JPH0826171B2 - Di-substituted benzylidene sorbitol composition - Google Patents

Description

The present invention relates to a composition based on a dibenzylidene sorbitol derivative, particularly dibenzylidene which is extremely useful when used as an additive for improving transparency, non-bleeding property and odorless property of polyolefin resin molded articles. Compositions based on sorbitol derivatives.

Dibenzylidene sorbitol and dibenzylidene sorbitol derivatives 1,3-2,4-di-p-methylbenzylidene sorbitol, 1,3-2,4-di-p-ethyl benzylidene sorbitol, 1,3-p chlorobenzylidene-2,4- It is known that p-methylbenzylidene sorbitol and the like are added to polyolefin resins such as polyethylene and polypropylene to improve the transparency of molded products of these resins (Japanese Patent Laid-Open No. 53-117044, Japanese Patent Publication No. 51/1974). −54
99 and U.S. Pat. No. 4,016,118, U.S. Pat. No. 4,483,952).

The present inventor has previously proposed a technique that improves the above-mentioned prior arts, provides transparency equivalent to that of the conventional method by adding a smaller amount of dibenzylidene sorbitol, and also improves rigidity and non-bleeding property. (JP-A-57-21440).
JP-A-57-21440 discloses a composition containing a solid powder of dibenzylidene sorbitol and a higher fatty acid, and the higher fatty acid is contained by coating the surface of the solid powder of dibenzylidene sorbitol. . In addition, the above-mentioned dibenzylidene sorbitol derivative, 1,3-2,4-dip
Methylbenzylidene sorbitol, etc. (JP-A-53-1170)
44, Japanese Examined Patent Publication No. 51-5499, U.S. Pat. No. 4,483,952), when blended with a polyolefin resin as an additive, it was quite highly evaluated in the actual market. It has become gradually clear that a slight offensive odor significantly hinders the growth of demand for the molded article when used in cosmetics containers and the like.

The present inventor has completed the invention of the present application as a result of repeated research to improve the above-mentioned various drawbacks of the prior art.

According to the present invention, as an essential component, the compound represented by the general formula (I) [In the formula, R and R ′ are each independently a chlorine atom,
Represents an atom or a group selected from the group consisting of a methyl group and an ethyl group], and a solid powder of a dibenzylidene sorbitol derivative of formula (II) CH ₃ (CH ₂ ) nCOOH (II) [wherein, n is preferably 14 to 30 18 to 22, most preferably
The number of 20] is included in the dibenzylidene sorbitol derivative composition, and the higher fatty acid is coated on the surface of the solid powder of the dibenzylidene sorbitol derivative.

Examples of the dibenzylidene sorbitol derivative of the general formula (I) used in the present invention include 1,3-, 2,4-di-p-methylbenzylidene sorbitol, 1,3-, 2,4-di-p-ethyl benzylidene sorbitol, 1, 3-p methylbenzylidene-
Examples thereof include 2,4-p chlorobenzylidene sorbitol, 1,3-p methylbenzylidene-2,4-p ethylbenzylidene sorbitol, and 1,3-p chlorobenzylidene-2,4p methylbenzylidene sorbitol.

In a preferred embodiment of the present invention, the above general formula (I)
In, a dibenzylidene sorbitol derivative in which R and R ′ each independently represent a methyl group or a chlorine atom is used.

Particularly preferred dibenzylidene sorbitol derivatives are 1,
3-2,4-di-p-methylbenzylidene sorbitol, 1,3-
p-methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chlorobenzylidene-2,4-p methylbenzylidene sorbitol.

Preferred examples of higher fatty acids of formula (II) used in the present invention are behenic acid, stearic acid and palmitic acid, of which behenic acid is most preferred and stearic acid is the second most preferred.

The particle size of the solid powder of the dibenzylidene derivative used in the composition of the present invention does not need to be particularly limited, and a particle size distribution of 30 to 100 mesh is preferably used.

The composition of the present invention contains 5 to 50 parts by weight, preferably 90 to 50 parts by weight, of a dibenzylidene derivative and 5 to 5 parts by weight of a higher fatty acid.
In the range of 50 parts by weight, preferably 10 to 50 parts by weight, the content of both components is 100 parts by weight.

