KR950010549B1 - Ethylee copolymer and process for producing said copolymer - Google Patents

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Description

Ethylene Copolymer and Method for Making the Same

1 is a graph showing the relationship between the copolymer composition and the thermal properties of the ethylene-dimethylaminopropylacrylamide copolymer of the present invention and the ethylene-dimethylamino ethyl methacrylate copolymer of the prior art,

2 is an infrared absorption spectrum of the ethylene-dimethylaminopropylacrylamide copolymer of the present invention,

3 is an infrared absorption spectrum of the ethylene-dimethylaminoethylmethacrylate copolymer of the prior art.

The present invention relates to novel ethylene copolymers obtained by radical copolymerization of ethylene and ethylenically unsaturated comonomers and methods of making such copolymers. In particular, the present invention relates to copolymers of ethylene and dialkylaminoalkyl acrylamide comonomers and to processes for preparing such copolymers by high pressure radical copolymerization.

The novel ethylene copolymers obtained have the inherent properties of polyethylene (e.g., excellent moldability, low temperature brittleness and flexibility, etc.), and also have better saltability than polyethylene. In the case of forming a quaternary salt having excellent miscibility with poly (α-olefin), a cationic electrically conductive polymer having excellent film forming properties and electrical conductivity can be provided.

Molded articles such as fibers, sheets and films obtained from the novel ethylene copolymers of the present invention have excellent performance of absorbing aqueous solutions of organic or inorganic acids and / or aqueous solutions of various metal salts.

As described above, the novel ethylene copolymers of the present invention have various functions and are therefore expected to have various uses. In particular, it is expected to be used in the following two fields. That is, one uses ethylene copolymer as an additive to impart salting property to poly (α-olefin), and the other uses ethylene copolymer as a starting material for an electrically conductive coating having excellent film forming properties and electrical conductivity. Is to use.

Conventional techniques in this first application of the novel ethylene copolymers of the present invention will be described later.

Poly (α-olefins), such as polyethylene or polypropylene, have good physical and mechanical properties and good processability, but because they are hydrophobic and chemically inert, it is very difficult to dye products of such polymers. In particular, crystalline polypropylene fibers have various characteristics such as being light, strong, and excellent in heat retention properties. Thus, in the early stages of development, these fibers were expected to be widely applied to clothing and the like as "dreamlike fibers," but these fibers are presently, for example, because they have serious drawbacks that cannot be dyed by conventional dyeing methods. For example, it is used in limited fields of application such as wadding, colored carpet yarns, and the like.

Therefore, there has been a great demand for improving the salting property of polypropylene fibers and various methods have been proposed.

For example, materials that can be dyeing sites for polypropylene and anionic dyes and fluoroscopy are practical methods, and the properties such as easiness and yarn strength of polypropylene inherently are not degraded. Attention has been paid to the fact that various dyes commonly used in nylon yarn and wool can be used.

In particular, as described in Japanese Patent Publication No. 222523/67, copolymers of dialkylaminoalkyl acrylate comonomers represented by ethylene and dimethylaminoethyl methacrylate are excellent in thermal stability. In addition, it can be dispersed very finely and uniformly in polypropylene by melt kneading, thereby providing a dyeable poly (α-olefin) composition having excellent bagability.

In addition, the effect of improving the flammability of the composition by adding various metal salts of organic carboxylic acids to the composition is described in the literature (see Japanese Patent Application No. 6666/73 and 41345/84). The term "OPI" as used herein is "Unexamined Japanese Patent Application").

On the other hand, with regard to the dyeing method, the effects of various dyeing aids and dyeing oils are described in the literature [see: Japanese Patent Application (OPI) Nos. 154583/81, 154584/81, 133283/82, 149389/83, and 1786/84.

However, as a result of several attempts by the present inventors for practical use, fibers obtained by spinning a variety of known dyeable polypropylene compositions containing copolymers of ethylene and dialkylamino alkyl acrylate comonomers as described above are presently present. In the case of dyeing using the dyeing method and apparatus widely and commonly used in the dyeing industry, the dyeing speed of the dye is slow even by using the above-described improved dyeing method, and therefore the dyeing time should be extended to an uneconomic level. It was confirmed that.

For example, tuft carpets made using fibers obtained from the dyeable polypropylene compositions mentioned previously as pile yarns are winds at 95 ° C. using a salt bath acidified with acetic acid to obtain satisfactory dyeing rates. When staining, the immersion time should be extended by about 1.5 to about 2 times as compared to dyeing tuft carpets prepared using the same type of 6-nylon yarn or mimic yarn. If the immersion time is shorter than the above-mentioned range, since the dyeability is insufficient, only the surface of the yarn is dyed, so that the dyed carpet has various fastnesses such as washing resistance, sun resistance and friction resistance.

A second field of application of the novel ethylene copolymers of the present invention, namely conventional techniques for electroconductive coatings, will be described later.

Cationic aqueous dispersion polymers obtained by reacting a copolymer of ethylene dialkylaminoalkyl acrylate with an acid in water are described in the literature (Japanese Patent Application No. 16542/72).

