JPH08208752A - Acrylamide copolymer - Google Patents

Abstract

PURPOSE: To obtain an acrylamide copolymer which can be desirably used as an antistatic agent by quaternization. CONSTITUTION: This copolymer has a weight-average molecular weight of 1000-50000 and is composed of linearly and randomly arranged repeating units comprising 65-99mol.% repeating ethylene units of formula I, 0-15mol.% repeating acrylate units of formula II (wherein R<1> is 1-4 C alkyl) and 1-35mol.% repeating acrylamide units of formula III (wherein R<2> is 2-8 C alkylene; and R<3> and R<4> are each 1-4 C alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acrylamide copolymer. More specifically, it relates to an acrylamide-based copolymer that can be suitably used as an antistatic agent by being quaternized.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyolefin resins, ABS resins, and vinyl chloride resins have been widely used for packaging materials such as films and bags, automobile parts, and the like. The resin generally has a large electric resistance, has 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 an antistatic ability to a thermoplastic resin, for example, (a) a method of applying an antistatic agent on the surface of the resin and then drying, and (b) an internal addition type antistatic agent in the resin. The method of kneading into the resin, (c) the method of applying a silicone compound to the surface of the resin, and (d) the method of modifying the resin itself have been proposed.

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, and thus permanent antistatic agent is used. There is a drawback that it is not possible to add Noh.

In the method (b), glycerin fatty acid ester, sorbitan fatty acid ester, alkyldiethanolamide, sodium alkylbenzenesulfonate, quaternary salt of alkylimidazole, etc. are used as the internal addition type antistatic agent. When these internal addition type antistatic agents are used, even if the antistatic agent on the surface is lost by washing, a new antistatic agent bleeds sequentially from the inside of the antistatic agent. There is an advantage that the preventive ability lasts for a relatively long period of time. However, in such an internal addition type antistatic agent, it takes a long time to recover the antistatic ability after washing, and when the antistatic agent bleeds excessively, tackiness is generated, rather In addition to the drawback that dust and the like tend to adhere, since these antistatic agents have low molecular weight, they volatilize due to heat during molding processing at high temperatures, so add more antistatic agents than necessary. It was difficult to adjust the effective amount and the disadvantage that it was necessary.

In order to solve the drawbacks of the above-mentioned internal addition type antistatic agents, recently, polymethylmethacrylate having 20-80 mol% of methoxy groups modified with diethanolamine (JP-A-1-170603), alkoxypolyethylene glycol. Graft copolymer of methacrylate (Japanese Patent Publication No. 58-39860), styrene-maleic anhydride copolymer imide-modified, and then quaternized and cationized polymer (Japanese Patent Publication No. 1-29820),
A comb-type copolymer of a high-molecular-weight monomer obtained by converting a terminal carboxyl group of polymethylmethacrylate with glycidylmethacrylate into a methacryloyl group and an aminoalkyl acrylate or acrylamide, and its quaternized cation-modified product ( JP 62-
No. 121717), a polymer compound having an antistatic functional group has been proposed. However, all of the above-mentioned polymer compounds have drawbacks such as deterioration of physical properties of the resin such as transparency and strength and elongation, and insufficient antistatic ability and durability.

In the above method (c), the antistatic ability lasts semipermanently, but the silicone compound is expensive.
Further, the work efficiency is poor, which is disadvantageous in terms of cost.

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

[0009]

Therefore, in view of the above-mentioned prior art, the inventors of the present invention have not only semipermanently excellent antistatic ability, but also hardly deteriorate the physical properties of the resin, and As a result of earnest research to find a compound that can be suitably used as an antistatic agent that is less likely to cause blocking of molded articles, a compound having all of the above physical properties at the same time was finally found, and the present invention was completed.

