JPS6058444A - Olefinic polymer composition - Google Patents

Abstract

PURPOSE:The titled polymer composition, consisting of an olefinic polymer, alkylamine and/or alkylamide and a glycerol monoester, having improved antistatic properties, and suitable to food containers without losing the antistatic effect even in hot molding, etc. CONSTITUTION:A polymer composition obtained by incorporating (A) 100pts.wt. olefinic polymer, preferably having 50,000-500,000 average molecular weight, with (B) 0.05-1.0pts.wt. alkylamine and/or alkylamide, e.g. N,N'-bis(2-hydroxyethyl)stearylamide or tetradecyl-dihydroxyethylamine, and (C) 0.1-2.0pts.wt glycerol monoester, e.g. glycerol monostearate. The total amount of the component (B) is preferably not more than that of the component (C). USE:Various parts, e.g. automobiles, household appliances, etc. and cassette case sheets of VTR, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION II] OBJECTS OF THE INVENTION The present invention relates to A-renoin polymer compositions with superior antistatic properties. More specifically, the following is a composition for an olefinic polymer consisting of (Δ) A lefin polymer, (B) al-4-lamine d3J, and/or alkylamide, and (C) glypyrin mono:[sunol. It is an object of the present invention to provide an A-refin-based I-mouth composite composition that not only has a poor antistatic property but also does not lose its antistatic effect even when subjected to thermoforming, high-speed injection molding, or uniaxial or biaxial stretching. 1. What is the target?

[■] Background of the Invention A Refin-based polymer not only has good processability, but also has good flexibility, and also has good properties such as stiffness 1/[ and hardness. It is molded into other shapes such as film, sheet 1~, and -zo, and is widely used as a general-purpose resin.In addition, items that are molded into sheet 1~ shapes can be further vacuum formed. It is widely used for various containers, industrial parts, etc., and is widely used for various containers, industrial parts, etc.

Since the main purpose of these scale containers, industrial parts, etc. is to protect the product, they are often used in direct contact with dust in the air, and there is a strong demand in the market for products that do not attract dust. However, because A-fin type polymers have high electrical insulation resistance, they have the disadvantage that they are easily charged with static electricity due to friction, etc., and that dust easily adheres to them. I often receive fli!I limited orders.

For these reasons, various antistatic agents have been proposed and commercially available to prevent charging of A-refine HP A bodies, and have been used in oriented films and sheets, as well as extruded molded articles, with sufficient effect. However, the films and sheets obtained by the above-mentioned secondary forming process (for various products, axially stretched or biaxially stretched)
In addition, for products in which the A renoin polymer is even slightly oriented during processing 0 and r, such as products that are injection molded at high speed in the layer, use only commonly used antistatic agents. The formulated composition has no effect at all on optical Fv.
Since it is not possible to do so, there is still no solution that satisfies these claims.

IHll Structure of the Invention In view of the above, the Ministry of the Invention and others have proposed that J3 be added to the molding side I (for example, the secondary molding side of n12) in which even a small amount of the A-refine polymer is blended in the additive I II;T. In order to obtain an A-renoin-based polymer composition that does not lose its antistatic effect (as a result of various searches, it was found that (A) A-renoin-based polymer 100%, (B) Al-1-renoine and/or ) 1 luamide and 豐 (C) Glyrelin [Noesjl 0.1 ~ 2.0 times the A-reno, r-based small combined composition consisting of 0.1 to 2.0 times the molding side opening 1 as described above. The present invention has been achieved by finding that the antistatic effect of the present invention is also a composition that does not lose its antistatic effect.

[rV] Effects of the Invention The A reflex polymer composition obtained according to the present invention exhibits the following effects.

Even if it comes into contact with jc9 dust in the air, it is difficult for dust to adhere to the molded product, and the FM end of the molded product has a high commercial value.

(2) Among the secondary forming processes mentioned above, what happens even if the Inaru jJ method is used? +) It is possible to obtain a molded product that exhibits an FFI prevention effect.

