JPH08337700A - Plasticizer composition - Google Patents

Abstract

PURPOSE: To obtain a plasticizer composition which, when added to a vinyl chloride resin, imparts high flexibility thereto and can give a composition excellent in performances, such as heat resistance, oil resistance, cold resistance and migration resistance. CONSTITUTION: This plasticizer composition is obtained by mixing 10-90wt.% plasticizer (A) comprising a polyester produced by using 3-methyl-1,5-pentanediol as the polyhydric alcohol component with 90-10wt.% trimellitic triester or pyromellitic tetraester. A vinyl chloride resin composition is obtained by adding 5-200 pts.wt. of the plasticizer composition to 100 pts.wt. vinyl chloride resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a plasticizer composition,
More specifically, the present invention relates to a plasticizer composition comprising a polyester plasticizer using a branched glycol and a mononuclear polycarboxylic acid ester compound and having excellent heat resistance, oil resistance, non-migration property and the like.

[0002]

2. Description of the Related Art A plasticizer is added to a vinyl chloride resin in order to give it flexibility. In order to obtain a highly flexible vinyl chloride resin composition, it is necessary to add a large amount of plasticizer, but for example, when a large amount of a general-purpose plasticizer such as dioctyl phthalate is added, bleeding occurs. Or the heat resistance decreases,
In addition, there is a defect that the plasticizer migrates to polystyrene or ABS resin when it comes into contact with it.

Therefore, when used in applications requiring high heat resistance, trimellitic acid triester,
Mononuclear polycarboxylic acid ester compounds such as pyromellitic acid tetraester are usually used alone. However, these have the drawback of being inferior in oil resistance and migration resistance.

On the contrary, polyester plasticizers are used when they are used in applications where oil resistance, migration resistance and the like are required. However, in this case, there is a drawback that the heat resistance is lowered.

In order to improve these drawbacks, a trimellitic acid plasticizer or pyromellitic acid plasticizer excellent in heat resistance and a polyester plasticizer excellent in oil resistance and migration resistance are added in combination. For example, in JP-A-59-213748, it is proposed to add a trimellitic acid-based plasticizer and a polyester-based plasticizer to a vinyl chloride resin in combination, and JP-A-62-58365. In the publication, vinyl chloride resin is mixed with a trimellitic acid ester plasticizer, and 2-ethyl-2- is used as a diol.
It has been proposed to add a polyester-based plasticizer having an average molecular weight of 1000 to 5000 using alkyl-1,3-propanediol, which is disclosed in JP-A-5-338101.
In the publication, as a plasticizer, a high molecular weight polyester plasticizer and a bulky trivalent to hexavalent mononuclear aromatic carboxylic acid ester plasticizer are mixed at a ratio of 1: 9 to 9: 1 (weight ratio). A vinyl chloride resin sheet has been proposed.

However, when a normal polyester plasticizer and a trimellitic acid plasticizer or a pyromellitic acid plasticizer are used in combination, they are inferior in compatibility, and therefore, it is necessary to weigh them separately. , The operation becomes complicated. Further, polyester plasticizers produced by using glycols having branching in the chain such as neopentyl glycol are compatible with trimellitic acid plasticizers and the like to obtain a uniform mixed plasticizer. A plasticizer has a high viscosity, and when blended with a vinyl chloride resin, its performance such as heat resistance and cold resistance is still insufficient.

Therefore, an object of the present invention is to provide a composition which, when added to a vinyl chloride resin, imparts high flexibility and is excellent in performance such as heat resistance, oil resistance, cold resistance and migration resistance. It is to provide a plasticizer composition that can be used.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a polyester plasticizer and a trimellitic acid plasticizer or pyromellitic acid using a specific branched glycol are used. It has been found that by mixing the system plasticizer, a plasticizer composition excellent in the above performance and uniformly mixed can be obtained.

The present invention was made on the basis of the above findings, and (a) 3-methyl-1, as a polyhydric alcohol component,
A plasticizer composition comprising 10 to 90% by weight of a polyester plasticizer containing 5-pentanediol and 90 to 10% by weight of (b) trimellitic acid triester or pyromellitic acid tetraester. is there.

The present invention also relates to vinyl chloride resin 100.
The present invention provides a vinyl chloride resin composition obtained by adding 5 to 200 parts by weight of the plasticizer composition to parts by weight.

