JPH07330952A - Lowly odorous plasticizer - Google Patents

Abstract

PURPOSE:To obtain a plasticizer reduced in odor. CONSTITUTION:This plasticizer comprises a mixture of at least two dialkyl adipates which differ in the number of carbon atoms and are represented by the formula (wherein R1 and R2 may be the same or different and each is a 6-15C linear or branched alkyl). When a mixture of the plasticizer and 0.010wt.% toluene is analyzed by head-space gas chromatography using a fused-quartz capillary column and an FID under the head-space conditions of 140+ or -10 deg.C and 2min and under such conditions as to result in a chromatogram having a toluene-assignable peak with a retention time of 2.6+ or -0.5min and an area of 30X10<4>+ or -5X10<4>, it gives a chromatogram satisfying the equation (SAX5)<=ST wherein SA is the total area of all peaks within the retention time range of from 4 to 11min and ST is the area of the peak assignable to toluene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to odor-reduced plasticizers.

[0002]

[Prior Art and Problems] Generally, a plasticizer is used by blending it with resin or rubber to plasticize it and improve workability, and also as a solvent of some kind or by applying it to equipment to prevent rust and scratches. Used for prevention.

For example, by adding a plasticizer to a vinylidene chloride resin or a vinyl chloride resin, flexibility can be imparted and various molded products, sheets, films and the like can be produced. In particular, the stretch film is used as a wrap film for food packaging, and in order to improve various properties such as film processability, stretchability and adhesiveness, improvement of plasticizer and devising of compounding recipe have been made.

Although the odor and toxicity of the stretch film is an important issue for food packaging, the toxicity is strictly controlled, while the odor is rarely studied. . Impurities contained in a mixture of at least two kinds of dialkyl adipates having different carbon numbers among the compounds represented by the general formula 2 used as a plasticizer for stretch film for food packaging cause the odor of the film. However, little has been done on the components that cause odor.

[Chemical 2] (R ₁ and R ₂ are each an alkyl group having 6 to 15 carbon atoms and may be linear or have a side chain, and may be the same or different.)

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a plasticizer with reduced odor.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors to solve the above-mentioned problems, the plasticizer is a compound represented by the general formula 3 in which at least two or more dialkylazides having different carbon numbers are used. In the case of a mixture of plates, 0.010% by weight of toluene was added to the plasticizer, the column was a fused silica capillary column, and the detector was FID.
Head space condition is 140 ± 10 ℃, 20
In minutes, the retention time of the peak based on toluene is in the range of 2.6 ± 0.5 minutes, and the peak based on toluene is
The total area of the detection peaks whose retention time is in the range of 4 to 11 minutes in the head space gas chromatograph measured under the condition that the area of the peak is 300,000 ± 50,000.
The area (S _T ) of the peak based on (S _A ) and toluene is S _A × 5
It was found that a plasticizer with reduced odor can be obtained when the relationship represented by ≦ S _T is satisfied, and the present invention has been completed.

[Chemical 3] (R ₁ and R ₂ are each an alkyl group having 6 to 15 carbon atoms and may be linear or have a side chain, and may be the same or different.)

That is, according to the present invention, the plasticizer contains at least two kinds of aliphatic saturated alcohols represented by the general formula (4), which have different carbon numbers, and carbon numbers obtained from adipic acid. In the case of a mixture of different dialkyl adipates (hereinafter referred to as DMAA),
Toluene of 0.010% by weight was added, a fused silica capillary column was used as the column, and FID was used as the detector. The head space condition was 140 ± 10 ° C., 20 minutes, and the retention time based on toluene was 2. In 6 ± 0.5 minutes,
The total area (S _A ) of the peaks existing in the retention time of the head space gas chromatograph measured from 4 to 11 minutes under the condition that the area of the peaks based on toluene is 300,000 ± 50,000 and the toluene. The area of the base peak (S _T ) is S
_The present invention provides a low-odor plasticizer characterized by satisfying the relationship of _A × 5 ≦ S _T.

[Chemical 4] (R ₁ and R ₂ are each an alkyl group having 6 to 15 carbon atoms and may be linear or have a side chain, and may be the same or different.)

A general method for producing DMAA is, for example, by first adding a mixture of at least two kinds of aliphatic saturated alcohols different in carbon number among the aliphatic saturated alcohols represented by Chemical formula 5 to adipic acid, and then adding acidity. After heat-reacting in the presence of a catalyst, the mixture is washed with a dilute aqueous alkali solution and water in this order, distilled under reduced pressure to recover unreacted alcohol, and purified by activated carbon to obtain a product.

[Chemical 5] (R is an alkyl group having 6 to 15 carbon atoms and may be linear or branched.)

As another method for producing DMAA, one of the aliphatic saturated alcohols represented by Chemical formula 6 or an aliphatic saturated alcohol mixture having the same carbon number is added to adipic acid to prepare an acidic catalyst. At least two kinds of dialkyl adipates having different carbon numbers may be mixed among those heated and reacted in the presence.

[Chemical 6] (R is an alkyl group having 6 to 15 carbon atoms and may be linear or branched.)

