JPH04198308A - Acrylamide copolymer - Google Patents

Abstract

PURPOSE:To provide the subject copolymer containing linearly and randomly arranged ethylene structural unit, acrylate structural unit and acrylamide structural unit containing quaternary ammonium salt and useful as an antistatic agent, etc., applicable without deteriorating the transparency, strength, elongation, etc., of the molded article. CONSTITUTION:The objective copolymer having a weight-average molecular weight of 1,000-50,000 and containing the structural unit of formula IV derived from the structural unit of formula III can be produced by dropping and reacting a compound of formula R<5>X (R<5> is 1-12C alkyl; X is halogen, etc.) (e.g. methyl iodide) to an organic solvent solution of a linear random copolymer of 65-99mol% of ethylene structural unit of formula I, 0-15mol% of acrylate structural unit of formula II (R<1> is 1-4C alkyl) and 1-35mol% of acrylic acid structural unit of formula III (R<2> is 2-8C alkylene; R<3> and R<4> are 1-4C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an acrylamide copolymer and intermediates useful therefor. More specifically, the present invention relates to an acrylamide copolymer that can be suitably used as an antistatic agent and intermediates useful therefor.

[Conventional technology]

Thermoplastic resins such as polyolefin resins, ABS resins, and vinyl chloride resins have traditionally been widely used as packaging materials such as films and bags, and as materials for automobile parts. However, these thermoplastic resins generally have low electrical resistance. is large,
It had the serious drawback that it easily became electrostatically charged due to friction and attracted dust.

Therefore, in recent years, methods for imparting antistatic properties to thermoplastic resins include (a) a method of applying an antistatic agent to the resin surface and then drying it, and (2) a method of kneading an internally added antistatic agent into the resin. (3) A method of applying a silicone compound to the resin surface, and (2) A method of modifying the resin itself.

However, in the method marked above, a surfactant solution is used as an antistatic agent, but such an antistatic agent is easily removed by washing, so it cannot impart permanent antistatic ability. The disadvantage is that it cannot be done.

In the method (b) above, glycerin fatty acid ester, sorbitan fatty acid ester,
Alkyl jetanolamide, sodium alkylbenzene sulfonate, quaternary salts of alkylimidazole, and the like are used. When these internally added antistatic agents are used, even if the antistatic agent on the surface is lost by washing, new antistatic agent bleeds from inside, so the static It has the advantage that the preventive ability lasts for a relatively long period of time.

However, such internally added antistatic agents,
It takes a long time for the antistatic ability to recover after cleaning, and if the antistatic agent bleeds out excessively, it becomes sticky, making it easier for dust to adhere to it. Since the antistatic agent has a low molecular weight, it volatilizes due to the heat generated during molding processing at high temperatures, so there is a disadvantage that it is necessary to add more antistatic agent than necessary, and it is difficult to adjust its effective amount. It was difficult.

In order to overcome the drawbacks of the internally added antistatic agent, polymethyl methacrylate (JP-A-1999-10001), in which 20 to 80 mol% of the methoxy groups are modified with jetanolamine, has recently been developed.
-170603), a graft copolymer of alkoxypolyethylene glycol methacrylate (Japanese Patent Publication No. 170603),
-3.9860 Publication), imide-modified styrene-maleic anhydride copolymer and then quaternized and cationized polymer (Special Publication Publication No.-29820), polymethyl methacrylate with a carboxyl group at the end and glycidyl methacrylate. A comb-shaped copolymer of a high molecular weight monomer whose terminal carboxyl group has been converted into a methacryloyl group and an aminoalkyl acrylic acid ester or acrylamide, and its quaternized cation-modified product (JP-A-62-12171
Polymer compounds having antistatic functional groups such as Japanese Patent Publication No. 7) have been proposed. However, the polymer compound
All of them had drawbacks such as deterioration of physical properties of the resin such as transparency and strength and elongation, and also insufficient antistatic ability and durability.