Such aqueous dispersions are used as electroconductive coatings or antistatic agents for electrical insulating materials such as paper or plastic films. The aqueous dispersion is excellent in accepting inorganic fillers such as semiconductors of metal oxides (e.g., zinc oxide, tin oxide and titanium oxide), coated on a support such as paper or plastic film, and obtained by drying the coated support. The coated film is semiconductive and is characterized by excellent flexibility, water resistance and solvent resistance.

As a result of the study by the present inventors, the method described in Japanese Patent Application (OPI) Nos. 98304/83 and 180697/83, that is, a copolymer of ethylene and dialkylaminoalkyl acrylate can be obtained. Wide range of humidity when alkylolamine is added to the aqueous dispersion obtained by the process characterized in that it is converted to a water soluble quaternary salt in water, which is further reacted with epihalohydrin and then the resulting mixture is heated. It has been found to be obtained in cationic aqueous dispersions which can provide a coating having a relatively low surface resistance over the range.

In the case where the electrostatic recording material is used as the electroconductive layer, the coating obtained by coating and drying the cationic aqueous dispersion obtained by using the above-mentioned ethylene-dialkylaminoalkyl acrylate copolymer on a support such as paper and plastic flue is dried. , Electrical conductivity is not high enough. In particular, when the thickness of the coating is as thin as about 1 mu m, a satisfactory clear recording pattern is not obtained.

It is an object of the present invention to provide novel ethylene copolymers and methods of making such copolymers. The novel ethylene copolymer overcomes the above-mentioned problems of ethylene-dimethylaminoalkyl acrylate copolymers and, when used as a caustic improver, absorbs dyes of nylon yarn and wool even in the early stages of the dyeing process, i.e. at relatively low temperatures. It is possible to produce poly (α-olefin) fibers exhibiting a dye adsorption rate almost equal to the rate, and when used as an electrically conductive coating agent, the electrical conductivity of the coated film obtained by coating on a support such as paper and plastic film Increase significantly. Even when the thickness of the coated film is thin, the surface resistivity of the coated film is sufficiently low, and thus can be used as the electroconductive layer of the electrostatic recording material.

The present invention consists of 40 to 95% by weight of ethylene, 60 to 5% by weight of at least one dialkylaminoalkylacrylamide comonomer of the following general formula (A) and 0 to 20% by weight of at least one ethylenically unsaturated comonomer It relates to an ethylene copolymer characterized in that the molecular weight is 5000 to 50,000. :

Wherein R ₁ is a hydrogen atom or a methyl group; R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms; n is an integer of 2-5.

The invention also provides a mixture of 40 to 99% by weight of ethylene, 60 to 1% by weight of one or more of the following dialkylamino alkyl acrylamide comonomers of Formula (A), and 0 to 20% by weight of one or more ethylenically unsaturated comonomers: And a copolymerization reaction in the presence of a radical polymerization initiator under conditions of a polymerization pressure of 500 to 3000 kg / cm ² and a polymerization temperature of 100 to 300 ° C. :

Wherein R ₁ is a hydrogen atom or a methyl group; R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms; n is an integer of 2-5.

G 807)의 값이다.1 shows the relationship between the copolymer composition and the thermal properties of the ethylene-dimethylaminopropylacrylamide copolymer of the present invention and the ethylene-dimethylaminoethyl methacrylate copolymer of the prior art. The abscissa represents the comonomer composition (mol%), and the ordinate represents the crystallization temperature (Tc) and the melting point (Tm) measured using a differential scanning calorimeter (DSC). At 0% comonomer composition, the value is low density polyethylene (Sumikaten manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)

G 807).

2 is an infrared absorption spectrum of the ethylene-dimethylaminopropylacrylamide copolymer of the present invention. Arrows indicate the location of the characteristic absorbing park.

3 is an infrared absorption spectrum of the ethylene-dimethylaminoethylmethacrylate copolymer of the prior art. Arrows indicate the location of characteristic absorption peaks.

Examples of preferred dialkylamino alkylacrylamide comonomers (A) for the ethylene copolymer of the present invention include dimethylaminoethyl acrylamide, dimethylaminopropyl acrylamide, dimethylaminobutyl acrylamide, diethylaminoethyl acrylamide, diethylamino Propyl acrylamide, diethylaminobutyl acrylamide, di-n-propylaminoethyl acrylamide, di-n-propylaminopropyl acrylamide, di-n-propylaminobutyl acrylamide, N- (1,1-dimethyl- 3-dimethylaminopropyl) -acrylamide, N- (2-methyl-3-dimethylaminopropyl) -acrylamide and their corresponding methacrylamide derivatives.

Particularly preferred comonomers are dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethylacrylamide, dimethylaminoethyl methacrylamide and the like.

The comonomers of general formula (A) having n of 1 or 6 or more and / or having 5 or more carbon atoms of R ₂ and R ₃ are relatively difficult and expensive to produce on a commercial scale, as well as unstable or very viscous under heating conditions. They can thus be applied to conventional high pressure ethylene polymerization processes.

