JP6929592B2 - A plasticizer for vinyl chloride resin having excellent durability and a vinyl chloride resin composition containing the plasticizer. - Google Patents

Description

The present invention relates to a plasticizer for a vinyl chloride resin having excellent durability and a vinyl chloride resin composition containing the same, and more specifically, a specific trimellitic acid triester and a specific phenolic antioxidant. It contains a plasticizer for vinyl chloride resin, which is contained in a specific ratio and has excellent flexibility and cold resistance, and has improved durability such as volatilization resistance, heat-resistant coloring resistance, and weather resistance. The present invention relates to a vinyl chloride resin composition suitable for automobile members and the like.

A plasticizer is added to the vinyl chloride resin for the purpose of imparting various performances such as flexibility, lowering the processing temperature during molding processing such as extrusion and calendar processing, and facilitating the molding process. It is often used as a vinyl chloride resin composition.

The performance required of the plasticizer used in such a vinyl chloride resin composition includes various performances such as flexibility, cold resistance, heat resistance, and electrical characteristics when the composition is used as a raw material for a molded product. Is in the place of adding or exerting. As a typical plasticizer used in such a vinyl chloride resin composition, higher alkyl esters of polybasic acids such as phthalates, adipates, and trimellitic acids are known, and may be used alone or. It is used in combination of two or more types. Until now, phthalates have often been used mainly in terms of price and performance balance, but for applications that require heat resistance that phthalates cannot handle, trimellitic acids with better heat resistance are available. It is widely used. Among them, tri-2-ethylhexyl trimellitic acid (hereinafter referred to as "TOTM"), triisononyl trimellitic acid (hereinafter referred to as "TINTM") and triisodecyl ester of trimellitic acid (hereinafter referred to as "TIDTM"). Is often used in heat-resistant electric wires, automobile parts, and the like as a phthalic acid ester alternative plasticizing agent having excellent heat resistance.

In addition, the applicant has become more and more demanding for cold resistance and volatility in the previous application, and the above TOTM, TINTM, and TIDTM lack volatility and cold resistance, or volatility resistance. The current situation is that satisfactory performance has not been obtained, such as a decrease in flexibility when the sex is improved, and it is stated that the improvement is desired. Trimellitic acid triester obtained by esterifying trimellitic acid or its anhydride is effective as a plasticizer for vinyl chloride resin having excellent cold resistance and volatility resistance and good flexibility. It is shown (Patent Document 1).

However, in view of recent changes in required performance, especially in automobile parts such as interior materials used under harsh conditions such as under the scorching sun, weather resistance and heat-resistant coloring are higher than the performance of the trimellitic acid triester. It is expected that further improvement in durability such as is desired.

Conventionally, as a method for improving weather resistance and the like in outdoor use, a method of blending an antioxidant is generally known, and actually 4,4'-(propane-2,2-diyl) diphenol (propane-2,2-diyl) diphenol ( Antioxidants such as bisphenol A (hereinafter referred to as bisphenol A) and dibutylhydroxytoluene (hereinafter referred to as BHT) are used, but they do not necessarily meet the increasingly strict requirements for heat-resistant coloring and weather resistance in recent years. It wasn't enough.

Japanese Unexamined Patent Publication No. 2014-189688

An object of the present invention is a vinyl chloride-based resin composition containing a plasticizer for vinyl chloride-based resin having excellent cold resistance and volatility resistance, flexibility, fogging resistance, heat-resistant coloring resistance, and weather resistance, and the plasticizer thereof. Is to provide.

In view of the current situation, the present inventors have diligently studied and found that trimellitic acid triester having a specific structure is useful as a plasticizer for vinyl chloride resin having excellent cold resistance and heat resistance and good flexibility. Revealed that there is. Then, as a result of further studies on improvement of volatility, heat-resistant coloring, weather resistance, etc., it was found that there is a new problem in fogging property.

The present inventors further studied and used a plasticizer for vinyl chloride resin containing the above-mentioned trimellitic acid triester having a specific structure and a specific amount of a phenolic antioxidant having a specific structure. , The present invention has been completed by finding a solution to the above-mentioned problems.

That is, the present invention provides the following plasticizer for vinyl chloride resin, a vinyl chloride resin composition containing the same, and a vinyl chloride resin molded product.

[Item 1] A plasticizer for vinyl chloride resin containing a trimellitic acid triester and a phenolic antioxidant.
The trimellitic acid triester is an esterified product of trimellitic acid or an anhydride thereof and a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, and a phenolic antioxidant is the trimellitic. It is contained in the range of 0.1 to 0.6% by weight with respect to the acid triester, and has at least two electron-donating substituents at the 2-position, 4-position or 6-position with respect to the hydroxyl group of the phenol moiety. In addition, it has at least one sterically-damaging substituent at the 2- or 6-position, its molecular weight is in the range of 300 to 3000, and the SP value according to the Phenols estimation method is in the range of 8 to 15. A plasticizer for vinyl chloride resins.

[Item 2] Vinyl chloride containing trimellitic acid or an anhydride thereof, a trimellitic acid triester composed of a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, and a phenolic antioxidant. A plasticizer for based resins
The phenolic antioxidant is contained in the range of 0.1 to 0.6% by weight with respect to the trimellitic acid triester, and at least 2 at the 2-position, 4-position or 6-position with respect to the hydroxyl group of the phenol moiety. It has one electron-donating substituent and at least one sterically-damaging substituent at the 2- or 6-position, and its molecular weight is in the range of 300 to 3000, and SP according to the Phenols estimation method. A plasticizer for vinyl chloride resins having a value in the range of 8 to 15.

[Item 3] Contains trimellitic acid or an anhydride thereof, a trimellitic acid triester made from a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, and a phenolic antioxidant. It is a plasticizer for vinyl chloride resin.
The phenolic antioxidant is contained in the range of 0.1 to 0.6% by weight with respect to the trimellitic acid triester, and at least 2 at the 2-position, 4-position or 6-position with respect to the hydroxyl group of the phenol moiety. It has one electron-donating substituent and at least one sterically-damaging substituent at the 2- or 6-position, and its molecular weight is in the range of 300 to 3000, and SP according to the Phenols estimation method. A plasticizer for vinyl chloride resins having a value in the range of 8 to 15.