In the method (c), the antistatic ability lasts semi-permanently, but the silicone compound is expensive and the work efficiency is poor, so it is disadvantageous in terms of cost.

In addition, the method (above) is a method of introducing hydrophilic groups into the resin, but in order to impart sufficient antistatic ability, it is necessary to introduce a considerable amount of hydrophilic groups. If a hydrophilic group is introduced into the resin, there is a risk that the moisture absorption resistance and mechanical properties of the resin itself will be lowered.

[Problem to be solved by the invention]

Therefore, in view of the above-mentioned conventional technology, the present inventors have developed a method that not only has excellent semi-permanent antistatic ability, but also hardly reduces the physical properties of the resin and is less likely to cause blocking of the molded product. As a result of intensive research in order to find a compound that can be suitably used as a drug, a compound that simultaneously possesses all of the above-mentioned physical properties was finally discovered, and the present invention was completed.

[Means to solve the problem]

That is, the present invention provides 65 to 99 mol% of ethylene structural units represented by the formula: % formula %, -acrylate structural units represented by the formula: (wherein R1 represents an alkyl group having 1 to 4 carbon atoms) 0 to 15 mol% and general formula: (wherein, R2 is an alkylene group having 2 to 8 carbon atoms, R and R4 are each an alkyl group having 1 to 4 carbon atoms, R5 is an alkyl group having 1 to 12 carbon atoms, carbon A linearly irregularly arranged acrylamide structural unit consisting of 1 to 35 mol% of an acrylamide structural unit represented by an arylalkyl group having 1 to 12 carbon atoms or a ring alkyl group having 1 to 12 carbon atoms, where X is a halogen atom, and represents CH0803 or CH0803. an acrylamide copolymer having a weight average molecular weight of 1,000 to 50,000, and 65 to 99 mol% of ethylene structural units represented by formula: acrylate structural unit θ to 15 mol% represented by the following formula: 1 to 35 mol% of acrylamide structural units represented by linearly irregularly arranged weight average molecular weight of 1000 to 35%
50 (Relating to an intermediate of the acrylamide copolymer of 100).

[Function and Examples]

As described above, the acrylamide copolymer of the present invention has 65 to 99 mol% of ethylene structural units represented by the formula: 0 to 15 mol% of acrylate structural units represented by the general formula: Alkyl group having 1 to 12 carbon atoms, arylalkyl group having 1 to 12 carbon atoms, or alicyclic alkyl group having 1 to 12 carbon atoms, X is a halogen atom, CH30SO3 or C2H50S03
acrylamide structural units 1 to 35 represented by
It is an acrylamide-based copolymer having a weight average molecular weight of 1,000 to 50,000 and randomly arranged in a linear manner consisting of mol%.

The proportion of ethylene structural units represented by the formula: % in the acrylamide copolymer of the present invention is 65 to 99 mol%. When the proportion of the ethylene structural unit is less than 65 mol%, the softening point of the acrylamide copolymer of the present invention becomes low, and when blended with a thermoplastic resin,
Tackiness and stickiness occur, and if it exceeds 99 mol%, the antistatic ability of the acrylamide copolymer of the present invention becomes too small. In the present invention, the proportion of the ethylene structural unit is particularly preferably 85 to 97 mol% from the viewpoint of balancing the softening point and antistatic ability.

The proportion of acrylate structural units represented by the general formula: (wherein R1 is the same as above) in the acrylamide copolymer of the present invention is 0 to 15 mol%.

If the proportion of the acrylate structural unit exceeds 15 mol%, the softening point of the acrylamide copolymer of the present invention will be low, resulting in tackiness or stickiness when blended into a thermoplastic resin. In the present invention, it is preferable that the acrylate structural unit is contained because it imparts toughness and impact resistance when blended into the thermoplastic resin. In the present invention, the proportion of the acrylate structural unit is particularly preferably 1 to 15 mol%, particularly 3 to 7 mol%, from the viewpoint of a balance between softening point, toughness, and impact resistance.