The polymerized unit of the dialkylaminoalkyl acrylamide comonomer in the ethylene copolymer of the present invention is 60 to 5% by weight, preferably 55 to 15% by weight, more preferably 50 to 20% by weight. If the polymerized unit is less than 5% by weight, the effect of improving the saltability of the poly (α-olefin) composition is less. If the copolymer is converted to a quaternary salt by reacting with an acid, the hydrophilicity is weakened, and thus, uniform fine particles It was not possible to obtain a stable aqueous dispersion containing On the other hand, when the polymerized unit of the dialkylaminoalkyl acrylamide comonomer exceeds 60% by weight, the poly (α-olefin) composition using the resulting copolymer has the yarn physical properties and economical standpoint. Not satisfactory When converted to quaternary salts by reaction with acid, the hydrophilicity is so increased that not only the water resistance of the coated film becomes weak, but also a strong coated film cannot be obtained. Thus, when used as an electrically conductive layer of electrostatic recording material, problems arise, for example, in writing characteristics.

In preparing the ethylene copolymer of the present invention, in some cases, for example, a pump may be used to copolymerize the dialkylaminoalkyl acrylamide comonomer with ethylene for the purpose of continuously and stably feeding the high pressure polymerization system. One or more other ethylenically unsaturated comonomers may be used in admixture. In this case, the polymerization unit of the ethylenically unsaturated comonomer to be used is 0 to 20% by weight, preferably 0 to 15% by weight. Preferred examples of the ethylenically unsaturated comonomers include methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, dimethylamino ethyl methacrylate, dimethylaminoethyl acrylate and the like.

The number average molecular weight of the ethylene copolymer of the present invention measured by comparing the peak number of the GPC chart measured using the tetrahydrofuran solution with the peak of standard polystyrene whose molecular weight is known is 5,000 to 50,000, preferably 8,000 to 40,000 Range. The number average molecular weight is approximately equal to the melt index (measured at 190 ° C. according to JIS K-6760) in the range of 1000 to 1 g / 10 min, preferably 500 to 50 g / 10 min.

When the molecular weight exceeds 50,000, when the copolymer is mixed with the poly (α-olefin), the miscibility is poor and the bag is not good, and when the copolymer is reacted with an acid to convert to a quaternary salt, the resulting aqueous dispersion is The dispersibility is poor and the viscosity increases, and therefore, a problem will arise when coating on a support such as paper or plastic film. On the other hand, if the molecular weight is less than 5,000, the washing resistance of the fibers of the dyed poly (α-olefin) composition is weak, and when used as an electrically conductive coating agent, the resulting coated film is weak in water resistance, solvent resistance, strength and the like.

The ethylene copolymer of the present invention comprises 40 to 99% by weight of ethylene, 60 to 1% by weight of dialkylaminoalkyl acrylamide copolymer of general formula (A) and 0 to 20% by weight of one or more ethylenically unsaturated comonomers at specified temperatures and It can be prepared by copolymerizing in the presence of a radical polymerization initiator under pressure conditions.

Copolymerization reaction for producing the ethylene copolymer, and is carried out under a polymerization pressure of 500 to 3,000kg / cm ^2, 700 to a range of 2,500kg / cm ² is preferred. The copolymerization reaction is carried out at a polymerization temperature of 100 to 300 ℃, preferably in the range of 150 to 250 ℃. If the polymerization pressure is less than 500kg / cm ² or the polymerization temperature is less than 100 ℃, the polymerization rate and conversion rate is significantly reduced in any case, a large amount of polymerization initiator is required, which is a disadvantage from an industrial point of view. Polymerization is difficult under pressures above 3000 kg / cm ² or above 300 ° C. and stable operation cannot be expected.

As the polymerization method of the present invention, a batch system, a semicontinuous system, a continuous system, or the like cannot be used. High pressure continuous processes are advantageous from an industrial standpoint.

In the present invention, the radical polymerization initiator for initiating the copolymerization reaction means an initiator which generates radicals under the polymerization conditions used, and includes oxygen, -O-O- bonds or compounds containing -N = N-bonds. As such a catalyst, oxygen, various organic peroxides, azo compounds and the like are suitable. Particularly effective are peroxides and azo compounds of the general formula:

Wherein X is an aralkyl group or derivative group thereof, or an allyl group; Y is an allyl group or derivative group thereof, an aralkyl group, an alkyl group, or a hydrogen atom; X and Y may be the same or different.

Specific examples include diethyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxbenzoate, tert-butyl peroxyacetate, tert-butyl Organic peroxides such as peroxy-2-ethylhexanoate, tert-butyl peroxy pivalate, 2-ethylhexanoyl peroxide, fibaryl peroxide, isopropyl peroxydicarbonate, azobis isobutyronitrile, azo Bis-2,2-diphenylacetonitrile, tert-butylazo-1-cyanocyclohexane, tert-butylazo-2-cyanopropane, tert-butylazo-2- Azo compounds, such as cyanobutane; And mixtures containing two or more of these compounds.

The amount of radical polymerization initiator to be used is in the range of 5 to 3,000 parts by weight per 1,000,000 parts by weight of ethylene.

