JPH09124868A - Chlorine-containing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chlorine-containing resin composition capable of reducing adhered depoints in a mold and an extruder generated during a continuous mold processing for a long time and improving physical characteristic together with appearances of molded products by adding two specific kinds of compounds to a chlorine-containing resin. SOLUTION: In this chlorine-containing resin composition, 100 pts.wt. chlorine- containing resin (e.g. polyvinyl chloride) is blended with (A) 0.01-10 pts.wt. α,β-unsaturated dicarboxylic acid anhydride (e.g. maleic anhydride) or, the reaction product of a 2-50C unsaturated hydrocarbon (e.g. 1,3-butadiene) with the α,β-unsaturated dicarboxylic acid anhydride or its hydrogen addition product and (B) 0.01-10 pts.wt. esterified compound between a 6-30C (un)saturated fatty acid (e.g. caproic acid) and a 5-30C neopentyl polyol (e.g.; neopentyl glycol). In addition, a lubricant can be added in a mold processing to reduce lord, etc., on a molding machine. As the lubricant, it is preferable to use a compound obtained by oxidatively modifying a two dimensional copolymer of ethylene/ propylene having 1000-10000 weight average molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a chlorine-containing resin composition. More specifically, the present invention relates to a chlorine-containing resin composition which is excellent in molding processability and can be continuously molded for a long period of time, and at the same time, is excellent in physical properties and appearance improving effects of molded products.

[0002]

BACKGROUND OF THE INVENTION Conventionally, polyvinyl chloride resin products such as pipes, gutters, and sheets have good thermal stability and workability, and at the same time, are very inexpensive in terms of price. , Tribasic lead sulfate, dibasic lead stearate, lead stearate, dibasic lead phosphite, etc., or a mixture of two or more thereof is used. However, lead-based compounds are highly toxic, and it is preferable not to use a lead-based stabilizer from the viewpoints of health care of the person who handles them, and environmental pollution due to elution of lead from the molded product. In fact, the elution of lead from tap stabilizers used in water pipes into tap water has been taken up as a very big social issue, and the use of lead stabilizers in this field is virtually regulated. is the current situation. Under these circumstances, the most recent trend is to use non-toxic or low-toxic stabilizers such as metal soaps such as calcium soap, barium soap, magnesium soap, zinc soap, alkyl tin mercaptides, alkyl tin carboxylates, and alkyl tins. The trend is toward the use of organotin compounds such as malates. However, a vinyl chloride resin composition containing such a stabilizer is inferior in moldability and, particularly when a tin-based stabilizer is used, the organotin compound itself does not have slipperiness, and thus the polyvinyl chloride gel composition A compound that delays oxidization, for example, a fatty acid salt of an alkaline earth metal such as calcium stearate or magnesium stearate, a weight average molecular weight of 1,000 to 10,
000 ethylene / propylene binary copolymers, so-called polyethylene waxes obtained by oxidatively modifying ethylene / propylene binary copolymers having a weight average molecular weight of 1,000 to 10,000 and JP-B-55-17054. Addition of pentaerythritol, ester compounds of dipentaerythritol and higher fatty acids as proposed,
Furthermore, 1 selected from the ethylene / propylene binary copolymers and the oxidation-modified ethylene / propylene binary copolymers.
One or a mixture of two or more kinds and an ester compound, for example, stearyl stearate, behenyl behenate, glycerin tristearate, glycerin monostearate, etc. are used in combination for molding. However, such a combination of compounds is accompanied by long-term continuous moldability, that is, when a long-term molding process is performed, adhesion of an inorganic substance such as a pigment, calcium carbonate, or titanium oxide to a mold / extruder occurs over time. Poor appearance of molded products,
It was difficult to improve the decrease in productivity. In order to solve these problems, compounds that improve the dispersibility of inorganic substances, that is, higher fatty acids, alkali metal salts of higher fatty acids, isobutylene and maleic anhydride as shown in JP-B-55-12469. Improvements such as salts of copolymers have been proposed. However, at present, no composition has been found that is sufficiently satisfactory in terms of long-term continuous moldability, improvement of physical properties, and improvement of appearance of a molded product with a combination of only these compounds.