[Item 4] A linear or branched saturated fatty alcohol having 8 to 11 carbon atoms contains a saturated fatty alcohol having 9 carbon atoms as a main component, and a linear or branched saturated fatty alcohol having 8 to 11 carbon atoms. Contains a linear saturated fatty alcohol having 9 carbon atoms having a content of 60% by weight or more and a branched saturated fatty alcohol having 9 carbon atoms having a content of 40% by weight or less. Item 4. Plastic for vinyl chloride resin according to any one of [Item 1] to [Item 3], wherein the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms has a linearity ratio of 60% or more. Agent.

[Item 5] At least two electron-donating substituents in the phenolic antioxidant are the same or different, acyloxy group, aralkyl group, allyl group, aryl group, alkynyl group, alkyl group, alkylthio group and alkenyl group. The plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 4], which is an alkoxy group, a cycloalkyl group, a hydroxy group, a heteroaralkyl group, a heteroaryl group or a heterocycloalkyl group.

[Item 6] At least one sterically-damaging substituent in the phenolic antioxidant is an acyl group, an acyloxy group, an amide group, an aralkyl group, an allyl group, an aryl group, an alkynyl group, an alkyl group, an alkylthio group or an alkenyl. Group, alkoxy group, cyano group, cycloalkyl group, nitro group, halogeno group, hydroxy group, heteroaralkyl group, heteroaryl group, heterocycloalkyl group or formyl group (when there are two sterically impaired substituents) , The same or different). The plasticizer for a vinyl chloride resin according to any one of [Item 1] to [Item 5].

[Item 7] The plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 6], wherein the phenolic antioxidant has a molecular weight in the range of 350 to 2500.

[Item 8] The plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 7], wherein the SP value of the phenolic antioxidant is in the range of 8.5 to 14.

[Item 9] The phenolic antioxidant is 3,9-bis [2- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionyloxy] -1,1-dimethylethyl]. -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, tetrakis- [methylene-3 -(3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol , Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate Item 4. The plasticizer for a vinyl chloride resin according to any one of [Item 1] to [Item 8], which is one kind or a mixture of two or more kinds selected from the group consisting of.

[Item 10] The plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 9], wherein the content of the phenolic antioxidant is 0.2 to 0.5% by weight.

[Item 11] The plasticizer for vinyl chloride resin according to [Item 10], wherein the content of the phenolic antioxidant is 0.3 to 0.4% by weight.

[Item 12] A linear or branched saturated fatty alcohol having 8 to 11 carbon atoms contains a saturated fatty alcohol having 9 carbon atoms as a main component, and a linear or branched saturated fatty alcohol having 8 to 11 carbon atoms. Contains a linear saturated fatty alcohol having 9 carbon atoms having a content of 70% by weight or more and a branched saturated fatty alcohol having 9 carbon atoms having a content of 30% by weight or less. Item 2. The vinyl chloride according to any one of [Item 1] to [Item 11], wherein the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms has a linearity ratio of 70% or more. Plasticant for based resin.

[Item 13] A linear or branched saturated fatty alcohol having 8 to 11 carbon atoms contains a saturated fatty alcohol having 9 carbon atoms as a main component, and a linear or branched saturated fatty alcohol having 8 to 11 carbon atoms. Contains 70-90% by weight of linear saturated fatty alcohol having 9 carbon atoms and 10 to 30% by weight of branched saturated fatty alcohol having 9 carbon atoms. The vinyl chloride resin plasticizer according to [Item 12], wherein the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms has a linearity ratio of 70 to 90%.

[Item 14] A linear or branched saturated fatty alcohol having 8 to 11 carbon atoms is hydrogenated to an aldehyde having 9 carbon atoms by a hydroformylation reaction of 1-octene, carbon monoxide and hydrogen to form an alcohol. The plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 11], which contains a saturated fatty alcohol having a linear structure and a branched chain structure reduced to.

[Item 15] A vinyl chloride-based resin composition containing a vinyl chloride-based resin and the plasticizer for vinyl chloride-based resin according to any one of [Item 1] to [Item 14].

[Item 16] The vinyl chloride-based resin composition according to [Item 15], wherein the vinyl chloride-based resin composition is for an automobile member.

[Item 17] A vinyl chloride-based resin molded product obtained from the vinyl chloride-based resin composition according to [Item 15] or [Item 16].

[Item 18] The vinyl chloride-based resin molded product according to [Item 17], wherein the vinyl chloride-based resin molded product is an automobile member.

The plasticizer for vinyl chloride resin of the present invention can be used as a plasticizer for vinyl chloride resin which is excellent in cold resistance and volatility, and has good flexibility, fogging resistance, heat resistance coloring property and weather resistance. In addition, by containing the plasticizer for vinyl chloride resin, it has excellent cold resistance and volatility resistance, and has good flexibility, fogging resistance, heat-resistant coloring resistance and weather resistance, especially durability when used outdoors. It is possible to obtain a vinyl chloride-based resin composition suitable for automobile members and the like, which is required for the above.

<Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride resin of the present invention is specific to trimellitic acid triester obtained by esterifying a specific saturated aliphatic alcohol (alcohol component) with trimellitic acid or its anhydride (acid component). The biggest feature is that it contains a phenolic antioxidant in a specific ratio.

The trimellitic acid triester (hereinafter referred to as "the present ester") has a predetermined acid component and an alcohol component according to a conventional method, preferably in an atmosphere of an inactivating gas such as nitrogen, without a catalyst or in the presence of a catalyst. It is easily obtained by esterification below.

[Saturated fatty alcohol]
The alcohol component used in the present invention is a linear or branched saturated fatty alcohol having 8 to 11 carbon atoms, and the saturated fatty alcohol is a mixture. If the number of carbon atoms is less than 8, the performance such as volatility tends to be insufficient, and if the number of carbon atoms exceeds 11, the flexibility and the like tend to decrease, which is not preferable.

Among them, the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms used in the present invention is preferably a saturated fatty alcohol containing a saturated fatty alcohol having 9 carbon atoms as a main component, and the main component thereof. The proportion of the saturated fatty alcohol having 9 carbon atoms is preferably 60% by weight or more (60 to 100% by weight) in the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms used in the present invention. %), More preferably 70% by weight or more (70 to 100% by weight), and particularly preferably 80% by weight or more (80 to 100% by weight).

Further, the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms according to the present invention has a linearity ratio of the saturated aliphatic alcohol preferably 60% or more, more preferably 70% or more. Particularly preferably, the range of 70 to 90% is recommended.