If necessary, use a printing transfer agent. For example, ethane, propane, propylene, butene-1, isobutene, hexane, heptane, methylcyclohexane, methanol and the like are used particularly effectively.

When the ethylene copolymer of the present invention is mixed with a poly (α-olefin), the above-described polymer components are uniformly mixed, there is no phase separation, and the excellent physical or mechanical properties and moldability inherent in the poly (α-olefin) are inherent. It is possible to obtain a poly (α-olefin) composition with significantly improved saltability and color fastness without deterioration.

When the ethylene copolymer of the present invention is mixed with a poly (α-olefin) exemplified as crystalline polypropylene, the ethylene copolymer is generally added in an amount of 1 to 20 parts by weight per 100 parts by weight of poly (α-olefin), An amount of 2 to 10 parts by weight is preferred. The amount of the ethylene copolymer added is less than 1 part by weight, and the saltability is not high enough. On the other hand, when it exceeds 20 weight part, the bag property and characteristic of a yarn will deteriorate.

In the poly (α-olefin) composition containing the novel ethylene copolymer of the present invention, various additives such as heat stabilizers, antioxidants, anti-UV decomposition agents, antistatic agents and flame retardants, and small amounts of inorganic fillers or pigments may be used. Can be added.

When the ethylene copolymer of the present invention is reacted with hydrochloric acid in water to reduce the quaternary salt, the resulting salt is further reacted with epichlorohydrin to form an aqueous dispersion, followed by alkylolamine compounds such as diethanol amine. Can be added and then heated to obtain a stable cationic aqueous dispersion which can provide a coated film with low surface resistance over a wide range of humidity.

When the above-mentioned aqueous dispersion polymer is coated on a support such as paper or plastic film and then dried, a good coating having a good transparency, flexibility and toughness can be obtained. The coating is very stable against moisture or water. Furthermore, when the above-mentioned aqueous dispersion polymer is used as the electroconductive layer of the electrostatic recording material, an electrostatic recording material is obtained which has a low humidity dependency on the recording density and little change in the recording properties with time. In addition, when the aqueous dispersion polymer is used as an antistatic agent, excellent members are obtained in maintaining the antistatic ability.

Products such as fiber sheets and films obtained by thermoforming the ethylene copolymer of the present invention have excellent performance of absorbing aqueous solutions of various organic and inorganic acids and / or aqueous solutions of metal salts. It is expected to melt in chelate resins and the like.

The invention is described in more detail with reference to the following examples.

Example 1

In a 2-liter stirred autoclave continuous reactor, as shown in Table 1, 17.4 kg / hr liquefied ethylene, 0.49 kg / hr dimethylaminopropyl acrylamide (as 80% by weight methanol solution), tertiary as polymerization initiator 2.5 kg / hr of butyl peroxy pibarate (as 2% by weight of n-heptane solution) and 1.61 kg / hr of methylcyclohexane as chain transfer agent were continuously introduced at a polymerization pressure of 1,700 kg / cm ² and a medium pressure temperature of 190 ° C. Prepare a copolymer.

The melt index (measured at 190 ° C. in JIS K-6760) of the ethylene copolymer obtained above was 108 g / 10 min. The dimethylaminopropyl acrylamide content measured by elemental analysis is 18% by weight. The number average molecular weight measured by GPC method under the following conditions with polystyrene (made by Toyo Soda manufacturing Co., Ltd.) whose molecular weight is known as a standard sample is 19,100.

Device: Room temperature type GPC ("CCP, 8000" manufactured by Toyo Soda Manufacturing Co., Ltd.)

Detector: Differential Refractometer (DRI)

겔-G6000H, G4000H, G3000H, G2000H 및 G1000H(Toyo Soda Manufacturing Co., Ltd. 제조)Column: TSK in series

Gels-G6000H, G4000H, G3000H, G2000H and G1000H manufactured by Toyo Soda Manufacturing Co., Ltd.

Temperature: 40 ℃

Solvent: Tetrahydrofuran

Flow rate: 1.2ml / min

Amount of sample: 1ml (polymer concentration 0.1% by weight)

Data analysis: YHP-9825 (manufactured by Yokokawa Hewlett Packard Co., Ltd.)

[Examples 2 to 8]

Various ethylene copolymers were prepared in the same manner as in Example 1 using the same apparatus as in Example 1. The polymerization reaction conditions and properties (comonomer copolymer content, melt index and number average molecular weight) of the obtained ethylene copolymer are shown in Table 1.

[Reference Examples 1 and 2]

The ethylene copolymer of the present invention is used to prepare a poly-α-olefin) composition and its saltability is evaluated. The staining of the fiber specimens and the evaluation of the color fastness and color fastness are carried out by the methods described below.

