JP2002121361A - Plasticizer and chlorine-containing paste resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasticizer excellent in extraction resistance and non-volatility and having excellent sag resistance and gelling property and suitable for processing a paste resin, and a chlorine-containing paste resin composition containing the same. Providing things. SOLUTION: A polyester plasticizer having an acid value of 0.5 mgKOH / g or less and an acid value of 0.5 mgKO having a specific structure.
A plasticizer comprising an aromatic terminal ester of H / g or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasticizer and a chlorine-containing paste resin composition containing the same.
(A) polyester-based plasticizer having an acid value of 0.5 mgKOH / g or less and an acid value of 0.5 mg represented by the above general formula (1)
A plasticizer characterized by being composed of (B) an aromatic terminal ester of KOH / g or less and having excellent extraction resistance and non-volatility, suitable for paste resin processing (sagging resistance and gelling properties). The present invention relates to a plasticizer and a chlorine-containing paste resin composition containing the same.

[0002]

2. Description of the Related Art An aromatic dicarboxylic acid ester is used as a plasticizer for a vinyl chloride resin for a paste which is a chlorine-containing resin. Among them, phthalic acid diester,
In particular, bis (2-ethylhexyl) phthalate (hereinafter DO)
P) has well-balanced physical properties and is suitable for paste resin processing such as dip molding, coating, rotational molding, slush molding, casting, etc. It is widely used in a wide variety of applications, such as sealants and other automotive applications, gloves, toys and food models, steel plate coats and canvas coats. However, DOP has a low molecular weight, is inferior in performance in applications requiring durability such as extraction resistance and non-volatility, and cannot be practically used.

[0003] As a solution to this problem, polyester plasticizers having a higher molecular weight than phthalate esters have attracted attention and have been studied in various ways. Polyester-based plasticizers have excellent properties in applications where extraction resistance and non-volatility are required, and the above problems have been solved. However, when a polyester-based plasticizer is used in the chlorine-containing paste resin composition, it is easy to sag at the time of molding as compared with the aromatic dicarboxylic acid ester, and the gelling property is poor, and a uniform and stable molded article can be produced. I have a problem of difficulty. Regarding the sagging resistance, the chlorine-containing paste resin itself is heated during the molding process and exhibits a minimum viscosity at around 60 ° C. However, the sagging resistance of the chlorine-containing paste resin at that temperature is important. If the starting temperature is delayed, it affects the final physical properties and the like of the molded article, so that there is a strong demand for improvement of both properties.

In order to solve these problems, Japanese Patent Laid-Open Publication No.
No. 9355 proposes to use a plasticizer (including a polyester-based plasticizer) having a specific viscosity and a benzoic acid-based condensate in a chlorine-containing paste resin composition in order to solve the gelling property. However, in the chlorine-containing paste resin compositions described therein, although the effect of improving the gelling property is observed, the effect of improving the sagging property is extremely small in any case. In fact, no chlorine-containing paste resin composition has been found which improves both properties of the chemical conversion.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the drawbacks of the above-mentioned prior art, and to provide a paste resin which is excellent in extraction resistance and non-volatility, and also has excellent sag resistance and gelling properties. An object of the present invention is to provide a plasticizer suitable for processing and a chlorine-containing paste resin composition containing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the state of the prior art as described above, and as a result, have found that a polyester plasticizer having a specific acid value and an aromatic compound having a specific acid value are used. It has been found that the object can be achieved by blending with a terminal ester, and the present invention has been completed.