The content of the linear saturated fatty alcohol having 9 carbon atoms is preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 70 to 70% by weight or more in the saturated fatty alcohol used in the present invention. The range of 90% by weight is recommended, and the content of the branched saturated fatty alcohol having 9 carbon atoms (for example, 2-methyloctanol) is preferably 40% by weight or less, more preferably 30% by weight or less. Particularly preferably, the range of 10 to 30% by weight is recommended.

As a detail of the aspect of the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms, as a preferable embodiment, the saturated fatty alcohol is mainly composed of the saturated fatty alcohol having 9 carbon atoms (preferably). Is 60% by weight or more), and the content of the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms is 60% by weight or more. And 40% by weight or less of a branched saturated fatty alcohol having 9 carbon atoms, and having a linearity ratio of a linear or branched saturated fatty alcohol having 8 to 11 carbon atoms of 60% or more. be. In a more preferred embodiment, the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms contains the saturated fatty alcohol having 9 carbon atoms as a main component (preferably 70% by weight or more) and has 8 carbon atoms. A linear saturated fatty alcohol having 9 carbon atoms having a content of 70% by weight or more in a linear or branched saturated fatty alcohol of ~ 11 and a branched chain-like alcohol having 30% by weight or less having 9 carbon atoms. It is recommended that the saturated fatty alcohol of the above is contained and the linearity or branched saturated aliphatic alcohol having 8 to 11 carbon atoms has a linearity ratio of 70% or more. A particularly preferable embodiment is carbon. The linear or branched saturated fatty alcohol having the number 8 to 11 contains the saturated fatty alcohol having 9 carbon atoms as a main component (preferably 80% by weight or more), and the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. A linear saturated fatty alcohol having 9 carbon atoms having a content of 70 to 90% by weight in a branched saturated fatty alcohol and a branched saturated fatty alcohol having 10 to 30% by weight having 9 carbon atoms. It is recommended that the linear or branched saturated fatty alcohol having 8 to 11 carbon atoms has a linearity ratio of 70 to 90%.

When the linearity ratio is 60% or more and the content of the linear saturated aliphatic alcohol having 9 carbon atoms is 60% by weight or more, the flexibility of the present invention is sufficiently maintained. It is easy to obtain the desired heat resistance and cold resistance. On the contrary, when the linearity ratio is less than 60% or the content of the linear saturated aliphatic alcohol having 9 carbon atoms is less than 60% by weight, the improvement of cold resistance and heat resistance, which is the object of the present invention, cannot be achieved. It may be sufficient, and it tends to be less flexible, which is not preferable.

Further, even in the above range, sufficient performance can be obtained in the heat resistance and cold resistance which are the objects of the present invention, but the linearity ratio is in the range of 70 to 90% and the content of the linear saturated alcohol having 9 carbon atoms is contained. By setting the amount in the range of 70 to 90% by weight, mixing with the vinyl chloride resin becomes easier, and as a result, tensile properties such as tensile elongation can be further improved.

In the present specification and the scope of patent claims, the linearity ratio of a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is the ratio (weight) of the linear alcohol to the saturated aliphatic alcohol. Ratio), and specifically, it can be obtained by a method of analysis by gas chromatography.

The saturated fatty alcohol having 9 carbon atoms used in the present invention includes, for example, (1) 1-octene, a step of producing an aldehyde having 9 carbon atoms by a hydroformylation reaction of carbon monoxide and hydrogen, and (2) 9 carbon atoms. It can be produced by a production method including a step of hydrogenating the aldehyde of the above to reduce it to alcohol.

In the hydroformylation reaction of the step (1), for example, an aldehyde having 9 carbon atoms can be produced by reacting 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

The hydrogenation in the step (2) can be reduced to alcohol by hydrogenating an aldehyde having 9 carbon atoms under hydrogenation in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst, for example.

Specific examples (commercially available) of the saturated aliphatic alcohol containing the saturated aliphatic alcohol having 9 carbon atoms obtained in the above step as a main component include about 70% by weight or more of linear nonanol and about 30% by weight or less. Lineball 9 (trade name, manufactured by Shell Chemicals Co., Ltd.), which is a mixture of branched nonanols of the above, and the like can be mentioned.

[Esterification reaction]
In carrying out the esterification reaction between the alcohol component and trimellitic acid or its anhydride, the alcohol component is preferably 3.05 to 4.00 mol with respect to 1 mol of trimellitic acid or its anhydride, for example. , More preferably 3.1 to 3.80 mol, especially 3.15 to 3.60 mol is recommended.

Examples of the catalyst used in the esterification reaction include mineral acids, organic acids, and Lewis acids. More specifically, the mineral acid is exemplified by sulfuric acid, hydrochloric acid, phosphoric acid and the like, the organic acid is exemplified by p-toluenesulfonic acid, methanesulfonic acid and the like, and the Lewis acid is an aluminum derivative, a tin derivative and the like. Titanium derivatives, lead derivatives, zinc derivatives and the like are exemplified, and one of these or two or more of them can be used in combination as appropriate.

Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, zinc oxide, zinc hydroxide, Lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferable. The amount used is preferably 0.01 to 5.0% by weight, more preferably 0.02 to 4.0% by weight, particularly, with respect to the total weight of the acid component and the alcohol component which are the ester synthesis raw materials. It is recommended to use 0.03 to 3.0% by weight.

The esterification temperature is exemplified by 100 ° C. to 230 ° C., and the esterification reaction is usually completed in 3 to 30 hours.

The trimellitic acid or its anhydride, which is the acid component of the raw material of the ester, is not particularly limited, and a commercially available one that is usually used can be used. Moreover, from the viewpoint of the esterification reaction, it is most recommended to use the above-mentioned trimellitic anhydride.

In the esterification reaction, a water companion such as benzene, toluene, xylene, or cyclohexane can be used to promote the distillation of water produced by the reaction.

Further, if an oxygen-containing organic compound such as an oxide, a peroxide, or a carbonyl compound is produced due to oxidative deterioration of the raw material, the produced ester, and the organic solvent (water companion) during the esterification reaction, the heat resistance, weather resistance, etc. are adversely affected. Therefore, it is desirable to carry out the esterification reaction in the system under an atmosphere of an inert gas such as nitrogen gas or an inert gas stream under normal pressure or reduced pressure. After the esterification reaction is completed, it is recommended to distill off the excess raw material under reduced pressure or normal pressure.