(1) dyeing

-K(Electrostripper

-K ; Kao Atlas Co., Ltd.가 제조한 칼륨 알킬 포스페이트의 상표명)로 이루어진 염욕(욕비=1 : 60)에 용해시키고, 50℃까지 가열한다. 각각 3g의 양으로 각종 섬유 표본을 상기의 염욕에 침지시킨다. 상하로 교반하면서, 온도를 1℃/min의 비율로 증가시킨다. 온도가 50분 이내에 100℃에 도달한 후, 30분 동안 계속 염색한다.Pre-measured amounts of various dyes were formic acid 2% owf (based on fiber weight), dye preparation 3% owf and electrostrippers.

-K (Electrostripper

-K; It is dissolved in a salt bath made of Kao Atlas Co., Ltd. (trade name of potassium alkyl phosphate) (bath ratio = 1: 60) and heated to 50 ° C. Various fiber specimens are immersed in the salt bath in amounts of 3 g each. While stirring up and down, the temperature is increased at a rate of 1 ° C / min. After the temperature reaches 100 ° C. within 50 minutes, the dyeing is continued for 30 minutes.

(Monogen

, Daiichi Kogyo Seiyaku Co., Ltd.가 제조한 알킬 설페이트의 나트륨 염의 상표명) 2g/ℓ를 함유하는 소오핑욕(욕비=160)에서 60℃에서 5분동안 소오핑하고, 이어서 물로 세척한 다음, 건조시킨다.Take out the stained fiber sample, wash with water, and then

(Monogen

, Sooping bath (bath ratio = 160) containing 2 g / l of sodium salt of alkyl sulfate manufactured by Daiichi Kogyo Seiyaku Co., Ltd. for 5 minutes at 60 ° C., followed by washing with water and drying Let's do it.

(2) DR ₇₀ (Dye Adsorption Rate at 70 ° C)

When the bath temperature reaches 70 ° C. in the temperature rising step of the dyeing method described above, the bath solution is taken in an amount of about 2 ml, and the residual dye concentration is measured by colorimetric method to calculate DR ₇₀ . That is, assuming that the absorbance at the dye intrinsic absorption wavelength of the dye solution before dyeing is a and the absorbance of the surface bath solution at 70 ° C is b, the following equation is given;

DR ₇₀ = 100x (ab-) / a

(3) DR ₁₀₀ (final adsorption rate at 100 ° C)

After dyeing at 100 ° C. for 30 minutes, assuming that the absorbance is c at the dye intrinsic absorption wavelength of the bath solution,

DR ₁₀₀ is as follows:

DR ₁₀₀ = 100x (ac) / a

(F) FR (final dyeing rate)

Assuming the absorbance in the dye intrinsic absorption wavelength of the residual solution after d oofing as d, FR is represented by the following equation:

FR = DR ₁₀₀ -100d / a

(5) light fastness

It is measured according to JIS L-0842.

The light source is a carbon arc. Light fastness is measured by comparing the color yarn with a blue scale after irradiation at 63 ° C. for 80 hours. Grades are as follows: Grade 1 (lowest) to Grade 8 (best).

(6) friction fastness

Measured according to JIS L-0849.

Friction fastness is measured after rubbing 100 times with wet cotton (JIS L-0803) at 30 frequencies per minute under a load of 200 g. The grades are as follows: Grade 1 (lowest) to Grade 5 (best).

Fiber specimens are prepared by the following method.

1010(Irganox

1010 ; Ciba Geigy AG의 상표명) 0.1 중량부와 자외선 흡수제로서의 스미소르브

300(Sumisorb

300 ; Sumitomo Chemical Co., Ltd. 의 상표명) 0.5중량부를 헨셀 혼합기를 사용하여 혼합한다. 생성된 혼합물을 직경이 30mm 압축기에서 용융혼련하여 표 2에 기재한 조성물 펠렛, DC-1 및 DC-2을 수득한다.Three components in a pre-measured amount, i.e., the polypropylene described in the footnote of Table 2, the ethylene copolymer EC-4 obtained in Example 4 and the organic carboxylic acid sodium salt were added, and Irganox as a stabilizer was added.

1010 (Irganox

1010; Trademark of Ciba Geigy AG) 0.1 parts by weight and Smithsorb as a UV absorber

300 (Sumisorb

300; Sumitomo Chemical Co., Ltd. 0.5 part by weight of the mixture is mixed using a Henschel mixer. The resulting mixture was melt kneaded in a 30 mm diameter compressor to obtain the composition pellets, DC-1 and DC-2, shown in Table 2.

The pellets thus obtained were fed to a spinning machine including a 25 mm compressor (L / D = 15) with a nozzle (number of holes: 12; diameter of holes: 0.8 mm) at the top of the extruder, and the resin temperature was 240 ° C. Melt spinning is performed under the condition that the extruded amount is 1 kg / hr and the winding speed is 450 m / min. The draw is run three times by running on a hotplate maintained at 110 ° C. to obtain a sample of 10 fpf multifilament.

The above operation is continued for 3 hours. No spinning problem occurs in any composition, and the uniform multifilament has a smooth and glossy surface.

