JPS58157845A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:The titled composition that is prepared by adding tri-isononyl trimellitate and a phenolic antioxidant to a vinyl chloride resin with a polymerization degree over a certain level, thus showing markedly improved resistance to heat aging. CONSTITUTION:To 100pts.wt. of a vinyl chloride resin of over 1,000 polymerization degree, are added 30-80pts.wt. of tri-isononyl trimellitate as a plasticizer and more than 0.01pts.wt., practically 0.05-1pt.wt. of a phenolic antioxidant melting over 160 deg.C such as 4,4'-triobis (3-methyl-6-tert.-butylphenol). The addition of 0.1-5pts.wt. of an epoxide further increases its heat aging resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a heat aging resistant vinyl chloride resin composition using a vinyl chloride resin and trimellitic acid triisononyl ester.

One of the plasticizers for heat aging-resistant soft vinyl chloride resin compositions is a trimellitic acid ester compound. Among the trimellitic acid esters, the compound that is used industrially is trimellitic acid tri-2-ethylhexyl ester (TO
TM) or trimellitic acid triisodecyl ester (TM than T).
.

TOTM has been awarded for its performance. however'
There are applications in various fields that require heat aging resistance that is more severe than that obtained by blending rOTM.

It is known that one method of meeting this requirement for a vinyl chloride resin composition is to increase the number of carbon atoms in the alkyl group of a trimellitic acid ester to use a trimellitic acid ester with lower volatility. However, TM is better than T mentioned above in terms of compatibility with vinyl chloride resin, plasticization efficiency, economic efficiency, etc.

Since it is inferior to TOTM, there are not many cases where IC11L is preferentially used unless there is a special need.

In view of these circumstances, trimellitic acid triisononyl ester (TINT
M) was developed.

When this T-Tech NTM is mixed with vinyl chloride resin, it should be used as an antioxidant with a melting point of less than 160°C, in the same way as the trimellitic acid esters currently used industrially. '-Inogropyride/bisphenol (BPA) etc. is added to improve thermal stability by adding 1% trimellitic acid ester VC6. For example, BPA, BHT, BHA, etc.
Thus, TINTM antioxidants with melting points below ℃
[The effect of addition showed similar results to the effect on trimellitic acid esters such as TOTM and TIDTM;
It has been found that Md also provides improved heat aging resistance.

However, when more severe heat aging resistance is required [Fi, vinyl chloride resin compositions containing these TINTMs have limitations.

One object of the present invention is to provide a vinyl chloride resin composition that further improves the heat aging resistance of FiT NTM.

The feature of the present invention is that 30 to 80 parts by weight of TINTM and 1 part by weight or more of phenolic antioxidant α0 with a melting point of 160°C or more are combined with 100 parts by weight of vinyl chloride resin with an average degree of polymerization of 1000 or more, and 1 part or more of F12. It is at the blending point.

The above-mentioned vinyl chloride resin having an average degree of polymerization of 1000 or more is an ethylene/vinyl chloride copolymer consisting of polyvinyl chloride and an ethylene content of [1L5~=5% by weight. Soft PVC sheets with an average degree of polymerization of 1000 or more require heat aging resistance of 168 hours or more at RI 100°C to 120°C or 12 (for applications requiring heat aging resistance of 168 hours or more at 1°C or more). The average degree of polymerization is set.

The vinyl chloride polymer used in the VC of the present invention refers to what is broadly called vinyl chloride resin.

For example, vinyl chloride homopolymer, vinyl chloride and ethylene,
Propylene, acrylic acid, acrylic ester and/
Alternatively, a copolymer with vinyl acetate or the like can be used.

In such a case, copolymerization components such as ethylene, which is a copolymerization partner with vinyl chloride, are treated as being defined as plastic components in the present invention in terms of their quantitative relationship.

In the present invention, in addition to the various plasticizers added to the vinyl chloride resin, ethylene, propylene, vinyl acetate, acrylic acid or its ester, etc., which are present as copolymer components in the vinyl chloride resin, are used when a specified heat aging resistance is required. important to
It must be treated as a "plastic component".

The halogen-containing resin used in the present invention also includes polyvinylidene chloride, chlorinated polyethylene, other copolymers, and graft polymers. For example, ethylene-vinyl chloride copolymer.

