JPS6355538B2 - - Google Patents

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. [Prior art] Polyolefins such as polyethylene, polypropylene, ethylene/vinyl acetate, etc. are non-polar or have low polarity, unlike polyamides and polyesters, so even if polyolefins and polyamides are laminated, there is no adhesion between the layers, so they cannot be used at all. I can't stand it.
For this reason, many proposals have been made to use modified polyolefin, in which part or all of 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 polyolefin. (For example, Japanese Patent Publication No. 51-43055, Japanese Patent Publication No. 53-36872, Japanese Patent Publication No. 55-49989, etc.), and 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 various applications such as food packaging films, sheets, and bottles. However, extrusion molded products such as films and hollow molded products made of the above-mentioned modified polyolefin have a slightly rough surface compared to unmodified polyolefin.
When laminated with a vinyl alcohol copolymer, etc., interfacial irregularities often occur at the interface between the polyolefin layer and the polyamide, ethylene/vinyl alcohol copolymer layer, etc., which can significantly impair the appearance of the molded laminate. Therefore, the current situation is that some kind of solution is desired. [Problems to be Solved by the Invention] In view of this situation, the present inventors have developed an extrusion molded product of a modified polyolefin in which part or all of the polyolefin is modified with a graft monomer consisting of an unsaturated dicarboxylic acid or its acid anhydride. superficial skin,
As a result of various studies aimed at improving transparency, surface roughness, etc., we added tetrakis (2,4-di-tert-butylphenyl) 4,4', a well-known stabilizer against the effects of oxygen, heat, and light, to modified polyolefin. -Biphenylene-diphosphonite (Special Publication 1972-
It has been found that the above object can be achieved by adding alkylphenol-based antioxidants (Japanese Patent Publication No. 35096), and further by adding an alkylphenol antioxidant, leading to the completion of the present invention. [Means for Solving the Problems] That is, the present invention provides a modified polyolefin (A) in which part or all of the polyolefin is modified with a graft monomer consisting of an unsaturated dicarboxylic acid or an acid anhydride thereof, based on 100 parts by weight of the polyolefin (A). Adding 0.001 to 3 parts by weight of tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite (C), and 0.01 to 3 parts by weight of an alkylphenol antioxidant (D). The object of the present invention is to provide a polyolefin composition characterized in that it contains a combination of 1 and 2 parts. [Function] 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
- Homopolymers of α-olefins such as pentene, α
- Copolymers of olefins, or copolymers of α-olefins and vinyl compounds such as vinyl acetate, vinyl chloride, methyl methacrylate, and styrene. Specifically, examples include 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 random copolymer, ethylene/propylene random copolymer, polypropylene (PP),
Propylene random copolymer, propylene block copolymer, propylene-ethylene random copolymer, propylene-1-butene random copolymer, poly-1-butene, 1-butene-propylene copolymer, poly-4-methyl- Examples include 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 (EEA), etc. are preferable because of their excellent transparency. . Graft-modified polyolefin (A) in the present invention
is a graft copolymer of part or all of the above polyolefin (B) with a graft monomer consisting of an unsaturated dicarboxylic acid or its acid anhydride, and its base structure is substantially linear and three-dimensionally crosslinked. It means that it has no 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 in the present invention refers to a polyolefin in which part or all of it is an unsaturated dicarboxylic acid or its acid anhydride, and the amount of grafting is
0.001 to 5% by weight, preferably 0.01 to 4%
% by weight, and the graft-modified product may be used alone or the graft-modified product may be diluted with unmodified polyolefin.
In either case, the final grafting amount of the graft monomer may be in the range of 0.001 to 5% by weight. The grafting amount of the grafting monomer is
If it is less than 0.001% 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 tends to be poor, and Tetrakis (2,
Even if 4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite is added, the extrusion surface may not be improved. Graft-modified polyolefin (A) in the present invention
The melt flow rate (MFR) of ethylene polyolefin is not particularly limited as long as it can be molded, and is usually 0.01 to 100g/
10min (ASTM D 1238, E), 0.01 to 200g/10min for propylene polyolefin
(ASTM D 1238, L). When using a graft-modified modified polyolefin diluted with an unmodified polyolefin, 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-LDPE and unmodified L-LDPE, modified HDPE and unmodified HP −
LDPE, modified HDPE and unmodified L-LDPE, modified
HDPE and unmodified EVA, modified LDPE and unmodified EVA,
Examples include combinations of modified PP and unmodified propylene copolymer, modified PP and unmodified poly-1-butene, and the like. Examples of unsaturated dicarboxylic acids or their acid anhydrides include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, and nadzic acid.
