JPH01126352A - Di-substituted benzylidienesorbitol composition - Google Patents

Abstract

PURPOSE:To obtain a composition, containing solid powder of a dibenzylidenesorbitol derivative having the surface coated with a specific higher fatty acid and especially useful as an additive capable of improving transparency, nonbleeding and odorless properties of molded polyolefin products. CONSTITUTION:A composition containing (A) solid powder, coated with (B) a higher fatty acid, preferably behenic acid expressed by formula II and prepared by adding the solid powder (A) to an aqueous emulsion containing (A) 95-9pts.wt., preferably 90-5pts.wt. solid powder of a dibenzylidenesorbitol expressed by formula I (R and R' are Cl, methyl or ethyl), preferably 1,3-2,4-di-p- methylbenzylidenesorbitol or 1,3-p-methylbenzylidene-2,4-p- chlorobenzylidenesorbitol and (B) 5-50pts.wt., preferably 10-50pts.wt. higher fatty acid expressed by formula II, stirring the resultant mixture, separating the powder by filtration, washing and drying the powder as an essential component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention discloses dibenzylidene sorbitol derivatives which are extremely useful when used as additives for improving the transparency, non-bleeding and odorlessness of polyolefin resin molded articles. Compositions based on sorbitol derivatives.

Dibenzylidene sorbitol and dibenzylidene sorbitol derivatives such as 1,3-2.4-P methyldibenzylidene sorbitol, 1.3-2゜4-diethyldibenzylidene sorbitol, 1゜3-p chlorobenzylidene-2,4- It is known that by blending P-methylbenzylidene sorbitol and the like with polyolefin resins such as polyethylene and polypropylene, the transparency of molded products of those resins is improved (Japanese Patent Application Laid-Open No. 1983-1972).
117044, Japanese Patent Publication No. 51-5499 and U.S. Patent No. 4
, 016,118, U.S. Patent No. 4.483.

(See No. 952).

The present inventor has previously proposed a technique that improves the above-mentioned prior art and provides transparency equivalent to the conventional method by adding a smaller amount of dibenzylidene sorbitol, and also improves rigidity and non-bleeding property. (Unexamined Japanese Patent Publication No. 57-21.440
JP-A-57-21440 discloses a composition containing a solid powder of dibenzylidene sorbitol and a higher fatty acid, the higher fatty acid coating the surface of the solid powder of dibenzylidene sorbitol. has been done. When the composition disclosed in JP-A No. 57-21440 was blended with polyolefin resin as an additive, it received a fairly high evaluation in the actual market, but molded products of polyolefin resin were used in food containers, cosmetic containers, etc. Since then, it has become increasingly clear that even slight off-odors are significantly inhibiting the growth in demand for molded products.

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

According to the present invention, as an essential component, the general formula (N■ -C-OH H-C-OH (1) [wherein R and R' are each independently a chlorine atom,
represents an atom or group selected from the group consisting of a methyl group and an ethyl group] and a solid powder of a dibenzylidene sorbitol derivative with the formula (
n) CH3(CH2)ncOOH(If) [where n is 1
4 to 30, preferably 18 to 22, most preferably 20 higher fatty acids, and the higher fatty acids are contained by coating the surface of the solid powder of the dibenzylidene sorbitol derivative. Benzylidene sorbitol derivative compositions are provided.

The dibenzylidene sorbitol derivative of general formula (II) used in the present invention includes 1.3-12°4-methylbenzylidene sorbitol.

]3-12,4-di p-ethylbenzylidene sorbitol 1.3-p methylbenzylidene-2,4-P chlorobenzylidene sorbitol, 1.3-p methylbenzylidene-2,4-p ethylbenzylidene sorbitol, and 1
．． Examples include 3-P chlorobenzylidene-2,4p methylbenzylidene sorbitol.

In a preferred embodiment of the present invention, a dibenzylidene sorbitol derivative is used in which R and R' each independently represent a methyl group or a chlorine atom in the above general formula (1).

Particularly preferred dibenzylidene sorbitol derivatives are: 1.
3-2.4-Zylmethylbenzylidene sorbitol, 1
．． 3-P methylbenzylidene-2,4-p chlorobenzylidene sorbitol and 1,3-p chlorobenzylidene-2,4-p methylbenzylidene sorbitol.