The present ester obtained by the above esterification reaction may be subsequently purified by base treatment (neutralization treatment) → washing treatment, liquid-liquid extraction, distillation (decompression, dehydration treatment), adsorption treatment, etc., if necessary. ..

The base used for the base treatment is not particularly limited as long as it is a basic compound, and examples thereof include sodium hydroxide and sodium carbonate.

Examples of the adsorbent used in the adsorption treatment include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. They can be used alone or in combination of two or more as appropriate.

The purification treatment after esterification may be carried out at room temperature, but it can also be carried out by heating to about 40 to 90 ° C.

[Phenolic antioxidant]
From the viewpoint of antioxidant performance, the phenolic antioxidant has at least two electron-donating substituents at the 2-position, 4-position or 6-position with respect to the hydroxyl group of the phenol moiety, and is at the 2-position or 6-position. A phenolic antioxidant having at least one sterically impairing substituent at the position is also a phenolic antioxidant having a molecular weight of 300 or more, preferably 350 or more, more preferably 400 or more from the viewpoint of volatile resistance. However, from the viewpoint of compatibility with the plastic agent and the vinyl chloride resin, the SP value of the antioxidant is in the range of 8 to 15, preferably in the range of 8.5 to 14, and more preferably in the range of 9 to 13. Phenolic antioxidants in the range of 5 and having a molecular weight of 3000 or less, preferably 2500 or less, more preferably 2000 or less are recommended. As long as it is a phenolic antioxidant satisfying the above conditions, it is possible to use one or a combination of two or more of the commonly used phenolic antioxidants for plastics.

When the molecular weight is less than 300, the volatility becomes large, and as a result, it becomes one of the causes of deterioration of fogging resistance and the like, which is not preferable. If the SP value is less than 8 or more than 15, it causes poor dispersion in the vinyl chloride resin, which makes it difficult to sufficiently improve the weather resistance and heat-resistant coloring property, as well as bleeding and heat resistance. It is easy to cause surface stains due to bloom or the like, and neither is preferable.

Here, the SP value in the present invention is a value defined by the regular solution theory introduced by Hildebrand, and is represented by the square root of the cohesive energy density of the solvent (or solute). It serves as a guide for the solubility of a two-component solution. Examples of obtaining the SP value include a method of calculating from the heat of vaporization, a method of calculating from the chemical composition, and a method of actually measuring the SP value from the compatibility with a known substance. It is a value calculated from the evaporation energy and molar volume of atoms and atomic groups by Fedors described in Basics and Engineering (page 53, by Yuji Harasaki, Processing Technology Study Group).

Specific examples of the phenolic antioxidant include 2,6-diphenyl-4-octadecyloxyphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 2- [1- (. 2-Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4) -Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3) -T-butyl-5-methyl-4-hydroxyphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3 -Tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mecitylene, tetrakis- [methylene- 3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methyl, bis [3,3-bis- (3'-t-butyl-4'-hydroxyphenyl) butyric acid ] Ethylene glycol ester, 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, bis [2-t-butyl-4-methyl-6- (2-hydroxy) -3-t-butyl-5-methylbenzyl) phenyl] terephthalate, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, α-tocopherol, β-tocopherol, γ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol, dodecyl asbestosate, hexadecyl asbestosate, stearyl asbestosate, octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate, 2,4-dimethyl-6- (1-Methylpentadecyl) -phenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4' − Butylidenebis (3-methyl-6-t-butylphenol), nordihydroguairetinic acid, 2,2′-methylenebis [4-methyl-6-nonylphenol], 2,2′-methylenebis [6- (1-methylcyclohe) Xyl) -4-methylphenol], 2,2'-[(2-hydroxy-5-methylbenzene-1,3-diyl) dimethanediyl] bis (4-methyl-6-nonylphenol), 2,2'-thio Diethylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (2-t-butyl-5-methylphenol), 2-hydroxy-4-n -Octyloxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) 5-chlorobenzotriazole, 2-t-butyl-6- (3-t-butyl-2-hydroxy) -5-Methylbenzyl) -4-methylphenyl acrylate, N, N'-(1,6-hexanediyl) bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], 1,3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) ) Isocyanurate, 2,2'-etylidenebis (4,6-di-t-butylphenol), 2,2'-etylidenebis (4-s-butyl-6-t-butylphenol), 1,3,5- Examples thereof include phenolic antioxidants such as tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate and curcumin. More preferably, 2,6-diphenyl-4-octadecyloxyphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 2- [1- (2-hydroxy-3,5-di). -T-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-5-methyl-) 4-Hydroxyphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl-5- t-butyl-4-hydroxyphenyl) butane, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mecitylene, tetrakis- [methylene-3- (3', 5'-) Di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3-bis- (3'-t-butyl-4'-hydroxyphenyl) butyric acid] ethylene glycol ester, 2,6- Bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-) Methylbenzyl) phenyl] terephthalate, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, α-tocopherol, α-tocotrienol, 3- (4-hydroxy-3,5-diisopropylphenyl) ) Octyl propionate, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis [4- Methyl-6-nonylphenol], 2,2'-methylenebis [6- (1-methylcyclohexyl) -4-methylphenol], 2,2'-[(2-hydroxy-5-methylbenzene-1,3-diyl) ) Dimethanediyl] bis (4-methyl-6-nonylphenol), 2,2'-thiodiethylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (2-t-butyl-5-methylphenol), 2-t-bu Chill-6- (3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, N, N'-(1,6-hexanediyl) bis [3- (3,5-diyl) -T-Butyl-4-hydroxyphenyl) propionamide], 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-) t-Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,2'-etylidenebis (4,6-di-t-butylphenol), 2,2'-etylidenebis (4-s-butyl) Phenol-based antioxidants such as -6-t-butylphenol), 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate are most preferred. Is 3,9-bis [2- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane, tetrakis- [methylene-3- (3', 5'-di) -T-Butyl-4'-Hydroxyphenyl) propionate] methane, 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, octadecyl-3- (3,5) Phenolic antioxidants such as -di-t-butyl-4-hydroxyphenyl) propionate and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate are recommended. Will be done.

