JPH06263944A - Chlorine-containing resin composition for foaming - Google Patents

Abstract

PURPOSE:To obtain the subject foaming composition containing a chlorine- containing resin, a foaming agent and a polyester-type plasticizer containing a monoglyceride, a diglyceride, a triglyceride, etc., as reaction components, free from environmental problem and having excellent processing workability. CONSTITUTION:A composition for forming a foamed article of a chlorine- containing resin, having excellent processing workability and giving a foamed article by thermal foaming while keeping uniform and dense foamed cells without causing processing and environmental problems is produced by compounding (A) a chlorine-containing resin (e.g. vinyl chloride resin), (B) a foaming agent (e.g. azodicarbodiamide) and (C) a polyester-type plasticizer containing at least one kind of glyceride such as monoglyceride, diglyceride and triglyceride, especially glyceride consisting of the triglyceride of linseed oil, soybean oil, tung oil, dehydrated castor oil, coconut oil, palm oil and palm kernel oil as a reaction component. The amount of the polyester-type plasticizer used as the component C is 1-150 pts.wt. based on 100 pts.wt. of the chlorine-containing resin used as the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-containing resin foam composition, and more particularly to a chlorine-containing resin foam composition having a uniform foam cell state and excellent workability.

[0002]

2. Description of the Prior Art Chlorine-containing resins such as vinyl chloride resins have excellent physical and chemical properties, are highly durable, and are inexpensive, so they are used in hard fields, soft fields, foams in leather, etc. It is used in large quantities in a wide range of fields.

Generally, a vinyl chloride resin foam is produced by heating a composition containing a vinyl chloride resin, a liquid plasticizer such as dioctyl phthalate, and a foaming agent to a high temperature to foam the composition. The foam has the advantages of being inexpensive and excellent in heat aging resistance, flame retardancy, mechanical strength and the like, and is often used for leather, sponge, pull cloth, building materials, daily necessities and the like.

Conventionally, when a vinyl chloride resin composition containing a liquid plasticizer is heated and foamed, the change in the melt viscosity of the resin composition with respect to temperature is extremely large, so that the foaming becomes unstable depending on the foaming conditions, resulting in a foamed product. It was easy to damage the appearance and feel. Therefore, in order to obtain a foam having optimum properties, the foaming agent and molding conditions must be strictly controlled within a very narrow range.

At that time, examples of the foaming agent used include azodicarbodiamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, oxybisbenzenesulfonylhydrazide, diphenylsulfone-3,3 '. -Organo-inorganic foaming agents such as disulfonyl hydrazide, toluene sulfonyl hydrazide, sodium bicarbonate, calcium azide, etc., carbon dioxide, inert gases such as nitrogen, low boiling point solvents, etc. are considered, but foaming ratio, colorless, odorless, flame retardant The azodicarboxylic acid type is excellent as the vinyl chloride type resin foam from the viewpoints of properties and ease of handling.

However, the decomposition temperature is as high as 190 to 210 ° C., the vinyl chloride resin is decomposed and the surface is colored and cured during foam molding, and the foam cells are disturbed to make it impossible to obtain a flexible foam.

Therefore, it has been proposed to use a foaming aid such as a urea-based or fatty acid metal salt-based foaming agent in combination with the foaming agent to lower the foaming temperature for practical use. However, a urea-based foaming aid such as urea- Ethanolamine has the drawback of being hygroscopic and inferior in weather resistance. On the other hand, fatty acid metal salt-based foaming aids such as zinc stearate and calcium stearate have been put to practical use because they have the effect of lowering the foaming temperature without deteriorating the heat resistance of the vinyl chloride resin.

However, when a fatty acid metal salt is added at a temperature lower than the foaming temperature, it exudes to the surface of the molded article and impairs its appearance, and in the processing step it exudes to the metal surface for molding to contaminate the mold and roll surface, It had the drawbacks of matte and color transfer.

In order to improve these points, addition of an elastic polymer such as a combination of a butadiene-acrylonitrile copolymer (NBR), chlorinated polyethylene and an ethylene-vinyl acetate copolymer (EVA) has hitherto been attempted.

However, in the case of NBR or chlorinated polyethylene, there is a drawback that the foam produced is markedly colored during foaming and with the passage of time. EVA has different compatibility depending on the composition ratio, but has excellent compatibility with vinyl chloride resin, not only makes the cell state of the foam uniform and dense, but also the texture of the foam is good, and leather, foam soles, It has been put to practical use as a cell conditioner for foamed molded products such as building materials. However, due to the tackiness of EVA, the tackiness to the molding machine or the color transfer to the sheet caused poor workability.