(endocys-bicyclo[2,2,1]hept-
Examples include unsaturated dicarboxylic acids such as (5-ene-2,3-dicarboxylic acid) or their acid anhydrides, such as maleic anhydride and citraconic anhydride.
Among these, unsaturated dicarboxylic acid anhydrides are preferred, and acid anhydrides of maleic acid and nadic acid are particularly preferred. To produce the modified polyolefin (A) by graft copolymerizing the graft monomer selected from the unsaturated dicarboxylic acid or its acid anhydride to the polyolefin (B), various conventionally known methods can be employed. . For example, there is a method in which polyolefin (B) is dissolved and a graft monomer is added to perform graft copolymerization, or a method in which polyolefin (B) is dissolved in a solvent and a graft monomer is added 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 ratio of radical initiator used is usually 0.001 to 1 per 100 parts by weight of polyolefin (B).
Parts by weight range. 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(peroxide benzoate) hexyne-3 ,1,
4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-
Butyl peracetate, 2,5-dimethyl-2,
5-di(tert-butylperoxy)hexyne-
3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate , tert-butyl perpivalate, cumyl perpivalate and tert-butyl perpivalate
-butylperdiethyl acetate, and other azo compounds such as 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(tert-butylperoxy)
Dialkyl peroxides such as hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred. Alkylphenol antioxidant used in the present invention
Specifically, as (D), for example, 2,6-di-tert
-butyl-p-cresol, 4-hydroxy-methyl-2,6-di-tert-butylphenol,
4,4'-methylene-bis(2,6-tert-butylphenol), 1,3,5-trimethyl-2,4,
6-Tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene, hexamethylene glycol-bis[β-(3,5-di-tert-butyl-4-hydroxy-phenol)propionate, n -Octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4 '-Butylidene-bis(3-methyl-6-tert-butyl-phenol), tetrakis[methylene-3(3,5-
di-tert-butyl-4-hydroxy-phenyl)
Propionate] methane, etc. can be exemplified. Among these, tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate]methane is preferred. The polyolefin composition of the present invention contains tetrakis(2,4-di-tert-butylphenyl) based on 100 parts by weight of the graft-modified polyolefin (A).
4,4′-biphenylene-diphosphonite (C)
0.001 to 3 parts by weight, preferably 0.005 to 1.5
Parts by weight and preferably 0.01 to 3 parts by weight of alkylphenol antioxidant (D), more preferably 0.02 parts by weight
or 1 part by weight. If the amount of (C) added is less than 0.01 part by weight, there is no effect of improving the surface texture, transparency, or interface roughness of extruded products, etc., and if it exceeds 3 parts by weight, the effect may become saturated and bleed out may occur. There is. Moreover, it is preferable to further add 0.01 part by weight of (D), since it is possible to improve thermal deterioration of the polyolefin composition during molding. On the other hand, the amount of (D) added is 3
If the amount exceeds the weight part, the effect may be saturated and bleed out may occur. To obtain the polyolefin composition of the present invention,
A method of mixing (A), (C) or (A), (C) and (D) in various known methods within the above range, such as a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc.; Single screw extruder after mixing,
A method of melt-kneading, granulating or pulverizing using a twin-screw extruder, kneader, Banbury mixer, etc. can be adopted. In addition to the above (C) and (D), the polyolefin composition of the present invention includes a rust preventive agent, a weathering stabilizer, an antistatic agent,
Various additives such as lubricants, 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 by extrusion molding and processing into pipes, films, hollow molded bodies, and the like. Examples of methods for processing the film include a water-cooled inflation film forming method, an air-cooled inflation film forming method, and a T-die film forming method. Since the polyolefin composition of the present invention has excellent adhesion with other materials such as polyamide and polyester, it can be co-extruded with these materials, or subjected to extrusion lamination, dry lamination, extrusion coating, etc. to form composites. It can also be converted into Specifically, these materials include the polyolefin
