JP2925723B2 - Method for producing acrylamide copolymer - Google Patents

Description

The present invention relates to a method for producing an acrylamide copolymer and a method for producing an intermediate useful for the acrylamide copolymer. More specifically, the present invention relates to a method for producing an acrylamide copolymer which can be suitably used as an antistatic agent, and a method for producing an intermediate useful therefor.

[Prior art] Thermoplastic resins such as polyolefin resins, ABS resins, and vinyl chloride resins have been widely used as materials for packaging and automobile parts as films and bags, but these thermoplastic resins have been widely used. Resins generally have high electrical resistance,
There is a serious drawback that it is easily charged by friction and sucks dust and the like.

Therefore, in recent years, as a method of imparting antistatic properties to a thermoplastic resin, for example, (a) a method in which an antistatic agent is applied to the resin surface and then dried, and (b) an internally added antistatic agent is kneaded into the resin. There are proposed a method, (c) a method of applying a silicone compound to a resin surface, and (d) a method of modifying the resin itself.

However, in the above method (a), a surfactant solution is used as an antistatic agent, but such an antistatic agent is easily removed by washing, so that a permanent antistatic property is imparted. There is a drawback that you can not.

In the method (b), glycerin fatty acid ester, sorbitan fatty acid ester, alkyldiethanolamide, sodium alkylbenzenesulfonate, quaternary salt of alkylimidazole, and the like are used as the internally added antistatic agent. When using these internally added antistatic agents, even if the antistatic agent on the surface is lost due to washing, the new antistatic agent bleeds sequentially from the inside, so the antistatic agent It has the advantage that its properties last for a relatively long time. However, such an internally added type antistatic agent requires a long time to recover its antistatic property after washing, and when the antistatic agent bleeds excessively, tackiness occurs, and In addition to the drawback that dust and the like tend to adhere, these antistatic agents are of low molecular weight, so they are volatilized by heat during molding at high temperatures, for example. The disadvantage was the cost and it was difficult to adjust the effective amount.

In order to solve the drawbacks of the internally added antistatic agent, polymethyl methacrylate in which 20 to 80 mol% of methoxy groups are modified with diethanolamine (Japanese Patent Laid-Open No.
170603), a graft copolymer of alkoxypolyethylene glycol methacrylate (Japanese Patent Publication No. 58-39860), and a styrene-maleic anhydride copolymer which is imide-modified and then quaternized and cationized. No. 29820), a comb-type copolymer of a high-molecular-weight monomer obtained by converting a terminal carboxyl group of polymethyl methacrylate having a carboxyl group into a methacryloyl group with glycidyl methacrylate, and an aminoalkyl acrylate or acrylamide; Polymer compounds having an antistatic functional group such as graded cation-modified products (JP-A-62-121717) are provided. However, all of the above-mentioned polymer compounds have disadvantages such as lowering of physical properties of the resin such as transparency and high elongation, and insufficient antistatic properties and durability.

In the method (c), the antistatic property is maintained semipermanently, but the silicone compound is expensive and the working efficiency is poor, so that it is disadvantageous in terms of cost.

The method (d) is a method of introducing a hydrophilic group into a resin. However, in order to impart sufficient antistatic properties, it is necessary to introduce a considerable amount of a hydrophilic group. When a hydrophilic group is introduced as described above, there is a possibility that the moisture absorption resistance of the resin itself and the mechanical properties are reduced.

[Problems to be Solved by the Invention] In view of the above-mentioned conventional technology, the inventors of the present invention not only have excellent semi-permanent antistatic properties but also hardly reduce the physical properties of the resin. As a result of intensive studies to find a compound that can be suitably used as an antistatic agent that does not easily cause blocking of a molded article, a method for producing a compound having all of the above physical properties was finally found, and the present invention was completed. .