블루 E-PRL(Aminyl

Blue-E-PRL ; Sumitomo Chemical Co., Ltd.의 상표명)를 사용하여 포름산-산성화된 욕에서 염색하고, 소오핑한다. 표 3에 기재한 바와 같이, 가염성과 색상 견뢰도는 양호하며, 더우기 DR₇₀은 수준이 높다.The multifilament sample obtained in this way is an acid dye aminyl

Blue E-PRL (Aminyl

Blue-E-PRL; Dyeing in a formic acid-acidified bath using the trade name of Sumitomo Chemical Co., Ltd. As shown in Table 3, the saltability and color fastness are good, and the DR ₇₀ is also high.

[Reference Examples 3 to 5]

Dyeable compositions DC-3, DC-4 and DC-5 are prepared using polypropylene and ethylene copolymers EC-5 or EC-8 in the same manner as in Reference Examples 1 and 2. Samples of the multifilaments obtained by spinning and stretching in the same manner as in Reference Examples 1 and 2 are stained and then sieved. The results are very satisfactory as described in Table 3.

Reference Reference Examples 1 to 5

Various dyeable polypropylene compositions containing copolymers of ethylene and dimethylaminoethyl methacrylate as described in Table 2 under the same method as in Examples 1 and 2 and the same conditions as in Reference Examples 1 and 2 ( RF-1 to RF-5) are prepared.

Each composition was spun and stretched using the same spinner as in Reference Examples 1 and 2 under the same conditions as in Reference Examples 1 and 2 to prepare 12 multifilament specimens each 10 dpf. Samples were stained as described in Reference Examples 1 and 2 and the results are shown in Table 3.

As for bagability, all compositions are satisfactory, and the quality of the filaments is also uniform and good. However, the dye, DR ₇₀ values, representing the dye adsorption rate are significantly lower than the compositions of Reference Examples 1 and 2 of the present invention, and furthermore, the compositions have the final results of Reference Examples 1 and 2 of the present invention in terms of final dyeing rate and color fastness. Inferior to dyeing rate and color fastness.

Reference Example 6

Cationic aqueous dispersions are prepared using the ethylene copolymers of the invention. The dispersion was coated to form an electrostatic recording material, and then surface resistance and recording characteristics were evaluated.

In a 1000 ml glass flask, 100 g of ethylene copolymer EC-4 as described in Table 4, 357 g of water and 26 g of 36% hydrochloric acid (corresponding to 100 mol parts per 100 mol parts of the amine group of the copolymer) were added, and the resulting mixture was brought to room temperature. Heat with stirring at -100 [deg.] C. for 30 min, then stir at reflux for 60 parts at 100 [deg.] C. The reaction mixture is then cooled to 80 ° C. with stirring, 24 g epiclohydrin (corresponding to 100 moles per 100 moles of amine group in the copolymer) is added and then reacted for 5 hours. An additional 27 g of diethanol amine (corresponding to 100 moles of diethanol amine per 100 moles of amine group in the copolymer) at 80 ° C. is added and the resulting mixture is stirred for 5 hours to complete the reaction. The reaction mixture is cooled and then filtered using a 200 mesh stainless steel mesh.

The reaction product obtained above is a light brown homogeneous aqueous dispersion with a particle diameter of 0.1 μm or less. The pH is 6.9 and the viscosity is 17 cps (25 ° C.). The solids content measured by evaporating the moisture by heating at 100 ° C. is 30% by weight.

Coat the aqueous dispersion with high grade paper (84 _g / m) using a # 10 bar coater and dry for 5 minutes at 100 ° C in a hot air circulation dryer to obtain a uniform coating film with a solid content of 1.2 g / m ² and no curling To form.

The surface electrical resistance of coated paper is an ultra-insulating meter manufactured by Toa Denpa Kogyo Co., Ltd. under the conditions of 100 V applied voltage, 30, 50 or 70% RH humidity, and 23 ° C temperature. Measured using model SM-10E). The surface electrical resistances are 5x10 polypropylene 7, 8x10 polypropylene 6 and 9x10 polypropylene 5 Ω, respectively. On the other hand, the paper surface resistance before coating was 4 kg / hr x 10 polypropylene 1 polypropylene 3 at a humidity of 50% RH.

Using a # 10 bar coater, a coating for dielectric layer (dielectric coating c manufactured by Sakata Shokai Co., Ltd.) was coated with a solution of 70 parts by weight and 30 parts by weight of calcium carbonate on coated paper having a semi-conductive surface. After drying with air in a ventilation chamber, it was dried for 5 minutes at 100 ° C. in a hot air circulation dryer to obtain an electrostatic recording paper having a coated solid content of 6.0 g / m ² .

This electrostatic recording paper was placed on an electrostatic recording tester (type electrostatic printer EP101.AD manufactured by Matsushita Denso Co., Ltd.) and subjected to an electrostatic recording test at 30% RH humidity. A very sharp print pattern is obtained.

[Reference Examples 7 and 8]

An aqueous dispersion was prepared using ethylene copolymers EC-4 and EC-6 in the same manner as in Reference Example 6. In addition, the surface resistance was measured in the same manner as in Reference Example 6, and an electrostatic recording test was performed.

The results are set forth in Table 4 together with the results of Reference Example 6.