Preferred examples of the higher fatty acids of formula (If) used in the present invention are behenic acid, stearic acid and valmitic acid, of which behenic acid is most preferred, followed by stearic acid.

There is no particular restriction on the particle size of the solid powder of the dibenzylidene derivative used in the composition of the present invention, and those having a particle size distribution of 30 to 100 mesh are preferably used.

The composition of the present invention has a dibenzylidene derivative of 95 to 50%.
The higher fatty acid is contained in an amount of 5 to 50 parts by weight, preferably 90 to 50 parts by weight, or 10 to 50 parts by weight, so that the total of the blue components is 100 parts by weight. Be faithful.

The composition of the present invention is prepared by adding and stirring solid powder of a dibenzylidene sorbitol derivative in the above proportion to an aqueous emulsion containing higher fatty acids in the above proportion, and forming a coating layer of higher fatty acid on the surface of the solid powder of the dibenzylidene sorbitol derivative. It can be produced by forming a dibenzylidene sorbitol derivative powder coated with a higher fatty acid by furnace separation, followed by washing and drying.

The aqueous emulsion of a higher fatty acid used in the above method is, for example, a solution of a higher fatty acid in an organic solvent with a concentration 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 a higher fatty acid. 1 to
It can be easily obtained by dispersing it in water using 10 parts, preferably 2 to 5 parts.

In addition, the presence of a higher fatty acid coating formed on the surface of the solid powder of the dibenzylidene sorbitol derivative can be confirmed by dyeing and observing the coating with a dye, as detailed in the Examples below. Can be done.

Examples of target polyolefin resins for which the composition of the present invention is used as an additive to improve transparency, non-broad properties, and odorlessness are aliphatic monoolefins having a number average molecular weight of 2 to 6 carbon atoms. Target 10,000 to about 200,000,
Preferred are polymers or copolymers of from about 30,000 to about 150,000, such as polypropylene, low density polyethylene, high density polyethylene, linear polyethylene and ethylene-propylene copolymers.

In the composition of the present invention, polyolefin resin 100
The dibenzylidene sorbitol derivative component is 0.05 to 15 to 1, or 0.1 to 1, based on the heavy it part.
A dibenzylidene sorbitol derivative coated with a higher fatty acid corresponding to 0.5 parts of heat is preferably used.

The composition of the present invention can be blended with a polyolefin resin by mixing it with any known mixing means.

The composition of the present invention can also be used as a masterbatch in a polyolefin resin containing a concentrated amount of the composition, 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, the present invention can be achieved. No effect is achieved.

Thus, compared to the prior art, when the composition of the present invention is blended with a polyolefin resin, it not only does not impair properties such as transparency, bleed resistance, and rigidity, but in some cases improves these properties. When using the composition of the present invention, the composition of the present invention has excellent odorlessness, reduces the appearance of white spots inside the molded product, and improves water devitrification resistance. For example, it is possible to simultaneously satisfy the above characteristics as well as odorlessness, which was previously impossible to achieve in polyolefin resin molded products such as films and containers, and it is suitable for polyolefin molded products in the fields of cosmetics and food products. This made it possible for the first time to develop an even wider field of use.

The reason why the composition of the present invention exhibits the above-mentioned excellent effects is not necessarily clear, but it is possible that benzaldehyde, which is the raw material for producing dibenzylidene sorbitol of JP-A No. 57-21440, and the raw material for producing the dibenzylidene sorbitol derivative of the present invention. Benzaldehyde derivatives such as certain ρ-substituted benzaldehydes have odors, and even after purification, a slight amount of benzaldehyde derivatives inevitably remain in dibenzylidene sorbitol (derivatives), which tends to cause off-odor in polyolefin resin molded products. In the composition of the present invention, (1) -i specific dibenzylidene sorbitol of formula (I) By simultaneously satisfying the requirements (1) and (2) of using solid particles of the derivative and (2) coating the particles with a specific higher fatty acid of general formula (II), raw benzaldehydes or decomposition products can be treated. The effects of the polyolefin resin molded article are that the off-odor that is presumed to be caused by the benzaldehydes is significantly reduced, and the above-mentioned physical properties such as transparency are also excellent.

In the following, the present invention will be explained in more detail with reference to Examples. Unless otherwise specified, the number of copies and percentages are based on heavy electrical equipment, and transparency (haze value), bleed resistance (
Bleed-out) and odorlessness were measured by the following methods.