[Means for Solving the Problems] The present invention provides an ethylene structural unit represented by the formula: CH ₂ —CH ₂ of 65 to 97 mol%, a general formula: (Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms) 1 to 15 mol% of an acrylate structural unit represented by the formula: A linearly and irregularly arranged copolymer comprising 1 to 30 mol% of acrylic acid structural units represented by the following general formula: (Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴
Wherein each represents an alkyl group having 1 to 4 carbon atoms), characterized by reacting a diamine represented by the formula: 65 to 97 mol% of an ethylene structural unit represented by CH ₂ —CH ₂ , a general formula: (Wherein R ¹ is as defined above) and 1 to 15 mol% of an acrylate structural unit represented by the following general formula: (Wherein R ² , R ³ and R ⁴ are the same as described above) Acrylamide copolymer having a weight average molecular weight of 1,000 to 50,000, which is linearly and irregularly composed of 1 to 30 mol% of acrylamide structural units And the formula: CH ₂ —CH ₂ , 65-97 mol% of ethylene structural units represented by the general formula: (Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms) 1 to 15 mol% of an acrylate structural unit represented by the following general formula: (Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴
Each represents an alkyl group having 1 to 4 carbon atoms), and an acrylamide-based copolymer having a weight average molecular weight of 1,000 to 50,000, which is linearly and irregularly composed of 1 to 30 mol% of acrylamide structural units represented by the general formula: R ⁵ —Χ (wherein, R ⁵ is an arylalkyl group having 7 to 12 carbon atoms or an alicyclic alkyl group having 6 to 12 carbon atoms, Χ is a halogen atom, CH
₃ OSO ₃ or C ₂ H ₅ OSO ₃ ) is reacted with an alkylating agent represented by the formula: CH ₂ —CH ₂ , 65 to 97 mol% of ethylene structural units represented by the general formula: (Wherein R ¹ is the same as described above) 1 to 15 mol% of an acrylate structural unit represented by the general formula: (Wherein, R ² , R ³ , R ⁴ and R ⁵ are the same as described above). An acrylamide system having a weight average molecular weight of 1,000 to 50,000, which is linearly and irregularly composed of 1 to 30 mol% of acrylamide structural units represented by The present invention relates to a method for producing a copolymer.

[Actions and Examples] The raw material of the acrylamide copolymer intended for the present invention is not particularly limited. For example, ethylene (C ₂
(Partial) hydrolyzate of a copolymer comprising H ₄ ) and an acrylate represented by the general formula (I): CH ₂ CHCHCOOR ¹ (I) (wherein R ¹ is the same as described above) is used. Is preferred. Such a copolymer can be easily obtained by copolymerizing ethylene and the acrylate represented by the general formula (I) by a high-pressure polymerization method.

The ratio of the ethylene structural unit derived from ethylene to the acrylate structural unit derived from the acrylate represented by the general formula (I) is determined based on the ethylene structural unit and the acrylate structural unit of the finally obtained acrylamide copolymer. The ratio with the acrylamide structural unit will be determined.

The ethylene-acrylate copolymer can be used as it is, but usually has a high molecular weight.
The molecular weight is preferably reduced by a known method, for example, a decomposition method in which hydrolysis is performed simultaneously with hydrolysis under high temperature and high pressure in the presence of water.

At this time, the general formula derived from the acrylate: (Wherein R ¹ is the same as described above), and a part of the acrylate structural unit represented by the formula is obtained by hydrolysis. Acrylic acid structural unit represented by

In order to prepare a copolymer having a reduced molecular weight, a reaction temperature of 150 to 500 ° C. and a reaction pressure of 3
What is necessary is just to thermally decompose under conditions of ~ 500 kg / cm < ² >.

In the present invention, the ratio of the acrylic acid structural unit can be arbitrarily adjusted by appropriately adjusting the amount of water charged, the reaction temperature, the reaction pressure, and the reaction time.

As a specific example of the degradation method, for example,
No. 57295, JP-A-53-65389, JP-A-60-7900
No. 8, JP-A-60-79015 and the like.