That is, the present invention provides: A polyester plasticizer (A) having an acid value of 0.5 mgKOH / g or less and an acid value of 0.5 represented by the following general formula (1)
B- (GA) n-GB (1) wherein B is a benzenemonocarboxylic acid residue, wherein the plasticizer comprises an aromatic terminal ester (B) of not more than mgKOH / g. , G is an alkylene glycol residue having 2 to 12 carbons or 4 carbons.
To 12 oxyalkylene glycol residues; A represents an alkylenedicarboxylic acid residue having 4 to 12 carbon atoms;
Represents an integer of 0 or more. ] 2. A chlorine-containing paste resin composition comprising the plasticizer described in 1 above.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The polyester plasticizer (A) having an acid value of 0.5 mgKOH / g or less constituting the present invention is obtained by condensation using a polybasic acid component, a polyhydric alcohol component, a monohydric alcohol component and / or a monohydric carboxylic acid component. Then, it can be manufactured in the same manner as a normal polyester plasticizer.

The polybasic acid component of the polyester plasticizer (A) of the present invention includes, for example, succinic acid, maleic acid,
Fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, preferably an aliphatic dicarboxylic acid having 4 to 12 carbon atoms such as dodecanedicarboxylic acid, and phthalic acid, aromatic dicarboxylic acids such as isophthalic acid or terephthalic acid and Alternatively, anhydrides and the like thereof are mentioned as main components. Each of these is used as one kind or a mixture of two or more kinds.

The polyhydric alcohol component of the polyester plasticizer (A) of the present invention includes, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, , 3-butanediol, 2-methyl-1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-
n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-
1,5-pentanediol 1,6-hexanediol,
2,2,4-trimethyl 1,3-pentanediol, 2
-Ethyl 1,3-hexanediol, 2-methyl 1,8
-Octanediol, 1,9-nonanediol, 1,1
Examples thereof include aliphatic glycols having 2 to 18 carbon atoms such as 0-decanediol and 1,12-octadecanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol. These glycols are used as one kind or as a mixture of two or more kinds.

[0011] One of the polyester plasticizers (A) of the present invention
Examples of the dihydric alcohol component include octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, 2-methyloctanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, and octadecanol. C8-C18 aliphatic alcohol, alicyclic alcohol such as cyclohexanol, benzyl alcohol, 2-phenylethanol,
-Phenylethanol, 2-phenoxyethanol, 3
Aromatic alcohols such as -phenyl-1-propanol and 2-hydroxyethylbenzyl ether;
It can be used as a species or a mixture of two or more.

As the monovalent carboxylic acid component, for example, caprylic acid, nonanoic acid, capric acid, undecylic acid, lauric acid and the like can be mentioned, and they can be used alone or as a mixture of two or more.

The polyester plasticizer (A) of the present invention may contain, if necessary, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, trimellitic acid, pyromellitic acid and the like.
Polyhydric alcohols and polybasic acids of higher valence or higher may be used as modifiers.

The reaction of the polyester plasticizer (A) of the present invention is carried out by, for example, acid catalysts such as paratoluenesulfonic acid and phosphoric acid, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, zinc chloride and the like. Usually, it is desirable to carry out the reaction in the presence of these catalysts because they are promoted by metal catalysts.
The reaction is usually carried out at 100 to 250 ° C., preferably 1 to 250 ° C.
It is obtained by heating to 30 to 250 ° C.

The polyester plasticizer (A) used in the present invention has a number average molecular weight of preferably 500 to 800.
0, more preferably in the range of 600-4000. Further, the acid value is preferably 0.5 mgKOH / g or less, and within this range, the sag resistance of the chlorine-containing paste resin composition becomes excellent, and the molding process of the chlorine-containing paste resin composition is excellent. Can be done.
The hydroxyl value is preferably 25 mgKOH / g or less, and within this range, good compatibility of the plasticizer with the chlorine-containing resin can be obtained.

More preferably, the acid value is 0.3 mgKOH / g.
Hereinafter, the hydroxyl value is 15 mgKOH / g or less, and within this range, the sag resistance of the chlorine-containing paste resin composition, the processability of the paste resin molded product, and the compatibility of the plasticizer with the chlorine-containing resin are further excellent. It will be.