[0003]

SUMMARY OF THE INVENTION The present invention is intended to solve such a problem, and makes it possible to reduce deposits deposited in a die / extruder during molding of a chlorine-containing resin composition, and The object of the present invention is to provide a chlorine-containing resin composition which improves continuous molding properties for a certain period of time and further satisfies the effects of improving physical properties and appearance of molded products.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that chlorine-containing resins contain α, β-unsaturated dicarboxylic acid anhydrides or unsaturated hydrocarbons. By mixing a reaction product of an α, β-unsaturated dicarboxylic acid anhydride or a hydrogenated product thereof with a saturated or unsaturated fatty acid ester of neopentyl polyol, a mold or It has been found that it is possible to reduce deposits deposited in the extruder, further improve the physical properties of the molded product, and improve the appearance of the molded product, and have completed the present invention based on this finding. That is, the present invention provides (1) 100 parts by weight of a chlorine-containing resin, (A) an α, β-unsaturated dicarboxylic acid anhydride or an unsaturated hydrocarbon having 2 to 50 carbon atoms and an α, β-unsaturated dicarboxylic acid. 0.01 to 10 parts by weight of a reaction product with an anhydride or a hydrogenated product thereof,
And (B) 0.01 to 10 parts by weight of an esterification product of a neopentylpolyol having 5 to 30 carbon atoms and a saturated or unsaturated fatty acid having 6 to 30 carbon atoms. It is intended to provide things. Further, as a preferred embodiment of the present invention, (2) a compound 0.05 to 5 in which 100 parts by weight of a chlorine-containing resin is further oxidatively modified with an ethylene / propylene binary copolymer having a weight average molecular weight of 1,000 to 10,000. The chlorine-containing resin composition according to the item (1), which is prepared by blending parts by weight, can be mentioned.

[0005]

The chlorine-containing resin used in the present invention is not particularly limited, and examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, copolymers of vinyl chloride and olefin, and vinyl chloride and vinyl acetate. Examples thereof include a copolymer, a copolymer of vinyl chloride and vinylidene chloride, and a copolymer of vinyl chloride and an acrylic acid ester or a methacrylic acid ester. The component (A) used in the present invention is α,
It is a reaction product of a β-unsaturated dicarboxylic acid anhydride or an unsaturated hydrocarbon having 2 to 50 carbon atoms with an α, β-unsaturated dicarboxylic acid or a hydrogenated product thereof. Examples of the α, β-unsaturated dicarboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, and the like. Examples of the unsaturated hydrocarbon having 2 to 50 carbon atoms include ethylene, propylene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 2,5-dimethyl. -2,4-
Hexadiene, 1,3,5-hexatriene, 1,3,5,
7-octatetraene, ocimene, etc., or 1-
Butene, 1-hexene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene, 1-hexadecene, 1
Examples include α-olefins obtained by polymerization of ethylene such as -octadecene and 1-eicosene, propylene, butylene, and aliphatic unsaturated hydrocarbons obtained by dehydrogenation of petroleum paraffin. The unsaturated hydrocarbon having 2 to 50 carbon atoms and the α, β-unsaturated dicarboxylic acid anhydride may be used alone or in combination of two or more to obtain an addition reaction product by reacting under pressure. . Furthermore, a hydrogenated product can be obtained by hydrogenating this reaction product using a known catalyst. In the present invention, when the number of carbon atoms of the unsaturated hydrocarbon that reacts with the α, β-unsaturated dicarboxylic acid anhydride exceeds 50, the affinity of the reaction product with the chlorine-containing resin decreases, and the appearance of the molded product becomes poor. Or physical properties may be deteriorated.
In the present invention, the compounding amount of the component (A) per 100 parts by weight of the chlorine-containing resin is 0.01 to 10 parts by weight,
It is preferably 0.1 to 5 parts by weight. If the blending amount of the component (A) is less than 0.01 parts by weight per 100 parts by weight of the chlorine-containing resin, the effect of reducing deposits in the mold / extruder may not be sufficiently exhibited during long-term continuous molding processing. There is.
If the amount of the component (A) to be blended exceeds 10 parts by weight per 100 parts by weight of the chlorine-containing resin, the effect of reducing the deposits in the mold / extruder will not improve in proportion to the increase in the amount of the blended resin. There is a possibility that the various characteristics of the product may deteriorate, for example, the appearance of the molded product may be poor.

