JPS61103954A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To provide a polyolefin composition giving a molded article having good appearance and excellent adhesivity, by adding tetrakis(2,4-di-t-butylphenyl) 4,4-biphenylene-diphosphonite to a polyolefin modified with an unsaturated dicarboxylic acid (derivative). CONSTITUTION:The objective composition can be prepared by compounding (A) 100pts.(wt.) of a modified polyolefin having a graft content of 0.001-5(wt)% and prepared by modifying at least a part of a polyolefin (preferably a high- pressure-processed low-density polyethylene, etc.) with an unsaturated dicarboxylic acid or its derivative (preferably maleic acid, etc.) with (B) 0.001-3pts. of tetrakis(2,4-di-t-butylphenyl) 4,4-biphenylene-diphosphonite and preferably (C) 0.01-3pts. of an alkylphenol-type antioxidant, preferably tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propion-ate]methane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyolefin composition that gives molded products such as sheets, films, bottles, etc. a good appearance and excellent adhesive properties.

[Conventional technology]

Unlike polyamide and polyester, polyolefins such as polyethylene, polypropylene, and ethylene/vinyl acetate are non-polar or have low polarity, so even if polyolefin and polyamide are laminated, there is no adhesion between the eyebrows and it is completely unusable.

For this reason, many proposals have been made to use a modified polyolefin, in which part or all of the polyolefin is graft-modified with a graft monomer consisting of an unsaturated carboxylic acid or its anhydride, as an adhesive layer between polyolefin and polyamide, or in place of the polyolefin. (for example,
Special Publication No. 51-43055, Special Publication No. 53-3687
2, Japanese Patent Publication No. 55-49989, etc.), some effects have been obtained.

On the other hand, in recent years, there has been an increasing demand for materials with excellent transparency, surface texture, etc., in order to achieve display effects in a variety of applications, including food packaging films, sheets, and bottles. However, extrusion molded products such as modified polyolefin films and blow molded products mentioned above tend to have a slightly rough surface compared to unmodified polyolefin. When laminated with polyolefin and polyamide, ethylene/vinyl alcohol copolymer, etc., interface irregularities often occur at the interface between the polyolefin layer and the polyamide, ethylene/vinyl alcohol copolymer layer, etc., which often seriously impairs the appearance of the molded laminate.Therefore, some kind of solution is desired. The current situation was that

[Problem that the invention attempts to solve]

In view of this situation, the present inventors have developed a method for improving the surface texture, transparency, interface roughness, etc. of extrusion molded products of modified polyolefins partially or wholly modified with graft monomers consisting of unsaturated dicarboxylic acids or derivatives thereof. As a result of various studies, we added tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene-diphosphonite (2,4-di-tert-butylphenyl), a well-known stabilizer against the effects of oxygen, heat, and light, to modified polyolefins. It has been found that the above object can be achieved by adding the compound (Japanese Patent Publication No. 50-35096) and further by adding an alkylphenol antioxidant in combination, and the present invention has been completed.

[Means for solving problems]

That is, in the present invention, based on 100 parts by weight of a modified polyolefin (A) partially or wholly modified with a graft monomer consisting of an unsaturated dicarboxylic acid or a derivative thereof,
Adding 0.001 to 3 parts by weight of tetrakis(2,4-tert-)tylphenyloni-(C), and an alkylphenol antioxidant (D)
The object of the present invention is to provide a polyolefin composition characterized in that it contains 0.01 to 3 parts by weight.

[For production]

The polyolefin (B) serving as the base of the modified polyolefin (A) in the present invention includes ethylene, propylene, 1
-butene, 1-hexene, 4-methyl-1-, 7f sweetfish. . -O. Twi,. Homopolymer,. - 'Copolymers of olefins, or copolymers of α-olefins and vinyl compounds such as vinyl acetate, vinyl chloride, methyl methacrylate, and styrene. Specifically, for example, high-pressure low-density polyethylene (HP- LDPE),
Medium/low pressure low density polyethylene (so-called L-LDPE)
, medium density polyethylene, high density polyethylene (HDPE)
), ethylene/1-butene lantum copolymer, ethylene/propylene random copolymer, polypropylene (P
P), propylene random copolymer, propylene block copolymer, propylene/ethylene random copolymer, propylene/1-butene random copolymer, bojan-butene, 1-butene/propylene copolymer, poly 4-
Examples include methyl-1-pentene, ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl methacrylate copolymer (EEA). Among these, HP
-LDPE, L-LDPE, ethylene/1-butene random copolymer, polypropylene, propylene random copolymer, ethylene/vinyl acetate copolymer (EVA
), ethylene-ethyl methacrylate copolymer (HE
A) etc. are preferable because they have excellent transparency.