First, the plasticizer composition of the present invention will be described in detail below.

(B) Used in the plasticizer composition of the present invention
The component polyester plasticizer is composed of a polyhydric alcohol component and a polybasic acid component, and optionally an alcohol and / or a monobasic acid as a terminal terminating component, and the polyester plasticizer is a polyhydric alcohol component. 3-methyl-1,5-pentanediol (hereinafter referred to as MP
Sometimes referred to as D) in the total amount of the polyhydric alcohol of 10
It is used in an amount of at least 15% by weight, preferably at least 15% by weight. When the amount of MPD used is less than 10% by weight based on the whole polyhydric alcohol, it is difficult to obtain a polyester plasticizer having excellent compatibility with trimellitic acid ester or pyromellitic acid ester.

Other polyhydric alcohol components that can be used in combination with the 3-methyl-1,5-pentanediol in the polyester plasticizer include ethylene glycol, diethylene glycol, 1,3-propanediol and 1,4-butanediol. , 1,5-pentanediol, 1,6-hexanediol and other linear glycols, 1,2-propanediol, 2-methyl-1,3-propanediol,
2,2-dimethyl-1,3-propanediol, 2,2
-Diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol,
2-ethyl-1,3-hexanediol, 2,2,4-
Examples include branched glycols such as trimethyl-1,3-pentanediol. In addition, small proportions of polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol can be used.

Examples of the polybasic acid component used for producing the polyester plasticizer include aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and dodecanedicarboxylic acid. In addition to this, a small proportion of phthalic acid,
Aromatic polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, or aliphatic polybasic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, tricarballylic acid and citric acid can also be used. .

In addition, the polybasic acid component and / or
Alternatively, a part of the polyhydric alcohol component may be replaced with 12-hydroxystearic acid, caprolactone or the like.

The alcohol used as the end-stopping component in the polyester plasticizer includes methanol, ethanol, propanol, isopropanol,
Butanol, isobutanol, pentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, decanol, isodecanol, undecanol, isoundecanol, dodecanol, tridecanol, isotrianol. Examples include decanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, cellosolve, carbitol, phenol, nonylphenol, benzyl alcohol, and mixed alcohols thereof, and monobasic acid. Examples include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, capric acid. Phosphoric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid,
Examples thereof include palmitic acid, heptadecanoic acid, stearic acid, benzoic acid, and mixed fatty acids thereof.

The ratio of the above-mentioned respective components in forming the polyester plasticizer varies depending on the kind of the components used, the characteristics of the intended polyester plasticizer, the molecular weight and the like, but in general, the polybasic acid component is 10 to 80. It is used in a ratio of 10% by weight, 10-80% by weight of polyhydric alcohol component, and 10-50% by weight of end-terminating component.

The polyester plasticizer has a number average molecular weight of 500 to 5,000, particularly 1,000 to 300.
Those having an acid value of 0 are preferable, and those having an acid value of 1 or less and a hydroxyl value of 30 or less are preferable.

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

Therefore, examples of the above-mentioned polyester plasticizer used in the present invention include those obtained from the components shown in the following [Table 1]. The number average molecular weight, acid value and hydroxyl value of each polyester plasticizer are shown together in [Table 1].

[0021]

[Table 1]

Used in the plasticizer composition of the present invention (b)
The trimellitic acid triester compound or pyromellitic acid tetraester compound, which is a component, is a trimester acid or a triester compound of pyromellitic acid and a monohydric alcohol, and a tetraester compound, respectively.

The monohydric alcohol used for producing the trimellitic acid triester compound or pyromellitic acid tetraester compound is, for example, methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, Dibutyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol, isodecanol, undecanol, dodecanol, tridecanol, isotrideca. Nole, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, Kosanoru, Hen'ikosanoru, such as docosanol and the like.

The plasticizer composition of the present invention comprises 10 to 90% by weight of the above polyester plasticizer (component (a)) and 90 to 10% by weight of the above trimellitic acid triester or pyromellitic acid tetraester ((b) component). % Of the polyester plasticizer, the performance such as oil resistance and migration resistance may decrease, and the trimellitic acid triester Alternatively, if the amount of the pyromellitic acid tetraester is less than 10% by weight, the performance such as heat resistance may decrease.