Since the acrylamide copolymer of the present invention impairs commercial value when colored, as a raw material used in the present invention, for example, a product obtained by the method exemplified in JP-A-60-79008 is used. It is preferably used.

The ethylene-acrylate-acrylic acid copolymer thus obtained can be used as a raw material of the acrylamide copolymer of the present invention.

In order for the acrylamide copolymer obtained by the production method of the present invention to have a preferable antistatic property, the ratio and the molecular weight of the constituent units of the ethylene-acrylate-acrylic acid copolymer as a raw material are as follows: It is necessary to be as follows.

That is, the ratio of the ethylene structural unit is 65 to 97 mol%. When the proportion of the ethylene structural unit is less than 65 mol%, the softening point of the acrylamide-based copolymer intended for the present invention becomes low, and tackiness or stickiness occurs when blended in a thermoplastic resin. If it exceeds 97 mol%, the antistatic property of the acrylamide copolymer becomes too small. In the present invention,
The proportion of the ethylene structural unit is particularly preferably from 85 to 97 mol% from the viewpoint of the balance between the softening point and the antistatic property. The ratio of the acrylate structural unit is 1 to
15 mol%. When the proportion of the acrylate structural unit exceeds 15 mol%, the obtained acrylamide-based copolymer has a low softening point, and tackiness or stickiness occurs when blended in a thermoplastic resin. In the present invention, since the acrylate structural unit is contained,
The toughness and impact resistance are imparted when blended in a thermoplastic resin. In the present invention, the ratio of the acrylate structural unit is 1 in view of the balance between the softening point and the toughness and impact resistance. 1515 mol%, especially 3-7 mol%.

In the acrylate structural unit, R ¹ has 1 to ¹ carbon atoms.
4 alkyl group. Specific examples of such R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Examples thereof include an n-butyl group and an i-butyl group, and these groups may be mixed in one molecule. Among these groups, a methyl group and an ethyl group are particularly preferable from the viewpoint of maintaining the softening point of the acrylamide copolymer obtained by the present invention.

In the present invention, the acrylic acid structural unit is converted into an acrylamide structural unit having a tertiary amino group, and the tertiary amino group is subsequently converted into a quaternary cationic group having antistatic properties.

Therefore, the ratio of the acrylic acid structural unit is an important factor in the present invention. The preferred proportion of the acrylic acid structural unit is 1 to 30 mol%. When the proportion of the acrylic acid structural unit is less than 1 mol%, the antistatic property of the acrylamide copolymer obtained by the present invention becomes too small, and when it exceeds 30 mol%, the present invention When the obtained acrylamide-based copolymer is mixed with a thermoplastic resin, hygroscopicity is generated. In addition,
In the present invention, the proportion of the acrylamide structural unit is 3 from the viewpoint of the balance between the antistatic property and the hygroscopicity.
It is particularly preferred that it is 〜15 mol%.

Further, the weight average molecular weight of the acrylamide copolymer intended for the present invention is from 1,000 to 50,000. Therefore,
The weight average molecular weight of the ethylene-acrylic acid ester-acrylic acid copolymer used as a raw material also needs to be used in accordance with this, but in gel permeation chromatography, which is generally well-known for molecular weight measurement,
A polymer compound having a relatively small number of polar groups such as an ethylene-acrylic acid ester-acrylic acid copolymer and a polymer compound having a tertiary amino group or a quaternary cation group, which is the object compound of the present invention, have the same molecular weight. Care must be taken because the elution times are different. Incidentally, the present inventors, the use of a monodisperse ethylene-acrylic acid ester-acrylic acid copolymer having a weight average molecular weight in terms of polystyrene of 3000 to 60000 as measured by gel permeation chromatography as a raw material, the present invention That an acrylamide-based copolymer having a weight-average molecular weight of 1,000 to 50,000, which falls within the target range, can be obtained.

