JPS59213748A - Vinyl chloride based resin mixture - Google Patents

Abstract

PURPOSE:The titled mixture, obtained by incorporating a vinyl chloride based resin with a trimellitic acid based plasticizer and polyester based plasticizer in combination, having a high flexibility, heat resistance, oil resistance and nonbleeding properties, and useful as insulating materials and film materials in electric wires and cables. CONSTITUTION:A vinyl chloride based resin compound obtained by incorporating 100pts.wt. vinyl chloride based resin with 60-80pts.wt. trimellitic acid based plasticizer and polyester based plasticizer at (3:4)-(1:5) compounding ratio. The polymerization degree of the resin is preferably 2,000-3,000. Furthermore, 1- 10pts.wt. antimony trioxide, etc. and 2-5pts.wt. barium-zinc based stabilizer, etc. are incorporated therein.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to vinyl chloride resins, such as straight PVO
By combining a trimellitic acid plasticizer and a polyester plasticizer in a certain ratio with ethylene/vinyl chloride copolymer, etc., it is possible to achieve high flexibility, heat resistance,
This product has excellent oil resistance and non-bleeding properties, and is useful for, for example, insulating materials and sheath materials for electric wires and couples, as well as ordinary film materials, sheet materials, floor materials, etc.

<Problems with the prior art> As described above, vinyl chloride resin mixtures are required to have not only high flexibility but also sufficient heat resistance, oil resistance, non-bleeding properties, etc., depending on the application. In some cases,
Conventionally, there has been no suitable product that satisfies each of these conditions at the same time.

Conventionally, in order to obtain flexibility in this type of vinyl chloride resin mixture, a large amount of plasticizer is often mixed in. At that time, depending on the plasticizer, by mixing a large amount with
It was said that the so-called bleed phenomenon occurs in which the plasticizer oozes out to the surface.

When heat resistance is required in addition to flexibility, conventionally, a composition in which a large amount of trimellitic acid plasticizer is mixed alone has been prepared and used. had extremely poor oil resistance. In addition, when oil resistance is required in addition to flexibility, a composition in which a large amount of a polyester plasticizer is mixed alone has been prepared and used, but in this composition, Heat resistance was insufficient and bleeding was likely to occur.

Therefore, it is considered that both the heat resistance and oil resistance of the vinyl chloride resin mixture can be improved by using the trimellitic acid plasticizer and the polyester plasticizer together and mixing them together.

However, if the two plasticizers are simply used together, the total amount of plasticizer increases, and there is a great possibility that a bleed phenomenon will occur, and each of the plasticizers is generally expensive.
The mixture itself becomes extremely expensive. Conversely, if the total amount of both plasticizers is reduced, sufficient flexibility cannot be obtained. Furthermore, if the blending ratio is not appropriate, heat resistance and oil resistance cannot be obtained. In other words, the desired flexibility, heat resistance, oil resistance, and non-bleeding property may not always be obtained simply by using both in combination.

Therefore, the present inventors have determined what is the appropriate blending ratio of both the trimellitic acid plasticizer and the polyester plasticizer, and what total blending amount is appropriate for the base resin of vinyl chloride resin. I paid attention to this question and carefully considered it.

First, mixtures with the following formulations were prepared with various blending ratios of trimellitic acid plasticizer and polyester plasticizer, and flexible Rigidity modulus (
When measured at 5℃), the result was ``C'' as shown in curve A in Figure 1.The higher the value of the rigidity modulus, the harder it is.
It means less flexibility.

<Mixture composition> Ethylene/vinyl chloride copolymer 100 parts by weight (P=
2800) Epoxidized fat bean oil 51 Barium/zinc stabilizer 51 Filler
25 l From the above curve A, the blending ratio of trimellitic acid plasticizer and polyester plasticizer is 3:4 (100:1
33) In the range of 1:5 (100:500), that is, when the proportion of the polyester plasticizer in both plasticizers is about 57.1 to 83.3 inches, good flexibility can be obtained. It was found that

Similarly, the total blending amount of both plasticizers was 70 parts by weight and 60 parts by weight.
When the parts by weight were also measured, the results were as shown in curve B1 and curve C in Figure 1. From these curves B and 0, it was found that good flexibility can be obtained when the blending ratio of trimellitic acid plasticizer and polyester plasticizer is in the range of 3:4 to 1:5. Also, regarding the total blending amount, from the point of view of rigidity, sufficient flexibility can be obtained at around 80 parts by weight, and there is no need to exceed the limit. So,
It has been found that there is a possibility that sufficient flexibility may not be obtained.

<Objective of the Invention> The present invention was made in view of the above facts, and it is possible to improve flexibility by combining a trimellitic acid plasticizer and a polyester plasticizer in a vinyl chloride resin mixture. The purpose is to provide a product that has high heat resistance, oil resistance, and non-bleeding properties.

