JPS58104933A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition preventive for the resulting formed products from foaming and coloring in an injection molding operation requiring a long time, capable of exhibiting high effectiveness of nucleating agent application over a long period, by incorporating a polyolefin resin with both a carboxylic acid metal salt and a specific DBS or DBX as a nucleating agent. CONSTITUTION:The objective composition can be obtained by incorporating (A) a crystalline polyolefin resin with (B) 0.03-10 (pref. 0.05-6)wt% of a compound of formula (R is lower alkyl, lower alkoxy, halogen, or nitro; n is 0 or an integer 1-5; p is 0 or 1) and 0.005-1 (pref. 0.01-0.5)wt% of a carboxylic acid metal salt. Furthermore, a pigment may be incorporated. This incorporation, however, would result in no surface gloss reduction.

Description

[Detailed description of the invention] The present invention relates to polyolefin thread resin compositions.

Crystalline polyolefin resins are widely used practically by injection molding, extrusion molding, blow molding, rotary molding, etc. Therefore, nucleating agents such as 1.3: 2,4-dibenzylidene silitol (DBS) and 1,3: 2,4-dibenzylidene silitol (DBX) are unique during molding of the polyolefin thread resin. It shows the effect of improving the consistency of resin, suppressing sink marks, improving dimensional stability, and improving gloss.
Effective for improving mechanical properties and shortening molding cycles.

However, according to the fire resistance of the present inventors, when injection molding or extrusion molding of a composition containing DBS or DBX in the polyolefin thread resin is carried out over a long period of time, the molded product will flood and become yellow or brown. It has been found that it is not possible to prevent coloring, and that it is not possible to prevent the nucleating agent effect of DBS or DBX from decreasing or disappearing.

As a result of further research in order to eliminate the above-mentioned drawbacks, the present inventors have found that the intended purpose of the present invention can be achieved when a metal salt of carboxylic acid is blended with DBS or DBX into polyolefin thread resin, and that DBS It has been found that the above object can be achieved even when using DBS+DEX in which a lower alkyl group, a lower alkoxyl group, a J10 gen atom, or a nido 0 group is substituted on the phenyl ring in place of DBX or DBX. Ta. The present invention was completed based on this knowledge.

That is, the transparent, crystalline, polyolefin thread resin of the present invention has a general formula [wherein Rd represents a lower alkyl group, a lower alkyl group, a halogen atom, or 0 groups. Rhinoceros indicates 0 or an integer from 1 to 5, and door indicates 0 or I. The present invention relates to a polyolefin thread resin composition characterized in that it contains a compound represented by the following and a metal salt of carboxylic acid.・l:1 1[1,.

The resin composition of the present invention, in which a compound represented by the above general formula Ll) and a metal salt of carboxylic acid are blended with a crystalline real toothed fin thread resin, cannot be processed by injection molding or extrusion molding over a long period of time. However, the molded product will not foam or be colored yellow or brown. Furthermore, even when injection molding or extrusion molding is carried out by applying the resin composition of the present invention for a long period of time, the nucleating effect of the compound represented by general formula (1) does not decrease or disappear, and the nucleating agent effect remains unchanged for a long period of time. It can exhibit excellent nucleating effect. The effects of the present invention are as follows:
This effect is exhibited only when the compound represented by the above general formula (1) and a metal salt of carboxylic acid are used together. Known nucleating agents other than the compound represented by the above general formula (1),
For example, even if a metal salt of a carboxylate salt is used in combination with aluminum soap, silica powder, phosphate, etc., the effects of the present invention described above will be exerted basolaterally.

In the compound represented by the above general formula (1) used in the present invention, the lower alkyl group defined by R is methyl,
Ethyl, propyl, butyl groups, etc. are lower alkoxy groups; Atoms, etc. are included respectively.

The compound of the above general formula (l) is a benzaldiyl group having or not having a lower alkyl group, a lower alkoxyl group, a JS O gen atom or a di- or tro group as a substituent, and tsurditol or silitol It is easily produced by carrying out a condensation reaction with a compound according to a conventional method.

As the metal salt of carboxylic acid used in the present invention, a wide variety of conventionally known metal salts can be used. As a carboxylic acid, C3-
Any C4° t- or polyhydric carboxylic acid can be used,
Examples of metal salts include potassium salts, sodium salts, lithium salts, calcium salts, magnesium salts, aluminum salts, barium salts, soot salts, and zinc salts. Examples of metal salts of carboxylic acids include higher fatty acid soaps of C°8 to C22, benzoic acid soaps, naphthenic acid soaps, and ; cystearic acid soap, lactate, citrate, succinate, +2-t:, do0 bovine distearic acid soap, distearic acid soap, distearic acid, soap, curconate, turjin rIN salt, salicylic acid soap Included are salt n-octyltin laurate, apple salt, dimer salt, trimellitate, phthalate, tetradolphthalate, tetradolphthalate, and the like.