The A-renoin polymer composition obtained according to the present invention can be used in a wide variety of ways in order to exhibit the above-mentioned effects. Typical uses are shown below1.

(1) Food containers for marcarine, 3J gelt, pudding, etc. (2) Automobiles, Sosho Electric products/. 'to which each second part,
Cl) Sea 1 for force 1 hex of V-dong R etc.
LVI Specific description of the invention (Δ) A-lenoin polymer In the present invention, the A-lenoin polymer used is a neutralized polymer of ethylene, a lj monopolymer of pyrene, carbon 91 German combination of α-A-refins with a number of 4 to 6, "-Random or Brane combination of Brene and propylene
] Ivy copolymer and. [Random or block copolymers of Brene and/or propylene and other α-A reflexes having a large number of carbon atoms and b12 (copolymerization ratio of α-A reflexes is at most 20% by weight)] can give.

The average molecular weight of these A-refine polymers is generally as follows:
2 to 1,500,000, preferably 2 to 100,000, and particularly preferred is an olefin resin with a molecular weight of 5 to 500,000. If an A-refine polymer with an average molecular weight of less than 20,000 is used, it has good fluidity and can be used for secondary molding, but it is not practical because the mechanical strength of the product is poor. On the other hand, when using an A-ref/r-type combination with a value exceeding 1.5 million, the flow rate is poor and it is difficult to process the composition.
Even if the composition is manufactured, the molding loadability is not good, so none of the compositions are IJr.

Mata, low density (0.900g 7cm3) /3 to high i″a degree (0.980 (17cm3))
Brene homopolymer 1 wood, pyrene medium polymer, butene-1 monomer, 4-methylbenzone-1 monomer A
body, nontum of ethylene and propylene, and t. L7
[J-tsuku copolymers <f and lantum or tungsten copolymers of ethylene 2 or propylene and other α-A reflexes [J-tsuku copolymers are preferred.

These A-renoin polymers have a catalyst system (so-called Daegler catalyst) consisting of a transition metal compound and an aluminum compound (so-called Daegler catalyst), and a chromium compound (e.g., chromium oxide) supported on a carrier (e.g., silica). μ
By homopolymerizing the Refine using a catalyst system (all Phillips catalysts) or a radical initiator (e.g., an organic peroxide), It is reduced by 1q.

Furthermore, in the present invention, modified polyolefins are produced by combining these olefin polymers with compounds having at least one double bond (for example, unsaturated carboxylic acids, vinyl silane compounds). Also included.

Regarding these A-refin-based vehicle composites J5 and modified polyolefins, their manufacture U h 21<J is well known.

These A reflex polymer a3 and modified polyolefin may be used alone or in combination of two or more. Furthermore, these A-renoin-based polymers and modified poly-A resins may be used in arbitrary proportions.

(B) Alkylamide J3 and Al-1-Ramide Furthermore, the general formula of Tb is one formula] (
1) Equation 1 and (1) Equation 1 are expressed by (1).

CI-12CI-1201-1 Cto1 2 ('; Ll 2 0 (1/ R2C0N (+1) \Cl (2CI-120N <1) Formula J Meyohi (II) +15 to formula C11 '1
3J: HR2 is the same as t) 5"c on a scale, it is an argyl group 31 with 10 or 22 carbon atoms, or an alkenyl group, especially an argyl group with 10 or 22 carbon atoms, or an alkenyl group with 10 or 22 carbon atoms. Preferred are alkenyl JJ. Typical alkyl amides J3 and alkyl mimids include N,
N'-bis(ゝ)1-≦'-hydroni-1-cy'-thyl)sjallylamine, j1-rad'cyl-dihyde'1-xyearylamine, N,N-bis(sai-ji1-yyyl ) to gylydecylamine, N,N'-bis(2-human 1koxy'niboul)dodecylamine, b and N,N
'-Bis(2-hydroxygoedel)sulfarylamide is extracted.