Further, the molecular weight of the acrylamide copolymer of the present invention is measured by an ultra-high temperature GPC method (Kinukawa, Journal of Polymers, Vol. 44,
No. 2, pages 139 to 141 (1987)). The molecular weight is
If the molecular weight is less than 3000, the molecular weight of the obtained copolymer is also
The acrylamide-based copolymer produced according to the present invention becomes 1000 or less and is blended in a thermoplastic resin, which is volatilized when heated, and when the molecular weight exceeds 60,000, the viscosity of the reaction system in carrying out the present invention is reduced. Is too large,
It becomes difficult to carry out, and the viscosity when the acrylamide-based copolymer as a product is melted becomes too large, resulting in poor workability. The preferred molecular weight is 6,000 to 40,000 for the raw material ethylene-acrylate-acrylic acid copolymer and 3,000 to 30,000 for the acrylamide copolymer.

Next, the ethylene-acrylic acid ester-acrylic acid copolymer is amidated.

In the present invention, a typical example of an amine that can be used in the amidation is a general formula: (Wherein R ² , R ³ and R ⁴ are the same as described above).

Specific examples of the R ² is, for example, ethylene group, propylene group, hexamethylene group, etc. neopentylene group, and these groups may coexist in a molecule. Among these groups, an ethylene group and a propylene group are preferable from the viewpoint of production easiness and economy,
Particularly, a propylene group is preferable.

Specific examples of R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group.
It may be mixed in the molecule. Of these groups, a methyl group and an ethyl group are preferred from the viewpoint of antistatic properties.

Specific examples of the amine include, for example, N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-dipropylaminoethylamine, N, N-dipropylaminopropylamine,
N, N-dibutylaminoethylamine, N, N-dibutylaminopropylamine, N, N-dimethylaminobutylamine, N, N-diethylaminobutylamine, N, N-dimethylaminoneopentylamine, N, N-dimethylaminohexylamine , N, N-dimethylaminooctylamine and the like, and these amines are used alone or in combination of two or more.

The amount of the amine to be used is 1 to 1.5 times, preferably 1.02 to 1.2 times, the mole of the acrylic acid component of the ethylene-acrylate-acrylic acid copolymer. When the amount of the amine used is less than the above range, the reaction requires a long time, and the amidation reaction may be incomplete, and the antistatic property of the obtained acrylamide copolymer is low. If it is too small, and if it is more than the above-mentioned range, no further improvement in the effect is observed, and it tends to be economically disadvantageous.

The amidation of the ethylene-acrylic acid ester-acrylic acid copolymer is carried out first as the first step.
The acrylic acid ester-acrylic acid copolymer and, if necessary, the catalyst are dissolved in an inert solvent by heating, and a neutralization reaction is caused by gradually adding the amine. The neutralization reaction between the ethylene-acrylic acid ester-acrylic acid copolymer and the amine proceeds promptly with some heat generation.

The amidation reaction can be performed without using the inert solvent. In order to allow the reaction to proceed homogeneously and to prevent a viscous reaction solution during the quaternization reaction, it is preferable to use an inert solvent.

Specific examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, ethyltoluene, propylbenzene, and diethylbenzene; methylcyclopentane, cyclohexane,
Ethylcyclopentane, methylcyclohexane, 1,1-
Alicyclic hydrocarbons such as dimethylcyclohexane and ethylcyclohexane; aliphatic hydrocarbons such as hexane, heptane, octane, decane, methylheptane, 3-ethylhexane and trimethylpentane; 2-hexanone, 4-methyl-2-pentanone; And ketone solvents such as cyclohexanone.

The amount of the inert solvent used is 0.3 to 5 times by weight, preferably 0.5 to 3 times by weight based on the ethylene-acrylate-acrylic acid copolymer. If the amount of the inert solvent used is smaller than the above range, the dilution effect is not sufficient, and if it exceeds the above range, it is economically disadvantageous.

