JPH05202258A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in flow in melting and capable of giving a molding having non-deteriorating heat resistance by mixing a vinyl chloride resin with a specified hydrogenated terpene resin. CONSTITUTION:100 pts.wt. vinyl chloride resin is mixed with 2-15 pts.wt. chlorinated hydrogenated terpene resin prepared by chlorinating a hydrogenated terpene resin of formula I (wherein n is a positive integer of 10 or below) or hydrogenated terpene/phenol copolymer of formula II (wherein m and p are positive integers of 7 or below) to obtain a vinyl chloride resin composition. This composition is excellent in flow in melting and capable of giving a molding having non-deteriorating excellent heat resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for molding, which has excellent fluidity during molding and does not reduce the heat resistance of a molded product obtained by molding.

[0002]

2. Description of the Related Art Vinyl chloride resins are used for weather resistance, water resistance,
A molded product molded by an extrusion molding method, an injection molding method or the like is widely used for various purposes because it has excellent mechanical strength and is flame retardant.

However, the vinyl chloride resin has a better heat resistance than the other general-purpose thermoplastic resins such as polyolefin, but has a problem that the flowability during molding is poor and the moldability is poor. ..

By the way, the simplest method for improving the fluidity of a vinyl chloride resin at the time of molding is to lower the degree of polymerization of the vinyl chloride resin. There is a problem that the impact strength of the molded product is reduced. Further, a plasticizer or a lubricant is added to the vinyl chloride resin to improve the fluidity, but in this case, there is a problem that the heat resistance is significantly lowered.

Therefore, a vinyl chloride resin composition has been proposed in which 0.1 to 20 parts by weight of polyvinyl acetate is added to 100 parts by weight of polyvinyl chloride (JP-A-60-7905).
No. 2).

[0006]

By the way, the above vinyl chloride resin composition has improved moldability because it has improved thermal stability during molding, but its fluidity is not so improved.
Therefore, the moldability was not sufficient.

In view of these points, an object of the present invention is to provide a vinyl chloride resin composition having good fluidity at the time of molding, good moldability, and excellent heat resistance of the obtained molded product. To do.

[0008]

The vinyl chloride resin composition of the present invention is a chlorinated product obtained by chlorinating a hydrogenated terpene resin represented by the following formula (1) with respect to 100 parts by weight of a vinyl chloride resin. The hydrogenated terpene resin or the hydrogenated terpene-phenol copolymer represented by the following formula (2) is contained in an amount of 2 to 15 parts by weight.

[0009]

[Chemical 3]

(In the formula, n represents a positive integer of 10 or less.)

[0011]

[Chemical 4]

(In the formula, m and p represent positive integers of 7 or less.) The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride, or a copolymer containing vinyl chloride as a main component. Mention may be made of copolymers with other possible one or more monomers, post-chlorinated polyvinyl chloride, or mixtures of these polymers.

The monomers copolymerizable with the above vinyl chloride include α, such as ethylene, propylene and 1-butylene.
-Olefins, vinyl-based monomers such as vinyl acetate and vinyl stearate, styrene-based monomers such as styrene and α-methylstyrene, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate such as methyl methacrylate. Examples thereof include system monomers, N-substituted maleimide monomers such as cyclohexylmaleimide and phenylmaleimide, ceryl vinyl ether, vinylidene chloride and the like.

Further, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer. It may be a graft copolymer obtained by graft-polymerizing vinyl chloride onto a polymer or polyurethane.