Further, one of the constituents represented by the general formula (1)
The aromatic terminal ester (B) having an acid value of 0.5 mgKOH / g or less represented by the formula (1) is a benzenemonocarboxylic acid residue represented by B and an alkylene glycol residue or oxyalkylene glycol represented by G in the formula (1). It is composed of a residue and an alkylenedicarboxylic acid residue represented by A, and is obtained by the same reaction as a usual polyester plasticizer.

The benzene monocarboxylic acid component of the aromatic terminal ester (B) used in the present invention includes, for example,
Benzoic acid, para-tert-butyl benzoic acid, orthotoluic acid, metatoluic acid, paratoluic acid, dimethyl benzoic acid, ethyl benzoic acid, normal propyl benzoic acid,
There are aminobenzoic acid, acetoxybenzoic acid, and the like, and these can be used as one kind or as a mixture of two or more kinds.

The alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal ester (B) of the present invention includes ethylene glycol, 1,2-propylene glycol,
3-propylene glycol, 1,2-butanediol,
1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), , 2-diethyl-
1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol,
There are 1,10-decanediol, 1,12-octadecanediol and the like.
Used as a mixture of more than one species.

The oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester (B) of the present invention includes, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like. Yes, these glycols can be used as one kind or as a mixture of two or more kinds.

The alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester (B) of the present invention includes, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, There are dodecanedicarboxylic acid and the like, each of which is used as one kind or as a mixture of two or more kinds.

The aromatic terminal ester (B) used in the present invention has a number average molecular weight of preferably from 250 to 200.
0, more preferably in the range of 300-1500. The acid value is 0.5 mg KOH / g or less, the hydroxyl value is 25 mg KOH / g or less, more preferably the acid value is 0.3 mg KOH / g or less, and the hydroxyl value is 15 mg KOH / g.
/ G or less is preferred. When the acid value is within the above range, the sag resistance of the chlorine-containing paste resin composition becomes excellent, and the chlorine-containing paste resin composition can be favorably molded. If the hydroxyl value is within the above range, good compatibility of the plasticizer with the chlorine-containing resin can be obtained.

The composition ratio of the (A) polyester plasticizer of the present invention and the (B) aromatic terminal ester is preferably 5 to 95% by weight of the (A) polyester plasticizer having an acid value of 0.5 mgKOH / g or less. It is composed of 95 to 5% by weight of an aromatic terminal ester (B) having an acid value of 0.5 mgKOH / g or less represented by the above general formula (1), and the ratio is within the above range, and the characteristics required for the resin composition are It is appropriately selected according to the situation.

The amounts of the polyester plasticizer (A) and the aromatic terminal ester (B) used in the chlorine-containing paste resin composition of the present invention are 20 to 300 parts by weight, preferably 100 to 100 parts by weight of the chlorine-containing resin. It is 30 to 200 parts by weight.

The chlorine-containing resin constituting the composition of the present invention includes polyvinyl chloride resin and polyvinyl chloride copolymer resin comprising a known monomer and vinyl chloride, such as polyvinyl chloride resin and vinyl chloride-vinyl acetate copolymer resin. In addition, a chlorinated polyvinyl chloride resin obtained by chlorinating a polyvinyl chloride resin or a polyvinyl chloride copolymer resin, and the like, can be used as one kind or a mixture of two or more kinds.

Further, the chlorine-containing paste resin composition of the present invention can be prepared from well-known plasticizers used in the field of plastic processing, for example, phthalates, adipates, sebacates, trimellites. , Pyromellitic esters, epoxy esters, chlorinated paraffins, phosphoric esters, and the like. Furthermore, the present resin composition is used in combination with a stabilizer, a filler, a gelling agent, a diluent, a thickener, a foaming agent, a pigment, a flame retardant, or other additives used in the plastic processing field. Can be used.

[0027]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the description, "parts" and "%" all indicate weight standards.

