, which may cause deterioration in antistatic properties.

An object of the present invention is to provide an antistatic agent which has an excellent antistatic property and which has sufficient heat resistance and flexibility (film followability) and which can solve the above problems, and an antistatic agent. It is to provide a useful polymer compound.

[0008]

As a result of intensive studies, the present inventors have found that the following phosphate-sulfonate type polymer compound has excellent antistatic properties, sufficient heat resistance and flexibility. Heading, completed the present invention.

That is, the present invention uses the formula (A)

[0010]

[Chemical 15]

[Wherein R ₁ is hydrogen or methyl, and R _{2 is}
Is the formula (II)

[0012]

[Chemical 16]

(Wherein l and m are 0 or an integer of 1 or more, n is 0 or 1, and 1 ≦ l + m + n ≦ 10), M ₁ and M ₂ are the same or different, and an alkali metal, Or formula (III)

[0014]

[Chemical 17]

(Wherein R ₃ , R ₄ and R ₅ are the same or different and represent hydrogen, alkyl having 1 to 18 carbons or hydroxyalkyl having 1 to 2 carbons). ] One or more structural units (A) represented by the formula (B)

[0016]

[Chemical 18]

(Wherein R ₆ is hydrogen or methyl, R _{7 is}
Is a single bond, methylene, phenylene, -COOCH ₂ CH
₂ - or _{-CONHC (CH 3) 2 CH 2} - and, M ₃
Represents an alkali metal or a group represented by the formula (III). )
The present invention relates to a polymer compound having one or more structural units (B) represented by as an essential structural unit, and an antistatic agent containing the polymer compound.

Further, the formula (I)

[0019]

[Chemical 19]

One or more of the monomers represented by the formula (wherein R ₁ , R ₂ , M ₁ and M ₂ have the same meanings as described above) (hereinafter referred to as the monomer (I)); (I
V)

[0021]

[Chemical 20]

[In the formula, R ₆ , R ₇ and M ₃ have the same meanings as described above.]
V))) or a combination of two or more of α-olefincarboxylic acid, a hydroxyl group-containing monomer, an amide group-containing monomer, an oxirane ring-containing monomer, or the formula (V).

[0023]

[Chemical 21]

(In the formula, R ₈ is hydrogen or methyl, and R _{9 is}
Is a polymer compound obtained by copolymerizing at least one monomer selected from monomers (hereinafter referred to as monomer (V)) represented by C 1 to C 12 alkyl, that is, structural unit (A ) One or more of
One or more structural units (B) and a formula (C)

[0025]

[Chemical formula 22]

[Wherein R_TenAnd R₁₁Are the same or different
R, hydrogen, methyl or carboxyl₁₂Is hydrogen,
Methyl or carboxymethyl, R₁₃Is -COOR
₁₄(R ₁₄Is hydrogen, alkyl having 1 to 12 carbons, and 1 carbon
~ 4 hydroxyalkyl, carboxyethylcarboni
Luoxyethyl, glycidyl or 1,2-epoxy
Chlorhexyl-4-methyl), -CONHCH₂
OR₁₅(R₁₅Is hydrogen or alkyl having 1 to 4 carbon atoms
), Glycidyloxymethyl, C 1-4 alkyl
Or phenyl optionally substituted with haloalkyl
Ru, alkoxy having 1 to 12 carbons or -OCOR
₁₆(R₁₆Is hydrogen or alkyl having 1 to 12 carbons
Is shown). ] One of structural units (C) represented by or
A polymer compound having two or more kinds of essential structural units, and
The present invention relates to an antistatic agent containing the polymer compound.

Further, the present invention relates to an antistatic agent containing the above polymer compound and a water-soluble melamine resin.

R ₃ , R ₄ and R ₅ in the present specification
The alkyl having 1 to 18 carbon atoms represented by may be linear or branched, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl ,
Octadecyl and the like can be mentioned. Examples of the hydroxyalkyl having 1 to 2 carbon atoms represented by R ₃ , R ₄ and R ₅ include
Examples include hydroxymethyl and hydroxyethyl. R
_The phenylene represented by ₇ may be o-, m-, or p-. The alkyl having 1 to 12 carbon atoms represented by R ₉ , R ₁₄ and R ₁₆ may be linear or branched, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl. , Decyl,
Dodecyl etc. are mentioned.