Further, although there is an acrylic foam cell adjusting agent, in the case of sol foaming, the acrylic becomes sloppy and a uniform sol cannot be prepared. Although there is a liquid acrylic foaming cell conditioner diluted with a solvent and sol foaming is possible, the solvent is not environmentally preferable.

[0012]

As described above, conventionally, when the plasticized vinyl chloride resin was heated and foamed, it was not possible to obtain a foam having uniform and dense foam cells without problems in processing and environment. .

An object of the present invention is to provide a composition for a chlorine-containing resin foam which has uniform and dense foam cells without the above-mentioned drawbacks.

[0014]

The present inventors have completed the present invention as a result of extensive studies on the above problems.

That is, according to the present invention, a polyester-based plasticizer using a chlorine-containing resin (A), a foaming agent (B), and at least one glyceride selected from the group consisting of monoglycerides, diglycerides and triglycerides as a reaction component ( The present invention provides a composition for a chlorine-containing resin foam, which comprises C).

(Structure) Examples of the chlorine-containing resin (A) used in the present invention include vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, and chlorinated polyolefin resin. Is mentioned.

Examples of the foaming agent (B) include azodicarbodiamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, oxybisbenzenesulfonylhydrazide, diphenylsulfone-3,3'-disulfonyl. There are organic and inorganic blowing agents such as hydrazide, toluenesulfonyl hydrazide, sodium bicarbonate, calcium azide, etc. or carbon dioxide gas, inert gas such as nitrogen, low boiling point solvent, etc., but the expansion ratio, colorless, odorless, flame retardant and handling The azodicarboxylic acid type is preferred from the viewpoint of simplicity.

As the polyester plasticizer (C), at least one glyceride of monoglyceride, diglyceride or triglyceride is used as an essential component, and a dibasic acid component, a glycol component and a monohydric alcohol or monobasic used as necessary. It is a polyester obtained by reacting constituent components of an acid polyester. Triglyceride is preferred for effectively carrying out the present invention in these glycerides. Further, among the triglycerides, animal and vegetable oils and fats or hydrogenated oils thereof, which can more effectively carry out the present invention, are more preferable.

The glycerides used to form the polyester of the present invention include, for example, natural triglycerides such as palm oil, palm oil, palm kernel oil, cocoa butter,
Animal and vegetable oils and fats such as wood wax, olive oil, kapok oil, castor oil, dehydrated castor oil, rapeseed oil, rice bran oil, cottonseed oil, soybean oil, safflower oil, linseed oil, tung oil, beef tallow, lard and cod oil, etc. Hydrogenated oils of animal and vegetable oils and fats obtained by hydrogenation are used, and they are used as one kind or a mixture of two or more kinds. Further, monoglyceride and diglyceride can be obtained by the commonly known transesterification reaction of the above oils and fats and glycerin. Further, the monoglyceride, the diglyceride and the residual triglyceride produced by adjusting the ratio of the oils and fats to be transesterified and the glycerin can be obtained in a ratio according to the production fraction of glycerolysis. These can be separated and used as individual glycerides, but it is technically and economically preferable to use them as a mixture. In addition, it is not particularly necessary to separate and remove glycerin remaining in glycerolysis.

Further, as glycerides, monobasic acids having 6 to 22 carbon atoms derived from the above oils and fats or hydrogenated oils thereof or acetic acid, butyric acid, isobutyric acid, heptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid and It is also possible to use monoglycerides, diglycerides and triglycerides obtained from glycerin and synthetic monobasic acids having 2 to 18 carbon atoms such as isostearic acid, or a mixture thereof.

Furthermore, as a result of the appropriate distribution of the fatty acid composition in the animal and vegetable oils and fats, linseed oil, soybean oil, tung oil, dehydrated castor oil, coconut oil, palm oil and palm kernel oil, whose quality performance is even more highly satisfactory. Are particularly preferably used.

The dibasic acid component used for constituting the polyester of the present invention includes succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like. 4-12 aliphatic dibasic acids, aromatic dibasic acids such as phthalic acid, isophthalic acid or terephthalic acid and alicyclic dibasic acids such as tetrahydrophthalic acid and hexahydrophthalic acid, or their anhydrides and esterified products Is mentioned.
Of course, these dibasic acids may be used alone or as a mixture of two or more.