These include vinyl acetate-vinyl chloride copolymers and graft copolymers obtained by graft-polymerizing vinyl chloride onto ethylene-vinyl acetate copolymers. Further, these halogen-containing resins may be used as a mixture, or an auxiliary agent such as another thermoplastic resin or a reinforcing agent tm may be added for the purpose of improving processability.

In general, nonanol, a raw material for producing trimellitic acid trinonyl ester ta, can be roughly divided industrially into products using the following four methods.

■ 5,5.5-)limethylhexanol-1 obtained by oxotation reaction and hydrogenation reaction of 2,4.4-)limethylpentene, which is a dimer of inobutene ■Acidic catalyst such as solid phosphoric acid catalyst The fraction corresponding to olefins having 8 carbon atoms in polymerized gasoline made from ethylene, propylene, butylene, etc., as raw materials is completely fractionated using a 100% olefin, and this is subjected to an oxation reaction and hydrogenation reaction to obtain nonanol ■ Ethylene oligomer Alternatively, nonanol obtained by oxotation reaction and hydrogenation reaction of olefin having 8 carbon atoms separated from wax cracked product. Nonanol produced by the method shown in Claim 5TIC of the present invention. The ability of trimellitic acid trinonyl ester obtained by esterification with an acid or trimellitic anhydride to make vinyl chloride resin is inferior to that from ■, and ■ and ■ are inferior in plasticization efficiency and cold resistance9. (2) is inferior in compatibility and volume resistivity. From the overall performance, it can be concluded that the nonanol of the present invention (ii) is preferable as the raw material nonanol for trimellitic acid trinonyl ester.

Incidentally, each of these trimellitic acid trinonyl esters has a similar effect of improving heat aging resistance when a tetraphenolic antioxidant is added.

To explain in more detail the trimellitic acid nonyl ester of nonanol produced by the method ① above, TI
NTM is obtained by subjecting octe/ obtained by dimerization of butene to nonanol through oquination and hydrogenation reaction, and then esterifying this nonanol with trimellitic anhydride to obtain TINTM.

More specifically, the butene is normal butene containing isobutene, and butadiene is generally removed from the butane/butylene fraction, including the B-B fraction generated from ethylene crackers or the butene fraction generated from FCC equipment. death.

Further, after removing the oxygen-containing compound, the mixture is polymerized in the presence of a nickel compound and a metal alkyl halognate to obtain an oligomer mixture of isobutyne and normal butylene. Here, the nickel compound is a nickel oxygen compound 9 such as nickel diacetylacetonate, a nickel sulfur compound 9 such as nickel butyl dithiocarbamate, or a nickel organic acid salt 1 such as nickel oleate. The metal alkyl halogenates are as follows.

R5AA! ,! .

RAIX, (here X: C1, BY
R: alkyl group) Then, from the oligomer mixture of isobutyne and normal butene described above, initial boiling point 116 ± 2 ° C, end point 125 ± 2 was determined by the method specified by J to K2254#'C.
A fraction consisting of octenes with a boiling point range of ℃ is separated. This octene is subjected to an oxation reaction and then hydrogenated to obtain nonanol. The nonanol of the kernels is subjected to an esterification reaction with trimellitic anhydride or trimellitic acid to obtain trinonyl emulsion ester of trimellitate (TINTM).

In addition, phenolic antioxidant 11i with a melting point of 160°C or higher
1J means 4.4'-thiobis(3-methyl-6-tert-butylphenol) [melting point 161-164°C].

2.6-bis(2'-hydroxy-3'-tert-butyl-
5-Methylbenzyl)-4-methyl-phenol (melting point 171-172°C), 2.5-diteramyl-hydroquinone (melting point 172°C or higher), 1+t5-tris(2-methyl-4-hydroxy- 5-tert-butyl-phenyl)butane (melting point 185-188°C), 4
．． 4'-butylidenebis(5-methyl-6-tert-butylphenol) [melting point 205-212°C], 2,5-di-tert-butyl-hydroquinone [melting point 204°C or higher],
tts-tris(45-di-tert-butyl-4-hydroxybenzyl)-8-)riazine-2,46-(I H
, SH, 5H)-trione [melting point 221°C
] etc. BH with a melting point of 160℃ or higher
A (melting point 57-63°C), BHT [melting point 69-71°C
], bisphenol A [melting point 156°C], etc., with a melting point of 16
This is because the effect of improving heat aging resistance of the aforementioned phenolic antioxidant having a melting point of 160°C or higher is extremely superior to that of the phenolic antioxidant having a temperature of less than 0°C. The amount is based on 100 parts of vinyl chloride resin.