For example, in a copolymer of vinyl chloride and ethylene, when the ethylene content exceeds 15% by weight, the heat resistance of the obtained molded article decreases, so the ethylene content is 15% by weight or less, more preferably It is preferably 9 to 4% by weight. In a copolymer of vinyl chloride and vinyl acetate, when the vinyl acetate content exceeds 5% by weight, the heat resistance of the obtained molded article decreases, so the vinyl acetate content is 5%.
It is preferably not more than 1% by weight, more preferably 1 to 4% by weight. Further, in the post-chlorinated polyvinyl chloride, the degree of chlorination is 72% by weight or less, and more preferably 57 to 68% by weight, because the fluidity is remarkably reduced when it exceeds 72% by weight.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but if it is less than 300, a molded product with sufficient strength cannot be obtained, and if it exceeds 1400, the molding performance is poor.
Generally, a vinyl chloride resin having an average degree of polymerization of 300 to 1400 is used.

As described above, the chlorinated hydrogenated terpene resin is obtained by chlorinating the hydrogenated terpene resin, but the chlorination method is not particularly limited, and for example, vinyl chloride resin can be chlorinated. A chlorination method similar to that for obtaining a chlorinated vinyl chloride resin is adopted. It is considered that this chlorination is performed on hydrogen of either of the two methyl groups of the above formula (1) which is a repeating unit of the hydrogenated terpene resin.

As the hydrogenated terpene resin, a mixture of different n-numbers is often used rather than a single n-number. When n exceeds 10, the chlorinated hydrogenated terpene resin has high heat resistance and low fluidity, and even if it is added to a vinyl chloride resin, the fluidity improving effect is small. However, it is more preferably 3 to 7.

With respect to the degree of chlorination of the chlorinated hydrogenated terpene resin, if the degree of chlorination is less than 10% by weight, the hydrogenated terpene resin has a small effect of modifying and the compatibility with the vinyl chloride resin is poor. Since the compatibility with the vinyl chloride resin is poor even when it exceeds 40% by weight, the range is preferably 10 to 40% by weight, more preferably 15 to 30% by weight.

Regarding the amount of the chlorinated hydrogenated terpene resin added to the vinyl chloride resin, vinyl chloride resin 1
If it is added in an amount of more than 15 parts by weight with respect to 00 parts by weight, slipperiness at the time of molding becomes too strong and molding becomes difficult, and if the amount added is less than 2 parts by weight, the fluidity is not sufficiently improved. 0.05 to 100 parts by weight of resin
It is 2 parts by weight, preferably 3 to 10 parts by weight.

In the hydrogenated terpene-phenol copolymer, m and p in the above formula (2) are positive integers of 7 or less, but the hydrogenated terpene-phenol copolymer in which p exceeds 7 is used. Has a low fluidity, and the effect of improving the fluidity is small even when it is added to a vinyl chloride resin, and the preferable p number is 2 to 5.

Regarding the amount of the hydrogenated terpene-phenol copolymer to be added to the vinyl chloride resin, if it is added in excess of 15 parts by weight per 100 parts by weight of the vinyl chloride resin, the slipperiness during molding becomes too strong. Molding becomes difficult, 2
Since the improvement of fluidity is not sufficient with an addition amount of less than parts by weight,
As described above, the amount is 0.05 to 2 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin composition of the present invention comprises
If necessary, heat stabilizers such as conventionally used organic compounds, lubricants such as stearic acid esters and polyethylene wax, acrylonitrile-butadiene-styrene copolymer ( ABS) and methyl methacrylate-butadiene-
A modifier such as styrene copolymer (MBS) and a filler such as glass fiber and calcium carbonate are added together.

As a method for molding a molded body from the vinyl chloride resin composition of the present invention, a conventional method can be adopted. For example, an extrusion molding method, an injection molding method, and the like.

[0025]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, parts by weight will be referred to as parts.

Examples 1 to 6 The composition as shown in Table 1 was mixed with a Henschel mixer (trade name) at 60 ° C. for about 15 minutes. Then, using a roll of 8 inches in diameter, the mixture was kneaded at 180 ° C. for 3 minutes to produce a sheet of about 1 mm, which was cut into pellets.