In the acrylate structural unit, I has 1 to 1 carbon atoms.
4 is an alkyl group. As a specific example of such R,
Examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and 1-butyl group, and these groups may be mixed in one molecule. Among these groups, methyl and ethyl groups are particularly preferred in order to maintain the softening point of the resulting acrylamide copolymer.

The proportion of acrylamide structural units represented by the general formula: % (in the formula, R, R, R and R5 are the same as above) in the acrylamide copolymer of the present invention is 1 to 35 mol%. When the proportion of the acrylamide structural unit is less than 1 mol%, the antistatic ability becomes too small, and when it exceeds 35 mol%, the acrylamide copolymer of the present invention is not used in the thermoplastic resin. When blended, it becomes hygroscopic. In the present invention, the proportion of the acrylamide structural unit is particularly preferably 3 to 15 mol% from the viewpoint of balancing antistatic ability and hygroscopicity.

In the acrylamide structural unit, R2 has 2 carbon atoms.
~8 alkylene group. Specific examples of such R2 include, for example, ethylene group, propylene group, hexamethylene group, neopentylene group, etc., and these groups may be mixed in one molecule. Among these groups, ethylene groups and propylene groups are preferred from the viewpoint of ease of production and economy, with propylene groups being particularly preferred.

R3 and R4 are each an alkyl group having 1 to 4 carbon atoms. Specific examples of such R and R4 include a methyl group, an ethyl group, a propyl group, a butyl group,
These groups may be mixed in one molecule. Among these groups, methyl and ethyl groups are preferred from the viewpoint of imparting antistatic ability.

R5 is an alkyl group having 1 to j2 carbon atoms, and 1 to 1 carbon atoms.
2 arylalkyl group or an alicyclic alkyl group having 1 to 12 carbon atoms. Specific examples of such R5 include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 5ec-butyl group, n-octyl group, n-lauryl group; Examples include arylalkyl groups such as benzyl group; alicyclic alkyl groups such as cyclohexyl group and methylcyclohexyl group, and these groups may be mixed in one molecule.

Note that R5 is preferably a linear alkyl group or an arylalkyl group from the viewpoint of heat resistance of the acrylamide copolymer of the present invention, and is preferably a lower alkyl group from the viewpoint of imparting antistatic ability. Particularly preferred R5
Examples include methyl and ethyl groups.

The above X is, for example, a halogen atom such as CI, Br, or 1, CH08O3 or C2H50S03, and these may be mixed in one molecule. Among these, C1, CH08O3 and CH08O3 are preferred from the viewpoint of antistatic ability.

The weight average molecular weight of the acrylamide copolymer of the present invention is 1,000 to 50,000. The weight average molecular weight is 1
If it is less than 000, the molecular weight will be too small and it will volatilize when the acrylamide copolymer of the present invention is blended with a thermoplastic resin and heated. When the acrylamide copolymer of the invention is melted, the viscosity becomes too high, resulting in poor workability.The preferred weight average molecular weight is 3000 to 35 NO.

Note that the weight average molecular weight as used herein refers to the weight average molecular weight in terms of monodisperse polystyrene measured by gel permeation chromatography (GPC).

The acrylamide copolymer of the present invention cannot be easily measured because it is poorly soluble in ordinary gel permeation eluents such as tetrahydrofuran (THF) and xylene. For silk, Polymer Papers, Vol. 44, No. 2, pp. 139-1'41 (1987)
) can be measured according to

The intermediate of the acrylamide copolymer of the present invention is an ethylene structural unit represented by the formula: %formula%
are the same as above) and acrylamide structural units represented by the general formula (wherein R, R and R4 are the same as above) linearly irregularly arranged with a weight average molecular weight of 1000 to 50,000 acrylamide copolymer intermediate can be obtained, for example, by the following method.