[0010]

That is, the present invention is
formula:

[0011]

[Chemical 4]

Ethylene structural units 65-99 represented by
Mol%, general formula:

[0013]

Embedded image

An acrylate structural unit represented by the formula (wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms) and 0 to 15 mol% and a general formula:

[0015]

[Chemical 6]

(Wherein R ² represents an alkylene group having 2 to 8 carbon atoms, and R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms).
The present invention relates to an acrylamide-based copolymer having a weight average molecular weight of 1,000 to 50,000, which is composed of 5 mol% and which is randomly arranged.

[0017]

ACTION AND EXAMPLE As described above, the acrylamide copolymer of the present invention has the formula:

[0018]

[Chemical 7]

Ethylene structural units 65 to 99 represented by
Mol%, general formula:

[0020]

Embedded image

An acrylate structural unit represented by the formula (wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms) and 0 to 15 mol% and a general formula:

[0022]

[Chemical 9]

(Wherein R ² represents an alkylene group having 2 to 8 carbon atoms, and R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms).
It is an acrylamide-based copolymer having a weight average molecular weight of 1000 to 50000, which is 5 mol% and is arranged randomly in a linear manner.

The formula in the acrylamide copolymer of the present invention:

[0025]

[Chemical 10]

The proportion of ethylene structural units represented by is 6
It is 5 to 99 mol%. The ratio of the ethylene structural unit is 6
When it is less than 5 mol%, the softening point of the acrylamide-based copolymer of the present invention becomes low, and when the quaternized product of the acrylamide-based copolymer of the present invention is blended with a thermoplastic resin, tack or When stickiness occurs and when it exceeds 99 mol%, 4 of the acrylamide copolymer of the present invention is used.
The antistatic ability of the graded compound becomes too small. In the present invention, the proportion of the ethylene structural unit is 85 to 97 from the viewpoint of the softening point and the antistatic ability of the quaternary product of the acrylamide copolymer of the present invention.
It is particularly preferable that it is mol%.

The general formula in the acrylamide copolymer of the present invention:

[0028]

[Chemical 11]

The proportion of the acrylate structural unit represented by the formula (wherein R ¹ is the same as above) is 0 to 15 mol%.
When the proportion of the acrylate structural units exceeds 15 mol%, the softening point of the acrylamide copolymer of the present invention becomes low, and the quaternary product of the acrylamide copolymer of the present invention is blended with a thermoplastic resin. When you do, tack and stickiness will occur. In the present invention, when the acrylate structural unit is included, toughness and impact resistance are imparted when the quaternary product of the acrylamide copolymer of the present invention is blended with a thermoplastic resin. preferable. In the present invention, the proportion of the acrylate structural unit is 1 to 15 mol%, especially 3 to 7 mol% from the viewpoint of the balance between the softening point and the toughness and impact resistance.
Is particularly preferable.

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

The general formula in the acrylamide copolymer of the present invention:

[0032]

[Chemical 12]

The proportion of the acrylamide structural unit represented by the formula (wherein R ² , R ³ and R ⁴ are the same as above) is 1 to
35 mol%. When the proportion of the acrylamide structural unit is less than 1 mol%, the antistatic ability of the quaternary compound of the acrylamide copolymer of the present invention becomes too small, and when it exceeds 35 mol%, When the quaternary product of the acrylamide-based copolymer of the present invention is blended with a thermoplastic resin, hygroscopicity is generated. In the present invention, the proportion of the acrylamide structural unit is particularly preferably 3 to 15 mol% from the viewpoint of the balance between the antistatic ability and hygroscopicity of the quaternary product of the acrylamide copolymer of the present invention. preferable.

In the acrylamide structural unit, R
² is an alkylene group having 2 to 8 carbon atoms. Specific examples of R ² include, for example, ethylene group, propylene group,
Hexamethylene group, neopentylene group and the like,
These groups may be mixed in one molecule. Among these groups, an ethylene group and a propylene group are preferable from the viewpoint of easiness of production and economy, and a propylene group is particularly preferable.