(C) Glyrelin L-Nisal Furthermore, the general formula of the Glyrelin moddiester used in this book is shown in Table 4 below [Formula (■)]. can give.

CH2-C○2R'] CI-101~1 (■) Cl-120l-1 Nil) In the formula (13), [ku3 has a carbon number of 10-2
There are two alkyl groups, especially those with carbon number 1().
~ 20 Furuni 1rujJ (Arishinoga 9LLi, 1
Typical 4r Glyrelin) As a soil sprue, Gurishi・
Lin Shinodamasu] Array 1, linoleic acid and nobrilelide, A leicic acid and nobrilelide Onibi Rishirun FI!
I can give you Hinokurirelite.

('')) Composition 1111 In the present invention, the composition ratio (blending ratio) of norkylamine and alkylamide to the C1100 weight a part olefin polymer is 0.05 to +, as their combined amount.
0 weight (fs, parts), preferably 0.07 to 08 parts by weight, and preferably 0.08 to 7 parts by weight for koma.10
The composition ratio of alkyl amine d3, l, and alkyl amide to 1 part of olefinic polymer is 21 f? ! If the amount is less than 8 parts by weight of 0.05, the antistatic effect cannot be sufficiently exhibited.

On the other hand, if it exceeds 1.0 weight and 171 parts, not only will the antistatic effect not be further improved, but the excess alkylamine and/or al-1-alamide will bleed out, causing the product to deteriorate. Only those that spray powder on the surface and have poor commercial value are 1! ? I can't do it.

In addition, the composition ratio of glycerin and Noesdel to the olefin polymer in the 1()O hand fh part (blending υ1) is 0.
．． 1 to 2.0 parts by weight, preferably 0.1 to 1.5 parts by weight, and preferably 0.1 to 1.0 parts by weight. The composition ratio of glycerin monoester to 100 parts by weight of olefin polymer is 0.01'1ffi
If the amount is less than 50%, the antistatic effect cannot be sufficiently exhibited. On the other hand, if the weight exceeds 2.0 parts, the antistatic effect can be further improved, and the excess glycerin monoester may bleed out and form powder on the surface of the product. , Product 1ii Only products with poor 1rTi can be produced.

; The total addition R of Al used: 1 Ruamine, Al-1-Ramide J3J, and Glycerol monoester was 1
If the amount of C2,5 Ichikawa exceeds 00 parts by weight of A reflex polymer, not only will the antistatic effect not be further improved, but also an excessive amount of antistatic agent (alkylamine, nofurkylamide, glycerin mono 1) will be added. Stell) sprays powder on the surface of the product with Bleed Ara 1~, and the product IIT
Only Ichino with poor IItfi can get 1!7.

Furthermore, 69 between an alkylamine and an al:1-lamide
1 amount should be equal to or less than glycerol mono]nystyl. In contrast, when a mixture of alkylamine and alkylamide (1n) is combined with a large amount of glycerin monoethnol J:
This is undesirable because the antistatic effect is not sufficiently exhibited.

(E) Production of Composition To produce the composition of the present invention, the Δrefine polymer, norkylamine j3J: and/or alkylamide, and glychlin monoesder are mixed in the proportions <26%. It should be blended uniformly.

Composition IJ of the present invention, the Δ reflex polymer composition thus obtained may be used as is, but depending on its use [1], it is generally formulated in the field of A reflex polymers. Stabilizers against oxygen, light (y8 external line) and heat, flame retardants, lubricants, processability improvers, fillers,
Additives such as colorants, electrical property improvers, and adhesion improvers may be added as long as they do not impair the above-mentioned characteristics (effects) of the fin-based car assembly composition of the present invention. good.

