JP3266289B2 - Plasticizer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a plasticizer composition,
Specifically, a phenolic compound,
The present invention relates to a plasticizer composition having an improved odor during heat processing by adding an organic phosphite compound or a hindered amine compound.

[0002]

2. Description of the Related Art Ester plasticizers such as dioctyl phthalate and dioctyl adipate are widely used to improve the processability and flexibility of synthetic resins such as polyvinyl chloride resins. Among them, polyester plasticizers are excellent in oil resistance, volatility resistance, migration resistance, etc., so oil-resistant hoses, tubes,
It is used for packing, electric wires and gaskets.

[0003] However, these polyester-based plasticizers have a problem that when added to a synthetic resin and heated, they generate an irritating odor, deteriorating the working environment and leaving the odor even in a product. is there.

[0004] Therefore, in order to improve the quality of resin products, there has been a strong demand for suppression of pungent odor derived from polyester plasticizers.

[0005]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies, and as a result, have been able to perform high-temperature processing by adding a phenol compound, an organic phosphite compound or a hindered amine compound to a polyester plasticizer. The present inventors have found that generation of a pungent odor at the time is suppressed, and arrived at the present invention.

[0006] That is, the present invention relates to a polyaniline containing adipic acid.
Separate the basic acid component and polyhydric alcohol component as necessary.
Monohydric alcohols and / or monohydric alcohols
Seihei produced by condensation with a basic acid
Polyester plasticizer 1 having an average molecular weight of 600 to 5000
00 parts by weight, phenolic compounds, formed by adding at least one 0.03-3 parts by weight selected from the group consisting of organic phosphite compounds and hindered amine compounds, there is provided a plasticizer composition.

Hereinafter, the plasticizer composition of the present invention having the above-mentioned gist will be described in detail.

As the polyester plasticizer in the present invention , a polybasic acid component mainly composed of adipic acid and a polyhydric alcohol component may be used as a terminal terminating component, if necessary, as a monohydric alcohol and / or monobasic acid. And those produced by condensation.

[0009] As polybasic acid component other than the adipic acid, for example, malonic acid, succinic acid, glutaric acid, Se Basi <br/> phosphate, azelaic acid, aliphatic dibasic acids such as dodecane dicarboxylic acid mainly Components, and in addition to this, a small percentage of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, aromatic polybasic acids such as pyromellitic acid, or butanetricarboxylic acid, tricarballylic acid, Aliphatic polybasic acids such as citric acid can also be used.

The polyhydric alcohol component includes, for example, ethylene glycol, diethylene glycol,
2-propanediol, 1,3-propanediol, 2
-Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-
1,3-propanediol, 1,2-butanediol,
1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, etc., which are mainly composed of aliphatic glycols. Polyhydric alcohols such as trimethylolpropane, trimethylolethane, and pentaerythritol can also be used.

[0011] Examples of the terminal terminating component include methanol, ethanol, propanol, isopropanol, butanol, secondary butanol, isobutanol, hexanol, isohexanol, heptanol, and the like.
Isoheptanol, octanol, isooctanol,
Aliphatic monohydric alcohols such as 2-ethylhexanol, isononyl alcohol, isodecanol, isoundecanol, isotridecyl alcohol, benzyl alcohol, and acetic acid, propionic acid, butyric acid, isobutyric acid, octylic acid, 2-ethylhexylic acid, and lauric acid Examples thereof include aliphatic monobasic acids such as acid, myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid.

The ratio of the above-mentioned components used in the production of the above-mentioned polyester-based plasticizer varies depending on the kind of the component to be used and the properties and molecular weight of the intended polyester-based plasticizer. It is used in a ratio of 10 to 80% by weight of an acid component, 10 to 80% by weight of a polyhydric alcohol component, and 0 to 50% by weight of a terminal terminating component.

The polyester-based plasticizer preferably has a number average molecular weight of from 600 to 5,000.
~ 4000 are more preferred. Further, the acid value is preferably 1 or less, and the hydroxyl value is preferably 30 or less.