R ³ and R ⁴ are each 1 to 1 carbon atoms.
4 alkyl group. Specific examples of such R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group, and these groups may be present in one molecule. Among these groups, a methyl group and an ethyl group are preferable from the viewpoint of the antistatic ability of the quaternized product of the acrylamide copolymer of the present invention.

The acrylamide copolymer of the present invention has a weight average molecular weight of 1,000 to 50,000. When the weight average molecular weight is less than 1000, the molecular weight becomes too small and the acrylamide copolymer of the present invention has
When the graded product is blended with a thermoplastic resin and volatilizes when heated, and when it exceeds 50,000, the viscosity of the acrylamide copolymer of the present invention when melted becomes too large, resulting in poor workability. . A preferred weight average molecular weight is 3,000 to 35,000.

The term "weight average molecular weight" as used herein means gel permeation chromatography (GP).
The monodisperse polystyrene-equivalent weight average molecular weight measured in C).

The acrylamide copolymer of the present invention is difficult to measure because it is hardly soluble in an eluent of ordinary gel permeation such as tetrahydrofuran or THF, but it cannot be easily measured. It can be measured according to the GPC method (Kinukawa, Kobunshi Kobun, Vol. 44, No. 2, 139-141 (1987)).

The acrylamide copolymer of the present invention can be obtained, for example, by the following method.

First, the raw material for producing the acrylamide copolymer of the present invention is not particularly limited,
More advantageously ethylene (C ₂ H ₄ ) and the general formula: CH ₂ C
A (partial) hydrolyzate of a copolymer composed of an acrylate represented by HCOOR ¹ (wherein R ¹ is the same as above) is used. Such a copolymer can be easily obtained by copolymerizing ethylene and the acrylate by a high-pressure polymerization method.

The ratio of the ethylene structural unit derived from the ethylene to the acrylate structural unit derived from the acrylate is determined by determining the ratio of the ethylene structural unit, the acrylate structural unit and the acrylamide structural unit of the obtained acrylamide copolymer. Therefore, the molar ratio of ethylene and the acrylate represented by the above general formula (ethylene / acrylate) is (ethylene structural unit) /
Copolymerization is performed so as to be equal to [(acrylate structural unit) + (acrylamide structural unit)].

The above-mentioned copolymer can be used as it is, but since it has a large molecular weight, it is preferably reduced in molecular weight by, for example, a degradation method in which hydrolysis and thermal decomposition are carried out at high temperature and high pressure in the presence of water. .

At this time, the general formula derived from acrylate:

[0044]

[Chemical 13]

All or part of the acrylate structural unit represented by the formula (wherein R ¹ is the same as above) is hydrolyzed to form the formula:

[0046]

Embedded image

It becomes an acrylic acid structural unit represented by:

In order to prepare a copolymer having a low molecular weight by thermally decomposing the copolymer, the copolymer is reacted in the presence of water at a reaction temperature of 150 to 500 ° C. and a reaction pressure of 3 to 500 kg. / Cm ² and can be produced by molecular cleavage by heat.

In the present invention, the proportion of the acrylic acid structural unit can be arbitrarily adjusted by the proportion of water charged, reaction temperature, pressure, time and the like.

Specific examples of the degradation method are, for example, JP-A-53-57295 and JP-A-53-6538.
9, JP-A-60-79008, JP-A-60-
The method described in JP-A-79015 and the like can be mentioned.

The acrylamide copolymer and the quaternary compound thereof of the present invention may impair the commercial value when colored, so that the raw material used in the present invention is, for example, JP-A-60. It is preferable to use the product of the method exemplified in JP-A 79008.

Using the thus obtained ethylene-acrylic acid ester-acrylic acid copolymer as a raw material, the acrylamide copolymer of the present invention and its quaternary product can be obtained.