(a) Haze value: ASTM DlooI-9T (b) Bleedout: Injection molding was performed using the polyolefin resin composition of Example 3, and judgment was made based on whether fog appeared on the mold after 100 injections. 6 (c) Odorlessness: A sensory test was conducted by 10 girls aged 20 to 25. That is, around 10 a.m., 10 women evaluated the presence or absence of a strange odor on the test piece using the following 5 levels: 1. There is no odor at all 2. I don't know what it is, but I feel something like an odor 3. I feel an odor 4. I feel a strong odor. 5. I feel a very strong odor. The values in the odorless column of the table of Example 3 are shown by the value of the evaluation stage that was the most popular among the 10 people.

Example 1 (Production of composition) 40 parts of behenic acid and 120 parts of methyl alcohol were placed in a glass-lined container and heated, stirred and dissolved at a temperature of 60°C.Next, 1.2 parts of a nonionic surfactant was added. 150 parts of warm water was gradually added and stirred to emulsify. 60 parts of 1.3-2.4-di-p-methylbenzylidene sorbitol was added to the obtained emulsion and stirred well to obtain a white viscous emulsion. This is separated into a furnace and washed with warm water to remove the activator.
After drying, 100 parts of white powder was obtained.

When 5 g of the obtained product was placed in a 100 cc glass beaker and 20 g of a 0.1% aqueous solution of Genkeyana violet, a microscope dye that stains higher fatty acids, was added and stirred, the powder was immediately dyed and turned into a purple viscous liquid, which was filtered. When dried, a powder is obtained which is dyed purple on the entire surface.

However, it can be seen from the test of 0 or more that G-p methyl benzylidene sorbitol, whose surface is not coated, is completely coated with higher fatty acids even when treated with the same dye as mentioned above, showing no staining at all.

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 the stearic acid. To this was added 1 part of a nonionic surfactant, and 150 parts of warm water was gradually added while stirring to emulsify. 70 parts of 1.3p chlorobenzylidene and 2.42 methylbenzylidene sorbitol were added to the resulting emulsion and stirred thoroughly to obtain a white viscous emulsion. This was separated, washed with warm water to remove the active agent, and dried to produce 100 parts of white powder.

get.

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 coated with behenic acid.

Example 3 (Application of composition) The compositions prepared in Example 1 and Example 2 were added to a pellet of random copolymer of ethylene propylene (Showa Aroma-MG410, manufactured by Showa Denko K.K.) as specified in the table below. The resin composition mixed in a blender was heated to an injection temperature of 24
A plate-shaped test piece with a thickness of 1 mm was prepared by injection molding at 0°C.

Z-p methyl-benzylidene sorbitol for relative softness,
1.3p chlorobenzylidene 2,4p methylbenzylidene A test piece made in the same manner as above except that sorbitol and behenic acid were used alone, or an additive-free polypropylene resin containing no dibenzylidene sorbitol derivative or behenic acid. Test pieces prepared in the same manner as above except for using the above were also tested for haze value, bleed-out, and odorlessness, and the results are shown in the table below.

Procedural amendment (voluntary) December 15, 1986

Claims (1)

[Claims] 1. As essential components, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R and R' each independently represent a chlorine atom,
represents an atom or group selected from the group consisting of a methyl group and an ethyl group] A solid powder of a dibenzylidene sorbitol derivative and a higher fatty acid of the formula CH_3(CH_2)nCOOH [where n represents a number from 14 to 30] A dibenzylidene sorbitol derivative composition comprising: the higher fatty acid coating the surface of a solid powder of the dibenzylidene sorbitol derivative. 2. Dibenzylidene sorbitol derivative is 1,3-2,
The composition according to claim 1, which is 4-di p methylbenzylidene sorbitol. 3. The composition according to claim 1, wherein the dibenzylidene sorbitol derivative is 1,3-p methylbenzylidene-2,4-p chlorobenzylidene sorbitol. 4. Dibenzylidene sorbitol derivative is 1,3-p
The composition according to claim 1, which is chlorobenzylidene-2,4-p methylbenzylidene sorbitol. 5. Claims 1 to 5, wherein the higher fatty acid is behenic acid.
The composition according to any one of Item 4.