In the present invention, a known catalyst can be used to shorten the reaction time.

The reaction temperature and reaction time of the amidation in the second step of the reaction vary depending on the solvent used and the presence or absence of a catalyst.
The temperature is usually 100 to 300 ° C, preferably 130 to 260 ° C, for 1 to 20 hours. If the reaction temperature is lower than 100 ° C, there is a disadvantage that the reaction takes a long time.If the reaction temperature is higher than 300 ° C, the coloring of the reactants and the deterioration of physical properties due to thermal decomposition of the copolymer may occur. It will be cool.

When the exotherm is no longer observed in the neutralization reaction, heat to the temperature at which the solvent refluxes. The progress of amidation can be confirmed by the generation of water azeotropic with the solvent. By removing the azeotropic water out of the reaction system using a Dean-Stark water separator or the like, the reaction can proceed more efficiently. During the reaction, it is preferable to perform the reaction under a nitrogen stream from the viewpoint of preventing the reaction mixture from being colored and more efficiently removing water.

Completion of amidation reaction, by measuring the infrared absorption spectrum was taken part and that the reaction mixture azeotropically water is no longer observed, the absorption based on carboxyl ions 1400 cm ^-1 had completely disappeared, a new 1650 It can be confirmed by the appearance of absorption of νc _{= 0} based on amide around 付 近 1670 cm ⁻¹ .

The intermediate of the acrylamide copolymer thus obtained of the present invention can be purified, if necessary, by pouring the reaction mixture after the amidation into a large amount of an immiscible solvent such as methanol. However, it can be usually led to the next quaternization reaction as it is.

The quaternizing agent used in the quaternizing reaction is an alkylating agent represented by the general formula: R ⁵ -Χ (wherein R ⁵ is the same as described above).

Examples of R ^5, in view of heat resistance of the obtained acrylamide copolymer, preferably a linear alkyl group and arylalkyl group, also a lower alkyl group from the viewpoint of antistatic property preferred. Particularly preferred R ⁵ is a methyl group and an ethyl group.

Is a halogen atom such as Cl, Br, I, etc.
CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ , which may be present in one molecule. Among these, Cl, CH ₃ OSO ₃ and C ₂ H ₅ OSO ₃ are preferred from the viewpoint of antistatic properties.

Specific examples of the quaternizing agent include, for example, alkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkyl disidyl chloride, benzyl chloride, methyl chloride,
Ethyl chloride, butyl chloride, propyl chloride, ethyl bromide, butyl bromide, methyl iodide, ethyl iodide, butyl iodide, α-chloroparaxylene, and the like. These quaternizing agents are usually used alone or in combination of two or more. These are used in combination.

The amount of the quaternizing agent used is usually 1.0 to 1.2 mole times, preferably 1.0 to 1.2 times the diamine used in the amidation reaction.
It is 1.03 to 1.1 mole times. If the amount of the quaternizing agent is less than the above range, the quaternization reaction becomes insufficient and no good antistatic property is exhibited. Disadvantaged.

The quaternization reaction is desirably performed at a reaction temperature of 70 to 110 ° C. in a nitrogen atmosphere from the viewpoint of preventing coloring of the reaction product. The reaction is carried out for about 1 to 6 hours after the addition of the
Aging at 110 ° C completes. After completion of the reaction, after distilling off the solvent, pulverize or methanol,
The acrylamide-based copolymer aimed at by the present invention can be obtained by depositing in an immiscible solvent such as ethanol, isopropanol, n-hexane or the like, precipitating and isolating, followed by drying.

The acrylamide-based copolymer thus obtained exhibits excellent antistatic properties, and thus can be used in various resins such as a polyolefin-based resin in an appropriate amount.