The component (B) used in the present invention has 5 to 5 carbon atoms.
It is an esterified product of 30 neopentyl polyol and a saturated or unsaturated fatty acid having 6 to 30 carbon atoms. In the present invention, neopentyl polyol refers to the compound represented by the general formula [1] and its dehydration condensation product.

Embedded image However, in the general formula [1], R ¹ and R ² are an alkyl group having 1 to 15 carbon atoms or a hydroxyalkyl group, and they may be the same or different from each other. Examples of the neopentyl polyol having 5 to 30 carbon atoms include neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane, Trimethylolpropane, trimethylolbutane,
In addition to pentaerythritol and the like, dehydration condensation products of neopentyl polyol typified by ditrimethylolpropane, tritrimethylolpropane, dipentaerythritol, tripentaerythritol and the like can be mentioned. Examples of the saturated fatty acid having 6 to 30 carbon atoms include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotonin. In addition to acids, montanic acid, melissic acid and the like, saturated fatty acids having a functional group other than a carboxyl group such as 12-hydroxystearic acid can be mentioned. As the unsaturated fatty acid having 6 to 30 carbon atoms,
Examples thereof include oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and stearolic acid. An esterification product used as the component (B) in the present invention can be obtained by subjecting neopentyl polyol and saturated or unsaturated fatty acid to an esterification reaction by a known method using one kind or two or more kinds respectively. . In the present invention, the blending amount of the component (B) per 100 parts by weight of the chlorine-containing resin is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.
If the blending amount of the component (B) is less than 0.01 part by weight per 100 parts by weight of the chlorine-containing resin, the appearance of the molded product may be deteriorated due to the decrease in lubricity. When the blending amount of the component (B) exceeds 10 parts by weight per 100 parts by weight of the chlorine-containing resin, the appearance of the molded product does not improve in proportion to the increase in the blending amount, and the various properties of the molded product are rather deteriorated. This may lead to deterioration of the physical properties of the molded product.

In the present invention, other lubricants may be blended in order to reduce the load applied to the molding machine during the molding process. Examples of other lubricants include ethylene / propylene binary copolymers having a weight average molecular weight of 1,000 to 10,000, and weight average molecular weights of 1,000 to 10,
Of so-called polyethylene waxes such as compounds obtained by oxidatively modifying 000 ethylene / propylene binary copolymers,
Paraffin waxes having a weight average molecular weight of less than 1,000, higher alcohols such as stearyl alcohol and behenyl alcohol, stearyl stearate, behenyl behenate, glycerin tristearate, glycerin monostearate and other ester compounds, higher carboxylic acids, Examples thereof include amides. Among these, a compound obtained by oxidatively modifying an ethylene / propylene binary copolymer having a weight average molecular weight of 1,000 to 10,000 can be particularly preferably used. In the present invention, the blending amount of the other lubricant per 100 parts by weight of the chlorine-containing resin is
It is preferably 0.05 to 5 parts by weight, and 0.2 to 1.
It is more preferably 5 parts by weight. If the blending amount of the other lubricant is less than 0.05 parts by weight per 100 parts by weight of the chlorine-containing resin, the appearance of the molded product may be deteriorated due to the decrease in lubricity. When the amount of the other lubricant compounded exceeds 5 parts by weight per 100 parts by weight of the chlorine-containing resin, the appearance of the molded product does not improve in proportion to the increase in the compounded amount, and the various properties of the molded product are rather deteriorated. The physical properties of the product may deteriorate. The chlorine-containing resin composition of the present invention is prepared by a method in which the chlorine-containing resin and the component (A), the component (B) and other additives, such as a stabilizer, a lubricant and a pigment, are blended together. Or, the component (A), the component (B) and other additives such as stabilizers, lubricants, pigments, etc. are first mixed to prepare a so-called one-pack product, and then the one-pack product is mixed with a chlorine-containing resin. It can be based on the method of blending. The chlorine-containing resin composition of the present invention, various stabilizers within the range not impairing the features of the invention, for example, metal soaps such as calcium soap, barium soap, magnesium soap, zinc soap, alkyl tin mercaptide, alkyl tin carboxy. Rate, organotin compounds such as alkyltin maleate, organophosphorus compounds, epoxy compounds, polyol compounds, β-diketone compounds,
Nitrogen-containing compounds, sulfur-containing compounds, etc., or fillers such as calcium hydroxide, calcium carbonate, talc, hydrotalcite, etc., as well as pigments, antistatic agents, processability improvers, flame retardants, UV inhibitors, etc. can do.