In the phenyl represented by R ₁₃ which may be substituted with alkyl having 1 to 4 carbons or haloalkyl, examples of the alkyl having 1 to 4 carbons include methyl, ethyl, propyl and butyl. Is 1 carbon atom substituted with fluorine, chlorine, bromine or iodine
~ 4 alkyl. Specific examples include chloromethylphenyl and fluoromethylphenyl. The alkoxy having 1 to 12 carbon atoms represented by R ₁₃ may be linear or branched, and specifically, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, Dodecyloxy and the like can be mentioned. Examples of the hydroxyalkyl having 1 to 4 carbon atoms represented by R ₁₄ include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and the like. The alkyl group having 1 to 4 carbon atoms represented by R ₁₅ may be linear or branched, and specific examples thereof include methyl, ethyl, propyl and butyl.

Monomer (I) used in the present invention
Is a phosphoric acid monomer containing an acryloyl group or a methacryloyl group, has a hydrophilic component (alkali metal salt or ammonium salt portion), has a heat-resistant phosphoric acid group, and has a (meth) phosphoric acid group It exhibits flexibility due to the (poly) alkyleneoxy groups present between the acryloyl groups. Further, since two salts can be added per one phosphoric acid group, it can have better hygroscopicity, water retention and antistatic properties than carboxylate and sulfonate having a similar structure. Further, by forming a salt, the counter ions easily transfer charges, and excellent antistatic properties can be exhibited even in an absolutely dry state.

The monomer (I) has the formula (I ')

[0032]

[Chemical formula 23]

An alkali metal salt or ammonium salt is added to a monomer represented by the formula (wherein R ₁ and R ₂ are as defined above) (hereinafter referred to as monomer (I ′)) by a conventionally known method. Obtained.

Table 1 shows typical examples of the monomer (I ').

[0035]

[Table 1]

Among the above, from the viewpoint of antistatic property, flexibility and reactivity, monomer PE, monomer A, monomer APE
Is preferred.

Here, in the polymer compound obtained by using the above monomer, the higher the proportion of the phosphate group portion, the better the antistatic property. That is, the larger the acid value of the monomer, the better the antistatic property.

The number of alkyleneoxy groups between the phosphate group and the (meth) acryloyl group, that is, the value of (l + m + n) in the formula (II) must be an integer of 1 or more and 10 or less. Yes, and preferably 4-6. (L +
The larger the value of m + n), the lower the Tg of the monomer,
The flexibility of the polymer compound obtained by using this monomer increases, but conversely the antistatic property and reactivity decrease. That is, when (l + m + n) is 0, the flexibility is poor (the followability in the stretching process of the polyester film is deteriorated), and when it exceeds 10, the antistatic property and the reactivity are deteriorated.

The above-mentioned monomer (I ') has an antistatic property without being neutralized with a base, but the effect of the antistatic property is improved by increasing the neutralization rate. An example thereof (in the case of the monomer M and the monomer PE) is shown in FIG. In FIG. 1, ◯ indicates the potassium salt of the monomer M, and ● indicates the potassium salt of the monomer PE.

Examples of the salt formed on the phosphoric acid moiety of the monomer (I ') include alkali metal salts and ammonium salts. Examples of the alkali metal salt include lithium salt,
Examples thereof include sodium salt, potassium salt, rubidium salt, and cesium salt.

Examples of the ammonium salt represented by the formula (III) include ammonia, methylamine, ethylamine, n-butylamine, dimethylamine, diethylamine, dibutylamine, trimethylamine, triethylamine, tri-n-butylamine, dimethylmonoethanolamine. , Triethanolamine, dimethylstearylamine, methyldilaurylamine and the like.

In the case of an alkali metal salt, the influence of the counterion depends on the ionization tendency of the alkali metal, and the magnitude of its surface resistivity is rubidium ≦ potassium <sodium <cesium <lithium. In the case of ammonium salt, the surface resistivity is triethanolamine <dimethylmonoethanolamine <triethylamine = ammonia. The larger the number of hydroxyalkyl groups in the nitrogen substituent, the smaller the surface resistivity and the antistatic property. Will get better. When the total number of carbon atoms in the three nitrogen substituents exceeds 20, the polyester film has good followability in the stretching step, but on the contrary, antistatic property is deteriorated.