Reference Control Examples 6 and 7 for Reference

A cationic aqueous dispersion was prepared in the same manner as in Reference Example 6 using a copolymer of ethylene and dimethylaminoethyl methacrylate or dimethylaminoethyl acrylate as a starting material, and the surface resistance was increased. After the measurement, the electrostatic recording test is performed. The results are shown in Table 4.

From the results in Table 4, in the performance as an electrically conductive layer of the electrostatic recording material, the cationic aqueous dispersion using the ethylene dialkylamino alkyl acrylamide copolymer as the starting material is ethylenedialkyl aminoalkyl acrylate air as the starting material. It is evident in terms of surface resistance and recording properties that the combination is superior to cationic aqueous dispersions.

Reference Example 9

The ethylene-dimethylamino propyl acrylamide copolymer EC-4 obtained in Example 4 was used to evaluate the absorption characteristics of various acid aqueous solutions and inorganic metal salt aqueous solutions. The results are shown in Table 5.

Pelletizing copolymer EC-4 and thermally compressing under conditions of 130 ° C. and 50 kg / cm ² to form a 0.5 mm thick sheet, and then a plurality of specimen pieces 2.5 cm long and 4 cm wide, respectively. Well represented from The specimens were immersed in 50 ml of each of the various aqueous acid and inorganic metal salt solutions whose concentrations are listed in Table 5 and stored for 4 hours at a temperature of 60 ° C. The sample is then taken out, the filter paper is used to remove the solution attached to the surface, and then the weight change is measured. The increase in weight is measured. In all cases, the shape of the sheet is maintained even after the solution is absorbed at high speed.

Reference Example 8 For Reference

The absorption characteristics of various acid aqueous solutions and inorganic metal salt aqueous solutions were measured using the same ethylene-dimethylaminoethyl methacrylate copolymer (E-1) as used in Reference Example 1 for reference. The results are shown in Table 5.

The ethylene copolymers EC-4 and E-1 are very similar in content and average molecular weight, but there are surprising differences in the absorption characteristics of the aqueous acid solution and the aqueous inorganic metal salt solution. Significant differences in properties are demonstrated in the chlorinating effect and reference example 6, as demonstrated in Reference Example 1, that the ethylene dialkylaminoalkylacrylamide copolymer is much better than the ethylene-dialkylaminoacrylate copolymer. It is considered to exhibit the performance as an electroconductive coating material as described above.

Reference Example 10

Differential scanning calorimetry (DSC) is used to determine the ethylene-dimethylamino propyl acrylamide copolymer and the ethylene-dimethylaminoethyl methacrylate copolymer at determined temperatures (Tc) and melting points (Tm). As shown in FIG. 1, it was found that there is a good linear relationship between the molar content of each copolymer and Tc and Tm.

That is, assuming that the amount of each copolymerized high monomer is M (mol%), the relationship can be expressed as follows.

Ethylene-Dimethylaminopropyl Acrylamide Copolymer:

Tm = -3.3 (M) +113 (° C)

Tc = -4.1 (M) +97 (° C.)

Ethylene-Dimethylaminoethyl Methacrylate Copolymer:

Tm = -4.6 (M) +113 (° C)

Tc = -5.1 (M) +97 (° C)

When compared at the same molar content, as can be seen in Figure 1, it is surprising that the ethylene-dimethylaminopropyl acrylamide copolymer has a much higher Tm and Tc than the ethylene-dimethylaminoethyl methacrylate copolymer. This fact cannot be explained solely by the effect of inhibiting the crystallization of the polyethylene backbone due to the introduction of comonomer side chains, given that the molecular weights of the two comonomers, i. Thus, this fact indicates that there is a significant difference between the intermolecular or intramolecular interaction mechanism of the amide bond and the intermolecular or intramolecular interaction mechanism of the ester bond.

This is evidenced by the large difference in the properties of absorbing aqueous acid solutions or inorganic metal salt solutions between the two ethylene copolymers described above, as can be seen in Reference Example 9 and Reference Control Example 8.

Reference Example 11

The ethylene-dimethylamino propyl acrylamide copolymer (EC-4) and the ethylene-dimethylamino ethyl methacrylate copolymer (E-1) are analyzed using an infrared spectrophotometer. The infrared absorption spectrum thus obtained is shown in FIGS. 2 and 3, respectively.

The frequency and assignment of each characteristic absorption peak is shown in Table 6.

First as shown in Fig. 2, the ethylene-dimethylaminopropyl acrylamide copolymer had characteristic absorption, i.e., has an amide I absorption band (1640cm ^-1) and amide II absorption band (1550cm ^-1) due to amide bond .

As shown in FIG. 3, the ethylene-dimethylaminoethyl methacrylate copolymer has characteristic absorption, namely absorption due to ester bonds (1730 cm ⁻¹ and 1150 cm ⁻¹ ).