The quaternary compound of the acrylamide copolymer of the present invention has the formula:

[0054]

[Chemical 15]

An ethylene structural unit represented by the general formula:

[0056]

Embedded image

(Wherein R ¹ is the same as above) and the general formula:

[0058]

[Chemical 17]

(In the formula, R ² , R ³ and R ⁴ are the same as described above, R ⁵ is an alkyl group having 1 to 12 carbon atoms, and 7 to 1 carbon atoms.
2 arylalkyl group or C 6-12 alicyclic alkyl group, X is a halogen atom, CH ₃ OSO ₃ or C
₂ H ₅ OSO ₃ ) and having a weight average molecular weight of 1,000 to 50,000, which are linearly and irregularly arranged and are composed of an acrylamide structural unit.

R ⁵ is an alkyl group having 1 to 12 carbon atoms,
Arylalkyl group having 7 to 12 carbon atoms or 6 to carbon atoms
12 is an alicyclic alkyl group. Specific examples of R ⁵ include, for example, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, sec-butyl group, n
An alkyl group such as an octyl group and an n-lauryl group; an arylalkyl group such as a benzyl group; a cyclohexyl group,
An alicyclic alkyl group such as a methylcyclohexyl group may be mentioned, and these groups may be present in one molecule. As R ⁵ , a linear alkyl group and an arylalkyl group are preferable from the viewpoint of the heat resistance of the quaternary product of the acrylamide copolymer of the present invention, and a lower alkyl group from the viewpoint of imparting antistatic ability. Is preferred. Particularly preferred R ⁵ includes a methyl group and an ethyl group.

X is, for example, a halogen atom such as Cl, Br or I, CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃
And these may be mixed in one molecule. Among these, from the viewpoint of the antistatic ability of the quaternary compound of the acrylamide copolymer of the present invention, Cl, CH ₃ OS is used.
O ₃ and C ₂ H ₅ OSO ₃ are preferred.

There is no particular limitation on the method for producing the acrylamide copolymer and the quaternary product thereof of the present invention from the above raw materials. An example thereof will be described below.

The raw materials are, for example, benzene, toluene,
Aromatic or aliphatic hydrocarbons such as xylene, cyclohexanone, decane, cumene, and cymene are dissolved in an inert solvent such as a ketone, and 100 to 150 mol% of dialkylaminoalkylamine based on the carboxyl group of the raw material is added thereto. After adding and reacting at 130 to 220 ° C. to convert the carboxyl group contained in the acrylic acid structural unit into a dialkylaminoalkylamide to form an acrylamide copolymer, for example, a known alkyl halide, dialkyl sulfate, etc. By cation-modifying with a quaternizing agent, a quaternized product of the linear acrylamide random copolymer of the present invention can be obtained.

The thus obtained quaternary product of the acrylamide copolymer of the present invention exhibits excellent antistatic ability.
Although the reason is not clear, the acrylamide structural unit contained in the quaternized product of the acrylamide copolymer of the present invention takes in water in the air,

[0065]

Embedded image

It is considered that this is due to a low electric resistance, since the ionized ion shows electric conductivity.

Further, in the present invention, since the acrylamide structural unit does not exhibit volatility even at high temperature and is chemically incorporated into the quaternized product of the acrylamide copolymer of the present invention, It is considered that there is no volatilization during processing, and that there is no occurrence of blocking or deterioration of the physical properties of the thermoplastic resin after processing.

Examples of the thermoplastic resin to which the quaternary product of the acrylamide copolymer of the present invention can be applied include polyolefin resins such as polyethylene and polypropylene; polystyrene resins such as polystyrene and ABS resin; polyamide resins; poly resins. Examples thereof include polyesters such as butylene terephthalate; polyethers such as modified polyphenylene ether, but the present invention is not limited to these examples.

Next, the acrylamide copolymer of the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited to these examples.

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

Next, in a nitrogen gas atmosphere, 350 ° C., 2
After the decomposition and degradation reaction was carried out for 4 hours under the condition of 00 kg / cm ² , it was cooled.