α01 part by weight or more, but if it is less than 0.01 part by weight, it shows a thermal stability effect, but the effect of improving heat aging resistance is poor.
This is because there is no The upper limit range is subject to restrictions due to economic considerations and compatibility of each compound, but in practice, α05 to 1 part by weight is preferred. Of course, depending on the purpose, 1 part by weight or more may be added.

In addition, when the above-mentioned phenolic antioxidant with a melting point of 160°C or higher is added to a vinyl chloride resin composition containing a phenolic antioxidant with a melting point of less than 160°C or other antioxidants, Aging effects may be exhibited by acid addition, or a sagging effect may appear depending on the formulation composition and heat aging test conditions.

Furthermore, when different types of phenolic antioxidants with melting points of 160° C. or higher are mixed and used, heat aging resistance almost equal to that of acidification is exhibited.

Furthermore, the composition comprising the specific polyvinyl chloride resin according to the present invention, trimellitic acid triinnonyl ester, and a phenolic antioxidant with a melting point of 160°C or higher can be made heat resistant by combining α1 to 5 parts by weight of an epoxy compound. It can also improve aging resistance.

The present invention [OI! From the viewpoint of its effectiveness, the epoxy compound to be used is [L1 to 5 parts by weight is added to the polyvinyl chloride resin and used in combination, but is preferably in the range of 15 to 5 parts by weight, and the amount of the epoxy compound is 5 parts by weight. If a large amount of the above is blended, it is undesirable as it may cause the predeg/g phenomenon and a decrease in residual elongation.

If the amount is less than 11 parts by weight, the aging resistance effect will be insufficient.

Epoxy compounds used in the present invention include:

For example, glycidyl methacrylate, glycidyl acrylate, glycidyl vinyl ether alcohol or butadiene/
Radical polymers of monomers having at least one oxyla/ring in the molecule, such as noeboxy compounds (epoxy compounds with a molecular weight of about 1,000 or more), and molecular weights of about 500 or more obtained by the condensation reaction of bisphenol A and epichlorohydrin. bisphenol type epoxy resin, and epoxidized soybean oil (Mark BF2: trade name, Adeka Argus), epoxidized linseed oil, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid butyl ester, 0-diphenylglycine Ruether.

Examples include epoxidized polybutadiene, epoxidized olefin/etc.

Examples of the organic metal salt or inorganic metal salt used in the present invention include metals 9 that have a stabilizing effect on halogen-containing resins, for example,
Od, Ba, Zn, Ca9Mg, Al, B
r.

It is a single or composite metal salt containing Pb, Eln, etc.

Furthermore, examples of the organometallic salts mentioned here are:

Refers to salts of organic saturated fatty acids and salts of organic unsaturated fatty acids having 6 to 22 carbon atoms9 For example, ophtonic acid, capric acid,
Lauric acid, stearic acid.

Ricinoleic acid, ricyluic acid, naphthenic acid.

There are organic metal salts such as phthalic acid. Other than this.

Typical examples of organic tin compounds include dibutyltin, diocteltin, and dipendyltin-based lauric acid and maleate. In addition, there are many examples of inorganic metal salts, such as dibasic lead sulfate.

Examples include dibasic lead sulfate, white lead, white zinc, lead carbonate, and dibasic lead/acid lead.

The above-mentioned stabilizers are not particularly limited, and any stabilizer used depending on the purpose can be used. Also,
Fillers, flame retardants (9), colorants, impact-resistant agents, ultraviolet absorbers, antistatic agents, lubricants (1), etc. may be used in combination as necessary.

Examples of the present invention and its effects will be described below, but the present invention is not limited thereto. The tensile properties used in these Examples and Comparative Examples were measured according to JIS K6725, and the heating conditions were changed according to the purpose according to the heat aging test i1t and T15K6723.

Example 1 (1) Production of T I N TM After extracting and removing butadiene, the extractant was removed and a trace amount of butadiene was removed by selective hydrogenation to produce 9 isobutyne 1.
1L 1% by weight, 70.5% by weight of normal butene, 241% by weight of isobutane, 18.4% by weight of normal butene. Nickel oleate α2f and ethylaluminum dichloride 0.5% as a catalyst per 100f of spent BB fraction VCBB fraction. - was added thereto, and the reaction was carried out continuously at a pressure of μC gauge and a temperature of 20°C. In reaction "a", two glass autoclaves each having an internal volume of 250 mm were connected in series, and the reaction residence time was 45 to 50 hours.

