JP2983314B2 - Polyolefin resin composition with improved transparency - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition having improved transparency, and more particularly, to a transparent polyolefin resin composition obtained by blending an alicyclic carboxylic acid amide compound of an aliphatic polyamine with a polyolefin resin. The present invention relates to a polyolefin resin composition having improved properties.

[0002]

BACKGROUND OF THE INVENTION Polyethylene, polypropylene, polybutene-1 and 1,2
-A crystalline polyolefin resin such as polybutadiene has advantages such as high mechanical strength and excellent electrical insulation, and is very useful as a raw material resin for films, sheets and various molded products.

[0003] However, these polyolefin resins have extremely low transparency, which limits their use.

[0004] In order to eliminate such disadvantages, various transparency improving agents have been proposed. Examples of these transparency improvers include aliphatic and aromatic dicarboxylic acids or anhydrides thereof, aromatic monocarboxylic acids, amine salts of aliphatic dicarboxylic acids, metal salts, aluminum salts of aromatic acids, dibenzylidene sorbitol, There are metal salts of aromatic acidic phosphoric acid esters and the like, but all of these compounds have insufficient effects, and furthermore, many of them promote the deterioration of the resin, lower the mechanical strength, and have a bad odor. However, there was a problem with any of them, and none was practically satisfactory.

[0005]

Means for Solving the Problems The present inventors have made various studies in view of the present situation, and as a result, by adding an alicyclic carboxylic acid amide compound of an aliphatic polyvalent amine to a polyolefin-based resin, the present invention has been made. Significantly improved the transparency of the resin,
In addition, they have found that the mechanical strength is also increased, and reached the present invention.

That is, according to the present invention, there is provided a transparent composition comprising 0.01 to 10 parts by weight of an alicyclic carboxylic acid amide compound of a divalent or higher aliphatic amine with respect to 100 parts by weight of a polyolefin resin. An object of the present invention is to provide an improved polyolefin resin composition.

Hereinafter, the polyolefin resin composition of the present invention will be described in detail.

[0008] The polyvalent amine constituting the alicyclic carboxylic acid amide compound of the aliphatic polyvalent amine added for improving the transparency of the polyolefin resin used in the present invention includes, for example, ethylenediamine, , 3-propylenediamine, 1,4-butylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N, N'-
Bisaminoethyl-ethylenediamine, N, N'-bisaminoethyl-hexamethylenediamine, N, N'-bisaminopropyl-ethylenediamine, N, N'-bisaminopropyl-hexamethylenediamine, tris (2
-Aminoethyl) amine, tris (3-aminopropyl) amine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, octamethylenediamine, decamethylenediamine,
Undecamethylenediamine, 3,9-bis (aminopropyl) -2,4,8,10-tetraoxaspiro [5,
5] undecane, 4-oxa-1,7-diaminopentane, 4,7-dioxa-1,10-diaminodecane,
4,8-dioxa-6,6-dimethyl-1,11-diaminoundecane, m-xylylenediamine, 1,6,1
1-triaminoundecane, 4-aminomethyl-1,8
Polyvalent amines such as diaminooctane.

The alicyclic carboxylic acid constituting the alicyclic carboxylic acid amide compound of an aliphatic polyamine used in the present invention includes, for example, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, -Methylcyclopentanecarboxylic acid, 3-methylcyclopentanecarboxylic acid, 2,5-dimethylcyclopentanecarboxylic acid, 1-isopropyl-2-methylcyclopentanecarboxylic acid, 1-phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexyl Carboxylic acid, 1
-Methylcyclohexanecarboxylic acid, 4-methylcyclohexylcarboxylic acid, 2,2-dimethylcyclohexylcarboxylic acid, 2,4-dimethylcyclohexylcarboxylic acid, 3,5-dimethylcyclohexylcarboxylic acid, 4-
Propylcyclohexylcarboxylic acid, 4-butylcyclohexylcarboxylic acid, 4-pentylcyclohexylcarboxylic acid, 4-hexylcyclohexylcarboxylic acid, 4-
Pentylcyclohexylcarboxylic acid, 4-octylcyclohexylcarboxylic acid, 4-phenylcyclohexylcarboxylic acid, 1-phenylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-cycloheptenecarboxylic acid, Examples thereof include 1-methylcycloheptanecarboxylic acid and 4-methylcycloheptanecarboxylic acid.

These aliphatic polyamine alicyclic carboxylic acid amide compounds are prepared by reacting the corresponding aliphatic polyamine with an alicyclic carboxylic acid, a lower ester thereof, an acid halide or an acid anhydride. It can be easily manufactured.

[Synthesis Example] Next, a typical synthesis example of an alicyclic carboxylic acid amide compound of an aliphatic polyvalent amine used in the composition of the present invention will be described.
However, the present invention is not limited by the following synthesis examples, and may be obtained by other synthesis methods.

[Synthesis Example 1] 1,6,11-triaminoundecanetricyclohexa
Synthesis of carboxamides.