Monomer (IV) used in the present invention
Is a sulfonic acid monomer, which has blocking resistance and heat resistance, and has high film strength when formed into a film or the like. Further, as in the case of the monomer (I), by forming a salt, the counter ions easily transfer charges, and excellent antistatic properties can be exhibited even in an absolutely dry state.

The monomer (IV) has the formula (IV ')

[0045]

[Chemical formula 24]

An alkali metal salt or ammonium salt is added to a monomer represented by the formula (wherein R ₆ and R ₇ are as defined above) (hereinafter referred to as monomer (IV ′)) by a conventionally known method. Obtained. Here, examples of the alkali metal salt or ammonium salt are the same as those mentioned above.

As a typical example of the monomer (IV '), o
-Styrene sulfonic acid, m-styrene sulfonic acid, p-
Examples thereof include styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, 2-sulfoethyl methacrylate and acrylamido-t-butyl sulfonic acid. Of these, o-styrene sulfonic acid, m-styrene sulfonic acid, p-styrene sulfonic acid, 2-sulfoethyl methacrylate, and acrylamido-t-butyl sulfonic acid are preferable from the viewpoints of antistatic property and copolymerizability.

By using the monomer (I) and the monomer (IV) in combination, a polymer compound having excellent antistatic property, heat resistance and flexibility can be obtained.

Monomer (I) and monomer (IV) are
Furthermore, a copolymer can be prepared with at least one monomer selected from α-olefincarboxylic acid, hydroxyl group-containing monomer, amide group-containing monomer, oxirane ring-containing monomer, and monomer (V).

As the α-olefin carboxylic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, mono-β-acryloyloxyethyl succinic acid (NK ester A-SA, manufactured by Shin-Nakamura Chemical Co., Ltd.) ),
Mono-β-methacryloyloxyethyl succinic acid (NK
Ester SA, manufactured by Shin-Nakamura Chemical Co., Ltd., etc., and acrylic acid, mono-β-, from the viewpoint of reactivity and flexibility.
Acryloyloxyethyl succinic acid and mono-β-methacryloyloxyethyl succinic acid are preferred.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate.
Examples thereof include hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. From the viewpoint of reactivity and flexibility, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate are preferable.

Examples of the amide group-containing monomer include N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide and N-butoxymethylmethacrylamide. From the viewpoints of reactivity and solubility, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide and N-methoxymethylmethacrylamide are preferred.

As the oxirane ring-containing monomer, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, alicyclic epoxy monomer [1,
2-epoxycyclohexyl-4-methyl acrylate (Cyclomer A-200, manufactured by Daicel Chemical Industries, Ltd.),
1,2-epoxycyclohexyl-4-methylmethacrylate (Cyclomer M-100, Daicel Chemical Industries, Ltd.)
Etc.] and the like, and glycidyl methacrylate and alicyclic epoxy monomers are preferable from the viewpoint of reactivity and flexibility.

The monomer (V) is a (meth) acrylic acid ester in which the number of carbon atoms of the alkyl in the alkyl ester portion is 1 to 12, and specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate. , N-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate and the like, and from the viewpoint of copolymerization, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, N-butyl acrylate and n-butyl methacrylate are preferred.

Other monomers copolymerizable with the monomer (I) and the monomer (IV) include styrene and α
-Aromatic monomers such as methylstyrene, 4-n-butylstyrene and α-chloromethylstyrene; vinyl formate,
Vinyl-based monomers such as vinyl acetate and vinyl propionate; vinyl-ether-based monomers such as methyl vinyl ether, butyl vinyl ether, and lauryl vinyl ether, and the like, which are substituted with a part or all of the (meth) acrylic acid ester of the monomer (V). You can also

The ratio of each component in the polymer compound obtained by copolymerizing the above-mentioned monomers is usually the monomer (I).
Component [structural unit (A)] is more than 0 wt% and less than 100 wt%, monomer (IV) component [structural unit (B)] is more than 0 wt% and 35 wt% or less, and structural unit (A) and structure The total amount of the units (B) is 50 to 100% by weight, and the monomer components other than the monomer (I) and the monomer (IV) [α
-Olefin carboxylic acid, hydroxyl group-containing monomer, amide group-containing monomer, oxirane ring-containing monomer, monomer (V), etc .: structural unit (C)] is 50 to 0% by weight.
Preferably, the structural unit (A) is 40 to 90% by weight, the structural unit (B) is 10 to 30% by weight, and the total of the structural units (A) and (B) is 70 to 100% by weight, and the structural unit (C) is 30.
~ 0% by weight. That is, the total of the structural unit (A) and the structural unit (B) is preferably 50% by weight or more from the viewpoint of antistatic property, and the structural unit (B) is 35% by weight from the viewpoint of flexibility. The following is preferable.