(Synthesis example) <Sample No. 1 (polyester plasticizer sample)
> 730 parts (5 mol) of adipic acid, 1,3-
297 parts (3.3 moles) of butanediol, 648 parts (4.5 moles) of isononanol and 0.17 part of tetraisopropyl titanate as a catalyst were charged all at once, and the resulting mixture was stirred in a nitrogen stream and attached with a reflux condenser. While refluxing the monohydric alcohol of 130 to 2 until the acid value becomes 2 or less.
Heating was continued at 50 ° C. to continuously remove generated water. Then, the distillate was removed at 200 to 230 ° C. under reduced pressure of 100 to finally 3 mmHg or less, and then filtered to obtain a polyester plasticizer having the following properties.

Viscosity (25 ° C., mPa · s); 120 acid value; 0.2

<Sample No. 2 (polyester plasticizer sample)> 730 parts (5 mol) of adipic acid, 380 parts (5 mol) of 1,2-propylene glycol, 216 parts (1.5 mol) of isononanol were placed in a reaction vessel. A polyester plasticizer having the following properties was obtained in exactly the same manner as in Sample No. 1 except that 0.13 parts of tetraisopropyl titanate was used as the catalyst.

Viscosity (25 ° C., mPa · s); 3010 acid value; 0.3

<Sample No. 3 (Sample of aromatic terminal ester)> 610 parts (5 moles) of benzoic acid were placed in a reaction vessel.
An aromatic terminal ester having the following properties was obtained in exactly the same manner as in Sample No. 1 except that 339.2 parts (3.2 mol) of diethylene glycol and 0.45 part of tetraisopropyl titanate were used as a catalyst.

Viscosity (25 ° C., mPa · s); 90 acid value; 0.05

<Sample No. 4 (Sample of aromatic terminal ester)> In a reaction vessel, 610 parts (5 mol) of benzoic acid,
An aromatic terminal ester having the following properties was obtained in exactly the same manner as in Sample No. 1 except that 388.6 parts (2.9 mol) of dipropylene glycol and 0.40 part of tetraisopropyl titanate were used as a catalyst.

Viscosity (25 ° C., mPa · s); 134 acid value; 0.03

<Sample No. 5 (Sample of aromatic terminal ester)> 365 parts (2.5 mol) of adipic acid, 418 parts of 1,2-propylene glycol (5.5 parts) were placed in a reaction vessel.
Mol), 610 parts (5 mol) of benzoic acid and 0.30 part of tetraisopropyl titanate as a catalyst were obtained in the same manner as in Sample No. 1 to obtain an aromatic terminal ester having the following properties.

Viscosity (25 ° C., mPa · s); 815 Acid value; 0.4

<Comparative sample No. 1 (polyester plasticizer sample)> 730 parts of adipic acid (5
Mol), 297 parts (3.3 mol) of 1,3-butanediol, 619 parts (4.3 mol) of isononanol, and 0.20 part of tetraisopropyl titanate as a catalyst. Thus, a polyester plasticizer having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 130 acid value; 0.6

<Comparative Sample No. 2 (polyester plasticizer sample)> 730 parts of adipic acid (5 parts
Mol), 190 parts of 1,2-propylene glycol (2.
5 mol), 225 parts (2.5 mol) of 1,3-butanediol, 216 parts (1.5 mol) of isononanol, and 0.16 part of tetraisopropyl titanate as a catalyst. Thus, a polyester plasticizer having the following properties was obtained.

Viscosity (25 ° C., mPa · s); 3480 acid value; 1.8

<Comparative Sample No. 3 (Sample of aromatic terminal ester)> 365 parts of adipic acid (2.
5 mol), 342 parts (4.5 mol) of 1,2-propylene glycol, 90 parts (1 mol) of 1,3-butanediol, 610 parts (5 mol) of benzoic acid and 0.20 part of tetraisopropyl titanate as a catalyst The aromatic terminal ester having the following properties was obtained in exactly the same manner as in Sample No. 1 except that

Viscosity (25 ° C., mPa · s); 840 acid value; 1.4

(Examples) Examples 1 to 6, Comparative Examples 1 to 7 Chlorine-containing paste resin compositions having the compositions shown in Tables 1 and 2 were prepared, and Examples 1 to 6 and Comparative Examples 1 to 7 were prepared. Was obtained. Tables 1 and 2 also show the results of tests performed on these compositions. The conditions for adjusting the composition and the test method are as follows.