 In addition, the acrylamide-based copolymer has an excellent charge.
The reason for the prevention is not clear, but probably
Acrylamide structure unit contained in luamide copolymer
Place takes in moisture in the air, Χ Is ionized and electricity
Conductivity, resulting in lower electrical resistance
It is thought that it is caused.

Further, in the present invention, the acrylamide structural unit does not exhibit volatility even at high temperatures, and is chemically incorporated into the acrylamide copolymer, so there is no volatilization during processing, and after processing, It is considered that blocking does not occur and physical properties of the thermoplastic resin do not decrease.

Examples of the thermoplastic resin to which the acrylamide copolymer can be applied include polyolefin resins such as polyethylene and polypropylene; polystyrene resins such as polystyrene and ABS resin; polyamide resins; polyesters such as polybutylene terephthalate; and modified polyphenylene ether. And the like, but the present invention is not limited to only these examples.

As described above, according to the production method of the present invention, a special acrylamide-based copolymer having a suitable molecular weight range and a suitable functional group composition for imparting antistatic properties can be efficiently provided at low cost. .

Next, the present invention will be described in more detail based on Production Examples and Examples, but the present invention is not limited to only these Examples.

Production Example 1 200 g of an ethylene-ethyl acrylate copolymer having a weight average molecular weight of 78,000 (ethyl acrylate content: 7 mol%) was added to 2 k of water.
Together with g, the mixture was charged in an autoclave having a magnetic stirrer and having a capacity of 4 liters. Next, after completely removing oxygen dissolved in water by bubbling nitrogen gas, the operation of pressurizing with nitrogen gas (50 kg / cm ² ) and degassing (1 kg / cm ² ) was repeated 5 times. Reduce the oxygen concentration in the system to 1
ppm or less.

Next, under a nitrogen gas atmosphere, a decomposition degradation reaction was performed at 350 ° C. and 200 kg / cm ² for 4 hours, followed by cooling.

As physical properties of the obtained product, a weight average molecular weight and an infrared absorption spectrum were examined according to the following methods.

(Weight average molecular weight) The measurement was carried out according to the method described in Jpn. Polymers, Vol. 44, No. 2, pp. 139-141 (1987).

Analyzer: Waters, GPC-244 Column: Showa Denko KK, Shodex A-80M / S 2 solvents: 1-chloronaphthalene Flow rate: 0.7 ml / min Column temperature: 210 ° C Detector: FID As a result, the weight-average molecular weight was 22,000 as determined by polystyrene conversion.

(Infrared absorption spectrum) It measured as a KBr tablet using A-202 type manufactured by JASCO Corporation.

As a result, at 730 cm ^-1 ν based on ethyl acrylate
Absorption of _{c = 0} and absorption of acrylic acid ν _{c = 0} at 1700 cm ⁻¹ were recognized. The copolymer obtained from the intensity ratio was 93 mol% of ethylene, 3 mol% of ethyl acrylate and 4 mol of acrylic acid. %.

Production Examples 2 to 5 An ethylene-acrylate-acrylic acid copolymer was obtained in the same manner as in Production Example 1 except that the ethylene-acrylate copolymer shown in Table 1 was used.

As the physical properties of the obtained copolymer, the weight average molecular weight and the infrared absorption spectrum were examined in the same manner as in Production Example 1. Table 1 shows the results.

Example 1 1 liter of 4 equipped with thermometer, stirrer, dropping funnel and Dean stark water separator
400 ml of xylene, 150 g of the ethylene-ethyl acrylate-acrylic acid copolymer obtained in Production Example 1, and 1.0 g of p-toluenesulfonic acid were placed in a one-necked flask.

Next, 21.1 g of N, N-dimethylaminopropylamine was charged and heated to 140 ° C. using an oil bath, and the generated water was continuously removed by azeotropy with xylene.
The reaction was carried out at 0 ° C. for 17 hours, and the amidation reaction was continued until azeotropic formation of generated water was not observed.