First, the raw materials for producing the intermediate of the acrylamide copolymer of the present invention are not particularly limited, but more preferably ethylene (c, , H4) and - formula: C82C) (COOR (in the formula , R1 is the same as above)).Such a copolymer can be easily produced by copolymerizing ethylene and the acrylate using a high-pressure polymerization method. available.

The ratio of the ethylene structural unit derived from ethylene and the acrylate structural unit derived from the acrylate is determined by the ethylene structural unit of the acrylamide copolymer to be obtained,
Since the ratio of acrylate structural units and acrylamide structural units is determined, the molar ratio of ethylene to acrylate (ethylene/acrylate) represented by the above formula is (ethylene structural units)/[(acrylate structural units) + ( acrylamide structural unit)].

The copolymer can be used as it is, but since it has a large molecular weight, it is preferable to reduce its molecular weight by a degradation method in which hydrolysis and thermal decomposition are simultaneously carried out under high temperature and high pressure in the presence of water, for example.

At this time, the general formula (where R
All or part of the acrylate structural unit represented by (1 is the same as above) becomes an acrylic acid structural unit represented by the formula: by hydrolysis.

In order to prepare a copolymer having a lower molecular weight by thermally decomposing the copolymer, the copolymer is heated at a reaction temperature of 150 to 500° C. and a reaction pressure of 3 to 500 K in the presence of water.
g/cm2 by thermal molecular cleavage.

Furthermore, in the present invention, the proportion of acrylic acid structural units is
It can be arbitrarily adjusted by adjusting the water charging ratio, reaction temperature, pressure, time, etc.

As a specific example of the above-mentioned degradation method, for example, JP-A-53-
Examples include methods described in JP-A No. 57295, JP-A-53-65389, JP-A-6O-790H, JP-A-60-79015, and the like.

Note that if the acrylamide copolymer of the present invention is colored, it may impair its commercial value.
It is preferable to use the product of the method exemplified in Japanese Patent No. 08.

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

There are no particular limitations on the method for producing the intermediate for the acrylamide copolymer of the present invention from the raw materials. An example will be explained below.

The raw material is dissolved in an inert solvent such as an aromatic or aliphatic hydrocarbon such as benzene, toluene, xylene, cyclohexanone, decane, cumene, or cymene, or a ketone.
After adding 150 mol% dialkylaminoalkylamine and reacting at 130 to 220°C to convert the carboxyl group contained in the acrylic acid structural unit to dialkylaminoalkylamide, it was made into an intermediate for an acrylamide copolymer. The linear acrylamide random copolymer of the present invention can be modified by cationic modification with a known quaternizing agent such as an alkyl halide or a dialkyl sulfate.

The acrylamide copolymer of the present invention thus obtained exhibits excellent antistatic ability. The reason for this is not clear, but it is because the acrylamide structural unit contained in the acrylamide copolymer of the present invention takes in moisture from the air, and Xe ionizes and exhibits electrical conduction, resulting in low electrical resistance. It is considered that

Furthermore, in the present invention, the acrylamide structural unit does not exhibit volatility even at high temperatures, and is chemically incorporated into the acrylamide-based copolymer of the present invention.
There is no volatilization during processing, and it is thought that there will be no blocking or deterioration of the physical properties of the thermoplastic resin after processing.

Examples of thermoplastic resins to which the acrylamide copolymer of the present invention can be applied include polyolefin resins such as polyethylene and polypropylene; polystyrene, ABS, etc.
Examples include polystyrene resins such as resins; polyamide resins; polyesters such as polybutylene terephthalate; and 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 explained in more detail based on production examples and examples, but the present invention is not limited to these examples.

Production Example 1 Ethylene-ethyl acrylate copolymer with a weight average molecular weight of 78,000 (ethyl acrylate content: 7 mol%) 200
g was charged together with 2 kg of water into an autoclave with a capacity of 41 and equipped with a magnetic stirrer. Next, after completely removing the oxygen dissolved in the water by bubbling nitrogen gas, pressurizing with nitrogen gas (50 kg/cd) and degassing (1 kg/aIr) were repeated 5 times.
The oxygen concentration in the system was reduced to 1 ppm or less.