[0008]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples and comparative examples, the resin compositions were evaluated according to the following methods. (1) Long-run molding processing test The prepared polyvinyl chloride resin composition was subjected to a pipe extrusion molding test using a Labo Plastmill tester 30C150 manufactured by Toyo Seiki Seisakusho. The test conditions were as follows. Extrusion torque, extrusion pressure, and resin temperature were measured, and the state of adhesion of inorganic substances to the mold / extruder after the molding test was visually evaluated. Furthermore, the appearance of the molded product was evaluated, and the falling strength of the molded product was measured. The evaluation criteria are as shown below. (Extrusion test conditions) Screw: Biaxial in different directions, parallel type, L / D = 2
5 Die: VP-20, straight die Set temperature: C1; 160, C2; 170, C3; 17
5, D; 180 Screw rotation speed: 30 rpm Test time: 6 hours (2) Long-run moldability (adhesion to mold / extruder) ◯: No adhesion is present in the mold / extruder. Δ: There is a slight amount of deposit in the die / extruder. X: A large amount of deposits are present in the die / extruder. (3) Appearance of molded product A: The surface of the molded product is glossy. ◯: The surface of the molded product is smooth although it has little gloss. Δ: The surface of the molded product is not glossy and wavy. X: The surface of the molded product is blunt. (4) Drop Weight Strength of Molded Article After cooling the molded pipe in ice water for 2 hours, a drop weight strength test was performed using a cylindrical weight having a weight of 1.0 kg. The evaluation method is JWWA, a test method prescribed by the Japan Water Works Association.
Test piece 25 is performed by the method based on K-118.
The book is evaluated by the height at which it breaks by 50%. Production Example 1 (Addition reaction of unsaturated hydrocarbon with α, β-unsaturated dicarboxylic acid anhydride) 54 g (1 mol) of 1,3-butadiene and 98 g (1 mol) of maleic anhydride were charged into an autoclave, The reaction was carried out at 200 ° C. for 6 hours under a nitrogen atmosphere. The acid value of the obtained reaction product was 739 mgKOH / g. This compound is designated as Compound A-2. Production Example 2 (hydrogenation reaction) After the addition reaction of 1,3-butadiene and maleic anhydride was carried out in the same manner as in Production Example 1, hydrogenation was further conducted at 200 ° C for 2 hours using a nickel catalyst. The acid value of the obtained reaction product was 723 mgKOH / g. This compound is designated as Compound A-1. Production Example 3 (Addition reaction between unsaturated hydrocarbon and α, β-unsaturated dicarboxylic acid anhydride) 112 g (1 mol) of 1-octene and 98 maleic anhydride
g (1 mol) was charged in an autoclave and reacted at 200 ° C. for 6 hours under a nitrogen stream. After the reaction was completed, the unreacted material was removed under reduced pressure to obtain the desired reaction product. The acid value of the obtained reaction product was 520 mgKOH / g.
This compound is designated as Compound A-3. Production Example 4 (Addition reaction of unsaturated hydrocarbon with α, β-unsaturated dicarboxylic acid anhydride) 168 g (1 mol) of 1-dodecene and 98 maleic anhydride
g (1 mol) and charged into an autoclave, Production Example 3
A reaction product was obtained in the same manner as in. The acid value of the obtained reaction product was 386 mgKOH / g. This compound is designated as Compound A-4. Table 1 shows the raw material compounds of Production Examples 1 to 4, the presence or absence of hydrogenation, and the acid value of the reaction product. The compounds A-1 to A-5 shown in Table 1 were used in the following Examples and Comparative Examples.