(Conditions for Adjusting Chlorine-Containing Paste Resin Composition) Mixing 1100 rpm × 4 minutes Degassing 30 minutes (under vacuum)

(Sol baking conditions) 190 ° C. × 10 minutes 0.4 mm thick

(Sagging test) A chlorine-containing paste resin composition was coated on a glass plate using an applicator, and
Leave still for 15 minutes in a dryer at 60 ° C. with a degree of inclination. After the test is completed, the paste resin composition is taken out and the sagging condition of the paste resin composition is evaluated.

○: no sagging △: accumulated at the bottom ×: sagging

(Gelability Test) Using an optical microscope, a change in transmittance of the chlorine-containing paste resin composition dropped on a slide glass is measured. At this time, the temperature was raised from 50 ° C. at 5 ° C./min, and the inflection point of the transmittance at which the temperature began to change from opaque to transparent was defined as the gelation start temperature. The evaluation standard at that time is 110
Pass below ℃.

(Kerosene Resistance Test) A chlorine-containing paste resin composition sheet prepared at a thickness of 0.4 mm was immersed in kerosene at 30 ° C. for 24 hours as a sample having a size of 5 × 5 cm. After taking out and wiping the surface, the weight loss is measured. The evaluation criteria at that time are that a weight loss of 30% or less is accepted.

(Soybean oil resistance test) A chlorine-containing paste resin composition sheet prepared at a thickness of 0.4 mm was immersed in soybean oil at 30 ° C. for 24 hours as a sample having a size of 5 × 5 cm. After removing from the surface and wiping the surface, the weight loss is measured. The evaluation criteria at that time are that a weight loss of 20% or less is accepted.

(Non-volatile test) A chlorine-containing paste resin composition sheet having a thickness of 0.4 mm was used as a sample having a size of 5 × 5 cm, and a heat aging test was carried out at 100 ° C. for 120 hours. Measure weight loss. The evaluation criteria at that time are judged to be acceptable if the weight loss is 10% or less.

[0053]

[Table 1]

* 1: Polyvinyl chloride resin for paste (degree of polymerization 1650) * 2: AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd. * 3: Grec ML- manufactured by Dainippon Ink and Chemicals, Inc.
610A

[0055]

[Table 2]

* 1: Polyvinyl chloride resin for paste (degree of polymerization: 1650) * 2: AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd. * 3: Grec ML- manufactured by Dainippon Ink and Chemicals, Inc.
610A

[0057]

The plasticizer of the present invention is particularly excellent in extraction resistance and non-volatility as compared with conventionally known plasticizers, and is suitable for paste resin processing (sagging resistance and gelling properties). The utility value of the chlorine-containing paste resin composition in the applied processing field is extremely large.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Keiji Takazawa 1-21-3-401 Arakicho, Kishiwada-shi, Osaka F-term (reference) 4J002 BD04Y BD08Y BD18Y CF00W CF00X CF03W CF03X CF04W CF05W CF22W CF22X EH096 EH106 EH126 EH156 FD02W

Claims (2)

[Claims] (A) having an acid value of 0.5 mgKOH / g or less (A)
A plasticizer comprising a polyester plasticizer and (B) an aromatic terminal ester having an acid value of 0.5 mgKOH / g or less represented by the following general formula (1). B- (GA) n-GB (1) [wherein B is a benzenemonocarboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms or 4 carbon atoms.
To 12 oxyalkylene glycol residues; A represents an alkylenedicarboxylic acid residue having 4 to 12 carbon atoms;
Represents an integer of 0 or more. ] 2. A chlorine-containing paste resin composition comprising the plasticizer according to claim 1.