The content of the phenolic antioxidant is 0.1 to 0.6% by weight, preferably 0.2 to 0.5% by weight, more preferably 0.2 to 0.5% by weight, based on the trimellitic acid triester according to the present invention. Is recommended in the range of 0.3 to 0.4% by weight. If the content of the phenolic antioxidant is less than 0.1% by weight, the effect of improving durability such as weather resistance and heat-resistant coloring, which is the effect of the present invention, is insufficient, and even if it exceeds 0.6% by weight. , The above-mentioned effect becomes an equilibrium state, and on the contrary, it may cause bleeding, bloom, etc., which is not preferable.

To contain the phenolic antioxidant of the present invention means to mix and dissolve the phenolic antioxidant in a plasticizing component (trimellitic acid triester) to obtain a transparent solution. Usually, it can be dissolved by adding an antioxidant to the plasticizer, heating, stirring and mixing the composition, or heating the plasticizer, adding, stirring and mixing the antioxidant. As a specific example, it is preferable to appropriately select a temperature and time at which the plasticizer for vinyl chloride resin does not deteriorate or color extremely. For example, it can be dissolved by heating and stirring at room temperature (25 ° C.) to 120 ° C. for 1 second to 1 hour. By mixing and dissolving the antioxidant in the plasticizing component in advance in this way, the combined effect of the plasticizing component and the phenolic antioxidant is likely to be exhibited.

<Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention can be obtained by blending the above-mentioned plasticizer of the present invention with a vinyl chloride resin.

[Vinyl chloride resin]
The vinyl chloride-based resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and the production method thereof is a conventionally known polymerization method, which is a general-purpose chloride. In the case of vinyl resin, a method of suspend polymerization in the presence of an oil-soluble polymerization catalyst can be mentioned, and in the case of vinyl chloride paste resin, a method of emulsifying polymerization in the presence of a water-soluble polymerization catalyst in an aqueous medium can be mentioned. The degree of polymerization of these vinyl chloride resins is usually 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, the heat resistance and the like tend to be lowered, and if it is too high, the molding processability tends to be lowered.

In the case of copolymers, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Α-olefins having 2 to 30 carbon atoms such as tridecene and 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether and the like. Polyfunctional monomers such as vinyl compounds and diallyl phthalates, copolymers of these mixtures and vinyl chloride monomers, ethylene-acrylic acid ester copolymers such as ethylene-ethyl acrylate copolymers, and ethylene-methacrylic acid esters Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene Examples thereof include a polymer (ABS), a styrene-butadiene copolymer, a polyethylene, a polymethyl methacrylate, and a graft copolymer obtained by grafting a vinyl chloride monomer onto a mixture thereof.

[Vinyl chloride resin composition]
The content of the plasticizer for vinyl chloride resin of the present invention in the vinyl chloride resin composition is appropriately selected depending on the intended use, but is usually 1 to 100 weight based on 100 parts by weight of the vinyl chloride resin. It is a part, preferably 5 to 50 parts by weight (the range of the content is shown by the content based on the trimellitic acid triester). If it is less than 1 part by weight, it is difficult to obtain a predetermined plasticizing effect, and if it is blended in excess of 100 parts by weight, bleeding to the surface of the molded product is severe, which is not preferable in either case. However, when a filler or the like is added to the above-mentioned vinyl chloride resin composition, the plasticizer can be blended beyond the above-mentioned range because the filler itself absorbs oil. For example, when 100 parts by weight of calcium carbonate is blended as a filler with 100 parts by weight of a vinyl chloride resin, about 1 to 500 parts by weight of the plasticizer can be blended.

Further, as a preferred embodiment of the content of each component of the plasticizer for vinyl chloride resin, the plasticizing component (trimellitic acid triester) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Yes, more preferably 5 to 50 parts by weight, and the antioxidant, including antioxidants other than phenolic agents, is preferably 0.3 parts by weight or less, more preferably 0.001 to 0.2 parts by weight. Is recommended.

In the vinyl chloride resin composition, other known plasticizers can be used in combination with the vinyl chloride resin plasticizer of the present invention as long as the effects of the present invention are not impaired. Further, if necessary, other than known flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, and phenolic antioxidants according to the present invention, which are usually used for plastics. Additives such as antioxidants (antioxidants), ultraviolet absorbers, light stabilizers such as hindered amines, lubricants or antistatic agents can be blended within a range that does not impair the effects of the present invention.

Other plasticizers and additives other than the plasticizer component of the above-mentioned plasticizer for vinyl chloride resin of the present invention may be blended together with the plasticizer of the present invention by one kind or a combination of two or more kinds as appropriate.

Known plasticizing agents that can be used in combination with the plasticizing component of the plasticizing agent for vinyl chloride resin of the present invention include, for example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), and di-phthalate. 2-Ethylhexyl (DOP), Diisononyl phthalate (DINP), Diisodecyl phthalate (DIDP), Diundecyl phthalate (DUP), Ditridecyl phthalate (DTDP), Bis terephthalate (2-ethylhexyl) (DOTP), Bis isophthalate Phthalate esters such as (2-ethylhexyl) (DOIP), di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS) , Alius dibasic acid esters such as diisononyl sebacate (DINS), pyromellitic acid esters such as tetra-2-ethylhexyl pyromalate (TOPM), tri-2-ethylhexyl phosphate (TOP), tricresyl phosphate Phthalate esters such as (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol, polyesters with a molecular weight of 800 to 4000 synthesized by polyesterification of dibasic acid such as adipic acid and glycol, epoxidized soybean oil. , Eoxidized esters such as epoxidized flaxseed oil, alicyclic dibasic acid esters such as hexahydrophthalate diisononyl ester (DINCH), fatty acid glycol esters such as dicapric acid 1,4-butanediol, acetylcitrate Examples thereof include tributyl (ATBC), isosorbidodiesters, chlorinated paraffins obtained by chlorinating paraffin wax and n-paraffin, chlorinated fatty acid esters such as chlorinated stearic acid ester, and higher fatty acid esters such as butyl oleate. Will be done. When the above-mentioned plasticizer that can be used in combination is blended, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide and zinc borate, cresyldiphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate and the like. Examples thereof include phosphorus compounds and halogen compounds such as chlorinated paraffin. When the flame retardant is blended, it is recommended that the amount of the flame retardant blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinolate, calcium stearate, barium laurate, barium ricinolate, barium stearate, zinc octylate, zinc laurate, zinc ricinolate, stearic acid. Examples thereof include metal soap compounds such as zinc, organic tin compounds such as dimethyltinbis-2-ethylhexylthioglycolate, dibutyltinmalate, dibutyltinbisbutylmalate, and dibutyltin dilaurate, and antimony mercaptide compounds. When a stabilizer is blended, it is recommended that the amount of the stabilizer blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Stabilizing aids include phosphite compounds such as triphenylphosphite, monooctyldiphenylphosphite and tridecylphosphite, beta-diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol and the like. Examples thereof include a polyol compound, a perchlorate compound such as a barium perchlorate salt and a sodium perchlorate salt, a hydrotalcite compound, and a zeolite. When the stabilizing aid is blended, it is recommended that the amount of the stabilizing aid blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, Benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange and the like. When a colorant is blended, it is recommended that the amount of the colorant blended with respect to 100 parts by weight of the vinyl chloride resin is about 1 to 100 parts by weight.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylenebis stearic acid amide, butyl stearate, calcium stearate and the like. When the processing aid is blended, it is recommended that the amount of the processing aid blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Fillers include calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, metal oxides such as ferrite, fibers and powders such as glass, carbon and metal, glass spheres, graphite, aluminum hydroxide, barium sulfate and magnesium oxide. , Magnesium carbonate, magnesium silicate, calcium silicate and the like are exemplified. When blending the filler, it is recommended that the amount of the filler blended with respect to 100 parts by weight of the vinyl chloride resin is about 1 to 100 parts by weight.