The mixing method is to mix propylene polymers using mixers such as extruders, mixing rolls, kneaders, roll mills, Panbury Milly D3, and continuous mixers, which are commonly used in the field of lenoin polymers. There is a method of kneading the molten state, but it is possible to make it more homogeneous by mixing in advance using one of these mixers and then mixing the resulting mixture using the same layer or another φ fff1 machine. It is possible to obtain a processed product or composition. In addition, before carrying out these mixings, tri-blending is performed in advance using a mixer such as a drum tumbler-A3 or Henshi Lumikizer, and the resulting mixture is further melted and processed (more uniformly). Furthermore, a part of these) konsei components (1#J components) is mixed in advance to produce a so-called master badge, and a 7 star batch (mixture) is obtained. ) It is difficult to mix it with the remaining mixture ingredients.

(F) Processing method The thus obtained olefin-based composite composition or a blend containing additives can be processed by extrusion molding or blow molding, which are commonly used in the field of A-refine polymers. Then, by processing methods such as index molding, it is molded into molded products having shapes such as film, sheet, container, etc., and is used in many directions. The effects of the present invention can be significantly exhibited by further processing the molded product in the shape of a strip, film, or sheet for secondary molding as described above. (゛Saru.

When producing the above composition (mixture), the kneading temperature during melt-kneading and the molding temperature of the platform used to produce the molded product by this processing/J-payment are both controlled by the BA synthetic acid component. It is higher than the softening point of the A-refine polymer. but,
If these temperatures are high, the Δrefine polymer will undergo thermal deterioration. For these reasons, these temperatures usually range from 180 to 250°C.

[IV] Example jd3 J: and Comparative Example The present invention will be explained in more detail with reference to Examples below.

In addition, the J3-C1 surface hardness resistance for Example JJJ and Comparative Example was measured using a high resistance measuring device (Yokogawa Hikore 1~ manufactured by Paracard Co., Ltd., trade name 111GII RESISTΔNC).
E METI3R4329A) was charged to C1500 volts for 3 seconds for one cycle, and the voltage was measured after 1 minute.

In addition, the physical properties d3 and types of the olefin polymer, alkylamine and/or alkyl amide, and glycerin monoester used in Examples and Comparative Examples are shown below. pyrene homopolymer [hereinafter referred to as rPP(1)J] whose average molecular weight is about 350,000, ethylene homopolymer whose average molecular weight is about 300,000 [density 0.960 g 7 cm3, J meshita “ρE(Δ
), a 10-pyrene-ethylene block copolymer with an average molecular weight of approximately 450,000 [ethylene content 13% by weight,
a butene-1 homopolymer with an average molecular m of about 280,000 [hereinafter referred to as r P P (2) J];
fl-1 pyrene-co-dylene lantum J+-polymer [ethylene-mediated rj
Hanging 3. o width 96, hereinafter referred to as r P P (3)
(+3) J].

[(B) Al71-ruamine and alkylamidocoalkylamine d5 and alkylamide, N, N
'-bis(2-human 1]xyethyl)ste)7lylamine [hereinafter referred to as ``compound (a)'' and N,N'-bis(2-hydroxyl)stearylamide [hereinafter referred to as ``+1 compound (b)''] I used 1.

[(C) Glyrelin Modiester] Glycerin Modiester 1 (hereinafter referred to as ``compound (C)'') was used as glycerin nystyl.

Examples 1 to 5, Comparative Examples 1 to 7 A resin polymer 100 heavy claw part whose types are shown in Table 1 and antistatic agent 11 whose types, J, and amount are shown in Table 1 were put into a Henschel mixer. (X-C Tri-blend was performed for 2 minutes in advance.

Each compound i obtained was processed using an extruder equipped with a die (diameter 6).
5mm) at a C resin temperature of 240℃, Pp
Sea 1- with a length of 0.7+nm (width 300fflB+)
The temperature was 23℃J3.
After being left for 70 minutes under the conditions of 50% relative ig.
The surface resistivity was measured. The obtained results are shown in Table 1 (Δ
) as shown in 1.