The number average molecular weight of the above polymer compound is usually
100,000-1,000,000, preferably 100,000-600,000
Is.

In the present invention, the above polymer compound may be further crosslinked to improve water resistance. In that case, it is premised that a copolymer of the monomer (I) and the monomer (IV) and a hydroxyl group-containing monomer and / or an amide group-containing monomer is used, and the crosslinking agent is a reaction rate, a crosslinking density, or a compatibility. From the point of view, the water-soluble melamine resin is most desirable.

As the water-soluble melamine resin, N-methylol melamine, methoxymethyl melamine, butylated melamine (partially alkyl-modified) and the like are preferable, but N-methylol melamine is most preferable from the viewpoint of water solubility. Is.

In this case, the melamine resin is used in an amount of 10 to 30% by weight, preferably 5 to 20% by weight of the above copolymer, and an ordinary acid catalyst (for example, ammonium monophosphate, ammonium chloride, p-toluene sulfone) is used. It is also possible to crosslink by using 1 to 3% by weight of the above copolymer in combination.

As the structure of the cross-linked polymer compound, for example, when N-methylol melamine is used as the cross-linking agent, in addition to the structural units (A), (B) and (C), for example, the formula (D)

[0062]

[Chemical 25]

(In the formula, R represents hydrogen or methyl, and R ₁₇ represents alkyl having 1 to 4 carbon atoms.) And the like including the structural unit (D).

The alkyl having 1 to 4 carbon atoms represented by R ₁₇ may be linear or branched, and specific examples thereof include methyl, ethyl, propyl and butyl.

The number average molecular weight of the above-mentioned crosslinkable polymer compound is usually several million or more.

Copolymerization of the above monomers can be carried out by a conventionally known method. That is, solution polymerization, emulsion polymerization,
Although it is carried out by suspension polymerization, bulk polymerization, etc., solution polymerization and emulsion polymerization are preferred from the viewpoint of reactivity and stability. Also,
Polymerization initiators (for example, persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, hydrogen peroxide, peroxides such as benzoyl peroxide and lauroyl peroxide, azoisobutyronitrile, azoisovaleronitrile Azo-based compounds such as) and the like can also be used.

In addition to the above-described polymer compound, a wetting agent or the like can be added to the antistatic agent of the present invention, if necessary. Examples of the wetting agent include anions, nonionics, and amphoteric surfactants, and those that adjust the surface tension of the aqueous solution containing the antistatic agent to a desired value to promote wetting of the synthetic resin molded product are available. preferable. (For example, when applied to polyester film, the surface tension is 40 dy.
It is preferably n / cm or less. Specific examples thereof include polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfonate, betaine type surfactant and the like.

Further, an ultraviolet absorber, a pigment, an organic filler, an inorganic filler, a lubricant, an antiblocking agent and the like may be used in combination unless the object of the present invention is impaired.

The antistatic agent in the present invention is applied to the resin molded product by a commonly used method. That is, an antistatic layer is formed by applying an aqueous solution containing an antistatic agent to a synthetic resin molded product, drying it, and optionally further thermally curing it. In particular, for a polyester film, it is preferable to apply the aqueous solution to the film surface immediately after the melt extrusion of the polyester and casting, or immediately after stretching in either one of the longitudinal and transverse directions. Usually, the aqueous solution is applied on a uniaxially stretched film stretched in the machine direction, and then transversely stretched while being heated, and then the film is heat-set at a high temperature, and the antistatic layer is dried and further heat-cured. Let

At this time, as a method for applying the antistatic agent-containing aqueous solution onto the synthetic resin molded product, a conventionally known method can be applied, for example, a spray coating method, an air knife method,
A reverse coat method, a Keith coat method, a gravure coat method, a Meyer bar method, a roll brush method, etc. are used.

The concentration of the aqueous solution containing the antistatic agent applied varies depending on the coating method, but is usually 0.5 to
It is 50% by weight, preferably 1 to 10% by weight. The coating amount is preferably 1 to 20 g / m ² as a wet amount.

[0072]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
In addition, "part" in Examples and Comparative Examples means "part by weight".