Examples of the antioxidant other than the phenolic antioxidant according to the present invention include sulfur compounds such as alkyl disulfide, thiodipropionic acid ester and benzothiazole, trisnonylphenyl phosphite, diphenylisodecylphosphite and triphenyl. Examples thereof include phosphoric acid compounds such as phosphite and tris (2,4-di-t-butylphenyl) phosphite, and organic metal compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate.

Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and pt-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and 5-. Examples thereof include benzotriazole-based compounds such as methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, as well as cyanoacrylate-based compounds. When a UV absorber is blended, it is recommended that the amount of the UV absorber blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

Examples of hindered amine-based light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl1. , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-) Dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, bisdecanoate (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethyl Hydroperoxide to octane reaction product, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol and higher fatty acid ester mixture, tetrakis (2) , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol, poly [{(6- (1,1,3) , 3-Tetramethylbutyl) Amino-1,3,5-triazin-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} Hexamethylene {(2,2,6) 6,6-Tetramethyl-4-piperidyl) imino}}, dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1, Polycondensate of 6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N', N'', N'''-tetrakis- (4,6) -Bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, etc. For example, when a light stabilizer is blended, the blending amount of the light stabilizer with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

Examples of the lubricant include silicone, liquid paraffin, barafin wax, fatty acid metal salts such as metal stearate and lauric acid metal salt, fatty acid amides, fatty acid wax, higher fatty acid wax and the like. When blending a lubricant, it is recommended that the amount of the lubricant blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

Examples of the antistatic agent include an alkyl sulfonate type, an alkyl ether carboxylic acid type or a dialkyl sulfosuccinate type anionic antistatic agent, a nonionic antistatic agent such as a polyethylene glycol derivative, a sorbitan derivative and a diethanolamine derivative, an alkylamide amine type and an alkyl. Examples thereof include quaternary ammonium salts such as dimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. When the antistatic agent is blended, it is recommended that the amount of the antistatic agent blended with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

The vinyl chloride resin composition of the present invention contains the vinyl chloride resin plastic agent of the present invention, the vinyl chloride resin and, if necessary, other plastic agents and various additives, for example, a pony mixer, a butterfly mixer, a planetary mixer, and the like. Stirrer / mixer such as dissolver, twin-screw mixer, three-roll mill, mortar mixer, henschel mixer, vanbury mixer, ribbon blender, conical twin-screw extruder, parallel twin-screw extruder, single-screw extruder, conider type kneader , A kneader such as a roll kneader can be used for stirring and melting and mixing to obtain a powdery, pelletized or pasty vinyl chloride resin composition.

[Vinyl chloride resin molded product]
The vinyl chloride resin composition according to the present invention includes vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, spread coating, dip coating, spray coating, paper casting, and extrusion. A desired shape can be formed by molding using a conventionally known method such as coating, gravure printing method, screen printing method, slush molding, rotary molding, casting, and dip molding.

The shape of the molded body is not particularly limited, but is, for example, a rod shape, a sheet shape, a film shape, a plate shape, a cylindrical shape, a circular shape, an elliptical shape, or a special shape such as a toy or an ornament, for example, a star shape. A polygonal shape is exemplified.

The resulting moldings are door trims, dashboards, instrument panels, consoles, door seats, AT shifts, armrests, undercarpets, trunk seats, wire harnesses, moldings, sashes, sealants, weather strips, gaskets, underscores. It is very useful for automobile parts such as coat materials, and other than that, pipes such as water pipes, fittings for pipes, gutters such as rain gutters, window frame siding, flat plates, corrugated sheets, various leathers, etc. Decorative sheets, agricultural films, food packaging films, wire coatings, foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, wallpaper, flooring, boots, curtains, soles, gloves, Heat resistance and durability even in applications such as water stop plates, toys, decorative plates, blood bags, infusion bags, tarpaulins, mats, water-impervious sheets, civil engineering sheets, roofing, waterproof sheets, insulating sheets, industrial tapes, glass films, etc. It is useful when there is a strong demand for.

Examples will be shown below and the present invention will be described in more detail, but the present invention is not limited to these examples. The abbreviations of the compounds in Examples and Comparative Examples and the measurement of each property are as follows.

(1) Linearity of Alcohol Component of Raw Material The linearity of the alcohol component of the raw material used in Examples and Comparative Examples of the present invention was measured by gas chromatography (hereinafter abbreviated as GC). The method for measuring the alcohol component of the raw material by GC is as follows.
<< GC measurement conditions >>
Model: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column DB-1 30m
Column temperature: Increased from 60 ° C to 290 ° C. Heating rate = 13 ° C / min Carrier gas: Helium Sample: 50% acetone solution Injection amount: 1 μL
Quantification: Quantification was performed using 1-hexanol as an internal standard substance.
In selecting the internal standard substance, it was confirmed in advance that 1-hexanol was below the detection limit in GC in the alcohol component of the raw material.