The plasticizer composition of the present invention contains a phenol compound, an organic phosphite compound, a hindered amine compound, perchlorates, etc. for the purpose of storage stability and prevention of generation of odor due to decomposition during processing. You may contain an additive.

Examples of the above-mentioned phenol compound include:
4,4′-isopropylidenediphenol, 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-ditertiarybutyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-) Hydroxyphenyl)
Propionic acid amide], 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) butyric acid] glycol ester, 4,4'-butylidenebis (6-tertiary) 3-butyl-m
-Cresol), 2,2'-ethylidene bis (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-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,3
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-ditert-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 are mentioned.

Examples of the organic phosphite compound include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl). -4-Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritol diphosphite, di Stearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite, bis (2,2
6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-tert-butyl-) 5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4)
-Hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
-Oxide, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and the like can be mentioned.

The hindered amine compound is a compound having at least one 2,2,6,6-tetramethylpiperidyl group in the molecule, and is, for example, 2,2,6,6.
-Tetramethyl-4-piperidyl benzoate, N-
(2,2,6,6-Tetramethyl-4-piperidyl) dodecyl succinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6 6-Tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
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) butane Tetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4
-Piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Di (tridecyl) butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butane tetracarboxylate, 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-tertiary octylamino-4,6-dichloro-s-triazine / N, N′-bis (2,2,2
6,6-Tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate and the like are mentioned.

The above-mentioned perchlorates include lithium perchlorate, potassium perchlorate, sodium perchlorate, barium perchlorate, zinc perchlorate, ammonium perchlorate and the like, which are anhydrous. May also be a hydrous material.

The plasticizer composition of the present invention is usually used as a plasticizer for vinyl chloride resins.

Next, the vinyl chloride resin composition of the present invention will be described. The vinyl chloride resin composition of the present invention,
The plasticizer composition of the present invention is added to a vinyl chloride resin. At this time, the plasticizer composition,
The vinyl chloride resin is used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight. If the amount of the plasticizer composition used is less than 5 parts by weight, sufficient flexibility cannot be imparted, and if it exceeds 200 parts by weight, the strength may be reduced.

If desired, a plasticizer used for ordinary vinyl chloride resins can be used together with the above-mentioned plasticizer composition. As the plasticizer, any plasticizer used in ordinary vinyl chloride resins can be used, and examples thereof include polyester plasticizers other than the component (a) according to the present invention, diheptyl phthalate, dioctyl phthalate, diisononyl. Phthalates such as phthalates, dioctyl adipate, diisononyl adipate,
Examples include adipate plasticizers such as di (butyldiglycol) adipate, phosphate plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, and epoxidized vegetable oils.

Here, as the vinyl chloride resin,
For example, polyvinyl chloride, post-chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene. Copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl, cycloalkyl or aryl maleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer , Vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer , Vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid Ester copolymer, vinyl chloride - acrylonitrile copolymer, vinyl chloride - such as urethane copolymers.

The vinyl chloride resin composition of the present invention contains P
b-based, organic Sn-based, metallic soap-based stabilizers used for ordinary vinyl chloride resins, amine-based, phenol-based,
It may contain a sulfur-based or phosphite-based antioxidant, various additives such as a hindered amine-based light stabilizer or an epoxy compound, and fillers such as calcium carbonate, talc, titanium oxide, clay and silica.

In addition to the above, the vinyl chloride resin composition of the present invention may optionally contain additives usually used in the vinyl chloride resin composition, such as a crosslinking agent, a filler, an antistatic agent, and the like.
Anti-plateout agent, surface treatment agent, lubricant, elastic agent, adhesion promoter, flame retardant, fluorescent agent, antifungal agent, bactericide, metal deactivator, pigment, processing aid, antioxidant, and light stabilizer. It can be blended.

The vinyl chloride resin composition of the present invention can be suitably used for processing methods such as calendar processing, roll processing, extrusion molding processing, pressure molding processing, paste processing and powder molding. .

Applications of the vinyl chloride resin composition of the present invention include building materials such as wall materials, floor materials and ceiling materials, paints, automobile interior materials, electric wire coating materials, leather, sheets, miscellaneous goods such as toys. To be

[0038]

EXAMPLES The present invention will now be described by way of examples, which should not be construed as limiting the present invention.

In the following examples, the plasticizer composition shown in the above [Table 1] and the comparative compound shown in the following [Table 2] were used.