Example 1 Acid phosphooxyethyl methacrylate (monomer M, acid value 519.8 mg) was placed in a 3-liter 4-necked flask.
KOH / g; trade name Hosmer M, Unichemical Co., Ltd.) 9
8 parts, sodium p-styrene sulfonate (monomer NaSS,
After adding 42 parts of trade name Spinomer NaSS, manufactured by Tosoh Corp.) and 2000 parts of water, 37.8 parts of sodium hydroxide was added for neutralization, and 48 parts of ethyl acrylate and 12 parts of 2-hydroxyethyl acrylate were added. , Stirring 8
The temperature is raised to 5 ° C, and 4 parts of potassium persulfate is added to 85
The reaction was carried out for 4 hours while maintaining the temperature at 0 ° C to obtain the polymer compound of the present invention. Number average molecular weight 380000.

Intrinsic viscosity (orthochlorophenol, 35
℃) 0.66 polyethylene terephthalate, 20 ℃
Was melt-extruded onto a rotary cooling drum maintained at a temperature of 0.5 to give an unstretched film, and the unstretched film was coated with 0.5 g / m ² of an aqueous solution of the above polymer compound by a Keith coat method to obtain an unstretched coated polyester film. . Further, the unstretched coated polyester film was passed through a preheat zone of 90 ° C., stretched 2 times in the transverse direction at 100 ° C., and further stretched 5 times in the longitudinal direction between a pair of rolls at 85 ° C. having different peripheral speeds. Then, heat setting was performed at 200 to 210 ° C. to obtain a stretched coated polyester film (film thickness: 0.05 μm).