The product is taken out at normal temperature and pressure, and after distilling off unreacted gas, 10? A 5% by weight aqueous sulfuric acid solution was added to decompose and remove the catalyst. The product 51 was charged into a glass batch rectification column with a can capacity of 51 and rectified.

Then, at normal pressure, an olefin fraction having 8 carbon atoms and a tower top temperature of 111°C to 124°C was charged, and the BB fraction IKf was charged. ) 4729 for 9. This olefin was charged into a stainless steel autoclave containing 1y45t2/4f of dicobalt octacarbonyl in terms of metal cobalt, and 16 oKg/c
The oxo reaction was carried out for 90 minutes using a IIi gauge at a temperature of 150° C. in the presence of oxocas at a hydrogen/carbon oxide molar ratio of t3:1. The reaction product was produced at a hydrogen pressure of 50'g/7 gauge in the presence of a mixed catalyst of a steel chromite catalyst and a nickel catalyst.

The hydrogenation reaction was carried out at a temperature of 170°C for about 2 hours.

The hydrogenation product was purified on the same equipment that used the catalyst to rectify the P side-drawn olefin. First, the hydrocarbons were almost completely distilled off at normal pressure, and then the alcohol was rectified at a relative pressure of 50 mmHy, and the fraction having a top temperature of 114°C to 121°C was collected. The boiling point range of this alcohol was: an initial boiling point of 19Z5°C and an end point of 204°C, according to the method of JI8 K2254.

For 5199 of this alcohol, 19 of trimellitic anhydride
2f and triisoglopyltitanate α2 as catalyst
The reaction was carried out for 4 hours using f at a reaction temperature of 2S 0°C, and 995% of trimellitic anhydride was esterified. After neutralizing this esterification reaction product and removing the catalyst, the pressure was 10 W.
sHy, unreacted alcohol was distilled off at a flask temperature of 200°C.

Then, it was treated with 7 tons of activated carbon to obtain product 5609. The membrane properties of this film were as follows: specific gravity (50''C): 11976, viscosity (30°C): 18 voids, and loss on heating as specified in J Engineering 5K6751: 0.015%.

(2) Heat aging test example 1 (TINTM of υ and commercially available TOTM (ADEKA Argus Chemical Co., Ltd. ADK Olger (!-8)
) was used to determine the effect of various phenolic antioxidants on heat aging resistance according to the formulation shown in Table 1. phenol) had the least decrease in elongation.

Table 1 (Average degree of polymerization 2800) +2) BBP: 4. Evelydenbis(3)
-methyl-6-tert-butylphenol), BHT: 2.6-di-tert-butyl-p-cresol BP
A:4. /-isopropylidene bisphenol HBP:
The n-octadecyl-6-(4-hydroxy-hen-5-tert-butylphenol) propionate tensile test was determined according to the method of J.Eng. 5K6723. In addition, the gear set used in the heat aging test was set to open at an air exchange rate of 10 times per hour.

Examples 2 to 4 According to the method described in Example 1, the following compounding composition: Vinyl chloride (E-2800) 100 parts by weight Tribase 7 #Dibasic lead stearate 11 Clay #33 5
l Ebonylated soybean oil 11 and the plasticizer shown in Table 2 were added, and the amount of 4,4'-butylidene bis(5-methyl-6-tert-butylphenol) (abbreviated as BBP) as a phenolic antioxidant was added. A heat aging test was conducted after changing the temperature. The results are shown in Table 2 (the effect of adding rIA to BBP was not so significant in TOTM, but showed improvement in heat aging resistance in TINTM).

Table 2 Examples 5 to 8 In the same manner as in Example 1, the effect of the type of antioxidant on heat aging properties was measured. As shown in Table 5, the results showed that almost the same effect on improving heat aging resistance was obtained in all cases.

Table 3 (1) BBP: 4,4'-butylizo/-bico (5-methyl-6-tert-butylphenol) TBP: 4,4'-thiobis (3-methyl-6-tert-butylphenol) HBB: 翫45-trimethyl-2,4,6-tris (
5,5-di-tert-butyl-4-hydroxybenzyl)benzene HBT: 1,5.5-)lis(5,5-di-tert-butyl-4(hydroxybenzyl)-S-triazine-2,4
,6-(1a, 5H,51()-) Rio/BPA:4. Einoglopylidene bisphenol Examples 9 to 12 Table 4 shows the test results of the combined effect of a phenolic antioxidant with a melting point of 160° C. or higher and other phenolic antioxidants. The implementation method and the symbols for the type of antioxidant in Table 4 are the same as those shown in Examples 5-8.