[0009]

[Table 1]

Table 2 shows the compound name, acid value and hydroxyl value of compounds B-1 to B-6 which are the compounds of component B used in the examples and comparative examples.

[0011]

[Table 2]

Example 1 Polyvinyl chloride [Dai-ichi PVC Sales Co., Ltd., 103EP] 10
0 parts by weight, dioctyl tin mercaptide 1.0 parts by weight,
Calcium stearate 0.6 parts by weight, pigment [Dainichi Seika Kogyo KK, PMP gray] 0.3 parts by weight, calcium carbonate 3.0 parts by weight, oxidized polyethylene wax [Mitsui Petrochemical Industry Co., Ltd., Hi-Wax 220MP ] 0.2 parts by weight, 0.3 parts by weight of compound A-1 and 2.0 parts by weight of compound B-6 were blended and mixed by a 75 L Henschel mixer to prepare a polyvinyl chloride resin composition. A long-run molding test was conducted on this polyvinyl chloride resin composition, and it was found that the extrusion torque was 2.3 kg · m and the extrusion pressure was 7
The resin temperature was 0.8 kg / cm ² , and the resin temperature was 180.1 ° C. The surface of the obtained pipe is glossy, and after extrusion for 6 hours,
There was no deposit in the die / extruder. Further, when the falling pipe strength test was conducted on the obtained pipe, the falling weight strength was 68 cm. Examples 2 to 8 and Comparative Examples 1 to 3 In the same manner as in Example 1, the formulations having the compositions shown in Table 3 were mixed with a 75L Henschel mixer to prepare a polyvinyl chloride resin composition. A long-run molding test was performed on these compositions to examine the extrusion characteristics, the appearance of molded products was observed for the obtained pipes, and the falling strength of the molded products was measured. The results are shown in Table 3.

[0013]

[Table 3]

[Note] 1) Daiichi PVC Sales Co., Ltd., 103EP 2) Mitsui Petrochemical Industry Co., Ltd., Hi-Wax 220MP
(Compound obtained by oxidative modification of ethylene / propylene binary copolymer, weight average molecular weight of 2,000) From the results shown in Table 3, the chlorine-containing resin composition of the present invention was used in a mold / extruder in a long run molding test. It is recognized that no adhered matter is observed, the molding processability is excellent, and the appearance and falling strength of the molded product are good. Also,
The polyvinyl chloride resin compositions of Comparative Example 1 and Comparative Example 3 in which the component (B) was not blended but the component (A) alone were blended, the appearance of the molded product was poor, and the deposit on the mold / extruder Is attached, and the falling weight strength is low. Further, the polyvinyl chloride resin composition of Comparative Example 2 in which the component (A) was not blended and only the component (B) was blended had a large amount of deposits in the die / extruder,
The falling weight strength is low. From these results, in the polyvinyl chloride resin composition of the present invention in which the component (A) and the component (B) are blended, the synergistic effect of the component (A) and the component (B) causes a mold / extruder even in long-run molding. It can be seen that the appearance and physical properties of the molded product are improved since there is no deposit on the surface. Example 9 Polyvinyl chloride [Daiichi PVC Sales Co., Ltd., 103EP] 10
0 parts by weight, dioctyl tin mercaptide 1.0 parts by weight,
0.6 part by weight of calcium stearate, 0.3 part by weight of pigment [PMP Gray, Dainichiseika Kogyo KK], 3.0 parts by weight of calcium carbonate, 0.2 part by weight of compound A-2 and compound B-6. Was blended in an amount of 1.0 part by weight and mixed by a 75 L Henschel mixer to prepare a polyvinyl chloride resin composition. A long-run molding test was conducted on this polyvinyl chloride resin composition. As a result, the extrusion torque was 3.5 kg · m, the extrusion pressure was 109.8 kg / cm ² , and the resin temperature was 180.4 ° C. The surface of the obtained pipe was glossy, and there was no deposit in the die / extruder after the extrusion molding for 6 hours. Further, when the falling pipe strength test was performed on the obtained pipe, the falling weight strength was 60 cm. Examples 10 to 14 and Comparative Examples 4 to 13 In the same manner as in Example 9, the compositions having the compositions shown in Table 4 were mixed by a 75 L Henschel mixer to prepare polyvinyl chloride resin compositions. A long-run molding test was performed on these compositions to examine the extrusion characteristics, the appearance of molded products was observed for the obtained pipes, and the falling strength of the molded products was measured. The results are shown in Table 4.