<Summary of the Invention> The vinyl chloride resin mixture according to the present invention comprises a vinyl chloride resin base resin, a trimellitic acid plasticizer and a polyester plasticizer in a blending ratio of 3:4 to 1:5. The composition is characterized by being mixed in a total amount of 60 to 80 parts by weight based on 100 parts by weight of the base resin.

That is, in the present invention, by using the above-mentioned plasticizers in combination at a mixing ratio of 314 to 1:5, it is possible to improve the composition of insulator materials for electric wires and cables, for example, with a smaller amount than when each of the above-mentioned plasticizers is used alone. , flexibility, heat resistance, oil resistance, etc. required for sheath materials, film materials, sheet materials, floor materials, etc. In addition, since only a small amount is required, this vinyl chloride resin mixture can be used as a fusible material.

There is no risk of lead phenomena occurring, non-bleeding properties are obtained, and the cost is low.

The blending ratio of the trimellitic acid plasticizer and the polyester plasticizer is 3:4 to 1:5, and the total blending ratio is 6 parts by weight to 100 parts by weight of the vinyl chloride resin pace resin.
The reason why the amount is set to 0 to 80 parts by weight is that, as is clear from the above-mentioned experimental examples, high flexibility and desired heat resistance and oil resistance can be obtained in this range.

The trimellitic acid plasticizer used in the present invention may be one that, when mixed with a vinyl chloride resin, not only gives the resin mixture flexibility but also improves heat resistance. Examples include trioctyl acid, tridecyl trimellitate, trinonyl trimellitate, and the like.

Further, the polyester plasticizer used in the present invention may be one that improves not only flexibility but also oil resistance of the resin mixture when mixed with vinyl chloride resin, for example,
Examples include polypropylene adibe (PPA), polypropylene sebacate (Pps), and modified esters thereof.

Furthermore, the vinyl chloride resin used in the present invention is not limited to vinyl chloride homopolymers such as Stray PTA.
Copolymers with other polymers may also be used. It may also be a cross-linked material, such as an engineered RV. The degree of polymerization of the resin is preferably about C12,000 to C3,000 in terms of the ability to retain the plasticizer and mechanical properties at high temperatures.

In addition, the vinyl chloride resin mixture may be mixed with various compounding agents suitable for its use, such as flame retardants, stabilizers, fillers, etc., to impart other necessary properties as appropriate. . For example, when using this resin mixture as an insulator material or sheath material for electric wires and cables, antimony trioxide or the like is added as a flame retardant to the base resin 1.
It is preferable to mix about 1 to 10 parts by weight per 00 parts by weight to make the resin mixture flame retardant.

In such a case, about 2 to 5 parts by weight of a barium-zinc stabilizer that does not have a decomposing effect on the plasticizer may be added to 100 parts by weight of the base resin to prepare the resin mixture. It is more preferable to stabilize the mixed state of. Further, in this case, it is more preferable to add about 2 to 5 parts by weight of something like epoxidized arrow bean oil (ffisBo) in terms of stability.

Furthermore, this vinyl chloride resin mixture is blended with fillers such as clay, calcium carbonate, talc, etc.
It is also possible to increase the amount and improve processability. The filler may be selected depending on the use of the resin mixture, and may be blended in an appropriate amount. For example, when using the above-mentioned insulator material and sheath material for a button, for example, clay 1133 etc.
Approximately 30 parts by weight may be added.

<Example> In accordance with the formulation shown in Table 1 below, the present inventors prepared Example 1 in which the blending ratio of trimellitic acid plasticizer and polyester plasticizer (average molecular weight: 2500) was 3:4.
(100:133), and the total tt blend t of both is the ethylene/vinyl chloride copolymer (polymerization degree 2) of the pace resin.
800) A vinyl chloride resin mixture was prepared in a proportion of 80 parts by weight to 100 parts by weight.

In addition, as Example 2, the blending ratio of the limellitic acid plasticizer and the polyester plasticizer (<Q) was 3:4 (
100:133), and the total blending amount of both is 70 parts by weight per 100 parts by weight of the base resin. l! Furthermore, as Example 3, the blending ratio of the trimellitic acid plasticizer and polyester softener is 5:7 (100:140), and the total blending amount of both is based on 100 parts by weight of the base resin. A resin blend of 60 parts by weight was prepared.

For comparison, the present inventors prepared a vinyl chloride resin mixture as Comparative Example 1, in which 80 parts by weight of the polyester plasticizer was solely blended with 100 parts by weight of the base resin. As Example 2, 80 parts by weight of the trimellitic acid plasticizer was added to 100 parts by weight of the base resin.
A resin mixture was prepared by blending parts by weight.