Example 15 Straight vinyl chloride resin H-1300 (Nikki Kagaku Products) and E-2 with an average degree of polymerization of 1500 were added to the vinyl chloride resin.
800 and TriPace 7PHR as other compounding agents
, Dibasic Lead Stearate I PHR, Southern Crane 335PHR, TINTM50PHR, Antioxidant B
BPαI PHR and epoxidized soybean oil 0-10PHH
The heat aging properties of the blended products at 160°C are summarized in Table 5K. In addition, as a comparison column, the results when the plasticizer was changed to TOTM are shown.

Table 5 Example 14 Vinyl chloride resin was coated with Chisso Co., Ltd.
Average degree of polymerization 2500), Nivolit CM (average degree of polymerization 2
900) and ethylene vinyl chloride resin E-2800
IAtj is TINTM50PHR as plasticizer using
, 'rO'rM50P)lR.
The results are shown in Table 6VC. In addition, the following additives other than those mentioned above were commonly used.

Antioxidant BPA α2PHR BBP 0.2PHR Tribase 7P, HR Dibasic lead stearate I FUR Southern clay-φ335PHR Epoxidized soybean oil I FIR Examples 15 to 18 To further examine the effect of raw material nonal.

A film was prepared using the following formulation and its plasticization performance was examined.

Table 8 PVC plasticizing performance blending composition of raw material nonanol and its trimellitate PVC (P=1450) 1ooiJ''e) base 5 Lead stearate 1 Plasticizer 50 The trimellitate of these nonanol is as shown in <Plasticization Efficiency J Cold Resistance Compared to ■, ■ and ■ are considerably inferior to ■, and ■ has a volume resistivity of 255, which is inferior to ■.

It was found that there was no difference in heat aging resistance.

Patent applicant: Nissan Chemical Industries, Ltd. Procedural amendment (spontaneous) January 22, 1980 Patent Office - Director Tsumako Shimada 1, Indication of case 1982 Patent application 40491, Name of invention Vinyl chloride resin composition Relationship with the person making the fifth amendment Patent applicant address 3-7-1 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 1-1
01 Contact phone number: 0474-65-11 11 Years old (5) Contents of the amendment in the "Detailed Description of the Invention" section of the specification subject to the amendment) JK amendment.

(2) Add "-" to the elongation column of Example 1 in Table 1 on page 18 of the specification.

(3) Compounding composition of Example 2 in Table 2 on page 20 of the specification, [(LllJ to l'-CLOIJ
Correct to.

(4) Physical properties before heating and elongation (4) of Comparative Example 8 in Table 3 on page 21 of the specification, column K 1155J is added.

(5) Comparative example 13-1' in Table 5 on page 25 of the specification
'17?
7'' to ``161'', Comparative Example 13-5' elongation 50 - ``161'' in the arrival time column to [174J, Comparative Example 15-
4' elongation 50 - Change [147J in the arrival time column to "179
JK correction.

(6) Example [14-5 in Table 7 on page 28 of the specification]
'J is corrected to '14-5J.

Claims (1)

[Claims] 1. Vinyl chloride resin 10 having an average degree of polymerization of 1000 or more
0 parts by weight of 50 to sol parts of trimellitic acid triisononyl ester and 141i with a melting point of 160°C or higher or two or more 7-enol antioxidants [LO 11 parts or more or more] Vinyl resin composition. 2. Epoxy (l product [lL1
A vinyl chloride resin composition characterized in that it is used in combination in an amount of 5 parts by weight. (5) In Claims 1 and 2, the trimellitic acid trinonyl ester is butane containing butadiene and n-butene after sufficient removal of oxygen-containing compounds and sulfur-containing compounds. Using butene fraction as a raw material, one or more of nickel oxygen compounds, sulfur compounds, or organic acid salts and R,
u2 X, fi or RAJX, (X: C1゜B
r, R: alkyl group) in the presence of one or more metal alkyl halogenates under pressure, and the dimer is oxidized and hydrogenated. A vinyl chloride resin composition obtained by reacting an alcohol composition with trimellitic anhydride or trimellitic acid.