The glycol component used to form the polyester of the present invention includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol and 1,3-butanediol. , 2-methyl 1,3-propanediol,
1,4-butanediol, neopentyl glycol,
1,5-pentanediol, 3-methyl 1,5-pentanediol, 1,6-hexanediol, 2,2,4-
Trimethyl 1,3-pentanediol, 2-ethyl 1,
Aliphatic glycols having 2 to 18 carbon atoms such as 3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-octadecanediol, and diethylene glycol and diethylene glycol. Examples include polyalkylene glycols such as propylene glycol. These glycols are used alone or as a mixture of two or more.

Monohydric alcohols or monobasic acids are optionally used to construct the polyesters of the present invention. Examples of the monohydric alcohol include butanol, hexanol, isohexanol, heptanol, octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, 2-methyloctanol,
Monohydric alcohols having 4 to 18 carbon atoms such as decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol and the like can be mentioned, and one or a mixture of two or more thereof can be used.

The monobasic acids include coconut oil, palm oil, palm kernel oil, cocoa butter, wax, olive oil, kapok oil, castor oil, dehydrated castor oil, rapeseed oil, rice bran oil, cottonseed oil,
C6-C22 aliphatic monobasic acids or acetic acid, butyric acid, isobutyric acid derived from animal and vegetable oils and fats such as soybean oil, safflower oil, linseed oil, tung oil, beef tallow, lard and cod oil or hardened oils thereof. , Heptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid, isostearic acid, and the like, and synthetic monobasic acids having 2 to 18 carbon atoms can be used, and they can be used as one kind or as a mixture of two or more kinds.

Further, the polyester of the present invention may optionally contain glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol,
Trivalent or higher polyhydric alcohols such as trimellitic acid and pyromellitic acid and polybasic acids may be used as the modifier. Further, lactones such as ε-caprolactone, methyl ε-caprolactone and β-methyl δ-valerolactone, or epoxidized methyl stearate, butyl and octyl esters can be appropriately used as a modifier.

The polyester plasticizer (C) of the present invention is
A molecular weight of 600 is obtained by reacting at least one selected from monoglyceride, diglyceride or triglyceride with the above-mentioned respective components as an essential constituent component.
A range of from 1 to 10,000, preferably from 1000 to 5000 is suitable. Such polyesters containing glyceride as an essential component can be produced by various methods.

For example, the above-mentioned glyceride, dibasic acid component, glycol component, and optionally polyester constituent components such as monovalent alcohol or monobasic acid are reacted at once or in reaction of two or three kinds. After that, the remaining components can then be reacted to obtain the targeted polyester. Glyceride is appropriately esterified or transesterified during these reactions to produce the desired polyester.

The reaction of the polyester of the present invention is usually promoted when the reaction is carried out in the presence of a metal catalyst. Examples of the metal catalyst include acid catalysts such as paratoluene sulfonic acid and phosphoric acid, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, zinc chloride and the like. The reaction is usually 100 to 250 ° C, preferably 130 to 250 ° C.
It is done by heating to.

The amount of glyceride used in the polyester plasticizer (C) of the present invention is 1 to 70% by weight, preferably 3 to 50% by weight, based on the polyester component. If the amount of glyceride used is less than 1% by weight, the uniformity and density of the foam cells will be insufficient, and if it exceeds 70% by weight, bleeding will occur and the surface of the foam will be contaminated.

The amount of the polyester plasticizer (C) thus obtained is 1 to 150 parts by weight, preferably 2 to 100 parts by weight, based on 100 parts by weight of the chlorine-containing resin. When the blending amount is 1 part by weight or less, the foaming cell adjusting effect becomes insufficient, and when the blending amount is 150 parts by weight or more, bleeding tends to occur under high temperature and high humidity.

The present invention provides the above polyester-based plasticizer,
It is preferable to use another plasticizer together. Examples of the plasticizer include di (2-ethylhexyl) phthalate, di-normal butyl phthalate, diisononyl phthalate and other phthalate ester systems, and tri (2-ethylhexyl).
Trimellitic acid ester type such as trimellitate, Pyromellitic acid ester type such as tetra (2-ethylhexyl) pyromellitate, Aliphatic dibasic acid ester type such as di (2-ethylhexyl) adipate, Phosphate ester such as tricresyl phosphate Examples of the plasticizer include epoxy resins such as epoxidized soybean oil, polyester resins other than the component (C) of the present invention, and chlorinated paraffin resins.
0 to 150 parts by weight with respect to 100 parts by weight of the chlorine-containing resin,
It is preferably 20 to 100 parts by weight. These plasticizers can be used alone or as a mixture of two or more kinds.

Further, the composition of the present invention may contain stabilizers, fillers, pigments and other additives used in the field of processing halogen-containing resins.