(2) Evaluation of Physical Properties of Trimellitic Acid Triester The ester obtained in the following production example or the ester outside the present invention was analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: Measured according to JIS K-0070 (1992).
Hue: The number of Hazen unit colors was determined by measurement according to JIS K-4101 (Hazen) (1993). The number of colors was used as the evaluation of hue.

(3) Preparation of Vinyl Chloride Resin Composition and Preparation of Roll Sheet and Press Sheet 100 parts by weight of vinyl chloride resin (straight, degree of polymerization 1050, trade name "Zest1000Z", manufactured by Shin-Daiichi PVC Co., Ltd.) Calcium stearate (manufactured by Nakaraitesk Co., Ltd.) and resin stearate (manufactured by Nakaraitesk Co., Ltd.) are blended as stabilizers in an amount of 0.3 parts by weight and 0.2 parts by weight, respectively, and then stirred and mixed with a mortar mixer. , 50 parts by weight of a plastic agent for vinyl chloride resin was added, and the mixture was handled and mixed until uniform to obtain a vinyl chloride resin composition. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using two rolls of 5 × 12 inches to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

[Evaluation of physical properties of resin]
(4) Tensile properties: 100% modulus, breaking strength, and breaking elongation of the press sheet were measured according to JIS K-6723 (1995). The smaller the value of 100% modulus, the better the flexibility, and the breaking strength and breaking elongation are indicators of the practical strength of the material. Generally, the larger the value, the more practical the strength. It can be said that it is excellent.

(5) Cold resistance: The flexible temperature (° C.) was measured according to JIS K-6773 (1999) using a Crashberg tester. The lower the flexible temperature, the better the cold resistance. The flexible temperature referred to here refers to a temperature at the low temperature limit showing a predetermined torsional rigidity (3.17 × 10 ³ kg / cm ^{2) in the measurement.}

(6) Heat resistance: Based on evaluation of volatilization loss and sheet coloring.
a) Volatile weight loss: The weight change of the roll sheet after heating the roll sheet at 170 ° C. for 60 minutes and 120 minutes in a gear oven was measured, and the volatilization weight loss (% by weight) was calculated according to the following formula. The smaller the volatile weight loss value, the higher the heat resistance.
Volatile weight loss (% by weight) = ((weight before test-weight after test) / weight before test) x 100
b) Sheet coloring: The strength of the coloring degree after heating the roll sheet at 170 ° C. for 30 minutes and 60 minutes in a gear oven was visually evaluated on a 5-point scale.
⊚: No coloring, ○: Slightly colored, ○ △: Slightly colored, Δ: Colored, ×: Strongly colored.

(7) Heat aging resistance: In accordance with JIS K-6723 (1995), a tensile test was conducted after heating under heating conditions of 120 ° C. × 120 hours. The results were shown as 100% modulus residual ratio (%) and breaking elongation residual ratio (%) of the press sheet after the test with respect to the normal state. The larger the value, the higher the heat aging resistance.
100% modulus residual ratio (%) = (1- (100% modulus after heating-100% modulus before heating) / 100% modulus before heating) x 100
Residual elongation (%) = (elongation after heating / elongation at break before heating) × 100

(6) Fogging resistance: 4 g of the press sheet was placed in a glass sample bottle and set in a fogging tester whose temperature was adjusted to 120 ° C. Further, after covering the sample bottle with a glass plate, a cooling plate through which cooling water whose temperature was adjusted to 20 ° C. was passed was placed on the sample bottle, and heat treatment was performed at 120 ° C. for 3 hours. After the heat treatment, the degree of fogging on the surface of the glass plate was visually observed and evaluated in four stages as follows.
⊚: There was no cloudiness at all, and there was no effect on the visibility beyond the glass plate. ○: There was slight cloudiness, although it did not affect the visibility beyond the glass plate.
Δ: Clearly cloudy occurred, which affected the visibility beyond the glass plate.
X: The surface of the glass plate was heavily clouded, and the visibility beyond the glass plate was greatly reduced.

[Manufacturing Example 1]
In a 2L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux cooling tube, 96.0 g (0.5 mol) of trimellitic anhydride (commercially available for industrial use) and a direct alcohol having 9 carbon atoms as a raw material alcohol. 259 g (1.8) of saturated aliphatic alcohol (manufactured by Shell Chemicals Co., Ltd .: lineball 9) containing 85.1% by weight of chain-like aliphatic saturated alcohol and 11.7% by weight of branched chain-like aliphatic saturated alcohol having 9 carbon atoms. Mol) and 0.13 g of tetraisopropyl titanate as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 185 ° C. The reaction was carried out until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing the raw material alcohol under reduced pressure to remove the produced water from the system. After completion of the reaction, the unreacted alcohol was distilled off from the system under reduced pressure, and then neutralized, washed with water, and dehydrated according to a conventional method to obtain 245 g of the target trimellitic acid triester (hereinafter referred to as ester 1). ..
The obtained ester 1 had an ester value of 285 mgKOH / g, an acid value of 0.01 mgKOH / g, and a hue of 15.

[Manufacturing Example 2]
236 g of trimellitic acid triester (hereinafter referred to as ester 2) was obtained in the same manner as in Production Example 1 except that 259 g of isononyl alcohol was used instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals Co., Ltd .: Lineball 9). rice field.
The obtained ester 2 had an ester value of 285 mgKOH / g, an acid value of 0.03 mgKOH / g, and a hue of 10.

[Manufacturing Example 3]
Same as Production Example 1 except that 181 g (1.3 mol) of n-nonyl alcohol and 78 g (0.5 mol) of isononyl alcohol were used instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals Co., Ltd .: Lineball 9). As a result, 240 g of trimellitic acid triester (hereinafter referred to as ester 3) was obtained.
The obtained ester 3 had an ester value of 282 mgKOH / g, an acid value of 0.04 mgKOH / g, and a hue of 20.

[Manufacturing Example 4]
242 g of trimellitic acid triester (hereinafter referred to as ester 4) was added in the same manner as in Production Example 1 except that 259 g of n-nonyl alcohol was used instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals Co., Ltd .: Lineball 9). Obtained.
The obtained ester 4 had an ester value of 284 mgKOH / g, an acid value of 0.03 mgKOH / g, and a hue of 10.