Accordingly, examples of the polyester plasticizer used in the present invention include the following Tables 1 to 3 (sample
Nos. 1 to 22).

[0015]

[Table 1]

[Table 2]

[Table 3]

It is well known that polyester plasticizers are produced using the above-mentioned components, and can be easily produced, for example, by reacting in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate.

The phenol compound used as an additive of the plasticizer composition of the present invention includes, for example, 4,4'-
Isopropylidene diphenol, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, Distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4'-butylidenebis (6- Tributyl-m
-Cresol), 2,2′-ethylidenebis (4,6-
Di-tert-butylphenol), 2,2′-ethylidenebis (4-tert-butyl-6-tert-butylphenol), 1,
1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4
-Methyl-6- (2-hydroxy-3-tert-butyl-5
-Methylbenzyl) phenyl] terephthalate, 1,
3,5-tris (2,6-dimethyl-3-hydroxy-
4-tert-butylbenzyl) isocyanurate, 1,3
5-tris (3,5-di-tert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3
5-di-tert-butyl-4-hydroxybenzyl) -2,
4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-
3-tert-butyl-5-methylbenzyl) phenol,
3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5 .5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

The organic phosphite compound used as an additive in the plasticizer composition of the present invention includes, for example, trisnonylphenyl phosphite, tris (2,4-ditertbutylphenyl) phosphite, tris [2 -Tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite Fight, di (tridecyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, di
(Nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-methylphenyl) pentaerythritol diphosphite, Tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,
4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-4-hydroxy-
5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like Is raised.

The hindered amine compound used as an additive in the plasticizer composition of the present invention is preferably a compound having at least one 2,2,6,6-tetramethylpiperidyl group in the molecule. 2,2
6,6-tetramethyl-4-piperidyl benzoate,
N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2 6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 , 2,
2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4) -Hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl)
Hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-
4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2 -{Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.
5] undecane, 3,9-bis [1,1-dimethyl-2
-Tris (1,2,2,6,6-pentamethyl-4-
Piperidyloxycarbonyloxy) butylcarbonyloxy {ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis} N- (2 , 2,6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-
Triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,
6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N'-bis (2,2
6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

The addition amount of the phenol compound, the organic phosphite compound or the hindered amine compound is 0.0 to 100 parts by weight of the polyester plasticizer.
3 to 3 parts by weight.

The synthetic resin to which the plasticizer composition of the present invention is added is not particularly limited, and examples thereof include a synthetic resin to which a usual polyester plasticizer is added and used.

EXAMPLES Hereinafter, the plasticizer composition of the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 An additive (see Table 4) was added to a polyester plasticizer (Sample No. 20, see Table 3) and blended at 110 ° C. for 1 hour to obtain a plasticizer composition. The following tests were performed using the plasticizer composition prepared here. For comparison, the same test was performed for the case where no additive was added (Comparative Example 1-1).

In order to grasp the state of deterioration of the polyester plasticizer, changes in the acid value were examined. The acid value of the unpromoted plasticizer composition and the acid value after promotion in a gear oven at 150 ° C. for 40 hours were measured according to JIS-K-6751.

Next, the rate of increase of the low boiling component of the plasticizer composition, which is considered to be a major cause of odor, by heating was confirmed. The test method used a gas chromatograph (GC-9A, manufactured by Shimadzu Corporation) under the following conditions of [gas chromatography setting conditions] to increase the peak area from the sample introduction to 6 minutes after the sample was introduced, and to increase the unpromoted plasticizer composition. What was accelerated at 2 ° C. for 2 hours was determined, and the increase rate was calculated.

[Setting Conditions for Gas Chromatography] Column PEG-HP 3 mm Column temperature 70 ° C. Injection temperature 280 ° C. Carrier N ₂ , 50 mm / min. Chart speed 10 mm / min.