[0015]

[Table 4]

[0016]

[Table 5]

[Notes] 1) Daiichi Vinyl Sales Co., Ltd., 103EP 2) Mitsui Petrochemical Industry Co., Ltd., Hi-Wax 220MP
(Compound obtained by oxidative modification of ethylene / propylene binary copolymer, weight average molecular weight 2,000) 3) Sodium salt of styrene / diisobutylene / maleic anhydride terpolymer, weight average molecular weight 100,00
0) From the results in Table 4, in the long-run molding test, the chlorine-containing resin composition of the present invention showed no deposits in the mold / extruder, was excellent in molding processability, and was excellent in the appearance of the molded product. It can be seen that the drop strength is also good. Further, the polyvinyl chloride resin compositions of Comparative Examples 4 to 6 and Comparative Examples 8 to 9 in which the component (A) is not blended and only the component (B) is blended, use conventionally known additives in combination. The appearance and / or long-run moldability of the molded product are poor, and the drop weight strength is low. Further, the polyvinyl chloride resin composition of Comparative Example 7 in which the component (B) was not blended but the component (A) alone was blended, was used in combination with dilauryl adipate.
The appearance of the molded product is poor, the long-run moldability is poor,
The falling weight strength is low. The polyvinyl chloride resin compositions of Comparative Example 10 in which both the component (A) and the component (B) are blended, but the blending amount of the component (A) is small and the blending amount of the component (B) are too large, Long run Moldability is poor and falling weight strength is low. The polyvinyl chloride resin compositions of Comparative Example 11 in which both the component (A) and the component (B) are blended, but the blending amount of the component (A) is too large, and the comparative example 12 in which the blending amount of the component (B) is small, The appearance of the molded product is poor and the falling weight strength is low. From these results, by adding an appropriate amount of component (A) and an appropriate amount of component (B), the components (A) and (B)
It can be seen that the synergistic effect of the components is exerted, and even in long-run molding, there is no deposit on the die / extruder, and the appearance and physical properties of the molded product are improved.

[0018]

EFFECTS OF THE INVENTION The chlorine-containing resin composition of the present invention has good molding processability, particularly long-term continuous molding processability, excellent appearance of molded products, and high impact strength.

Claims (1)

[Claims] 1. 100 parts by weight of a chlorine-containing resin, (A) α,
0.01 to 10 parts by weight of a reaction product of a β-unsaturated dicarboxylic acid anhydride or an unsaturated hydrocarbon having 2 to 50 carbon atoms and an α, β-unsaturated dicarboxylic acid anhydride, or a hydrogenated product thereof, and ( B) A chlorine-containing resin composition, which comprises 0.01 to 10 parts by weight of an esterification product of a neopentyl polyol having 5 to 30 carbon atoms and a saturated or unsaturated fatty acid having 6 to 30 carbon atoms.