[0034]

EXAMPLES In order to further clarify the features of the present invention, examples will be specifically described below. All "parts" in the text are based on weight.

First, in Reference Examples 1 to 7, a polyester plasticizer (C) was produced. Reference Example 1 730 parts of adipic acid, 218 parts of 1,3-butanediol, 218 parts of 1,4-butanediol, 88.6 parts of linseed oil and 169 parts of 2-ethylhexanol were charged into a reaction vessel while stirring in a nitrogen stream. The reaction was carried out for 5 hours while distilling off water produced at 140 to 230 ° C. Next, 0.62 parts of dibutyltin oxide was added and reacted at 220 to 230 ° C. until the acid value became 15 or less. Further, the reaction was carried out at that temperature under reduced pressure of 100 to 5 mmHg for 6 hours while removing the distillate. Then, filtration was performed to obtain a polyester having the following properties. Viscosity (25 ° C., cps); 3210 Acid value; 0.30 Reference Example 2 730 parts of adipic acid, 484 parts of 3-methyl-1,5-pentanediol, glycerin 92 parts, linseed oil 886 parts and a catalyst in a reaction vessel. Polyester component 0.0
0.66 parts of dibutyltin oxide corresponding to 3% was charged all at once, and the reaction was carried out for 8 hours until the acid value became 15 or less while distilling off water produced at 140 to 230 ° C. under stirring in a nitrogen stream. It was

Next, at 220 to 230 ° C., 100 to 5 mmHg
The reaction was continued for 5 hours under reduced pressure while removing the distillate. Then, filtration was performed to obtain a polyester having the following properties. Viscosity (25 ° C, cps); 1910 Acid value; 0.66 Reference Example 3 Adipic acid 730 parts, 1,3-butanedio-in a reaction vessel.
90 parts, 3-methyl 1,5-pentanediol 454
And 46 parts of glycerin were charged and stirred in a nitrogen stream,
The reaction was carried out for 5 hours while distilling off water produced at 140 to 230 ° C.

Then, 880 parts of dehydrated castor oil and 0.17 part of tetraisopropyl titanate were added to 220 to 230.
Under reduced pressure of 100 ~ 5mmHg at ℃ 5 while removing the distillate
Reacted for hours. Then, filtration was performed to obtain a polyester having the following properties. Viscosity (25 ° C, cps); 2040 Acid value; 0.26 Reference Example 4 Adipic acid 730 parts, 1,4-butanedio-in a reaction vessel.
194 parts, 3-methyl 1,5-pentanediol 31
9 parts, 46 parts of glycerin and 660 parts of palm oil were charged, and the reaction was carried out for 5 hours while stirring in a nitrogen stream while distilling off the produced water at 140 to 230 ° C. Then, 0.58 part of dibutyltin oxide corresponding to 0.03% of the polyester constituent was added as a catalyst and reacted at 220 to 230 ° C. until the acid value became 15 or less. 1 at that temperature
The mixture was reacted for 6 hours under a reduced pressure of 00 to 5 mmHg while removing the distillate. Then, filtration was performed to obtain a polyester having the following properties. Freezing point: 30 ° C. Acid value: 0.26 Reference Example 5 Adipic acid 730 parts, 1,3-butanedio-in a reaction vessel.
185 parts, 1,4-butanediol 185 parts, glycerin 92 parts, and linseed oil 886 parts were charged and reacted for 5 hours while stirring in a nitrogen stream while distilling off water produced at 140 to 230 ° C. . Then dibutyltin oxide 0.
62 parts was added and the reaction was carried out at 220 to 230 ° C. until the acid value became 15 or less. Further, the reaction was carried out at that temperature under reduced pressure of 100 to 5 mmHg for 6 hours while removing the distillate. Then, filtration was performed to obtain a polyester having the following properties. Viscosity (25 ° C, cps); 2010 Acid value; 0.40 Reference Example 6 Adipic acid 730 parts, neopentyl glyco-in a reaction vessel.
252 parts, 3-methyl 1,5-pentanediol 28
6 parts, glycerin 46 parts, soybean oil 886 parts, and 2-ethylhexanol 52 parts were charged, and the mixture was stirred in a nitrogen stream under stirring to give 1
The acid value is 30 while distilling off water generated at 40 to 230 ° C.
Reacted until below.