Further, an odor test based on human odor was also conducted. After heating at 150 ° C. for 2 hours, the presence or absence of irritating odor was examined for 20 randomly selected panelists, and the number of persons who felt the irritating odor was judged according to the following [Odor test evaluation criteria].

[Odor test evaluation criteria] Number of people who felt an irritating odor ◎: No irritating odor 0 to 1 ○: Almost no irritating odor 2 to 4 people △: There was an irritating odor 5 to 9 ×: There was a strong irritating odor 10 More than

The results are shown in Table 4 below.

[0029]

[Table 4] * Sample No. 20 Parts by weight based on 100 parts by weight.

Example 2 Polyester plasticizer (see Table 5 and Tables 1 to 3) 100
In parts by weight, the additive [bis (2,6-di-tert-butyl-4-
[Methylphenyl) pentaerythritol diphosphite] was added and blended at 150 ° C. for 1 hour to obtain a plasticizer composition. The same test as in Example 1 was performed using the plasticizer composition prepared here. For comparison, when no additive was added (Comparative Examples 2-1 and 2
The test was similarly performed for -2). The results are shown in Table 5 below.

[0031]

[Table 5]

Example 3 In the same manner as in Example 1, 2 g (0.14% by weight) of an additive (see Table 6) was dissolved in 1400 g of a polyester plasticizer (Sample No. 20, see Table 3). Using this polyester-based plasticizer, an odor test was conducted at the time of preparing a compound according to the following formulation. The test method is
The following components were charged into a Henschel mixer (20-liter tank), stirred at 1600 rpm, taken out when the temperature in the tank reached 110 ° C. (about 20 minutes after the start), and immediately evaluated for odor. Evaluation criteria are based on the odor test of Example 1.

For comparison, a case where no additive was added (Comparative Example 3-1) and a case where the additive and the polyester plasticizer were separately added at the time of preparing the compound without using the plasticizer composition of the present invention (Comparative Examples 3-2 and 3-3)
A similar test was also conducted.

[Blending] Vinyl chloride resin [Geon-103EP manufactured by Zeon Corporation] 2000 g Polyester plasticizer (Sample No. 20, see Table 3) 1400 g Barium stearate 12 g Calcium stearate 8 g Additive (see Table 6) 2g

The results are shown in Table 6 below.

[0036]

[Table 6]

From the results shown in Tables 4 to 6, the plasticizer composition of the present invention obtained by adding a phenol compound, an organic phosphite compound or a hindered amine compound to a polyester-based plasticizer can suppress decomposition at high temperatures, It can be seen that the generation of pungent odor is small. Also, when the plasticizer composition of the present invention is added to the resin composition, the generation of pungent odor is significantly suppressed, whereas the polyester plasticizer and these compounds (the plasticizer of the present invention) are used. Compound used as an additive in the dispersant composition), the odor improving effect is not seen at all, and the plasticizer composition of the present invention is effective in improving odor at high temperatures such as during processing. It is clear that there is.

[0038]

The plasticizer composition of the present invention suppresses the generation of irritating odor during high-temperature processing, and does not generate irritating odor when added to a synthetic resin and subjected to heat processing. Do not worsen.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Haruo Sugita 5-2-113, Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (56) References JP-A-62-295935 (JP, A) JP-A-59-38250 (JP, A) JP-A-2-281061 (JP, A) JP-A-61-136533 (JP, A) JP-A-60-4543 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C08L 27/06 C08L 67/02-67/03

Claims (1)

(57) [Claims] 1. A polybasic acid component mainly composed of adipic acid and a polybasic acid component.
A polyhydric alcohol component may be used as a terminal terminating component if necessary.
Using monohydric alcohols and / or monobasic acids
And the number average molecular weight produced by condensation is 6
To 100 parts by weight of a polyester plasticizer 00-5000, phenolic compounds, formed by adding at least one 0.03-3 parts by weight selected from the group consisting of organic phosphite compounds and hindered amine compounds, plasticizers composition.