Example 2 A polymer compound was obtained in the same manner as in Example 1 except that 42 parts of p-styrenesulfonate ammonium was used instead of 42 parts of monomer NaSS. Number average molecular weight 260000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 3 A polymer compound was obtained in the same manner as in Example 1 except that 42 parts of potassium p-styrenesulfonate was used instead of 42 parts of the monomer NaSS. Number average molecular weight 410000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 4 98 parts of acid phosphooxyethyl acrylate (monomer A, acid value 572 mg KOH / g; trade name Light Ester PA, manufactured by Kyoeisha Chemical Co., Ltd.) was used in place of 98 parts of monomer M, and sodium hydroxide 37. A polymer compound was obtained in the same manner as in Example 1 except that 41.7 parts of sodium hydroxide was used instead of 8 parts. Number average molecular weight 34,000
0. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 5 Acid phosphooxypolyoxyethylene glycol monomethacrylate (monomer PE, acid value 319.2 mg KOH / g; trade name Phosmer P instead of 98 parts of monomer M)
E, manufactured by Uni Chemical Co., Ltd., 98 parts, and sodium hydroxide 23.3 instead of sodium hydroxide 37.8 parts
A polymer compound was obtained in the same manner as in Example 1 except that parts were used. Number average molecular weight 280000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 6 98 parts of acid phosphooxypolyoxyethylene glycol monomethacrylate (monomer LPE, acid value 192.2 mg KOH / g) was used in place of 98 parts of the monomer M, and 37.8 parts of sodium hydroxide was used in place of the hydroxide. A polymer compound was obtained in the same manner as in Example 1 except that 14.0 parts of sodium was used. Number average molecular weight of 180,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 7 A polymer compound was obtained in the same manner as in Example 1 except that 42 parts of sodium vinyl sulfonate (monomer SVS) was used instead of 42 parts of monomer NaSS. Number average molecular weight 12000
0. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 8 A polymer compound was obtained in the same manner as in Example 1 except that 42 parts of 2-sodium sulfoethyl methacrylate (monomer SEM) was used instead of 42 parts of monomer NaSS. Number average molecular weight 370000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 9 A polymer compound was obtained in the same manner as in Example 1 except that 42 parts of sodium m-styrenesulfonate (monomer M-NaSS) was used in place of 42 parts of the monomer NaSS. Number average molecular weight 2
90,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 10 A polymer compound was obtained in the same manner as in Example 1 except that 42 parts of sodium o-styrenesulfonate (monomer O-NaSS) was used in place of 42 parts of the monomer NaSS. Number average molecular weight 2
60,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 11 42 parts of sodium allylsulfonate (monomer SSA) was used instead of 42 parts of monomer NaSS, and the reaction time was from 4 hours to 4 hours.
A polymer compound was obtained in the same manner as in Example 1 except that the time was changed to 8 hours. Number average molecular weight 160000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 12 42 parts of acrylamido-t-butylsulfonic acid (monomer TBAS, molecular weight 207) were used instead of 42 parts of monomer NaSS, and 45.9 parts of sodium hydroxide were used instead of 37.8 parts of sodium hydroxide. A polymer compound was obtained in the same manner as in Example 1 except that the above was used. Number average molecular weight 31,000
0. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 13 A polymer compound was obtained in the same manner as in Example 1 except that 12 parts of acrylic acid was used instead of 12 parts of 2-hydroxyethyl acrylate. Number average molecular weight 400000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 14 N instead of 12 parts of 2-hydroxyethyl acrylate
-A polymer compound was obtained in the same manner as in Example 1 except that 12 parts of methylolacrylamide was used. Number average molecular weight 580000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 15 A polymer compound was obtained in the same manner as in Example 1 except that 12 parts of glycidyl methacrylate was used instead of 12 parts of 2-hydroxyethyl acrylate. Number average molecular weight 49
0000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 16 In a 3-liter four-necked flask, 140 parts of Monomer M,
After adding 60 parts of monomer NaSS and 2000 parts of water, 54 parts of sodium hydroxide was added to neutralize and 85 ° C with stirring.
The temperature was raised to 4 parts, 4 parts of potassium persulfate was added, and the reaction was carried out for 4 hours while maintaining the temperature at 85 ° C to obtain the polymer compound of the present invention. Number average molecular weight 320,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 17 A polymer compound was obtained in the same manner as in Example 16 except that 60 parts of ammonium p-styrenesulfonate was used instead of 60 parts of monomer NaSS. Number average molecular weight 210000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 18 A polymer compound was obtained in the same manner as in Example 16 except that 60 parts of potassium p-styrenesulfonate was used in place of 60 parts of the monomer NaSS. Number average molecular weight 410000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 19 A polymer compound was prepared in the same manner as in Example 16 except that 140 parts of the monomer A was used instead of 140 parts of the monomer M and 59.4 parts of sodium hydroxide was used instead of 54 parts of sodium hydroxide. Obtained. Number average molecular weight 350,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 20 A polymer compound was prepared in the same manner as in Example 16 except that 140 parts of monomer PE was used instead of 140 parts of monomer M, and 33.2 parts of sodium hydroxide was used instead of 54 parts of sodium hydroxide. Obtained. Number average molecular weight 280000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 21 A polymer compound was obtained in the same manner as in Example 16 except that 140 parts of the monomer LPE was used instead of 140 parts of the monomer M, and 20 parts of sodium hydroxide was used instead of 54 parts of sodium hydroxide. . Number average molecular weight 120,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 22 A polymer compound was obtained in the same manner as in Example 16 except that 60 parts of monomer SVS was used instead of 60 parts of monomer NaSS. Number average molecular weight 150,000. Example 1 using this
A coated polyester film was obtained in the same manner as in.

Example 23 A polymer compound was obtained in the same manner as in Example 16 except that 60 parts of monomer SEM was used instead of 60 parts of monomer NaSS. Number average molecular weight 340000. Example 1 using this
A coated polyester film was obtained in the same manner as in.

Example 24 A polymer compound was obtained in the same manner as in Example 16 except that 60 parts of monomer M-NaSS was used instead of 60 parts of monomer NaSS. Number average molecular weight 260000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 25 A polymer compound was obtained in the same manner as in Example 16 except that 60 parts of monomer O-NaSS was used instead of 60 parts of monomer NaSS. Number average molecular weight 210000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 26 60 parts of monomer SSA was used in place of 60 parts of monomer NaSS, and the reaction time was changed from 4 hours to 48 hours.
A polymer compound was obtained in the same manner as in Example 16. Number average molecular weight 100,000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 27 A polymer compound was prepared in the same manner as in Example 16 except that 60 parts of monomer TBAS was used instead of 60 parts of monomer NaSS and 65.6 parts of sodium hydroxide was used instead of 54 parts of sodium hydroxide. Obtained. Number average molecular weight 270000. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 28 A polymer compound was obtained in the same manner as in Example 1, except that 133 parts of the monomer M was used instead of 98 parts of the monomer M, and 7 parts of the monomer NaSS was used instead of 42 parts of the monomer NaSS. Number average molecular weight 350,000. Example 1 using this
A coated polyester film was obtained in the same manner as in.