458 g of the reaction mixture was cooled to 80 ° C., 10 g of the reaction mixture containing the intermediate in the present invention was separated, and methyl iodide 2 was added to the remaining reaction mixture from a dropping funnel under a nitrogen stream.
8.7 g was gradually added dropwise over 1 hour. During this period, heat generation was observed, but the reaction temperature was maintained at 90 ° C. by cooling, and after completion of the dropwise addition, an aging reaction was performed at 100 ° C. for 4 hours.

The previously separated intermediate and the obtained reaction mixture were taken out, separately poured into a large amount of methanol, and the formed precipitates were collected and dried under vacuum to obtain each product.
The yield was 3.5 g of the intermediate and 187.5 g of the acrylamide copolymer. The yields were 96.7% and 98
%Met.

When the characteristic absorption of infrared absorption spectrum and chemical shift of ¹ H-NMR of the obtained intermediate and acrylamide copolymer were measured, as shown in Table 2, the introduction of amide group by diamine and quaternary It was confirmed that the introduction of a new alkyl group due to the chemical conversion had been attempted.

In addition, ¹ H-NMR was measured by the following method.

⁽¹ H-NMR spectra) using the manufactured JMN-GSX270 JEOL Ltd., was conducted at 55 ° C. deuterochloroform as solvent. Note that in Table 2, ^one H of ¹ H type and quaternary products of intermediates is as follows.

Examples 2 to 7 and Comparative Examples 1 and 2 In Example 1, instead of the ethylene-ethyl acrylate-acrylic acid copolymer obtained in Production Example 1,
The amidation and quaternization reactions were carried out under the conditions described in Table 3, using the copolymers shown in the table, and using the diamines, quaternizing agents, and reaction solvents shown in Table 3. In the same manner as in Example 1, an acrylamide copolymer was obtained.

Experimental Examples 1 to 7 and Comparative Experimental Examples 1 and 2 10 parts by weight of the acrylamide-based copolymer obtained in each of Examples and Comparative Examples and 90 parts by weight of polypropylene (JS1429, manufactured by Mitsui Toatsu Co., Ltd.) 200 parts of blend
Introduced into a T-die type film forming apparatus heated to
m, an unstretched film having a width of 500 mm.

The film was cut into 10 cm × 10 cm to obtain a test film.

Next, the obtained test film was examined for surface resistivity, blocking resistance, transparency, and elongation in accordance with the following methods. Table 4 shows the results.

(A) Surface resistivity 24 hours After leaving the test film for 24 hours at 20 ° C, 30% RH or 20 ° C, 60% RH, super insulation meter R-503, manufactured by Kawaguchi Electric Mfg. Co., Ltd. Was used to measure the surface resistivity.

After 30 days (persistence) After storing the test film at room temperature for 30 days,
The sample was allowed to stand for 24 hours at 60 ° C. and 60% RH, and the surface resistivity was measured in the same manner as the surface resistivity.

After washing with water (water resistance) For a film consisting only of acrylamide copolymer, store it at room temperature for 30 days, and for a film consisting of acrylamide copolymer and polypropylene, aged in an oven at 40 ° C for 14 days. Wash the surface thoroughly with an aqueous solution of detergent (Mama Lemon: manufactured by Lion Corporation), rinse thoroughly with ion-exchanged water, and then wash
After standing for 24 hours in an atmosphere of 60 ° C. and 60% RH, the surface resistivity was measured in the same manner as the surface resistivity.

(B) Blocking resistance Two films made of an acrylamide copolymer and polypropylene were stacked, sandwiched between glass plates of 20 cm × 20 cm, placed in an oven at 40 ° C., and aged for 14 days.
After 14 days, the film was taken out, peeled off by hand, and the presence or absence of blocking was determined based on the following criteria.

(Criterion criteria) ○: No blocking ×: Blocking (c) Transparency The permeability of the film composed of the acrylamide-based copolymer and polypropylene was visually observed and determined based on the following criteria.

