JPS59197445A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent mechanical strength, rigidity, heat resistance, transparency gloss, etc., by blending a specified heterocyclic monocarboxylic acid compd. with a polyolefin. CONSTITUTION:0.01-2pts.wt. heterocyclic monocarboxylic acid compd. of the formula (wherein one of R1-R4 is a carboxyl group in which H ion may be substituted with a metal ion and the remaining three groups of R1-R4 are each a hydrocarbon gruop, halogen, amino, hydroxyl, H; X is O, S, imino) is blended with 100pts.wt. polyolefin such as an ethylene/4-methyl-1-pentene copolymer. USE:Household goods, electrical equipment, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyolefin composition having excellent mechanical strength, rigidity, oil resistance, etc., and excellent optical properties such as transparency and gloss.

Polyolefin resins such as polyethylene and polypropylene are widely used as raw material resins for various molded products such as films and sheets because of their high mechanical strength and excellent electrical insulation properties. However, polyolefin resins are crystalline and have extremely poor transparency, which limits their uses.

In order to solve these problems, various methods of improving transparency have been proposed in the past. For example, proposals have been made to vary the processing conditions of polyolefin, such as performing high-magnification stretching, rapidly cooling the molten resin, or combining stretching and rapid cooling. However, high-magnification stretching limits the shape and precision of the molded product obtained. In the rapid cooling method, the mold, cooling roll, etc. must be cooled to below room temperature, which causes problems such as dew condensation and complicated equipment. Moreover, the crystallinity of the molded product decreases,
Impairs mechanical strength and rigidity. In a method that combines stretching and quenching, the orientation effect is small when stretched in a molten state, and there are problems during quenching as described above.

For this reason, attempts have been made to improve transparency by adding a nucleating agent to polyolefin to promote crystallization during solidification of the polyolefin in a molten state, and to reduce the crystal form. However, many of the conventionally known nucleating agents have a strong effect of promoting crystallization, resulting in mechanical strength of 1. Although a molded article with excellent rigidity etc. could be obtained, one with excellent optical properties such as transparency or gloss could not be obtained.

Therefore, the inventors of the present invention have conducted repeated studies to provide a polyolefin that not only has excellent mechanical strength and rigidity, but also has excellent optical properties such as transparency and gloss. It has been found that the above problem can be solved by blending the carboxylic acid compound.

That is, in the present invention, at least one heterocyclic monocarboxylic acid compound selected from the following general formula is added to 100 parts by weight of polyolefin in an amount of 0. A polyolefin composition characterized in that it contains ol to 2 parts by weight of the general formula (wherein any one of R1 to R4 is a carboxyl group (
hydrogen ions may be substituted with metal ions], the remaining six groups are hydrocarbon groups, halogens, amino groups, hydroxyl groups, or hydrogen, and X is oxygen, sulfur, or imino groups. ).

The heterocyclic monocarboxylic acid compound used in the present invention is
When R1-R4 other than the carboxyl group is a hydrogen atom, if X is oxygen, a 7-run monocarboxylic acid,
If X is sulfur, it is thiophene monocarboxylic acid, and if X is an imino group, it is virol monocarboxylic acid. Of course, among R1 to R4, the groups other than the carboxylic group are groups other than hydrogen, such as alkyl groups, phenyl groups,
It may be substituted with a hydrocarbon group such as a benzyl group or a naphthyl group, a halogen, an amide group, a hydroxyl group, or the like.

Further, the hydrogen ion of the carboxyl group may be substituted with a metal ion. Metal ion, as I
Metal ions of the A group, IA group, l'llA group, ■E group, JE group, and ■ group are mentioned, especially lithium, potassium,
Metal ions of Group IA (alkali metals) such as sodium and Group IIA (alkaline earth metals) such as magnesium and calcium are preferred.

Examples of such heterocyclic monocarboxylic acid compounds include 2-furancarboxylic acid, 6-furancarboxylic acid,
3-methyl-2-furancarboxylic acid, 4-methyl-2-
Furocarboxylic acid, 5-methyl-2-furancarboxylic acid, 2-methyl-3-7-rancarboxylic acid, 4-methyl-3
-Furancarboxylic acid, 5-methyl-6-furocarboxylic acid, sodium 2-furancarboxylate, O-sodium furoate, lithium 2-furancarboxylate, 3
-Furancarboxylic acid compounds such as calcium furoate, 2-thiophenecarboxylic acid, 6-thiophenecarboxylic acid, ro-methyl-2-thiophenecarboxylic acid, 4
-Methyl-2-thiophenecarboxylic acid, 5-methyl-2
-thiophenecarboxylic acid, 2-methyl-6-thiophenecarboxylic acid, 4-methyl-3-thio7enecarboxylic acid,
Thiophenecarboxylic acid compounds such as 5-methyl-6-thiophenecarboxylic acid, sodium 2-thiophenecarboxylate, sodium 6-thiophenecarboxylate, lithium 2-thiophenecarboxylate, calcium 6-thiophenecarboxylate, 2-pyrrolecarboxylate , 6-pyrrolecarboxylic acid, 3-methyl-2-pyrrolecarboxylic acid, 4-
Methyl-2-pyrrolecarboxylic acid, 5-methyl-2-pyrrolecarboxylic acid, 2-methyl-6-pyrrolecarboxylic acid, 4-methyl-5-pyrrolecarboxylic acid, 5-methyl-6-pyrrolecarboxylic acid, 2- Examples include virol carboxylic acid compounds such as sodium virol carboxylate, sodium 6-pyrrole carboxylate, lithium 2-pyrrole carboxylate, and calcium ro-pyrrole carboxylate.