The composition of the present invention has a coating layer of higher fatty acid on the surface of the solid powder of dibenzylidene sorbitol derivative by adding and stirring the solid powder of dibenzylidene sorbitol derivative to the aqueous emulsion containing the above proportion of higher fatty acid. Is formed and the dibenzylidene sorbitol derivative powder having a higher fatty acid coating is separated, followed by washing and drying.

The aqueous emulsion of the higher fatty acid used in the above method is, for example, a solution of an organic solvent having a concentration of the higher fatty acid of 5 to 50% by weight, preferably 10 to 50% by weight, and a small amount of a surfactant, for example, 100 parts by weight of the higher fatty acid. It can be easily obtained by dispersing 1 to 10 parts by weight, preferably 2 to 5 parts by weight, in water.

The presence of a coating of higher fatty acid formed on the surface of the solid powder of dibenzylidene sorbitol derivative should be confirmed by observing the coating with a dye, as described in detail in Examples below. You can

Examples of the polyolefin resin to which the composition of the present invention is used as an additive for improving transparency, non-bleeding property and odorless property include a number average molecular weight of an aliphatic monoolefin having 2 to 6 carbon atoms. About 10,000 to about 200,000, preferably about 30,000 to about 150,000 polymers or copolymers, such as polypropylene, low density polyethylene, high density polyethylene, linear polyethylene and ethylene-propylene copolymer.

In the composition of the present invention, the polyolefin resin 100
A dibenzylidene sorbitol derivative coated with a higher fatty acid corresponding to 0.05 to 1 part by weight, preferably 0.1 to 0.5 part by weight, as a dibenzylidene sorbitol derivative component is suitably used.

The composition of the present invention can be blended with the polyolefin resin by mixing by any known mixing means. Further, the composition of the present invention can be used as a masterbatch in a polyolefin resin containing the composition in a concentrated amount, if necessary.

In the composition of the present invention, it is important that the surface of the solid particles of the dibenzylidene sorbitol derivative is coated with a higher fatty acid, and even if the dibenzylidene sorbitol derivative and the higher fatty acid are simply added and mixed to the polyolefin resin, No effect is achieved.

Thus, the composition of the present invention, when compared to the prior art, when blended with a polyolefin resin, transparency, bleed resistance,
Not only does the property such as rigidity not be impaired, but in some cases, these properties are further improved, and at the same time, it has excellent odorlessness, and at the same time, white spots are less likely to appear inside the molded product and water resistance to devitrification It has an excellent effect that the property is improved. By using the composition of the present invention, it is possible to simultaneously satisfy the odorlessness which could not be realized conventionally in a molded article of polyolefin resin, for example, a film, a container, etc., together with the above various characteristics. In the fields of cosmetics and foods, it has made possible by opening up a wider field of application.

The reason why the composition of the present invention exerts the above excellent effects is not always clear, but it is a raw material for producing benzaldehyde and a dibenzylidene sorbitol derivative of the present invention which are raw materials for producing dibenzylidene sorbitol in JP-A-57-21440. Some benzaldehyde derivatives such as p-substituted benzaldehyde have an odor, and both of them tend to inevitably remain in dibenzylidene sorbitol (derivative) after purification and cause an offensive odor of a polyolefin resin molded product, and dibenzylidene sorbitol ( It is conceivable that the derivative) may be slightly decomposed even when a polyolefin molded article is molded, which may cause an offensive odor. In the composition of the present invention, (1) solid particles of the specific dibenzylidene sorbitol derivative of the general formula (I) are used, and (2) the particles are coated with a specific higher fatty acid of the general formula (II). By satisfying the requirements (1) and (2) at the same time, the offensive odor presumed to be derived from the raw material benzaldehyde or decomposed benzaldehyde is remarkably reduced in the polyolefin resin molded article, and the above-mentioned various matters such as transparency. The physical properties are also excellent at the same time.

Hereinafter, the present invention will be described in more detail with reference to Examples.
Parts and percentages are by weight unless otherwise indicated. The transparency (haze value), bleed resistance (bleed out) and odorlessness were measured by the following methods.

(A) Haze value: ASTM D1001-59T (B) Bleed out: Injection molding was performed using the polyolefin resin composition of Example 3, and it was judged by whether or not the mold became cloudy after 100 injections. .