[0013]

Embedded image

1,6,11-triaminoundecane
06 g (0.02 mol), 7.1 g of triethylamine
(0.07 mol) and 200 g of dioxane were placed in a reaction vessel, and 8.8 g (0.06 mol) of cyclohexanecarboxylic acid chloride was slowly added dropwise over 30 minutes while stirring at 35 to 40 ° C. Then, it was kept at the same temperature for 2 hours. 100 ml of hot water of 80 ° C. was added to the reaction system,
For 1 hour. Then, cool down to 30 ° C,
The precipitate was separated by filtration, washed several times with warm water, and dried to obtain 9.5 g of the desired amide compound. White powder Melting point
120 ° C

From the infrared absorption spectrum, the carboxylic acid chloride disappeared, and the absorption of the carboxylic acid amide was confirmed.

Elemental analysis (as C32H57N303)

In the present invention, examples of the polyolefin resin having improved transparency include α-ethylene, propylene, butene, pentene, 3-methylbutene, hexene, 4-methylpentene, heptene, octene and 1,2-butadiene. Homo- or copolymers of olefins; a majority of these α-olefins and vinyl esters such as vinyl acetate, unsaturated organic acids such as acrylic acid, maleic anhydride and methyl methacrylate (including esters, salts, amides and amines) ), Random, block or graft copolymers such as vinylsilane such as vinyltrimethoxysilane; or modified polymers such as chlorination, sulfonation and oxidation of these polymers.

Specifically, low, medium or high density polyethylene, polypropylene, polybutene, 1,2-polybutadiene, ethylene-propylene random or block copolymer, ethylene-propylene-butene copolymer, ethylene-4-methyl Penten copolymer, propylene-hexene copolymer, propylene-hexene-butene copolymer and the like can be mentioned.

The polyolefin resin composition of the present invention may contain, if necessary, a phenolic antioxidant, an organic phosphorus-containing compound such as an organic phosphite, a thioether antioxidant, an ultraviolet absorber or a hindered amine compound. Can be added to further improve its oxidative and light stability.

The phenolic antioxidants usable in the present invention include, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-
Di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-ditertbutylphenol),
1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4
-Methyl-6- (2-hydroxy-3-tert-butyl-5
-Methylbenzyl) phenyl] terephthalate, 1,
3,5-tris (2,6-dimethyl-3-hydroxy-
4-tert-butylbenzyl) isocyanurate, 1,3
5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3
5-di-tert-butyl-4-hydroxybenzyl) -2,
4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl)
[Bropionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyl) Oxy-
3-tert-butyl-5-methylbenzyl) phenol,
3,9-bis [1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5
5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5-butylphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-4
-Hydroxy-5-methylphenyl) propionate]
And the like.

These phenolic antioxidants are added in an amount of 0.0 to 100 parts by weight of the polyolefin resin.
01 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

Examples of the organic phosphorus-containing compound include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tridecyl phosphite, di (tridecyl) pentaerythritol diphosphite, and distearyl. Pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) Isopropylidene diphenol diphosphite, tetra (tridecyl)-
4,4'-n-butylidenebis (2-tert-butyl-5-
Methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2′-methylenebis (4,6-di Tributylphenyl) octylphosphite, 2,2′-methylenebis (4,6-ditertbutylphenyl) octadecylphosphite, 2,2′-methylenebis (4,6-ditertbutylphenyl) fluorophosphite, And tetrakis (2,4-ditertbutylphenyl) biphenylenediphosphonite.

The amount of the organic phosphorus-containing compound added is 0.001 to 100 parts by weight of the polyolefin resin.
5 parts by weight, preferably 0.01 to 3 parts by weight.

Examples of the thioether antioxidants include thiodipropionic acid dilauryl, dimyristyl,
And dialkylthiodipropionates such as myristylstearyl and distearyl esters, and β-alkylmercaptopropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

The addition amount of these thioether-based antioxidants is 0.0 to 100 parts by weight of the polyolefin-based resin.
The amount is from 0.01 to 5 parts by weight, preferably from 0.05 to 3 parts by weight.

As the ultraviolet absorber, for example, 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2′-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′,
5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- 2- (2'-hydroxyphenyl) benzotriazoles such as hydroxy-3 ', 5'-dicumylphenyl) benzotriazole and 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol Phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-
Benzoates such as 3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-
Substituted oxanilides such as 2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- And cyanoacrylates such as (p-methoxyphenyl) acrylate.

The amount of these ultraviolet absorbers is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin.

Light stabilizers such as hindered amine compounds include, for example, 2,2,6,6-tetramethyl-4
Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6
6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, tetrakis (2,2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrates (1,2,2,6,6-
Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ', 5'-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl)-
2,2,6,6-tetramethyl-4-piperidinol /
Diethyl succinate polycondensate, 1,6-bis (2,2,
6,6-tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,
6,6-tetramethyl-4-piperidylamino) hexane / 2,4-chloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Hindered amine compounds such as piperidylamino) hexane / 2,4-chloro-6-tert-octylamino-s-triazine polycondensate.

These light stabilizers are added in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the polyolefin resin.
Preferably it is 0.05 to 3 parts by weight.