Example 29 To 100 parts of the polymer compound obtained in Example 1, 2 parts of hexamethylolmelamine (HMM) and 0.2 part of p-toluenesulfonic acid (PTS) were added to prepare a crosslinked polymer. A molecular compound was obtained, and using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 30 HMM2 was added to 100 parts of the polymer compound obtained in Example 7.
And 0.2 parts of PTS were added to obtain a cross-linked polymer compound. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 31 HMM2 was added to 100 parts of the polymer compound obtained in Example 8.
And 0.2 parts of PTS were added to obtain a cross-linked polymer compound. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 32 HMM2 was added to 100 parts of the polymer compound obtained in Example 9.
And 0.2 parts of PTS were added to obtain a cross-linked polymer compound. Using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 33 To 100 parts of the polymer compound obtained in Example 10 was added HMM.
2 parts and 0.2 parts of PTS were added to obtain a cross-linked polymer compound, and using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 34 100 parts of the polymer compound obtained in Example 11 was added with HMM.
2 parts and 0.2 parts of PTS were added to obtain a cross-linked polymer compound, and using this, a coated polyester film was obtained in the same manner as in Example 1.

Example 35 To 100 parts of the polymer compound obtained in Example 12 was added HMM.
2 parts and 0.2 parts of PTS were added to obtain a cross-linked polymer compound, and using this, a coated polyester film was obtained in the same manner as in Example 1.

Comparative Example 1 Intrinsic viscosity (orthochlorophenol, 35 ° C.) 0.66
Polyethylene terephthalate of was melt-extruded on a rotary cooling drum maintained at 20 ° C. to obtain an unstretched film, which was stretched in the same manner as in Example 1 to obtain a polyester film having no coating layer.

Comparative Example 2 To a 3 liter four-necked flask, 140 parts of p-styrenesulfonic acid sodium and 2000 parts of water were added and sufficiently dissolved with stirring, and then 48 parts of ethyl acrylate and 12 parts of 2-hydroxyethyl acrylate were added. 85 ° C with stirring
The temperature was raised up to. Then, 4 parts of potassium persulfate was added, and the reaction was carried out for 4 hours while maintaining the temperature at 85 ° C. to obtain a polymer compound. Using this, a coated polyester film was obtained in the same manner as in Example 1.

With respect to the coated polyester films (before and after stretching) obtained in the above Examples and Comparative Examples, the surface specific resistance value, transparency and heat resistance were measured according to the following methods. Regarding the surface resistivity, transparency and heat resistance of the coated polyester film before stretching, an unstretched coated polyester film was dried at 120 ° C. for 1 minute and then heat treated at 220 ° C. for 30 seconds (film thickness 0 0.5 μm). The results are shown in Table 2.
Shown in.

Surface resistivity The film was allowed to stand at 25 ° C. and 50% RH for 24 hours, and then measured using a trace ammeter TR-8601-TR-42 (measuring unit) (manufactured by Takeda Riken Co., Ltd.). Transparency The transparency of the film (participating in the followability of the antistatic agent) was visually measured and judged according to the following criteria. [1: transparent, 2: slightly cloudy, 3: partially cloudy, 4:
When the thermal decomposition temperature of the film was measured, the thermal decomposition temperature of all the samples was 200 ° C. or higher, and neither thermal decomposition nor volatilization in the high temperature treatment step was observed.

[0113]

[Table 2]

As can be seen from Table 2, the polymer compound of the present invention has an excellent antistatic property, and contains p-styrene sulfonate sodium, which is a conventionally known anionic polymer type antistatic agent, as a main component. It is much more film-following than the copolymer. It also has sufficient heat resistance.

[0115]

INDUSTRIAL APPLICABILITY The polymer compound of the present invention has excellent antistatic properties, heat resistance, and flexibility, and is useful as an antistatic agent. Therefore, the molded product obtained by applying the polymer compound and the antistatic agent of the present invention has both excellent antistatic property and heat resistance, and particularly, magnetic tapes such as video tapes, audio tapes, computer tapes and floppy disks. It is useful as a base material for recording media and as a base material for general industrial films such as membranes, telephone cards, labels, microfilms, diazo films and OHP films.

[Brief description of drawings]

FIG. 1 is a graph showing the effect of antistatic property as the neutralization rate increases.