(Judgment criteria) ○: Good transparency ×: There is a problem in transparency (d) Strong elongation Cut out from a film made of acrylamide copolymer and polypropylene into 10 mm width and 100 mm length, thickness (Tmm)
Was measured. This sample was put on a Tensilon type tensile tester with the chuck distance set to 50 mm, and 300 mm / min
, The breaking strength (S) and the breaking elongation (s) were measured, and the tensile strength and elongation were determined by the following formulas.

Comparative Experimental Example 3 In each of Experimental Examples 1 to 7 and Comparative Experimental Examples 1 and 2, only polypropylene was used as the resin, and a film was formed in the same manner as in Experimental Examples 1 to 7 and Comparative Experimental Examples 1 and 2.

The physical properties of the obtained films were examined in the same manner as in Experimental Examples 1 to 7 and Comparative Experimental Examples 1 and 2. The result is the fourth
It is shown in the table.

Comparative Experimental Example 4 A film was prepared in the same manner as in Experimental Examples 1 to 7 and Comparative Experimental Examples 1 and 2, using what was obtained by adding 3 parts by weight of stearyl diethanolamide as an antistatic agent to 100 parts by weight of polypropylene.

The physical properties of the obtained films were examined in the same manner as in Experimental Examples 1 to 7 and Comparative Experimental Examples 1 and 2. The result is the fourth
It is shown in the table.

[Effects of the Invention] According to the production method of the present invention, it is possible to easily produce a polymer type antistatic resin which has excellent antistatic properties and does not deteriorate the physical properties of the thermoplastic resin.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08F 220: 06 220: 60) (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 8/30-8/32 C08F 8 / 44 C08F 10/02 C08F 210/02 C08F 20/00-20/60 C08F 220/00-220/60

Claims (2)

(57) [Claims] (1) An ethylene structural unit represented by the formula: CH ₂ —CH _{2 (} 65-97 mol%), a general formula: (Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms) 1 to 15 mol% of an acrylate structural unit represented by the following formula: A linearly and irregularly arranged copolymer comprising 1 to 30 mol% of acrylic acid structural units represented by the following general formula: (Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴
Each represents an alkyl group having 1 to 4 carbon atoms), characterized by reacting a diamine represented by the formula: 65 to 97 mol% of an ethylene structural unit represented by CH ₂ —CH ₂ , a general formula: (Wherein R ¹ is as defined above) and 1 to 15 mol% of an acrylate structural unit represented by the following general formula: (Wherein R ² , R ³ and R ⁴ are the same as described above) Acrylamide copolymer having a weight average molecular weight of 1,000 to 50,000, which is linearly and irregularly composed of 1 to 30 mol% of acrylamide structural units Manufacturing method. _2. An ethylene structural unit represented by the formula: CH ₂ —CH ₂ 65-97 mol%, a general formula: (Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms) 1 to 15 mol% of an acrylate structural unit represented by the following general formula: (Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴
Each represents an alkyl group having 1 to 4 carbon atoms), and an acrylamide-based copolymer having a weight average molecular weight of 1,000 to 50,000, which is linearly and irregularly composed of 1 to 30 mol% of acrylamide structural units represented by the general formula: : R ⁵ -Χ (wherein, R ⁵ is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms or an alicyclic alkyl group having 6 to 12 carbon atoms, Χ is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ ), characterized by reacting an alkylating agent represented by the formula: 65-97 mol% of ethylene structural units represented by CH ₂ —CH ₂ , general formula: (Wherein R ¹ is the same as described above), and 1 to 15 mol% of an acrylate structural unit represented by the general formula: (Wherein, R ² , R ³ , R ⁴ and R ⁵ are the same as described above). An acrylamide system having a weight average molecular weight of 1,000 to 50,000, which is linearly and irregularly composed of 1 to 30 mol% of acrylamide structural units represented by A method for producing a copolymer.