[0040]

[Table 2]

Example 1 The plasticizers were mixed in a beaker at a weight ratio shown in the following [Table 3] to [Table 5] at 25 ° C. with a mag mixer, and the compatibility was evaluated according to the following evaluation criteria.

[Compatibility Evaluation Criteria] ○: Completely dissolved (transparent) △: Some turbidity ×: Opaque xx: Separation started in several hours.

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

Example 2 The following composition was sheeted by a calendering method, and a 1 mm laminated sheet was prepared by pressing.
A test piece was prepared according to SK-7113, and a tensile test was conducted.
A heat aging test (136 ° C. × 168 hours) and an oil resistance test (ASTM No. 2 oil 100 ° C. × 96 hours) were performed. In addition, to evaluate cold resistance, Crash &
The soft temperature was measured by the Berg method. Furthermore, a test piece of 10 × 30 mm is prepared from the press sheet, and AB
Place on S plate and polystyrene plate, put a weight of 1 kg on the vinyl chloride sheet so that the load is evenly applied, and at 65 ° C.
After leaving for 72 hours, the traces on the plate were visually evaluated according to the following criteria. The results are shown in [Table 6] below.

(Transferability Evaluation Criteria) ○: No traces △: Some traces are seen ×: Large traces

(Compounding) parts by weight vinyl chloride resin (average degree of polymerization 1300) 100 plasticizer (see [Table 6] below) 50 epoxidized soybean oil 2 RUP-14 (Ba / Zn powder stable manufactured by Asahi Denka Co., Ltd.) Agent) 2 AC-186 (Ba / Zn liquid stabilizer manufactured by Asahi Denka Co., Ltd.) 1

[0049]

[Table 6]

The following is clear from the above embodiment. Most of the polyester plasticizers other than the component (a) according to the present invention have poor compatibility with trimellitic acid plasticizers or pyromellitic acid plasticizers, and it is difficult to prepare a mixed composition in advance. Therefore, when used as a plasticizer for vinyl chloride resin, it is necessary to mix the required amounts immediately before use or to mix them separately, and in any case, not only the operation becomes complicated but also a mixing error easily occurs. Moreover, the performance is not satisfactory (Comparative Example 1-
1,1-2,1-5,1-6,1-9,1-10,2-6,2-7). Also, polyester plasticizers that use some special polyhydric alcohol components such as neopentyl glycol have excellent compatibility with trimellitic acid plasticizers or pyromellitic acid plasticizers, and a uniform mixture can be obtained, but heat resistance , Inferior in oil resistance, especially in cold resistance (Comparative Examples 1-7, 1-8, 1-11, 1-12, 2-8, 2-9).

In contrast, 3-methyl-according to the present invention
Polyester plasticizers containing 1,5-pentanediol as a polyhydric alcohol component have excellent compatibility with trimellitic acid plasticizers or pyromellitic acid plasticizers and can be mixed arbitrarily, simplifying the charging process. And exhibit excellent synergistic effects such as heat resistance, oil resistance, cold resistance, and migration resistance (Examples 1-1 to 1-21, 2-1 to 2-5).

[0052]

The plasticizer composition of the present invention (claim 1) is
When added to a vinyl chloride resin, it can give a composition having high flexibility and excellent heat resistance, oil resistance, cold resistance, migration resistance and the like. The plasticizer composition (claim 2) of the present invention has excellent compatibility between the component (a) and the component (b). The vinyl chloride resin composition of the present invention (claim 3) is obtained by adding the above plasticizer composition, and is excellent in flexibility, heat resistance, oil resistance, cold resistance, migration resistance and the like. Is.

Claims (3)

[Claims] 1. (a) 10 to 90% by weight of a polyester plasticizer comprising 3-methyl-1,5-pentanediol as a polyhydric alcohol component and (b) trimellitic acid triester or pyromellitic acid tetraester. 9
A plasticizer composition obtained by mixing 0 to 10% by weight. 2. The plasticizer composition according to claim 1, wherein the 3-methyl-1,5-pentanediol is used in an amount of 10% by weight or more based on the whole polyhydric alcohol. 3. A vinyl chloride resin composition obtained by adding 5 to 200 parts by weight of the plasticizer composition according to claim 1 to 100 parts by weight of the vinyl chloride resin.