(B), polyvinyl chloride, polyvinylidene chloride, vinyl chloride/vinylidene chloride copolymer, vinyl copolymers such as polystyrene, polyacrylate, polyacrylonitrile, nylon-6, nylon-
66, nylon 7, nylon 10, nylon 11, nylon 12, nylon 610, polyamides such as polymethaxylene adipamide, polyesters such as polyethylene terephthalate, polyethylene terephthalate/isophthalate copolymers, polybutylene terephthalate, polyvinyl alcohol, ethylene・
vinyl alcohol copolymer, polycarbonate,
Examples include cellophane. [Effects of the Invention] The polyolefin composition of the present invention has a superior film appearance compared to conventional polyolefins when extrusion molding such as inflation film molding is performed, and the polyolefin HP-LDPE serving as a base material,
Products using L-LDPE, polypropylene, propylene random copolymer, and ethylene/vinyl acetate copolymer have excellent transparency and adhesive properties, so they can be used alone or with polyamide, polyester, and ethylene/vinyl alcohol copolymer. It can be used for applications such as food packaging films, pharmaceutical packaging films, etc. by laminating with the above-mentioned materials. [Examples] 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 1 MFR 1.7 g/10 min, 95 parts by weight of EVA with vinyl acetate content 8.0 wt% and graft modified high density polyethylene (MAH) with MFR 4.2 g/10 min, maleic anhydride graft amount 2.2 wt%, density 0.95 g/cm ³ −
HDPE) 5 parts by weight and EVA+MAH−HDPE=
Tetrakis (2,4-di-
tert-butylphenyl) 4,4'-biphenylene
Diphosphonite (product name: Sandostab P-
After mixing 0.1 part by weight of EPQ (manufactured by Sandoz Co., Ltd.) in a Henschel mixer,
= 25) at 200°C to obtain a polyolefin composition (composition -). Next, the composition was applied to a water-cooled inflation film molding machine equipped with a 40 mmφ extruder (molding temperature 210 mm).
℃) at a molding speed of 10 m/min to a thickness of 50 μm.
A film was produced. The obtained film was evaluated by the following method. Haze (%): ASTM D 1003 Gloss (%): ASTM D 523 Fixtures: Number of spots with a diameter of 0.3 mm or more in 1 ^m2 (N ₃ ), Number of spots with a diameter of 0.3 to 0.2 mm (N ₂ ),
Find the number of fisheyes (N ₁ ) with a diameter of 0.1 mm or less,
Obtain the fisheye occurrence index using the formula below. F=10N ₃ +5N ₂ +N ₁ Evaluation was made in the following 7 stages based on the number of F. Fishery Level 1 F≧1500 2 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 the composition used in Example 1 instead of the composition used in Example 1
MAH−HDPE5 parts by weight and EVA+MAH−
0.1 part by weight of P-EPQ and tetrakis[methylene-3 (3.5-di-tert-
A composition prepared by adding 0.1 part by weight of butyl-4-hydroxyphenyl)propionate]methane (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 Examples 1 and 2 The same procedure as in Example 1 was conducted except that P-EPQ and Irganox 1010 were mixed in the proportions shown in Table 1. The results are shown in Table 1. Example 4 HP- with MFR1.0g/10min, density 0.92g/ ^cm2
Graft-modified high ^- density polyethylene (MAH-
HDPE) 10 parts by weight and HP−LDPE+MAH−
The same procedure as in Example 1 was conducted except that P-EPQ and Irganox 1010 were used in the proportions shown in Table 1 with respect to 100 parts by weight of HDPE. The results are shown in Table 1. Example 5 MFR2.0g/10min, density 0.92g/cm ³ , 4-methyl-1-pentene content 3.2mol% L-
LDPE75 parts by weight and MFR5.4g/10min, density 0.88
g/cm ³ , ethylene with a propylene content of 19 mol%
15 parts by weight of propylene random copolymer (EPR), 5 parts by weight of graft-modified high-density polyethylene (MAH-HDPE) with MFR 4.2 g/10 min, maleic anhydride graft amount 2.2% by weight, density 0.95 g/ ^cm3 , and L-LDPE+EPR+MAH- P-EPQ and P-EPQ in the proportions shown in Table 1 for HDPE=100 parts by weight
The same procedure as in Example 1 was conducted except that Irganox 1010 was used. The results are shown in Table 1.