Claims (6)

[Claims] 1. Formula (A): [In the formula, R ₁ represents hydrogen or methyl, and R ₂ represents formula (II): (Wherein, 1 and m are 0 or an integer of 1 or more, n is 0 or 1, and 1 ≦ l + m + n ≦ 10), a group represented by M ₁
And M ₂ are the same or different and are an alkali metal, or are represented by the formula (III) (In the formula, R ₃ , R ₄ and R ₅ are the same or different,
Hydrogen, alkyl having 1 to 18 carbons or hydroxyalkyl having 1 to 2 carbons) is shown. ] One or more structural units (A) represented by the formula (B) (In the formula, R ₆ is hydrogen or methyl, R ₇ is a single bond, methylene, phenylene, —COOCH ₂ CH ₂ — or —
CONHC (CH ₃ ) ₂ CH ₂ —, M ₃ represents an alkali metal or a group represented by the formula (III). ) A polymer compound having one or more structural units (B) represented by the formula (1) as essential structural units. 2. Formula (I): [Wherein R ₁ is hydrogen or methyl, and R ₂ is of the formula (II): (Wherein, 1 and m are 0 or an integer of 1 or more, n is 0 or 1, and 1 ≦ l + m + n ≦ 10), a group represented by M ₁
And M ₂ are the same or different and are an alkali metal, or have the formula (III) (In the formula, R ₃ , R ₄ and R ₅ are the same or different,
Hydrogen, alkyl having 1 to 18 carbons or hydroxyalkyl having 1 to 2 carbons) is shown. ] One or more of the monomers represented by
V) [Chemical 8] (In the formula, R ₆ is hydrogen or methyl, R ₇ is a single bond, methylene, phenylene, —COOCH ₂ CH ₂ — or —
CONHC (CH ₃ ) ₂ CH ₂ —, M ₃ represents an alkali metal or a group represented by the formula (III). ) One or more of the monomers represented by the formula (1), and further an α-olefincarboxylic acid, a hydroxyl group-containing monomer, an amide group-containing monomer, an oxirane ring-containing monomer, or a compound of the formula (V): (In the formula, R ₈ is hydrogen or methyl, and R ₉ is 1 to 1 carbon atoms.
A polymer compound obtained by copolymerizing at least one monomer selected from the monomers represented by 12). 3. Formula (A):[In the formula, R₁Is hydrogen or methyl, R₂Is of formula (II)(In the formula, l and m are 0 or an integer of 1 or more, and n is 0 or
Or 1, 1 ≦ l + m + n ≦ 10) is a group represented by M₁
And M₂Are the same or different, alkali metal, or
Formula (III):(In the formula, R₃, R_FourAnd R_FiveAre the same or different,
Hydrogen, alkyl having 1 to 18 carbons, or alkyl having 1 to 2 carbons
A group represented by (indicating hydroxyalkyl) is shown. 〕so
One or more structural units (A) represented, and a formula
(B)(In the formula, R₆Is hydrogen or methyl, R₇Is a single bond,
Tylene, phenylene, -COOCH₂CH₂-Or-
CONHC (CH₃)₂CH₂− To M₃Is alkaline gold
A genus or a group represented by formula (III) is shown. )
One or more kinds of building units (B) and a compound of the formula (C):[In the formula, R_TenAnd R₁₁Are the same or different and
Chill or carboxyl, R₁₂Is hydrogen, methyl or
Carboxymethyl, R₁₃Is -COOR₁₄(R ₁₄Is water
Elemental, C1-C12 alkyl, C1-C4 hydro
Xyalkyl, carboxyethylcarbonyloxyethyl
Glycidyl or 1,2-epoxycyclohexyl
-4-methyl), -CONHCH₂OR₁₅(R₁₅
Represents hydrogen or alkyl having 1 to 4 carbon atoms), glycy
Diloxymethyl, alkyl having 1 to 4 carbons or halo
Phenyl optionally substituted with alkyl, having 1 to 1 carbon atoms
12 alkoxy or -OCOR₁₆(R₁₆Is hydrogen
Represents an alkyl having 1 to 12 carbon atoms). ]]
One or more of the structural units (C)
The polymer compound according to claim 2, wherein 4. An antistatic agent comprising the polymer compound according to claim 1. 5. An antistatic agent comprising the polymer compound according to claim 2 or 3. 6. The antistatic agent according to claim 5, further comprising a water-soluble melamine resin.