After leaving each sheet 1- obtained as described above under the above conditions for 7 days, it was transferred to a coal continuous molding test 1 machine (manufactured by Asano Kokyusho Co., Ltd., model name: F L X-02 type, A Vacuum forming was carried out using a double-sided infrared heating method) to create containers (length: 140 mm, width: 14 (1111111, depth: 45 mm, bottom thickness: 0.6 mm). Each of the obtained containers The surface resistivity was measured after placing the bottom of the above-mentioned strip 1 for a distance of 71 degrees.The obtained results are shown in Table 1 as (B).

(Leaving space below) Table 1 1) Application of antistatic agent 11 or anti-static i'A (7 leads 7 1-) twins on the surface of the molded product (from the results of 9g & 3 and comparative example, the results obtained by the present invention The composition obtained by the secondary molding process has a lower antistatic property than the containers obtained by the secondary molding process. On the other hand, if the -C1 antistatic agent is outside the composition ratio range of the present invention, even if the antistatic properties of the sheet formed by pressurizing the second molding are poor, the second molding process will not be possible. Containers manufactured by 151 have extremely low antistatic properties, or are sprayed on the surface of the molded product (bleeding error 1~), and only those with poor quality (!l <, -) are used. it is obvious.

100 weight ■ 0.2 car f11 part compound (△) or compound (B) d3 and (), 6 m as an antistatic agent
Triblending of m parts of compound (C) was performed in the same manner as in Example 1. Each of the mixed mixtures was molded using a thin-wall high-speed indexing machine [K rauss Mar
f: ) Made in '44, model name KM 250- +30
0Δ] using T jJJ exit) Crystallinity is 280℃ II Nika is 200kg /CllI2, jJj exit opening time, 5
QJrJ + molding is not performed for 4'i under the conditions of 1 second for cooling interval and 1 to 4 seconds for 1 second, B M (vertical 14 (hn
m, Iiii 140rrr river, depth 45mm, thickness 0.4mm) and lJo? The bottom of each container was left for 7 days with the same strip 1 as in Example 1, and the surface resistivity was measured. jLI results are shown in Table 2.8J.

From the results of the above Examples (13J and Comparative Examples), it is clear that the device of the present invention ([I et al. It is clear that he is not performing well.

Examples 8-70. II; tQ Example 10.11 Seed strength 1 is shown in Table 3.
As a l'l anti-static agent, 0.2 heavy machinery part of compound (A) or compound (B) and 0.6 quick part of compound (C) were triblended in the same manner as in Example 1. Using an extruder (diameter 40 mm) equipped with a T-type tube, each of the mixed mixtures was heated to a resin temperature of 240°C. 1 to create a film (200 mm thick, 300 mm wide, called "original film").

Each original film was stretched for 71'' under the same strip A'1 as in Example 1, and then stretched using a biaxial stretching machine at the stretching ratio listed in Table 3. Stretch or (
Perform uniaxial stretching/=.

This J: sea urchin Cjq film of the stretching machine and the above-mentioned raw film were each stretched into the same strip fl' as in Example 1.
After leaving it for 71EI between l' and C', the surface resistivity was measured. The results are shown in Table 3.
From the results of Example A3 J and Comparative Example above, it is clear that even if the composition obtained according to the present invention is formed into a film and the film is stretched to f!1- does not decrease.On the other hand, with compositions other than the present invention, even if the original film has an antistatic effect, the antistatic effect disappears by stretching, and the antistatic effect of the present invention disappears. It is clear that even when the composition is stretched, the 11 effect before charging is exhibited.

From the above results, it is clear that the A reflex polymer of the present invention is particularly effective when performing the above-mentioned secondary molding process in which the polymer is oriented even if it is diluted.

Special δ' [Applicant: Showa Den] 2 Co., Ltd. Agent: Rishichi Kikuchi -

Claims (1)

[Claims] (△) Olefin polymer 100 Sarakawabe, (B) Alkylamine and/or lζ is argylnoamide 0.0
A composition consisting of 5 to 1.0 parts by weight and <C> 0.1 to 2.0 parts by weight of glycerin monoester; A lenoin-based polymer composition that does not contain as much of a compound as it does.