The physical properties of the obtained ethylene-ethyl acrylate-acrylic acid copolymer were examined for weight average molecular weight, infrared absorption spectrum and ¹ H-NMR spectrum according to the following methods. The weight average molecular weight and the content of each structural unit are shown in Table 1. An infrared absorption spectrum is shown in FIG. 1 and a ¹ H-NMR spectrum is shown in FIG.

(Weight Average Molecular Weight) Polymers, 44
It was measured according to the method described in Vol. 2, No. 1, pp. 139-141 (1987). Waters GPC-24
4 (column: Showa Denko KK, Shodex, A-8)
0M / S (2), 1-chloronaphthalene as a solvent, flow rate 0.7 ml / min, column temperature 2
It was measured at 10 ° C.

(Infrared absorption spectrum) The measurement was carried out with KBr tablets using A-202 manufactured by JASCO Corporation.

( ¹ H-NMR spectrum) JHN-GSX270 manufactured by JEOL Ltd. was used for measurement at 55 ° C. using deuterated chloroform as a solvent.

Production Examples 2 to 5 Ethylene-acrylic acid ester used as a raw material of the present invention in the same manner as in Production Example 1 except that the ethylene-acrylic acid ester shown in Table 1 was used in Production Example 1. An acrylic acid copolymer was obtained.

The physical properties of the obtained copolymer were examined for the weight average molecular weight and the content of each structural unit in the same manner as in Production Example 1. Table 1 shows the results.

[0078]

[Table 1]

Example 1 Thermometer, stirrer, dropping funnel and Dean Stark
(Dean stark) In a four-necked flask with an internal capacity of 1 liter equipped with a water separator, 400 ml of xylene, 150 g of ethylene-ethyl acrylate-acrylic acid copolymer (raw material) obtained in Production Example 1 and paratoluenesulfonic acid 1.0 g was charged.

Next, 21.1 g of N, N-dimethylaminopropylamine was charged, and 140% was added using an oil bath.
The mixture was heated to 0 ° C., the produced water was continuously removed by azeotropic distillation with xylene, and the mixture was reacted at 140 ° C. for 17 hours, and the amidation reaction was continued until the azeotropic distillation of produced water was not observed.

458 g of the reaction mixture was cooled to 80 ° C., and the reaction mixture 10 containing the acrylamide copolymer of the present invention was added.
2 g of methyl iodide was gradually added dropwise to the remaining reaction mixture from the dropping funnel over 1 hour. Although heat generation was observed during this period, the reaction temperature was maintained at 90 ° C. by cooling, and after completion of dropping, aging reaction was carried out at 100 ° C. for 4 hours.

The acrylamide copolymer of the present invention and the reaction mixture obtained above were taken out and charged separately into a large amount of methanol, and the formed precipitate was recovered and dried under vacuum to obtain the product. I got it. The yields were 3.5 g of an acrylamide copolymer and 187.5 g of a quaternary product of an acrylamide copolymer, and the yields were 96.7 each based on the raw material ethylene-ethyl acrylate-acrylic acid copolymer.
% And 98%.

Next, the infrared absorption spectrum, ¹ H-NMR spectrum, weight average molecular weight and number average molecular weight of the obtained acrylamide copolymer of the present invention and the quaternary product of the acrylamide copolymer were examined. The results of infrared absorption spectrum, weight average molecular weight and number average molecular weight are shown in Tables 2 and 3.

[0084] FIG infrared absorption spectrum of the acrylamide copolymer 3, ¹ H-NMR spectrum in FIG. 4, also the infrared absorption spectrum of the quaternary product of acrylamide copolymer FIG 5, ¹ H-NMR The spectrum is shown in FIG.

The molecular weight distribution curves of the acrylamide copolymer and the quaternary product of the acrylamide copolymer are shown in FIGS. 7 and 8, respectively.