Next, under nitrogen gas atmosphere at 350℃ and 200kg/c
After carrying out the decomposition and degradation reaction for 4 hours under the conditions of d, it was cooled.

The physical properties of the obtained ethylene-acrylic acid-ethyl acrylic acid copolymer were examined for weight average molecular weight, infrared absorption spectrum, and IH-NMR spectrum according to the following methods. Table 1 shows the weight average molecular weight and the content of each structural unit.

Further, the infrared absorption spectrum is shown in FIG. 1, and the +H-NMR spectrum is shown in FIG. 2.

(Weight average molecular weight) Kobunshi Journal, Vol. 44, No. 2, pp. 139-141 (19
It was measured according to the method described in 1987). Manufactured by Waters, GPC-244f column: Manufactured by Showa Denko K.K., 5
Hodex, ^-80M/S (2 bottles)), using 1-chloronaphthalene as the solvent, flow rate 0.7 ml
/min, and the column temperature was 210°C.

(Infrared absorption spectrum) Measurement was performed using a KBr tablet using JASCO Kogyo ■, ^-202.

(Jtl-NMR spectrum) From JEOL Ltd., JMN-GSX270J:
Measurement was performed at 55°C using deuterated chloroform as a solvent.

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

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

[Margin below]

Example 1 Volume II 4 with thermometer, stirrer, addition funnel and Dean Bark water separator
400 ml of xylene in a two-glass flask, ethylene-ethyl acrylate-acrylic acid copolymer (preparation example)
raw materials) 150 g and para-toluenesulfonic acid 10
I prepared g.

Next, N1 dimethylaminopropylamine 21, I
g was charged and heated to 14[i °C] using an oil bath, the produced water was continuously removed by azeotropy with xylene, and the reaction was further carried out at 140 °C for 17 hours, and azeotropy of the produced water was observed. The amidation reaction was continued until there was no more residue.

458 g of the reaction mixture was cooled to 80° C., the reaction mixture [Og] containing the intermediate of the present invention was separated, and 287 g of methyl iodide was gradually added dropwise to the remaining reaction mixture from a dropping funnel over 1 hour. During this time, heat generation was observed, but the reaction temperature was maintained at 90°C by cooling, and after the completion of the dropwise addition, l[l
The aging reaction was carried out at 0° C. for 4 hours.

The previously separated intermediate of the present invention and the obtained reaction mixture were taken out and separately poured into a large amount of methanol,
The generated precipitate was collected and dried under vacuum to obtain a product.

Yield: Intermediate 3, Sg.

The amount of the acrylamide copolymer was 187.5 g, and the yields were 96.7% and 98%, respectively, based on the raw material ethylene-ethyl acrylate-acrylic acid copolymer.

Next, the infrared absorption spectrum, )1-NMII spectrum, weight average molecular weight, and number average molecular weight of the obtained intermediate and acrylamide copolymer of the present invention were examined.

The results of the infrared absorption spectrum, weight average molecular weight, and number average molecular weight are shown in Table 2.

Figure 3 shows the infrared absorption spectrum of the intermediate, ')I-NMI
The I spectrum is shown in FIG. 4, the infrared absorption spectrum of the acrylamide copolymer is shown in FIG. 5, and the H-NMR spectrum is shown in FIG.

Further, the molecular weight distribution curves of the intermediate and the acrylamide copolymer are shown in FIG. 7 and FIG. 8, respectively.

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

The yield, infrared absorption spectrum, H-NMR spectrum, weight average molecular weight, and number average molecular weight of the obtained acrylamide copolymer were examined in the same manner as in Example 1. yield,
The measurement results of the infrared absorption spectrum, weight average molecular weight, and number average molecular weight are shown in Table 2 together with the yield.