(C) Odorless: A sensory test was conducted by 10 girls aged 20 to 25. That is, the degree of presence or absence of an offensive odor on the test piece was evaluated by 10 girls at about 10 am on the following 5 levels: 1. No odor 2. No odor, but something odorous 3. Feeling odor 4. Feeling a strong odor 5. Feeling a very strong odor The numerical value in the odorless column of the table of Example 3 is the numerical value at the evaluation stage, which was the largest number among 10 persons.

Example 1 (Production of Composition) 40 parts of behenic acid and 120 parts of methyl alcohol are placed in a glass-lined container, heated, and dissolved by stirring at a temperature of 60 ° C. Next, add 1.2 parts of nonionic surfactant and add 150 parts of warm water.
Parts are gradually added and stirred to emulsify. In the obtained emulsion
60 parts of 1,3-2,4-di-p-methylbenzylidene sorbitol was added and well stirred to obtain a white viscous milky substance. Separate this, wash with warm water to remove the activator, and dry to a white powder.
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Take 5 g of the obtained product in a glass beaker with a content of 100 cc, add 20 g of 0.1% aqueous solution of gentian violet, a dye for microscopes for dyeing higher fatty acids, and stir it. This gives a powder whose entire surface is colored purple.

However, di-p-methylbenzylidene sorbitol which does not cover the surface is not dyed at all even when treated with the same dye as above. From the above test, it can be seen that the surface is completely covered with the higher fatty acid.

Example 2 (Production of composition) 30 parts of behenic acid and 90 parts of methyl alcohol are placed in a glass-lined container and heated to 60 ° C. to dissolve behenic acid. Add 1 part of nonionic surfactant to this and add warm water.
Stir 150 parts and gradually add to emulsify. To the obtained emulsion, 70 parts of 1.3p chlorobenzylidene 2.4p methylbenzylidene sorbitol was added and well stirred to obtain a white viscous milky substance. Separate this and wash with warm water to remove the activator and dry to obtain 100 parts of white powder.

The powder thus obtained was tested in the same manner as in Example 1 and it was confirmed that the surface of 1,3p chlorobenzylidene 2,4p methylbenzylidene sorbitol was completely covered with behenic acid.

Example 3 (Application of composition) A blender was prepared by adding the compositions prepared in Example 1 and Example 2 to pellets of a random copolymer of ethylene-propylene copolymer (Show Allomer MG410 manufactured by Showa Denko KK) in the following table. Injection temperature of the resin composition mixed at
A plate-shaped test piece having a thickness of 1 mm was prepared by injection molding at ℃.

For comparison, a test piece or a dibenzylidene sorbitol derivative or a dibenzylidene sorbitol derivative prepared in the same manner as above except that di-p-methyl-benzylidene sorbitol, 1.3p chlorobenzylidene 2,4p methylbenzylidene sorbitol and behenic acid were used alone, respectively. The haze value, bleed-out and odorlessness were also tested on test pieces prepared in the same manner as above except that an additive-free polypropylene resin containing no behenic acid was used. The results are shown in the table below.

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Claims (5)

[Claims] 1. A general formula as an essential component [In the formula, R and R ′ are each independently a chlorine atom,
Represents an atom or a group selected from the group consisting of a methyl group and an ethyl group] solid powder of a dibenzylidene sorbitol derivative of and a formula of CH ₃ (CH ₂ ) nCOOH [where n represents a number of 14 to 30] A dibenzylidene sorbitol derivative composition comprising a fatty acid, the higher fatty acid being contained by coating the surface of a solid powder of the dibenzylidene sorbitol derivative. 2. The dibenzylidene sorbitol derivative is 1,3.
A composition according to claim 1 which is -2,4-di-p-methylbenzylidene sorbitol. 3. The dibenzylidene sorbitol derivative is 1,3
A composition according to claim 1, which is -p-methylbenzylidene-2,4-p-chlorobenzylidene-sorbitol. 4. The dibenzylidene sorbitol derivative is 1,3
A composition according to claim 1, which is -p chlorobenzylidene-2,4-p methylbenzylidene sorbitol. 5. The composition according to any one of claims 1 to 4, wherein the higher fatty acid is behenic acid.