[Example 1]
In 100 parts by weight of the trimellitic acid triester (ester 1) obtained in Production Example 1, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane ( (Hereinafter referred to as antioxidant A) was blended at a ratio of 0.3 parts by weight and stirred at 70 ° C. for 20 minutes to obtain a transparent plasticizer for vinyl chloride resin. Subsequently, using the obtained plasticizer, a roll sheet and a press sheet were produced according to the above-mentioned production method, and the tensile properties, cold resistance, heat resistance, heat aging resistance, and fogging resistance were measured. The results obtained are summarized in Table 1. The obtained plasticizer for vinyl chloride resin was transparent.

[Example 2]
The same procedure as in Example 1 was carried out except that 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane (antioxidant B) was used instead of the antioxidant A. A roll sheet and a press sheet were prepared, and the tensile properties, cold resistance, heat resistance, heat aging resistance, and fogging resistance were measured. The results obtained are summarized in Table 1. The obtained plasticizer for vinyl chloride resin was transparent.

[Example 3]
Same as Example 1 except that 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate (antioxidant C) was used instead of the antioxidant A. A roll sheet and a press sheet were prepared, and the tensile properties, cold resistance, heat resistance, heat aging resistance, and fogging resistance were measured. The results obtained are summarized in Table 1. The obtained plasticizer for vinyl chloride resin was transparent.

[Example 4]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that the ester 2 obtained in Production Example 2 was used instead of the ester 1, and the tensile properties, cold resistance, heat resistance, and heat aging resistance were prepared. , Fogging resistance was measured. The results obtained are summarized in Table 1. The obtained plasticizer for vinyl chloride resin was transparent.

[Example 5]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that the ester 3 obtained in Production Example 3 was used instead of the ester 1, and the tensile properties, cold resistance, heat resistance, and heat aging resistance were prepared. , Fogging resistance was measured. The results obtained are summarized in Table 1. The obtained plasticizer for vinyl chloride resin was transparent.

[Example 6]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that the ester 4 obtained in Production Example 4 was used instead of the ester 1, and tensile properties, cold resistance, heat resistance, and heat aging resistance were prepared. , Fogging resistance was measured. The results obtained are summarized in Table 1. The obtained plasticizer for vinyl chloride resin was transparent.

[Comparative Example 1]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that the ester 1 obtained in Production Example 1 was used as it was without adding an antioxidant, and the tensile properties, cold resistance, and heat resistance were determined. Heat aging resistance and fogging resistance were measured. The results obtained are summarized in Table 1.

[Comparative Example 2]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that bisphenol A (antioxidant D) was used instead of the antioxidant A, and tensile properties, cold resistance, heat resistance, and heat aging were prepared. The properties and fogging resistance were measured. The results obtained are summarized in Table 1.

[Comparative Example 3]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that BHT (antioxidant E) was used instead of the antioxidant A, and tensile properties, cold resistance, heat resistance, and heat aging resistance were prepared. , Fogging resistance was measured. The results obtained are summarized in Table 1.

[Comparative Example 4]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that propyl gallate (antioxidant F) was used instead of the antioxidant A, and tensile properties, cold resistance, heat resistance, and heat resistance were obtained. Aging resistance and fogging resistance were measured. The results obtained are summarized in Table 1.

[Comparative Example 5]
A roll sheet and a press sheet were prepared in the same manner as in Example 1 except that hydroquinone (antioxidant G) was used instead of the antioxidant A, and tensile properties, cold resistance, heat resistance, and heat aging resistance were prepared. , Fogging resistance was measured. The results obtained are summarized in Table 1.

From the results in Table 1, it is clear that the trimellitic acid triesters containing the antioxidants in the range of the present invention (Examples 1 to 6) are heat-resistant colored as compared with those not containing the antioxidants (Comparative Example 1). It can be seen that the properties and heat aging resistance are greatly improved. Further, it can be seen that the heat-resistant coloring property or the heat-resistant aging property is excellent as compared with the conventional antioxidant compounding system (Comparative Examples 2 to 5). It should be noted that a decrease in the value of heat aging resistance in the table by 10% or more indicates that there is a concern that it may become a big problem in practical use. In addition, good fogging resistance was also obtained in Examples 1 to 4.

Furthermore, from the results in Table 1, the systems containing the antioxidant within the scope of the present invention (Examples 1 to 6) are the systems not containing the antioxidant (Comparative Example 1) and the systems containing the conventional antioxidant. It can be seen that the fogging resistance is also excellent as compared with (Comparative Examples 2 to 5). This indicates that the improvement of heat resistance by blending the above-mentioned antioxidant within the scope of the present invention is also very effective with respect to the fogging resistance, which is a problem especially in automobile members and the like.

The plasticizer for vinyl chloride resin of the present invention can be used as a plasticizer for vinyl chloride resin having excellent cold resistance and volatilization resistance, flexibility, fogging resistance, heat color resistance and weather resistance, and chloride thereof. The molded processed product obtained from the vinyl chloride resin composition containing a plasticizer for vinyl resin has excellent cold resistance and volatilization resistance, flexibility, fogging resistance, heat resistance coloring resistance and weather resistance, and is weather resistant. Door trims, dashboards, instrument panels, consoles, door seats, AT shifts, armrests, undercarpets, trunk seats, wire harnesses, various moldings, sashes, sealants, weather, etc. that require durability such as resistance and color resistance It is very useful in automobile member applications such as strips, gaskets, and undercoat materials.

Claims (1)

A plasticizer for vinyl chloride resin containing a trimellitic acid triester and a phenolic antioxidant.
A phenolic antioxidant is contained in a state of being mixed and dissolved in advance in the range of 0.2 to 0.5% by weight with respect to the trimellitic acid triester, and the trimellitic acid triester is further mixed with trimellitic acid or The anhydride and the saturated fatty alcohol having 9 carbon atoms are the main components, and the content of the saturated fatty alcohol having 9 carbon atoms is 60% by weight or more. % Or less, containing a branched saturated fatty alcohol having 9 carbon atoms, and having a linear or branched saturated fatty alcohol having 8 to 11 carbon atoms having a linearity ratio of 60% or more. It is an esterified product of 8 to 11 linear or branched saturated fatty alcohols.
In addition, the phenolic antioxidant has at least two electron-donating substituents at the 2-position, 4-position or 6-position with respect to the hydroxyl group of the phenol moiety, and at least one steric hindrance at the 2-position or 6-position. A plasticizer for vinyl chloride resins, which has a substituent of the above, has a molecular weight in the range of 300 to 3000, and has an SP value in the range of 8 to 15 according to the estimation method of Phenols.