Examples 2 to 9 In Example 1, instead of the ethylene-ethyl acrylate-acrylic acid copolymer obtained in Production Example 1, the copolymers shown in Table 2 were used, and amine and 4 An acrylamide-based copolymer and a quaternized product of the acrylamide-based copolymer were obtained in the same manner as in Example 1 except that the one shown in Table 2 was used as the grading agent.

The yield, infrared absorption spectrum, ¹ H-NMR spectrum, weight average molecular weight and number average molecular weight of the obtained acrylamide copolymer and quaternary product of the acrylamide copolymer were the same as in Example 1. I looked it up. The measurement results of yield, infrared absorption spectrum, weight average molecular weight and number average molecular weight are shown in Tables 2 and 3 together with the yield.

[0088]

[Table 2]

[0089]

[Table 3]

The measurement results (chemical shift (ppm)) of ¹ H-NMR spectrum are as follows.

(Measurement Results of ¹ H-NMR Spectrum) (a) Example 1

[0092]

[Chemical 19]

(B) Example 2

[0094]

Embedded image

(C) Example 3

[0096]

[Chemical 21]

(D) Example 4

[0098]

[Chemical formula 22]

(E) Example 5

[0100]

[Chemical formula 23]

(F) Example 6

[0102]

[Chemical formula 24]

(G) Example 7

[0104]

[Chemical 25]

(H) Example 8

[0106]

[Chemical formula 26]

(I) Example 9

[0108]

[Chemical 27]

Experimental Examples 1 to 9 Quaternary product of acrylamide copolymer obtained in each Example or 10 parts by weight of quaternary product of the copolymer and polypropylene resin (Mitsui Toatsu Co., Ltd .: JS1429). 90 parts by weight of the blended product was introduced into a T-die type film forming apparatus heated to 200 ° C. to obtain an unstretched film having a thickness of 50 μm and a width of 500 mm.

The obtained film was cut into a size of 10 cm × 10 cm and used as a test film. As a control product, a product prepared without using the acrylamide copolymer was also prepared. Next, the obtained film was examined for surface specific resistance, water resistance, blocking resistance, transparency and strength and elongation according to the following methods. The results are shown in Table 4.

(A) Surface specific resistance The surface specific resistance was allowed to stand for 24 hours under the conditions of 20 ° C., 30% RH (relative humidity) or 20 ° C., 60% RH.
The surface resistivity value was measured using a super insulation meter R-503 type manufactured by Kawaguchi Electric Co., Ltd.

Sustainability After the test film was stored at room temperature for 30 days, it was stored at 20 ° C. for 60 hours.
After standing for 24 hours under the condition of% RH, the surface specific resistance value was measured in the same manner as above.

Water resistance The film made of the quaternary product of the acrylamide copolymer of the present invention was stored at room temperature for 30 days, and the film made of the quaternary product of the acrylamide copolymer of the present invention and the polypropylene film was 40. After aging in an oven at ℃ for 14 days, the surface was thoroughly washed with an aqueous solution of Mama Lemon (manufactured by Lion Corporation) as a detergent,
Rinse thoroughly with deionized water, then at 20 ℃, 60%
The sample was left to stand in an atmosphere of RH for 24 hours, and the surface resistivity was measured in the same manner as above.

(B) Blocking resistance Two films prepared by blending the quaternary product of the acrylamide copolymer of the present invention with polypropylene are 20 cm ×
It was sandwiched between 20 cm glass plates, placed in an oven at 40 ° C., and aged for 14 days. After 14 days, the film was taken out, peeled by hand, and the presence or absence of blocking was measured.

◯: No blocking x: Blocking (c) Transparency The transparency of the film prepared by blending the quaternary product of the acrylamide copolymer of the present invention with polypropylene was visually evaluated.