The graft-modified polyolefin (A) in the present invention is obtained by graft copolymerizing part or all of the polyolefin (B) with a graft monomer consisting of an unsaturated dicarboxylic acid or a derivative thereof, and its base structure is substantially linear. This means that it has no three-dimensional crosslinked structure. This can be confirmed by the fact that it dissolves in an organic solvent such as p-xylene and that no gel-like substance is present.

The graft-modified polyolefin (A) in the present invention usually has a grafting amount of 0.001 to 5% by weight of a graft monomer consisting of an unsaturated dicarboxylic acid or a derivative thereof;
Preferably it is in the range of 0.01 to 4% by weight. When using a graft-modified modified polyolefin diluted with an unmodified polyolefin, the amount of the graft monomer in the entire diluted mixture may be within the above range. Graft amount of graft monomer is 0.001% by weight
If it is less than 5% by weight, the adhesion to polyamide, polyester, etc. tends to be poor, while if it exceeds 5% by weight, the adhesion is sufficient, but the moldability and water resistance tend to be poor. -di-tert-butylphenyl>
4. Even if 4'-biphenylene diphosphonite is added, there is a possibility that the extrusion surface etc. will not be improved.

The melt flow rate (MFR) of the graft-modified polyolefin (A) in the present invention is not particularly limited as long as it can be molded, and usually in the case of ethylene polyolefin, it is 0.01 to 100 g/10 m1n (
ASTM D 1238, E), 0.01 to 200 g/for propylene polyolefins
10n+in (ASTM D 1238, L).

When a graft-modified modified polyolefin is diluted with an unmodified riboliolefin and used, the grafting amount of the graft monomer of the modified polyolefin may be kept at a high concentration. Furthermore, the modified polyolefin and the unmodified polyolefin to be diluted do not necessarily have to be of the same type as long as they can be mixed uniformly; for example, modified HP-LD
PE and unmodified L-LDPE, modified FIDPE and unmodified HP-LDPE, modified HDPI! and native L-LD
PR, denatured H[lPE and undenatured EVA, denatured LDPR
Examples include combinations of EVA and unmodified EVA, modified PP and unmodified propylene copolymers, modified PP and unmodified poly-1-butene, and the like.

Examples of unsaturated dicarboxylic acids or derivatives thereof include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, nadic acid (endocys-bicyclo(2,2,1)hept-5-ene-2,3- unsaturated dicarboxylic acids such as (dicarboxylic acid), or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc. Specifically, examples include [maleyl, maleimide, maleic anhydride, citraconic anhydride, Examples include monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, particularly maleic acid,
Nadic acid (2) or acid anhydrides thereof are preferred.

selected from the unsaturated dicarboxylic acids or derivatives thereof.
.

Various conventionally known methods can be employed to produce the modified polyolefin (A) by graft copolymerizing the modified polyolefin (B) with the graft monomer. For example, there is a method of melting the polyolefin (B) and adding a graft monomer to perform graft copolymerization, or a method of melting the polyolefin (B) in a solvent and adding a graft monomer to perform graft copolymerization. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The grafting reaction is usually carried out at a temperature of 60 to 350°C. The proportion of the radical initiator used is usually in the range of 0.0OL to 1 part by weight per 100 parts by weight of the polyolefin (B). As radical initiators, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2
．． 5-dimethyl-2,5-di(peroxidebenzoate)hexyne-3,1,4-bis(tert-butylperoxyisoprobyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5 -di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-
butyl peroxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-
Butylperu 5ec-octoate, tart-butyl perpivalate, cumyl perpivalate and tert
-butyl perdiethyl acetate, other azo compounds,
Examples include azobisisobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)
Hexyne-3,2,5-dimethyl-2,5-di(ter
t-butylperoxy)hexane, 1,4-bis(te
Dialkyl peroxides such as rt-butylperoxyisopropyl)benzene are preferred.