[Margin below]

Note that the measurement results (chemical shift (ppm)) of the 'H-NMR spectrum are as follows.

('H-NMR spectrum measurement results) (a) Example 1 (Chemical shift (ppm)) ■: 3.4, ■: 2.2, ■: 3.8, ■: 34, ■:
41, ■=15 (b) Example 2 C12■ (Chemical shift (ppm)) ■: 3.4, ■: 2.2, ■: 3.7, ■: 3,1, ■
:35, ■:], 5, ■:1.5, ■=4.1, ■:4
．． ], [phase]=1.5 (c) Example 3 c=o c=.

CF3OCF2O (chemical shift (ppm)) ■・3.3, ■・2.2, ■: 3.7, ■: 31, ■:
4.6, ■=7.2~7.4, ■, 2,3, ■・41,
■: 1.5 (d) Example 4 (Chemical shift (ppIII)) ■: 3.8, ■: 38, ■=33, ■: 4.9, ■near, 4-7.6, ■: 4 ．． l, ■: 1.5 (e) Example 5 NH CF2O CF2O CF2O (chemical shift (ppm)) ■: 3,4, ■: 2. I, ■: 3.5, ■=3.1, ■
・3, 5, ■・1.5, ■: 1.5, ■: 4.1 (to)
Example 6 c=o c=.

CH3 [phase] H3C-C-CH3■ CH2■ (Chemical shift (ppm)) ■・3.5, ■:], 5, ■=39, ■=311■:3
5, ■=15, ■・15, ■:411■:tl, [phase]
:1.5 (G) Example 7 NH CF2O CF2O CF2O (Chemical shift (ppm)) ■: 3.4, ■: 22, ■・3.8, ■=3.1, ■
:3.5, ■2 1.5 (H) Example 8 c=o c=.

ONH eo3s -0-CH2-C) 13 ■ ■ (Chemical shift (ppm)) ■: 3.8, ■: 3. ll, ■: 3.1, ■: 3.5,
■: 1.5, ■: 15, ■: 4.1, ■=4.1, ■:
1.5, [phase] = 1.5 (S) Example 9 (Chemical shift (ppm)) ■: 3. ll, ■: 3.8, ■: 3.5, ■: 1.5,
■: 4.9, ■=7.4~7,6, ■: 40, ■: I5
, ■・1.5, [Phase]・1.5 Experimental Examples 1 to 9 10 parts by weight of the acrylamide copolymer obtained in each example or the copolymer and polypropylene resin (Mitsui Toatsu (
Co., Ltd.: JS]429) 90 parts by weight of the blend was introduced into a T-die type fR film apparatus heated to 200°C to form an unstretched film with a thickness of 5011 m and a width of 500 cm.

Cut the obtained film into ]OcmX ]Qcm,
This was used as a test film. In addition, as a control field, one prepared without using an acrylamide copolymer was also prepared.

Next, the obtained film was examined for surface resistivity, water resistance, blocking resistance, transparency, and strength and elongation according to the following methods. The results are shown in Table 3.

(a) Surface specific resistance ■Surface specific resistance test After leaving the film under the conditions of 20°C and 30% RH (relative humidity) or 20°C and 60% RH for 24 hours,
The surface resistivity value was measured using Kawaguchi Denki Seisakusho's new model Chozetsu Soto R-503.

■ Sustainability test After storing the film at room temperature for 30 days, 20℃, 60%
After being left for 24 hours under RH conditions, the surface resistivity value was measured in the same manner as in (2) above.

■Water resistance The film made of the acrylamide copolymer of the present invention is stored at room temperature for 30 days, and the film made of the acrylamide copolymer of the present invention and polypropylene is aged for 14 days in an oven at 40°C. , mama lemon (lion) as a detergent on its surface.
After thoroughly washing with an aqueous solution (manufactured by Co., Ltd.), rinsing thoroughly with ion-exchanged water, and then washing in an atmosphere of 20°C and 60% RH for 24 hours.
After leaving it for a while, the surface resistivity was measured in the same manner as in (2) above.