In addition, the polyolefin resin composition of the present invention may contain, if necessary, an inorganic filler such as talc, calcium carbonate and glass fiber, a metal soap such as calcium stearate and calcium stearyl lactate, and an aluminum-p-tert. Butyl benzoate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, bis (4-tert-butylphenyl) phosphate sodium salt, 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate sodium salt, etc. Other nucleating agents, metal soaps, pigments, dyes, fillers, foaming agents, flame retardants, antistatic agents, lubricants, processing aids, and the like may be added as desired.

The composition of the present invention can be prepared by injection molding, extrusion molding,
It can be molded by a conventionally known method such as blow molding, and is not limited by the molding method or its form.

Further, the surface properties of the composition of the present invention can be improved by subjecting the composition to a well-known treatment such as a low-temperature plasma treatment after molding.

[0033]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited in any way by these examples.

Example 1 To 100 parts by weight of an ethylene-propylene random copolymer, 0.3 part by weight of a transparency improver shown in the following Table 1 was added, and the mixture was mixed with a grinder for 5 minutes. Pellets were granulated using an extruder under the conditions of 20 ° C. and a rotation speed of 20 rpm. Using these pellets, an injection molding machine was used to obtain a temperature of 2
A sheet having a thickness of 1 mm was formed under the conditions of 30 ° C., cooling 60 ° C., and 10 seconds, and the haze (%) was measured by ASTM D 1003-52. Further, the pellet was put in a differential calorimeter, melted at 230 ° C. for 10 minutes, and then measured for an exothermic peak temperature (crystallization temperature ° C.) obtained from an exothermic curve when the temperature was lowered at 5 ° C./min. Table 1 shows the results.

[0035]

[Table 1]

* Amine-1: hexamethylenediamine * Amine-2: 3,9-bis (aminopropyl) -2,
4,8,10-tetraoxaspiro [5,5] undecane * Amine-3: 1,6,11-triaminoundecane * Carboxylic acid-1: Cyclopentanecarboxylic acid * Carboxylic acid-2: 4-methylcyclohexanecarboxylic acid Acid * Carboxylic acid-3: 4-butylcyclohexanecarboxylic acid * Carboxylic acid-4: 4-phenylcyclohexylcarboxylic acid

Example 2 Roll kneading was performed at 180 ° C. for 5 minutes using the following formulation.
Further, compression molding was carried out at 180 ° C. and 250 kg / cm ² for 5 minutes, and then the mixture was rapidly cooled to 60 ° C. to prepare a test piece having a thickness of 1 mm. The haze of this test piece was measured in the same manner as in Example 1. Also, Izod impact strength at 20 ° C. was measured. Table 2 shows the results. <Combination> parts by weight Unstabilized polypropylene resin 100 stearyl-β- (3,5-di-tert-butyl-4-0.1 hydroxyphenyl) propionate distearylthiodipropionate 0.2 Transparency improver (Table 2) 0.3

[0038]

[Table 2]

* Amine-4: 4,8-dioxa-6,6
-Dimethyl-1,11-diaminoundecane * Amine-5: 4-aminomethyl-1,8-diaminooctane * Carboxylic acid-5: 4-hexylcyclohexanecarboxylic acid * Carboxylic acid-6: 4-octylcyclohexanecarboxylic acid

Example 3 <Combination> parts by weight Unstabilized polyethylene resin 100 4,4-thiobis (3-methyl-6-tert-butyl 0.1 phenol) Transparency improver (Table 3) 2 Roll-knead the above mixture at 160 ° C for 5 minutes,
It was compression molded under the conditions of 60 ° C. and 200 kg / cm ² for 5 minutes, and then rapidly cooled to 60 ° C. to prepare a 1 mm thick test piece, and the haze was measured in the same manner as in Example 1. Table 3 shows the results.

[0041]

[Table 3]

[0042]

As can be seen from the results of the examples, the alicyclic carboxylic acid amide compound of the aliphatic polyamine according to the present invention significantly improves the transparency of the polyolefin resin and also improves the mechanical strength of the resin. It is clear that there is an excellent effect that does not decrease. Also, almost no odor is felt during processing.

On the other hand, when the aliphatic polyamine alicyclic carboxylic acid amide compound is not used, or when the aliphatic polyamine fatty acid amide or the aromatic acid aluminum salt is used, the polyolefin resin is used. Has little effect of improving the transparency and has the disadvantage of lowering the mechanical strength of the resin.

Continuation of front page (72) Inventor Shinji Anabane 5-2-13-1 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 23 / 00-23/36 C08K 5/00-5/59

Claims (2)

(57) [Claims] 1. A polyolefin having improved transparency, comprising 0.01 to 10 parts by weight of an alicyclic carboxylic acid amide compound of a divalent or higher aliphatic amine per 100 parts by weight of a polyolefin resin. -Based resin composition. 2. The divalent or higher valent aliphatic amine is hexamethylenediamine, 3,9-bis (aminopropyl) -2,
The polyolefin resin composition according to claim 1, wherein the composition is selected from 4,8,10-tetraoxaspiro [5,5] undecane, 1,6,11-triaminoundecane and 4-aminomethyl-1,8-diaminooctane.