Specific examples of the alkylphenol antioxidant (D) used in the present invention include 2,6-tert-butyl-p-cresol, 4-hydroxy-methyl-2,6
-tert-butylphenol, 4,4'-methylene-bis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-)lis(3
, 5-tert-butyl-4-hydroxy-benzyl)benzene, hexamethylene glycol-bis[β-
(3,5-tert-butyl-4-hydroxy-phenol)propionate, n-octadecyl-3-(
4'-Hydroxy-3', s/-di-tert-butylphenol)propionate, 2,2'-methylene-
Bis(4-methyl-6-tert-butylphenol'
), 4,4-butylidene-bis(3-methyl-6-t
tert-butyl-phenol), tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate comethane, etc.].

Among these, tetrakis[methylene-3(3,5-di-tart-butyl-4-hydroxy-phenyl)propionate comethane is preferred.

The polyolefin composition of the present invention contains 4. tetrakis (2,4-di-tert-butylphenyl) based on 100 parts by weight of the graft-modified polyolefin (A).
4-biphenylenediphosphonite (C) 0.0
01 to 3 parts by weight, preferably o, oos to 1.00 parts by weight.
5 parts by weight and preferably an alkylphenolic antioxidant (D>0.01 to 3 parts by weight, more preferably 0.01 to 3 parts by weight, more preferably 0.
02 to 1 part by weight.

If the amount of (C) added is less than 0.01 part by weight, there will be no improvement effect on the surface texture, transparency, or interface roughness of extruded products, etc., and if it exceeds 3 parts by weight, the effect will be saturated and bleed out will occur. There is a risk.

Furthermore, it is preferable to add 0.01 parts by weight of (D) because it can improve thermal deterioration of the polyolefin composition during molding.On the other hand, if the amount of (D) added exceeds 3 parts by weight, the effect is There is a risk of saturation and bleed out.

In order to obtain the polyolefin composition of the present invention, (A), (
C) or (A), (C), and CD) are mixed in various known methods within the above range, such as a Henschel mixer, a V-Blengie, a ribbon blender, a tampler blender, etc., and furthermore, after mixing, a shaft extruder is used.・0-axis press ratio machine・'
-T-・t<7t<.

A method of melting and kneading with a G-mixer or the like, followed by granulation or pulverization can be adopted.

The polyolefin composition of the present invention includes the above (C) and (
In addition to D), rust preventives, weather stabilizers, antistatic agents, lubricants,
Various additives such as slip agents, anti-blocking agents, nucleating agents, pigments, dyes, etc. which are commonly added to polyolefins may be added to the extent that the purpose of the present invention is not impaired. Furthermore, other heat stabilizers may be used in combination.

The polyolefin composition of the present invention is suitably used after being processed into pipes, films, hollow molded articles, etc. by extrusion molding. Examples of the method for processing into a film include a water-cooled inflation film forming method, an air-cooled inflation film forming method, and a T-gui film forming method. Since the polyolefin composition of the present invention has excellent adhesive properties with other materials such as polyamide and polyester, it can be composited by coextrusion molding with these materials, or by performing extrusion lamination, dry lamination, extrusion coating, etc. on these materials. You can also do that. Specifically, these materials include the above polyolefin (B), polyvinyl chloride, polyvinylidene chloride, vinyl chloride/vinylidene chloride copolymer, polystyrene, polyacrylate, vinyl copolymers such as polyacrylonitrile, and nylon. -6, nylon-66, nylon 7, nylon 10, nylon 11,
Polyamides such as nylon 12, nylon 610, polymethaxylene adipamide, polyethylene terephthalate,
Polyethylene terephthalate/isophthalate copolymerization.