As the crystalline polyolefin thread resin, a wide variety of conventionally known ones can be used, such as ethylene copolymers (high density, medium density, and low density polyethylene), ethylene copolymers with an ethylene content of 5051 or more, zuojishinhot polymer, Examples include a polymer having a polymer content of 5096 or more, a butene copolymer having a latin content of 50% or more, a methylhentene homopolymer, a methylpentene copolymer having a methylpentene content of 50% or more. The above-mentioned copolymer 6, mercury, or lantum copolymer may be used, or a block copolymer may be used. Furthermore, the copolymers that can constitute the above copolymer are
Any of various substances that can be copolymerized with ethylene, polyethylene, butene, or methylpentene can be used as the polyethylene, specifically, vinyl acetate, ethylene, polyethylene, butene,
Examples include methacrylic acid esters such as pentene, methyl hedecacrylate, and ethyl methacrylate. .

The amount of the compound represented by the general formula (1) in the olefin thread resin is not particularly limited and can be appropriately selected from a wide range, but is usually 0.03 to 10
The amount is preferably 0.05 to 6% by weight. The amount of the metal salt of carboxylic acid added to the olefin thread resin is not particularly limited and can be appropriately selected within a wide range, but is usually 0.005 to 1% by weight, preferably 0.01 to 0.01% by weight. 1. It is preferable to use 5 weight strips. By blending within these ranges, the desired effects of the present invention can be sufficiently exhibited.

The polyolefin thread resin composition yc of the present invention can also contain a pigment. When a pigment is blended into a conventional polyolefin thread rosin composition, it has been thought that a decrease in the surface gloss of the resulting molded product is unavoidable. On the other hand, even when a pigment is blended into the polyolefin thread resin composition of the present invention, no decrease in the surface gloss of the resulting molded product is observed. This point is also an advantage of the composition of the present invention. A wide variety of conventionally known inorganic pigments and organic pigments can be used as the IIA material, such as titanium white, cyanide blue, carbon black, bovine nacridone, toluidine red, cadmium yellow, titanium yellow, Bengara, ultramarine, dovetail thread pigment, helilene thread pigment. , anthracite non-thread pigments, isoindolinone thread pigments, and the like.

The amount of such pigment to be blended is not particularly limited and can be appropriately selected from a wide range, but it is usually less than 200 years, preferably 0.5 to
It is preferable to mix 120% by weight.

The composition VCI/i of the present invention may be appropriately added with various components such as oxidation stabilizers, ultraviolet absorbers, lubricants, crosslinking agents, crosslinking accelerators, foaming agents, dispersants, fillers, and antistatic agents depending on the purpose and use. Can be blended.

In producing the non-exploding QEj composition, any conventionally known method can be applied. For example, the compound of general formula [1] and the metal salt of carboxylic acid may be pre-precipitated directly onto the polyurethane thread resin, or the resin may be pre-precipitated with the above-mentioned The compound and the metal salt of carboxylic acid may be blended and then pelletized.

Furthermore, when molding the composition of the present invention, any conventionally known molding method can be employed.

Examples and comparative examples are listed below. Note that each part means part by weight.

East Example l 100 parts of ethylene epoxy resin random copolymer, D
After driving and stirring 3 parts of B SQ and 0.1 part of calcium stearicate, mix #8M for 5 minutes at 250° with a twin-screw three-wheel, and then add K 150/cA.

Press molding was performed at 250° C. for 3 minutes to obtain a sheet with a thickness of 1 mm. The 19 degrees of the ethylene-propylene lantum copolymer was 71g6, while the 19 degrees of the sheet obtained above was 2296.

In addition, tri-blend with the above composition and use it at 250°C for 1
5. Injection molding was carried out for 8 hours using a disposer pull syringe, and even after 8 hours, no discoloration (coloration) or foaming was observed in the molded product, and the transparency was improved. A molded product could be obtained.

Comparative Example 1 100 parts of Ethyreceive 0 dilene random copolymer and D
B S Q, 3 parts were blended and the following Example 1 was prepared.
In the same manner as above, obtain a sheet of cod with a thickness of: [. The Iu content of the sheet obtained above was 46%, whereas the 19° Iu content of the ethylene-ethylene random copolymer was 71%.

In addition, the above combination is a dry friend, and the following 9! ! When injection molding was performed in the same manner as in Example 1, the molded product obtained turned yellow and foaming was observed after 1 hour had elapsed.