Examples of the saturated aliphatic alcohol having 6 to 15 carbon atoms include n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-nonyl alcohol.
Le, n-decyl alcohol, n-undecyl alcohol
N-dodecyl alcohol, n-tridecyl alcohol
, N-tetradecyl alcohol, n-pentadecyl alcohol, isoheptyl alcohol, isooctyl alcohol, isononyl alcohol, isodecyl alcohol
Isodedecyl alcohol, isododecyl alcohol
, Isotridecyl alcohol, isotetradecyl alcohol, isopentadecyl alcohol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 2-
Ethyl butanol, etc. can be mentioned.

However, D produced by the above general method
MAA has a large odor component remaining, and S _A and S _T of the head space gas chromatograph measured by adding 0.010% by weight of toluene do not satisfy the relationship represented by S _A × 5 ≦ S _T. There is an odor, which is not preferable.

On the other hand, after manufacturing DMAA by the above-mentioned general method, using a thin film evaporator or the like, 0.010% by weight is obtained.
It was found that the DMAA from which impurities were removed until the S _A and S _T of the head space gas chromatograph measured by adding the above-mentioned toluene satisfied the relation represented by S _A × 5 ≦ S _T had almost no odor and was good. .

The impurities can be removed by any method such as a distillation method such as vacuum distillation or steam distillation, and a method using a strip column as long as the object of the present invention can be achieved.

The DMAA in the present invention may be blended with a resin or rubber and used, or may be applied to a solvent or equipment to be used for rust prevention and scratch prevention.

The DMAA of the present invention is particularly useful as a stretch film for packaging low odor foods by blending it with vinylidene chloride resin or vinyl chloride resin. The vinylidene chloride resin is a generic term for vinylidene chloride homopolymers and copolymers of vinylidene chloride and vinyl chloride, acrylic acid, acrylonitrile, or the like. The vinyl chloride resin is a generic term for a vinyl chloride homopolymer and a copolymer of vinyl chloride and vinyl acetate or ethylene.

The DMAA in the present invention is used by blending it with vinylidene chloride resin, vinyl chloride resin or the like, but additives such as stabilizers, fillers and lubricants can be blended appropriately.

[0017]

EFFECT OF THE INVENTION A plasticizer with reduced odor can be obtained.

[0018]

【Example】

<Examples 1 to 10, Comparative Examples 1 to 10> Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. (1) Method for Purifying DMAA After charging 200 g of crude DMAA in a 500 ml flask, the mixture was heated to 135 ° C. and water was added dropwise under reduced pressure to remove impurities, thereby obtaining DMAA purified products of Examples 1 to 10.
Comparative Examples 1 to 10 are crude DMAA treated with activated carbon.

(2) Headspace Gas Chromatograph Measuring Method A headspace gas chromatograph was measured by the following method by adding 0.010% by weight of toluene to DMAA. Headspace sample amount: 1 ml Column: Fused silica capillary column Detector: FID Headspace conditions: 140 ° C, 20 minutes

(3) Odor determination method 50 ml of DMAA was added to a flask with internal volume of 100 ml stoppered.
After putting in and sealing, after heating for 5 minutes in a heating furnace at 125 ° C., the odor was evaluated by the sensory test of 5 panelists according to the following criteria. ◯: Almost no odor. Δ: There is an odor and it is slightly unpleasant. X: Strong odor and uncomfortable.

(4) Evaluation Results The results are shown in Table 1. Examples 1 to 10 in which S _A and S _T in the head space gas chromatographic measurement of DMAA added with 0.010% by weight of toluene satisfy the relationship represented by S _A × 5 ≦ S _T As a result, the DMAA of Comparative Examples 1 to 10 in which S _A and S _T do not satisfy the relationship represented by S _A × 5 ≦ S _T, which has almost no odor, has an odor and is slightly unpleasant or unpleasant. there were.

[0021]

[Table 1] ¹⁾ alcohol - le composition (weight _{ratio) a) C 7 H 15 -OH} 3): C 9 H 19 -OH 3) = 48: 52 b) n-C 6 H 13 -OH: n-C 8 H 17 _{-OH: n-C 10 H 21} -
OH = 35: 45: 20 ²⁾ Ester composition (weight ratio) c) Di-n-hexyl adipate: di-n-octyl adipate = 1: 1 d) Di-n-heptyl adipate: Di-isononyl adipate 1: 1 ^{3) In} DMAA, the retention time of the head space gas chromatograph measured by adding 0.010% by weight of toluene was 4 to 11 minutes.
Ratio of the total area of the smoke (S _A ) to the area of the toluene peak (S _T ).

Claims (1)

[Claims] 1. When the plasticizer is a mixture of at least two dialkyl adipates having different carbon numbers among the compounds represented by the general formula 1, the plasticizer contains 0.0
10% by weight of toluene was added, a fused silica capillary column was used as the column, and FID was used as the detector. The head space condition was 140 ± 10 ° C., 20 minutes, and the retention time of the peak based on toluene was It is in the range of 2.6 ± 0.5 minutes, and the area of the peak based on toluene is 300,000 ±.
Head space gas chromatograph measured under the condition of 50,000, the total area of detection peaks (S _A ) with retention times in the range of 4 to 11 minutes and the area of peaks based on toluene (S _T ) Is a low odor plasticizer characterized by satisfying the relationship represented by S _A × 5 ≦ S _T. [Chemical 1] (R ₁ and R ₂ are each an alkyl group having 6 to 15 carbon atoms and may be linear or have a side chain, and may be the same or different.)