(b) Blocking resistance Two films prepared by blending the acrylamide copolymer of the present invention with polypropylene were mixed into 2 [1cIIIX 2
Place it between DCm glass plates and put it in an oven at 40℃.
It was aged for 14 days. After 14 days, the film was taken out, peeled off by hand, and the presence or absence of blocking was measured.

○No ni-blocking×With co-blocking (c) Transparency The transparency of a film prepared by blending the acrylamide copolymer of the present invention with polypropylene was visually determined.

○: Good transparency
mn) was measured. This sample was chucked with a distance of 59 mm.
It was applied to a Tensilon type tensile tester set to
It was pulled at a speed of +nm/nin, and the breaking strength (S+) and breaking elongation (s) were measured, and the tensile strength and elongation were determined by the following equations.

s (mm) [Elongation] l = xlO [1 (%) 50m
n+ Comparative Experimental Example 1 Test films were produced in the same manner as in Experimental Examples 1 to 9, except that polypropylene was used instead of the blend, and various physical properties were measured.

The results are shown in Table 3.

Comparative Experimental Example 2 Test films were 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 stearyl jetanolamide as an antistatic agent was used instead of the blend. Physical properties were measured. The results are shown in Table 3.

As is clear from the results shown in Table 3, the acrylamide copolymer of the present invention imparts excellent antistatic ability to thermoplastic resins, and also reduces the transparency and strength and elongation of thermoplastic resins. It can be seen that there was no problem, and that it had excellent blocking resistance.

〔Effect of the invention〕

The acrylamide copolymer of the present invention imparts excellent antistatic properties to thermoplastic resins, and also improves the transparency of films and molded products formed using thermoplastic resins.
Since it does not reduce physical properties such as strength and elongation and has excellent punching resistance, it can be widely applied to various thermoplastic resins.

[Brief explanation of the drawing]

Figures 1 and 2 are graphs of the infrared absorption spectrum Oyohi'H-NMR spectrum of the ethylene-ethyl acrylate-acrylic acid copolymer used as the intermediate obtained in Production Example 1, respectively, and Figure 3 is a graph of the Oyohi'H-NMR spectrum. and FIG. 4 are graphs of the infrared absorption spectrum and IH-NMR spectrum of the acrylamide copolymer intermediate obtained in Example 1 of the present invention, respectively, and FIG. 5 and FIG. The infrared absorption spectrum and '1-NMR spectrum of the acrylamide copolymer obtained in Example 1, Figures 7 and 8 are the molecular weight distribution curve and the intermediate obtained in Example 1 of the present invention, respectively. It is a molecular weight distribution curve of an acrylamide-based copolymer.

Claims (1)

[Claims] 1 Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 65 to 99 mol% of ethylene structural units represented by General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^ 1 indicates an alkyl group having 1 to 4 carbon atoms) 0 to 15 mol% of acrylate structural units and general formula: ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R^2 is an alkyl group having 2 to 4 carbon atoms) 8 alkylene group, R^3
and R^4 are each an alkyl group having 1 to 4 carbon atoms, R
^5 is an acrylamide structural unit represented by an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 1 to 12 carbon atoms, or an alicyclic alkyl group having 1 to 12 carbon atoms; An acrylamide-based copolymer consisting of 1 to 35 mol% and randomly arranged in a linear manner and having a weight average molecular weight of 1,000 to 50,000. 2 Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Ethylene structural units represented by 65 to 99 mol%, General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a carbon number of 1 to 0 to 15 mol% of acrylate structural units represented by (representing the alkyl group of 4) and the general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 is an alkylene group having 2 to 8 carbon atoms, R ^3
and R^4 each represent an alkyl group having 1 to 4 carbon atoms) consisting of 1 to 35 mol% of acrylamide structural units arranged irregularly in a linear manner and having a weight average molecular weight of 10.
00 to 50,000 acrylamide copolymer.