[Table] Example 6 Polyolefin composition (composition-) used in Example 1, MFR 1.3 g/10 min, density 1.19 g/cm ³ ,
Ethylene/vinyl alcohol copolymer with ethylene content of 32 mol% (Product name: Kurera Eval EP-
A two-layer water-cooled inflation film having an EVAL/polyolefin composition of 20μ/50μ was molded under the following conditions under the following conditions. Molding conditions Extruder: 40 mmφ 2 units Molding temperature: 210°C Molding speed: 15 m/min The obtained film was evaluated for haze, gloss, and stickiness by the method shown in Example 1. Furthermore, the interface roughness and adhesive strength were evaluated using the following methods. Surface roughness: Place two 110W fluorescent lamps in parallel at 1cm intervals at a distance of 3m from the eyes, place a film between the fluorescent lamps and the eyes at a distance of 30cm from the eyes, and look through the film. Evaluation was made by observing fluorescent light. It is clearly visible that the outline of the fluorescent lamp is clear. ...1 Although the outline of the fluorescent lights is a little blurred, it is clearly visible that there are two lights. ...2 Although the outline of the fluorescent lights is blurred, it is still visible that there are two lights. …3 The outline of the fluorescent light is very blurred, barely 2
It is visible that it is a book. ...4 The outlines of the fluorescent lights were so blurred that it was no longer visible that there were two lights at all. ...5 Adhesive strength: T-
It was peeled off and the adhesive strength was determined. The results are shown in Table 2. Examples 7 to 10 and Comparative Examples 3 and 4 Examples 2 to 5 and Comparative Examples 1 and 2, except that the polyolefin compositions used in Comparative Examples 1 and 2 were used, and a two-layer water-cooled inflation film was molded in the same manner as in Example 6. I did the same as step 6. The results are shown in Table 2. Example 11 100 parts by weight of maleic anhydride-grafted LDPE (MAH-LDPE) having an MFR of 3.7 g/10 min, a density of 0.92 g/cm ³ and a maleic anhydride graft amount of 0.3 wt%, P in the proportion shown in Table 2 −EPQ and
The same procedure as in Example 6 was conducted except that a polyolefin composition containing Irganox 1010 was used. Table 2 shows the results.
Shown below. Example 12 MFR5.3g/10min, ethylene content 2.5mol%
Random PP (R-PP) 90 parts by weight, MFR 1.5 g/
10min, ethylene with 1-butene content of 10mol%
5 parts by weight of 1-butene copolymer (EBR), [η]
Maleic anhydride grafted PP (MAH-
PP) 5 parts by weight and R-PP+EBR+MAH-PP=
P-EPQ and P-EPQ in the proportions shown in Table 1 per 100 parts by weight
The same procedure as in Example 6 was conducted except that a polyolefin composition containing Irganox 1010 was used. Table 2 shows the results.
Shown below. Example 13 Nylon 6 (Toray Alamine) was used instead of the ethylene/vinyl alcohol copolymer used in Example 10.
CM 1021XF, MFR: 1.74g/10min: ASTM
D 1238, Q, manufactured by Toray Industries, Inc.), and the molding temperature was adjusted to
The same procedure as in Example 10 was conducted except that the temperature was 260°C. The results are shown in Table 2. Comparative Example 5 P in the proportion shown in Table 1 was added to the EVA used in Example 1.
- The same procedure as in Example 10 was conducted except that a polyolefin composition containing EPQ and Irganox 1010 was used. The results are shown in Table 2.

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【table】

Claims (1)

[Claims] 1. Part or all of a polyolefin is graft-modified with a graft monomer consisting of an unsaturated dicarboxylic acid or its acid anhydride, and the amount of grafting is
Tetrakis (2,4-di-tert-
1. A polyolefin composition characterized in that 0.001 to 3 parts by weight of 4,4'-biphenylene diphosphonite (butylphenyl) is added. 2 Part or all of the polyolefin is graft-modified with a graft monomer consisting of an unsaturated dicarboxylic acid or its acid anhydride, and the amount of grafting is
Tetrakis (2,4-di-tert-
1. A polyolefin composition comprising 0.001 to 3 parts by weight of (butylphenyl) 4,4'-biphenylene diphosphonite and 0.01 to 3 parts by weight of an alkylphenol antioxidant.