Polymers, polyesters such as polybutylene terephthalate, polyvinyl alcohol, ethylene/vinyl alcohol copolymers, polycarbonates, cellophane, and the like can be mentioned.

〔Effect of the invention〕

The polyolefin composition of the present invention has an excellent film appearance compared to conventional polyolefins when extrusion molding such as blown film molding is performed, and the polyolefin serving as the base material is HP-LDPESL-LDPR, polypropylene, propylene random copolymer. Products using ethylene/vinyl acetate copolymers have excellent transparency and adhesive properties, so they can be used alone or laminated with the above materials such as polyamide, polyester, and polyethylene/vinyl alcohol copolymers. Can be used for food packaging films, pharmaceutical packaging films, etc.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples as long as the elements thereof are not exceeded.

Example I MFR 1.7 g/LoIllin, 95 parts by weight of EVA with a vinyl acetate content of 8.0% by weight and Liver R 4.2 g/
and f! V.A.
+MAR-HDPE-tetrakis(2,4-di-tert-butylphenyl>4.4'
-Biphenylene diphosphonite (trade name 5and
ostab P-EPQ (manufactured by Sandoz Co., Ltd.) in a Henschel mixer, and then granulated at 200°C using a 40mφ-screw extruder (L/D-25) to form a polyolefin composition. (Composition-■) was obtained. Next, a film having a thickness of 50 μm was produced from the composition-① at a molding speed of 10 m/min using a water-cooled blown film molding machine (molding temperature: 210° C.) equipped with an extruder having a diameter of 40 mm. The obtained film was evaluated by the following method.

Haze (%): ASTM D 1003 gross (
%): ASTM D 523 Fisheye: Number of fisheyes with a diameter of 0.3m or more in the ld (N,
), fish eye number (
NZ), the number of fish eyes (Nρ) with a diameter of 0.1 fl or less is determined, and the fish eye occurrence index is determined by the following formula.

F -1ON, +5N2+N.

Based on the number of F, evaluation was performed in the following 7 stages.

Fish eye level I F≧15002 1500>
F≧700 3 700>F≧300°4 300>F≧200 5 200>F≧50 6 50>F≧25 7 25>F The results are shown in Table 1.

Example 2 95 parts by weight of EVA used in Example 1 and MAR-HD used in Example 1 instead of composition-■ used in Example 1
Pf! 5 parts by weight and EVA +MAH-HDPI! =
0.11 parts by weight of P-EPQ and tetrakis[methylene-3 (3,5-di-tert-
Composition prepared by adding 0.1 part by weight of butyl-4-hydroxyphenyl) propionate comethane (trade name, Irganox 1010, manufactured by Musashino Geigy) -■
The same procedure as in Example 1 was carried out except that . The results are shown in Table 1.

Example 3 and Comparative Example 1.2 The same procedure as Example 1 was carried out except that P-HPQ and Irganox 1010 were mixed in the proportions shown in Table 1. The results are shown in Table 1.

Example 4 MFR1, Og/10m1n, density 0.92g/cf
fl HP-LDPE 90 parts by weight and MFR4.2g/1
0mln, maleic anhydride graft amount 2.2% by weight,
10 parts by weight of graft-modified high-density polyethylene (MAI(-)IDPE) with a density of 0.95 g/aII and HP-
LDPR+MAR-HDPE=100 parts by weight, P-EPQ and Irganox in the proportions shown in Table 1
The same procedure as in Example 1 was conducted except that 1010 was used. The results are shown in Table 1.

Example 5 MFR2.0g/10m1n, density 0.92g/cl
, 4-methyl-1-pentene content 3,211101%
of L-LDPE 75 wt.

and MFR5.4g/10m1n, density 0.88g/
ad, 15 parts by weight of ethylene-propylene random copolymer (EPR) with a propylene content of 19 mo1% and a graft modification height of 4,2 g/lQmin, a maleic anhydride graft amount of 2.2 wt%, and a density of 0.95 g/cIa. Density polyethylene (MAH-HDPE) 5 parts by weight and L-LDPE + EPR + MAH-HDPE
= P-EPQ in the proportion shown in Table 1 per 100 parts by weight
Example 1 except that Irganox 1010 and Irganox 1010 were used.
same as .