Therefore, each of Examples 1-12.3 was tested to see what kind of heat resistance, oil resistance, flexibility, etc. it had.

Regarding heat resistance, the superiority or inferiority of the resin mixture was determined by measuring the residual tensile strength and residual elongation after the resin mixture was left in an apparatus under high temperature conditions of 136° C. for 7 days.

Similarly, oil resistance can be determined by measuring the residual tensile strength and residual elongation of the resin mixture after storing it at a temperature of 100°C for 96 hours in accordance with the UL standard. (I refused.

Regarding the superiority and inferiority of flexibility, please refer to jlTM J) 104
3, we investigated the bending characteristics of electric wires using resin mixtures as insulators by measuring the rigidity at a temperature of 5°C and by measuring the amount of deflection by a deflection test as shown in Figure 2. Well, we each made our own decisions. In this case, the non-bending test is carried out by horizontally fixing one end of the long test piece 1 to the test stand 3 using the fixture 2, and applying a downward load wit to the free end 1a of the test piece 1. , bend the test piece 1 downward,
This is a method of measuring the amount of deflection χ of the test piece 1 (conditions: core wire 4010.08 TA, core thickness 0.8 mm, span (1) 30 mm, load 5 g).

Furthermore, since this resin mixture is often used as an insulating material, it would be useful to measure its volume resistivity, so I decided to investigate its electrical insulation properties as well.

In addition, even if Comparative Example 1.2 was reached, the same measurement tests as in Example 1.2.3 were carried out to determine the heat resistance etc. of Example 1.
．． I decided to compare it with 2.3.

The above results are shown in Table 2 below.

According to Table 2 above, when comparing Example 1 and Comparative Example 1.2, when given in terms of rigidity, even with the same amount of plasticizer, the mixture of the present invention is significantly more flexible. You can see that it is rich in According to this Example 2.3, it can be seen that the plasticizer can provide at least 20% of the flexibility, the same level of flexibility, or more than that of the comparative example. Furthermore, regarding the heat resistance and oil resistance, the composition of Example 1.2.3 was compared with that of Comparative Example 1.2. It shows better heat resistance than Comparative Example 2, and its value is almost the same as Comparative Example 2 with the conventional heat resistant formulation.Also, in terms of oil resistance, it is much better than Comparative Example 2.
It can also be seen that the value of tτ is the same as that of Comparative Example 1.

It can be seen that there is no

The present vinyl chloride resin having the above properties can be used for various materials. For example, conventionally, trimellitic acid 1
When the mixture of the present invention is used in a flexible PvC insulator (insulating layer of electric wire, cable, etc.) containing 00 parts by weight, it has the same flexibility as the conventional one. ,
It can be used even in hot and humid places where it could not be used, and there was no bleed phenomenon. Furthermore, for the sheaths of electric wires and cables that require oil resistance, conventionally PVC mixtures with poor connectivity, or P'VA mixtures with good readability but poor heat resistance, have been used. According to the mixture of the present invention, the plasticizer powder has at least sufficient flexibility and oil resistance, so it has performance comparable to conventional vulcanized rubber, and is suitable for expensive rubber-sheathed electric wires and gooples. Something with the same performance? It becomes possible to manufacture it at low cost. Furthermore, for internal wiring in equipment that requires high readability, PVA mixtures containing 100 parts of trimellitic acid have traditionally been used; However, when the mixture of the present invention was used, the total amount of plasticizer only needed to be about 80 parts by weight to provide the same flexibility, so the problem of plasticizer migration was solved. Nakatsuta.

<Effects of the Invention> As explained above, the vinyl chloride resin mixture according to the present invention contains a trimellitic acid plasticizer and a polyester plasticizer in a blending ratio of 3=4 to 1:5 and the total of both. The blending amount is 1 o of vinyl chloride resin.

From the fact that 60 to 80 parts by weight of each plasticizer is added to the parts by weight, heat resistance and oil resistance are improved. The resin mixture has the readability required for insulator materials, sheath materials, etc., and there is no risk of bleed phenomena, making it even more useful as insulator materials, sheath materials, etc. We are looking at the effectiveness of being able to provide products at low prices.

[Brief explanation of the drawings] Figure 1 shows the results of a vinyl chloride resin mixture containing both a trimellitic acid plasticizer and a polyester plasticizer when the blending ratio of both plasticizers and their total blending ratio are changed. A graph showing changes in rigidity at 5° C., and FIG. 2 is a diagram showing a method of a printing test for a vinyl chloride resin mixture. 11 Figure 2

Claims (1)

[Claims] 1003 parts of vinyl chloride resin and a blending ratio of 3:4 to 1:
5. Trimellitic acid plasticizer and polyester plasticizer 6
A vinyl chloride resin mixture comprising 0 to 80 parts by weight.