(1) MMA: Methyl Me

(Noblen

) FL800(Sumitomo chemical Co., Ltd.가 제조한 폴리프로필렌의 상표명, 단독중합체 등급, JIS K-6758에 따라 측정, MFI-10g/min), 펠렛형P-1: Noble

(Noblen

) FL800 (trade name of polypropylene manufactured by Sumitomo chemical Co., Ltd., homopolymer grade, measured according to JIS K-6758, MFI-10 g / min), pelletized

E-1: Copolymer 60/40 (weight) (89.5 / 10/6, mol) of ethylene and dimethylaminoethyl methacrylate (measured according to JIS K-6760, MFI = 360g 10min), pellet form

E-2: copolymer 71/29 (weight) (93.2 / 6.8, mol) of ethylene and dimethylaminoethyl methacrylate (measured according to JIS K-6760, MFI = 100 g / 10 min), pellet form

S-1: higher fatty acid mixture contains sodium salt (5 parts by weight of sodium myristate, 30 parts by weight of sodium palmidate and 65 parts by weight of sodium stearate), flaky, 3 parts by weight of mole

(Noblen

) WF727R(Sumitomo chemical Co., Ltd.가 제조한 폴리프로필렌의 상표명, 랜덤 공중합체 등급, 에틸렌 함량 : 4중량%, JIS K-6758에 따라 측정, MI=30), 펠렛형P-2: Noble

(Noblen

) WF727R (trade name of polypropylene manufactured by Sumitomo chemical Co., Ltd., random copolymer grade, ethylene content: 4% by weight, measured according to JIS K-6758, MI = 30), pellet type

E-3: copolymer 49/51 (weight) (84.3 / 15.7, mol) of ethylene and dimethylaminoethyl methacrylate (measured according to JIS K-6760, MFI = 160 g / 10min), pellet form

(Aminyl

) : 산성염료(Sumitomo Chemical Co., Ltd. 제조)1) Aminyl

(Aminyl

): Acid dyes (manufactured by Sumitomo Chemical Co., Ltd.)

(Lanyl

) : 예비금속화 산성염료(Sumitomo Chemical Co., Ltd. 제조).2) Ranil

(Lanyl

): Premetallic acid dye (manufactured by Sumitomo Chemical Co., Ltd.).

Immersion condition: 60 ℃, 4 hours

Weight increase rate: Weight of sample after immersion

As described above, the novel ethylene-dialkylamino alkyl acrylamide copolymer of the present invention, when mixed with poly (α-olefin), provides a poly (α-olefin) composition having excellent salting properties. Moreover, when the copolymer of the present invention is used as a starting material of an aqueous dispersion, when the aqueous dispersion is coated on a support such as paper or plastic film and dried, a coating layer having a very increased electrical conductivity can be formed. Such a coating layer can be used as a conductive recording material as the electroconductive layer.

While the invention has been described in detail and with reference to specific embodiments thereof, those skilled in the art will recognize that various changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (8)

40 to 95% by weight of ethylene, 60 to 5% by weight of at least one dialkylaminoalkyl acrylamide comonomer of the following general formula (A) and 0 to 20% by weight of one or more ethylenically unsaturated comonomers with a number average molecular weight of 5000 Ethylene copolymer, characterized in that from to 50,000.

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms, and n is an integer of 2 to 5; The ethylene copolymer of claim 1 wherein the dialkylaminoalkyl acrylamide comonomer is at least one of dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylamide and dimethylaminoethyl methacrylamide. The ethylene copolymer of claim 1 wherein the ethylenically unsaturated comonomer is at least one of methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, dimethylaminoethyl methacrylate and dimethylaminoethyl acrylate. 40 to 99% by weight of ethylene, 60 to 5% by weight of at least one dialkylaminoalkyl acrylamide comonomer of the following general formula (A) and 0 to 20% by weight of at least one ethylenically unsaturated comonomer of 500 to 3000 kg / cm ² Characterized by copolymerization in the presence of a radical polymerization initiator under conditions of polymerization pressure and polymerization temperature of 100 to 300 ° C., 40 to 95% by weight of ethylene, at least one dialkylaminoalkyl acrylamide comonomer of the following general formula (A) A process for preparing an ethylene copolymer consisting of 60 to 5% by weight and 0 to 20% by weight of at least one ethylenically unsaturated comonomer and having a number average molecular weight of 5,000 to 50,000.

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms, and n is an integer of 2 to 5; The method of claim 4 wherein the dialkylaminoalkyl acrylamide comonomer is at least one of dimethylaminopropyl acrylamide, dimethylamino propyl methacrylamide, dimethylaminoethyl acrylamide and dimethylaminoethyl methacrylamide. The method of claim 4 wherein the ethylenically unsaturated comonomer is at least one of methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, dimethylaminoethyl methacrylate and dimethylaminoethyl acrylate. 3. The ethylene copolymer of claim 2 wherein the dialkylaminoalkylacrylamide comonomer is dimethylaminopropyl acrylamide. 8. The ethylene copolymer according to claim 7, wherein when the content of dimethylaminopropyl acrylamide comonomer is expressed as M (mol%), the melting point (Tm) and the crystallization temperature (Tc) of the copolymer have the following relationship. Tm = -3.3 (M) +113 (° C) Tc = -4.1 (M) +97 (° C.)

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