I went to The results are shown in Table 1.

Example 6 Polyolefin composition used in Example 1 (composition-process)
and MFR1.38/iomin, density 1.19g/c
+d, ethylene/vinyl alcohol copolymer with ethylene content of 32 mo1% (product name: Kurera Eval EP-F
(2) Made by Kurera) was used as a raw material to form a two-layer water-cooled inflation film of EVAL/polyolefin composition = 20μ150μ under the following conditions.

Molding conditions Extruder: 40n+φ 2 units Molding temperature: 210°C Molding speed: 15 m/min The obtained film was evaluated for haze, gloss, and fish eye by the method shown in Example 1. Furthermore, the interface roughness and adhesive strength were evaluated using the following methods.

Surface roughness: At a distance of 3m from your eyes, turn on a 110W fluorescent lamp.
Arrange two lights in parallel at intervals, and place 30a from the eye between the fluorescent light and the eye.
The evaluation was made by placing the film at a distance of m and observing the fluorescent light through the film.

The outline of the fluorescent lights is clear and it is clearly visible that there are two lights. ------1Although the outline of the fluorescent lamp is slightly blurred, it is clearly visible that there are two fluorescent lamps. -・-2゛Although the outline of the fluorescent lamps is blurred, it is still visible that there are two of them. -3 The outline of the fluorescent lamps is very blurry, and you can barely see that there are only two. ------The outline of the four fluorescent lamps was so blurred that it was no longer visible that there were two of them. -...-5 T-
It was peeled off and the adhesive strength was determined.

The results are shown in Table 2.
Examples 7 to 10 and Comparative Example 3.4 A two-layer water-cooled inflation film was formed in the same manner as in Example 6 except that the polyolefin composition used in Examples 2 to 5 and Comparative Example 1.2 was used. The same procedure as in Example 6 was carried out. The results are shown in Table 2.

Example 11 MFR3.7g/10m1n, density 0.92g/a+
1. Maleic anhydride grafted t, opE (MAu-t, opE) with a maleic anhydride graft amount of 0.3% by weight
The ratio of P- shown in Table 2 to the t00ffi quantity is
The same procedure as in Example 6 was conducted except that a polyolefin composition containing EPQ and Irganox 1010 was used. The results are shown in Table 2.

Example 12 MFR5.3g/10m1n, ethylene content 2.5
90 parts by weight of random PP (R-PP) with mo1%,
MFR1.5g/10m1n.

Ethylene-1-butene copolymer (ERR) with 1-butene content of 10 mo1% 5 parts by weight, [η) 1.21 g/d
l, P-EPQ and P-EPQ in the proportions shown in Table 1 for 5 parts by weight of maleic anhydride grafted PP (MAR-PP) with a maleic anhydride grafting amount of 2.5% by weight and 100 parts by weight of R-PP+EBR+MAH-PP- Irgano
The same procedure as in Example 6 was conducted except that a polyolefin composition containing x 1010 was used. The results are shown in Table 2.

Example 13 Nylon 6 (Toshi Alamine CM 10) was used instead of the ethylene/vinyl alcohol copolymer used in Example 10.
21XF, MFR: 1.74g/10m1n
The same procedure as in Example 10 was carried out except that the molding temperature was 260° C. using ASTM D1238, Q, manufactured by Toshi Corporation. The results are shown in Table 2.

Comparative Example 5 P-EPQ in the proportion shown in Table 1 was added to the OVA used in Example 1.
The same procedure as in Example 10 was conducted except that a polyolefin composition containing Irganox 1010 and Irganox 1010 was used.

The results are shown in Table 2.

Claims (2)

[Claims] (1) Tetrakis (
1. A polyolefin composition comprising 0.001 to 3 parts by weight of 2,4-di-tert-butylphenyl)4,4'-biphenylene-diphosphonite (C). (2) 0.0 parts by weight of the alkylphenol antioxidant (D) was added to 100 parts by weight of the modified polyolefin (A).
The polyolefin composition according to claim (1), characterized in that it contains 1 to 3 parts by weight of 0.01 to 3 parts by weight.