Example 2 Low density polyethylene (d = 0.920, Ml25)
100 parts, titanium oxide, 50 parts, D B S □, 1 part and potassium benzoate 0.05 part in Henschel Sanju 1
00r and tri-blend at room temperature for 5 minutes. The mixture was melt-mixed for 5 minutes at 170°C in a two-screw three-wheel machine, and after cooling, it was pulverized. An aluminum plate (180° C.) with a thickness of 1 sw x 5 tys x 20 ex was spray coated and the coating was completed by air cooling. [obtained] - The surface gloss of the dyed product was 85 at 60 parts reflectance and 1'1. ,.

Comparative Example 2 A coach ink product is obtained in the same manner as in Example 2 except that DBS and potassium benzoate are not blended. .

This] - surface gloss of tinted material #i 60° reflectance 65
Met.

An ink product was obtained in the same manner as in Example 2 except that DBS was not blended. Surface light of this coach ink material 60
The reflectance was 65.

A coated product was obtained in the same manner as in Example 2 except that potassium benzoate was not added. This coach ink had a surface glossy 60° reflectance of 80.

Example 3 - Obtaining a tainted product in the same manner as in Example 2 using the polyolefin thread resin, pigment, compound of general formula Ll) and metal salt of carboxylic acid described in Table 1 of F. ”-The surface gloss of the tainted objects is also shown in Table 1.

Example 4 Ethylene-di-O-herene block coagulation (Ml=15)
100 parts, 12-hydrogen 0+stium cystearicate 0.
Part 1, Nacridone 0.3 part, DBSo, Part 5, 2.2
After triblending 0.1 part of '-methylene di(4-ethyl-6-tart-phthylphenol) and 0.18 part of trilistylthiodibionate, 2aX 30011! A plate of 100 g was continuously molded using 1 ton of resin at a resin temperature of ff 260'C1. According to ASTM 1) 747, the stiffness (
u/d)''-a was determined, and the stiffness modification rate was determined according to the following formula.

The gloss modification rate was also determined according to the following formula.

FIG. 1 shows the relationship between the amount of molding resin (continuous), the rigidity modification rate, and the gloss modification rate for a 1m-long piece of molding resin.

Comparative Example 3 A molding product with a resin amount of 100 was continuously molded in the same manner as in Example 4 except that 12-siloxane + lithium distearate was not blended. Figure 1 shows the relationship between the (continuous) amount of molding resin, the stiffness modification rate, and the gloss modification rate.

In Figure 1, 0) indicates the relationship between the amount of molding resin and the stiffness modification rate in Example 4.
This figure shows the relationship between the amount of molding resin and the stiffness modification rate. Moreover, e) is the molding Ii in Example 4! The graph shows the relationship between the oil content and the gloss modification rate, and the relationship between the amount of molding resin and the gloss modification rate in Ni) Company Comparative Example 3.

Example 5 “Polyolefin thread resin described in Table 2, general formula (1)
Continuous injection molding of a flat plate was carried out in the same manner as in Example 4 using the compound, a metal salt of carboxylic acid, and a pigment. Communicating! Iy, shape fat amount is O, Ikq or 100#'''c
In some cases, the haze degree, rigidity modification rate, and sink mark of the obtained molded products were investigated, and the results are also shown in Table 2.

In addition, as the polyolefin ridge resin in Table 2, -P,
E stands for Ethyreceive 0-jiren range lock copolymer, r-P-E stands for a certain company's ethylene lantum copolymer, and h-p-'p stands for poly-zilene lantum copolymer. , LDPE means low density polyethylene.
DPE means high density polyethylene.

The mark in Table 2 above indicates that the molded product was colored yellow to pale yellow and that foaming was observed.

Example 6 100 parts of linear low density polyethylene (MI=1), E;
-(/-Methylbenzylidene)-6 parts of sorbitol and 0.1 part of calcium stearate were melt-mixed at 230°C to form master patch pellets.

Next, 100 parts of linear low-density polyethylene, 0.02 parts of olecyamide (a lubricant), and 3 parts of master pellets were blended, and after melting, a blown film with a thickness of 200 mm was formed at 200°C.

Even 8 hours after the start of molding, no discoloration or foaming was observed, and the degree of haze of the molded product was 4.0.

Comparative Example 4:11 Example 6 except that calcium stearate was not used.
A film was formed in the same manner. Discoloration (yellowing) and foaming were already observed by the time 30 minutes had passed after the start of molding, and the haze of the molded product was 5.5.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the (continuous) amount of molding resin, the rigidity modification rate, and the gloss modification rate. (hereafter ”)

Claims (1)

[Scope of Claims] ■ A crystalline polyolefin thread resin having a general formula [wherein R represents a lower alkyl group, a lower alkoxyl group, or a halogen atom-shaped nitro group]. It represents ItaO or an integer from 1 to 5. t
indicates 0 or 1. ] A polyolefin thread resin composition comprising a compound represented by the following and a metal salt of carposidic acid.