◯: Good transparency X: There is a problem with transparency (d) Strength and elongation A film prepared by blending the quaternary product of the acrylamide copolymer of the present invention was cut into a piece having a width of 10 mm and a length of 100 mm to obtain a thick film. (Tmm) was measured. This sample was applied to a Tensilon type tensile tester with a chuck distance set to 50 mm, pulled at a speed of 300 mm / min, the breaking strength (S) and the breaking elongation (s) were measured, and the tensile strength and the elongation were determined by the following equations. .

[0117]

[Equation 1]

Comparative Experimental Example 1 A test film was prepared in the same manner as in Experimental Examples 1 to 9 except that polypropylene was used instead of the blended product, and various physical properties were measured. The results are shown in Table 4.

Comparative Experimental Example 2 A test film was prepared in the same manner as in Experimental Examples 1 to 9 except that a mixture of 100 parts by weight of polypropylene and 3 parts by weight of stearyldiethanolamide as an antistatic agent was used in place of the blended product. , Various physical properties were measured. The results are shown in Table 4.

[0120]

[Table 4]

As is clear from the results shown in Table 4, the quaternized product of the acrylamide copolymer of the present invention imparts excellent antistatic ability to the thermoplastic resin, and further, the transparency and the transparency of the thermoplastic resin are improved. It can be seen that the strength and elongation do not decrease and the blocking resistance is excellent.

[0122]

EFFECT OF THE INVENTION 4 of the acrylamide copolymer of the present invention
The graded product imparts excellent antistatic ability to the thermoplastic resin, and does not deteriorate the physical properties such as the film molded using the thermoplastic resin, the transparency of the molded product, and the strength and elongation. Moreover, since it has excellent blocking resistance, it can be widely applied to various thermoplastic resins.

[Brief description of drawings]

FIG. 1 is a graph of an infrared absorption spectrum of an ethylene-ethyl acrylate-acrylic acid copolymer obtained in Production Example 1.

FIG. 2 is a ¹ H-NMR spectrum graph of an ethylene-ethyl acrylate-acrylic acid copolymer obtained in Production Example 1.

FIG. 3 is a graph of an infrared absorption spectrum of the acrylamide-based copolymer obtained in Example 1 of the present invention.

FIG. 4 is a ¹ H-NMR spectrum graph of the acrylamide-based copolymer obtained in Example 1 of the present invention.

FIG. 5 is a graph of an infrared absorption spectrum of a quaternized product of the acrylamide-based copolymer obtained in Example 1 of the present invention.

FIG. 6 is a ¹ H-NMR spectrum graph of the quaternary product of the acrylamide-based copolymer obtained in Example 1 of the present invention.

FIG. 7 is a molecular weight distribution curve of the acrylamide-based copolymer obtained in Example 1 of the present invention.

FIG. 8 is a molecular weight distribution curve of a quaternized product of the acrylamide copolymer obtained in Example 1 of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Manabu Kikuta 19 in 16 Hatta, Osamu Kanauchi, Tanabe-cho, Tsuzuki-gun, Kyoto Prefecture (72) Inventor Shigeo Kamehishiishi 1-1-1, Sonoyama, Otsu, Shiga Prefecture Toray Co., Ltd. Shiga Business Site (72) Inventor Masashi Takeda 1-1-1, Sonoyama, Otsu City, Shiga Prefecture Toray Co., Ltd. Shiga Business Site (72) Inventor, Risa Wada 1-1 1-1 Sonoyama, Otsu City, Shiga Prefecture Toray Co., Ltd. Ceremony company Shiga business site

Claims (1)

[Claims] 1. The formula: An ethylene structural unit represented by the formula: 65 to 99 mol%, the general formula: (Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms), the acrylate structural unit is represented by 0 to 15 mol% and the general formula: (In the formula, R ² represents an alkylene group having 2 to 8 carbon atoms, and R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms). Randomly arranged weight average molecular weight 1000-
50,000 acrylamide copolymers.