The following substances were used as shown in Table 1. Polyvinyl chloride: average degree of polymerization 540 V-E-Vc copolymer: vinyl chloride-ethylene-vinyl acetate copolymer, average degree of polymerization 500, vinyl chloride content 9
2.5% by weight, ethylene content 5.6% by weight Chlorinated hydrogenated terpene resin: Hydrogenated terpene resin having a number average molecular weight of 700 (Clearon P125: manufactured by Yasuhara Chemical Co., Ltd.) is chlorinated at 15% and 35%, respectively. Dibutyltin malate: RC40FT (manufactured by Sansha Machinery Synthesizer) Dibutyltin mercapto: JF-9B (manufactured by Sansha Machinery Synthesizer) Butyl stearate: Exepearl BS (manufactured by Kao Corporation) Stearyl alcohol: Calcol 86 (Kao Corporation) Ester lubricant: Roxyol G70S (manufactured by Henkel Hakusui Co., Ltd.) For the fluidity evaluation of each vinyl chloride resin composition, the above pellets were supplied to a Koka type flow tester, and a diameter of 1
mm, length 10mm die, load 150kg / c
It depends on the result of measuring the discharge rate (cc / sec) per unit time at m ² and a temperature of 180 ° C.

Regarding the evaluation of heat resistance, the above
180 ℃, 150kg / cm ²Press-mold with
A test piece is prepared, and the test piece is compliant with JIS-K-7206.
The softening temperature (° C) was measured.

The results are shown in Table 1. Comparative Examples 1 to 4 The following compounding compositions were used except that no chlorinated hydrogenated terpene resin was used as shown in Table 1 or 20 parts were added to 100 parts of vinyl chloride resin as shown in Table 1. Same as Examples 1 to 6.

The results are shown in Table 1. When 20 parts of the chlorinated hydrogenated terpene resin was used, the slipperiness was so strong that roll forming was difficult and a sheet could not be obtained, and the physical properties could not be measured.

[0031]

[Table 1]

Examples 7 to 10 Hydrogenated terpene-phenol copolymers (number average molecular weight 600, YS Polystar TH130, manufactured by Yasuhara Chemical Co.) were added in the proportions shown in Table 2 instead of the chlorinated hydrogenated terpene resin. Except for the above, the same procedures as in Examples 1 to 6 were performed.

The results are shown in Table 2. Comparative Examples 5 and 6 Instead of the chlorinated hydrogenated terpene resin, hydrogenated terpene-phenol copolymer (number average molecular weight 600, YS Polystar TH130, manufactured by Yasuhara Chemical Co., Ltd.) was added as shown in Table 2, respectively, except that 20 parts were added. Same as Examples 1 to 6.

In any of the cases, the lubricity was too strong, roll forming was difficult, and a sheet could not be obtained, and the physical properties could not be measured.

[0035]

[Table 2]

As is clear from the above results, the vinyl chloride resin composition of the present invention does not impair heat resistance and has good fluidity. On the other hand, when the chlorinated hydrogenated terpene resin or hydrogenated terpene-phenol copolymer is not added, the fluidity is poor,
When 0% was added, the slipperiness was too strong and roll forming could not be difficult.

[0037]

Industrial Applicability As described above, the vinyl chloride resin composition of the present invention has excellent fluidity during heat melting and good moldability, and a molded product having excellent heat resistance can be obtained.

Claims (2)

[Claims] 1. To 2 to 15 parts by weight of a chlorinated hydrogenated terpene resin obtained by chlorinating a hydrogenated terpene resin represented by the following formula (1) with respect to 100 parts by weight of a vinyl chloride resin. A vinyl chloride resin composition comprising: [Chemical 1] (In the formula, n represents a positive integer of 10 or less.) 2. A vinyl chloride containing 2 to 15 parts by weight of a hydrogenated terpene-phenol copolymer represented by the following formula (2) with respect to 100 parts by weight of a vinyl chloride resin. -Based resin composition. [Chemical 2] (In the formula, m and p represent positive integers of 7 or less.)