In order to improve the mechanical strength, rigidity, oil resistance, or optical properties such as transparency and gloss of polyolefin, the above-mentioned heterocyclic monocarboxylic acid compound is blended.

For example, even if the same carboxylic acids are furan, thiophene, and virol, polyvalent carboxylic acids of dicarboxylic acid or higher do not exhibit the above-mentioned improvement in properties.

Among the above-mentioned heterocyclic monocarboxylic acid compounds, particularly preferred in the present invention are monocarboxylic acids having no substituent other than a carboxyl group. These are 2-furancarboxylic acid, 2-thiophenecarboxylic acid, and 2-pyrrolecarboxylic acid, which are substituted with zyl, f, and xyl groups.

Examples of polyolefins include ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 5-methyl-1-butene, 6-methyl-1
- Homopolymers of α-olefins such as pentene and 4-methyl-1-pentene, or copolymers of two or more comonomers, and also monomers copolymerizable with α-olefins such as styrene, acrylonitrile, etc. Copolymers with vinyl chloride, vinyl acetate, acrylic esters, methacrylic esters, etc., as well as blends with the above or other thermoplastic resins, block copolymers, ground copolymers, etc. Any polyolefin may be used.

The heterocyclic monocarboxylic acid compound is polyolefin 10
It is preferable to mix 01 to 2 parts by weight, particularly 0.05 to 1 part by weight, to 0 parts by weight.

If it is less than 0.01 part by weight, no improvement in mechanical strength, rigidity, transparency, gloss, etc. will be observed, and if it is added in excess of 2 parts by weight, the original properties of the polyolefin will be impaired and bleed-out will occur easily. So I don't like it. Furthermore, when blending, the monocarboxylic acids or derivatives thereof may be blended alone or in combination of two or more.

The polyolefin composition of the present invention also includes: a weathering stabilizer,
Various compounding agents, such as heat stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, lubricants, fillers, pigments, dyes, etc., which are usually added to polyolefins, may not be used without impairing the purpose of the present invention. They may be blended within a certain range.

In order to obtain the polyolefin composition of the present invention, polyolein and the monocarboxylic acid or its derivative are mixed within the above range using various known methods, such as a ■-blender, ribbon blender, Henschel mixer, tumbler blender, etc. It can be easily obtained by a method of mixing and granulating with an extruder or the like, or a method of kneading and granulating with an extruder, kneader, Banbury mixer, or the like.

The polyolefin composition of the present invention thus obtained has excellent mechanical strength, rigidity, and heat resistance, as well as transparency and
It also has excellent optical properties such as gloss, so it can be widely used in various household goods, electrical appliances, etc.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way unless the gist of the invention is exceeded.

Examples 1 to 12 and Comparative Examples 1 to 5 Melt flow rate 2.10 g/1010 m1n (AS
T 1238, E), density 0.920 g/α3 (AS
To 100 parts by weight of ethylene/4-methyl-1-pentene copolymer (TM D1505) was added 0.0% of the compound shown in Table 1.
3 parts by weight were blended, melt-mixed using an extruder, and pelletized. The pellets were molded into a 1 mm thick sheet at 200°C, and the following tests were conducted. The results are shown in Table 1.

Crystallization temperature (Tc) Differential scanning calorimeter (DSO)
Humidity haze showing an endothermic peak determined from an exothermic curve at a cooling rate I O'C/min: ATSM D 1003-52 Rigidity: ASTM D 1043-72 Example 16
-21 and Comparative Examples 6-9 Melt Flow Ray) 1.5g/1010m1n (AS
T 1238 L), density 0.91 g, 10n6 (A
0.3 parts by weight of the compounds shown in Table 2 were added to 100 parts by weight of polypropylene (Mitsui Petrochemical Polypropylene J300) of STM D1505), and the same test as in Example 1 was conducted. The results are shown in Table 2.

Claims (4)

[Claims] (1) A polyolefin composition comprising 0.01 to 2 parts by weight of at least one heterotetracyclic/carboxylic acid compound selected from the following general formula based on 100 parts by weight of the polyolefin; However, the general formula (where any one of R1-R4 is a carboxyl group (
hydrogen ions may be substituted with metal ions), the remaining filter group is either a hydrocarbon group, a nitrogen group, an amide group, a hydroxyl group, or hydrogen, and X is oxygen, sulfur, or a cumino group. be). (2) The polyolefin composition according to claim 1, wherein the metal ion replacing the hydrogen ion of the carboxyl group is an alkali metal ion or an alkaline earth metal ion. (3) The polyolefin composition according to claim 1 or 2, wherein the substituent other than the carboxyl group is hydrogen. (4) The polyolefin composition according to claim 6, wherein the carboxyl group is an unsubstituted carboxyl group.