Then, tetraisopropyl titanate 0.
18 parts were added, and the mixture was reacted at 220 to 230 ° C. under reduced pressure of 100 to 5 mmHg for 7 hours while removing the distillate. After this,
A polyester having the following properties was obtained by filtration. Viscosity (25 ° C., cps); 1450 Acid value; 0.23 Reference Example 7 For comparison, a polyester plasticizer from which the glyceride was removed from the polyester constituents of Reference Example 1 was obtained as follows.

In a reaction vessel, 730 parts of adipic acid, 573 parts of 3-methyl-1,5-pentanediol, 169 parts of 2-ethylhexanol and 0.44 of dibutyltin oxide corresponding to 0.03% of polyester constituents as a catalyst.
All parts were charged together and stirred in a nitrogen stream at 140-23.
While distilling off water generated at 0 ° C., the reaction was carried out for 8 hours until the acid value became 15 or less.

Then, at 220 to 230 ° C., 100 to 5 mmHg
The reaction was continued for 5 hours under reduced pressure while removing the distillate. Then, filtration was performed to obtain a polyester having the following properties. Viscosity (25 ° C, cps); 3980 Acid value; 0.66

Next, in Examples 1 to 6, chlorine-containing resin foams were prepared and evaluated. Examples 1 to 6 For the polyester plasticizers obtained in Reference Examples 1 to 6, sol foam sheets were prepared according to the following formulation and foaming conditions, the expansion ratio was measured by the thickness, and the foam cell state of the cross section of the foam sheet was determined. The evaluation was performed visually. The results are shown in Table 1, Table 2, Table 3 and Table 4.

(Compounding) Vinyl chloride resin: 100 parts Zeon 121 Plasticizer DOP manufactured by Nippon Zeon Co., Ltd. DOP; 75 parts Foaming agent Azodicarbon Amide: 4 parts Uniform AZ-S polyester plasticizer manufactured by Otsuka Chemical Co., Ltd. 5 parts Stabilizer (liquid Ba / K / Zn-based composite); 3 parts Dainippon Ink and Chemicals, Inc. Grec ML-911 (molding conditions) After adjusting the vinyl chloride sol by mixing the above ingredients with a vacuum mixer , 0.3 using a knife coater
A sheet of mm was obtained.

Semi-cure; 130 ° C. × 1 minute Foaming; 220 ° C. × 1 minute or 2 minutes, or 2
30 ° C x 1 minute

[0044]

[Table 1] The abbreviations in the table are as follows.

AA: adipic acid, 3MPD: 3-methyl
-1,5-Pentanediol, 13BD: 1,3-butanediol, 14BD: 1,4-butanediol, linseed: linseed oil, DCO: dehydrated castor oil, palm: palm oil,
SBO: Soybean oil

[0046]

[Table 2] The cell state was judged as ○ when the cell size was small and uniform, and as × when the cell size was large and non-uniform.

Comparative Example 1 With respect to the polyester type plasticizer obtained in Reference Example 7, a sheet was prepared according to the same composition and foaming conditions as in Example,
An evaluation was made. The results are shown in Tables 3 and 4.

Comparative Example 2 A sheet was prepared and evaluated according to the same formulation and foaming conditions as in Example except that 80 parts of DOP was used instead of using the polyester plasticizer. The results are shown in Tables 3 and 4.

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

EFFECTS OF THE INVENTION The chlorine-containing resin foam composition of the present invention, when foamed by heating, can provide a foam having uniform and dense foam cells without problems in processing and environment.
It has extremely high utility value in the applied processing field.

Claims (6)

[Claims] 1. A chlorine-containing resin (A), a foaming agent (B), and a polyester plasticizer (C) containing at least one glyceride selected from the group consisting of monoglycerides, diglycerides and triglycerides as a reaction component. A chlorine-containing resin foam composition comprising. 2. With respect to 100 parts by weight of the chlorine-containing resin (A),
The composition for a chlorine-containing resin foam according to claim 1, wherein the polyester plasticizer (C) is used in an amount of 1 to 150 parts by weight. 3. The chlorine-containing resin foam composition according to claim 1, wherein the polyester plasticizer (C) contains 1 to 70% by weight of glyceride as a reaction component. 4. The composition for a chlorine-containing resin foam according to any one of claims 1 to 3, wherein the glyceride is triglyceride. 5. Triglyceride is used as animal and vegetable oils and fats and / or
Alternatively, the composition for a chlorine-containing resin foam according to claim 4, comprising a hardened oil thereof. 6. Triglyceride is linseed oil, soybean oil,
The chlorine-containing resin foam composition according to claim 4, which is at least one selected from the group consisting of tung oil, dehydrated castor oil, coconut oil, palm oil, and palm kernel oil.