JP2017019942A - Polyvinyl chloride resin composition, and wire and cable prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl chloride resin composition that has excellent weather resistance and bleeding resistance even when using terephthalic acid ester as plasticizer, and a wire and a cable prepared therewith.SOLUTION: A wire 10 comprises an insulating layer 2 comprising a polyvinyl chloride resin composition around a conductor 1, where the polyvinyl chloride resin composition has terephthalic acid ester as plasticizer, and the polyvinyl chloride resin composition also has, based on polyvinyl chloride resin 100 pts.mass, the terephthalic acid ester 100 pts.mass or less, silicone oil 0.1 pts.mass or more, and adipic acid ester 1 pts.mass or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a vinyl chloride resin composition and electric wires and cables using the same.

  Vinyl chloride resin (PVC) is a low-cost and flame-retardant material, and is used as a wire coating material by adding a plasticizer to impart flexibility.

  As a plasticizer, di-2-ethylhexyl phthalate (DOP), which is inexpensive and highly compatible with PVC, is mainly used (see, for example, Patent Document 1). In recent years, in addition to the REACH regulations, substances prohibited to use in the RoHS directive are used. In the future, there is a risk that it will be designated, and its future use is in danger.

  Alternatives to DOP include diisononyl phthalate (DINP), which has been used as a wire covering material after DOP (see, for example, Patent Document 2), but DINP is also used in rubber applications and may cause supply tightness. Therefore, practical application of other plasticizers is desired.

  As another plasticizer, there is a plasticizer having a terephthalic acid ester structure having compatibility with PVC equivalent to DOP and DINP (for example, see Patent Documents 3 to 4). Patent Document 5 describes a vinyl chloride resin composition in which di (2-ethylhexyl) terephthalate is blended as a medical instrument.

JP2015-89934A JP 2014-159507 A JP 2003-226788 A Special table 2009-504851 gazette JP 2013-64113 A

However, since the terephthalic acid ester represented by the following general formula (1) is inferior in weather resistance compared to the phthalic acid ester represented by the following general formula (2), there is a problem in using it outdoors for electric wires. (R in each formula represents the number of carbon atoms in the alkyl chain).

  Further, some additives are difficult to be compatible with PVC and terephthalic acid ester, and bleed on the surface of the composition and cause stickiness.

  Therefore, an object of the present invention is to provide a vinyl chloride resin composition having good weather resistance and bleed resistance even when terephthalic acid ester is used as a plasticizer, and an electric wire and cable using the same.

  In order to achieve the above object, according to the present invention, the following vinyl chloride resin composition, and electric wires and cables using the same are provided.

[1] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer,
A vinyl chloride resin composition comprising 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of silicone oil, and 1 part by mass or more of adipic acid ester with respect to 100 parts by mass of the vinyl chloride resin.
[2] The vinyl chloride resin composition according to [1], wherein 0.1 to 2.5 parts by mass of the silicone oil and 1 to 30 parts by mass of adipic acid ester are contained with respect to 100 parts by mass of the vinyl chloride resin. .
[3] The vinyl chloride resin composition according to [1] or [2] above, containing 10 to 100 parts by mass of the terephthalic acid ester with respect to 100 parts by mass of the vinyl chloride resin.
[4] The vinyl chloride resin composition according to any one of [1] to [3], wherein the terephthalic acid ester is a terephthalic acid ester having 8 to 10 carbon atoms per alkyl chain. .
[5] The vinyl chloride resin composition according to any one of [1] to [4], wherein the adipic acid ester is an adipic acid ester having 8 to 10 carbon atoms per alkyl chain. .
[6] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein the terephthalic acid ester is 100 parts by mass or less and the silicone oil is 0.1 part by mass or more with respect to 100 parts by mass of the vinyl chloride resin. The electric wire provided with the insulating layer which consists of a vinyl chloride resin composition containing 1 mass part or more of adipic acid ester.
[7] A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein the terephthalic acid ester is 100 parts by mass or less and the silicone oil is 0.1 part by mass or more with respect to 100 parts by mass of the vinyl chloride resin. A cable having a sheath made of a vinyl chloride resin composition containing 1 part by mass or more of adipic acid ester.
[8] The cable according to [7], including the electric wire according to [6].

  ADVANTAGE OF THE INVENTION According to this invention, even if it uses a terephthalic acid ester as a plasticizer, a weather resistance and bleeding resistance are favorable, and an electric wire and a cable using the same are provided.

It is a cross-sectional view which shows typically an example of the electric wire which concerns on embodiment of this invention. It is a cross-sectional view which shows typically an example of the cable which concerns on embodiment of this invention.

[Vinyl chloride resin composition]
A vinyl chloride resin composition according to an embodiment of the present invention is a vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, and 100 parts by mass of the terephthalic acid ester with respect to 100 parts by mass of the vinyl chloride resin. Hereinafter, 0.1 part by mass or more of silicone oil and 1 part by mass or more of adipic acid ester are contained.

  The present inventor considered that the reason that terephthalic acid ester is inferior in weather resistance is that terephthalic acid ester has a structure in which the carboxyl group of the ester is open, so that it can easily contact water entering from the outside and has high hydrolyzability. .

  Then, in order to suppress the weather resistance deterioration at the time of terephthalic acid ester use, as a result of examining addition about various additives, it discovered that a weather resistance could be improved by adding the silicone oil which is excellent in water repellency.

  However, silicone oil is difficult to be compatible with PVC and terephthalic acid ester, and bleeds on the surface of the composition, causing stickiness.

  Therefore, the vinyl chloride resin composition of the present invention that has both weather resistance and bleed resistance is developed by adding an adipic acid ester that is compatible with both terephthalic acid ester and silicone oil and is compatible with PVC. I was able to.

(Terephthalic acid ester)
The terephthalic acid ester used as a plasticizer in the vinyl chloride resin composition according to the embodiment of the present invention is preferably a terephthalic acid ester having 8 to 10 (C8 to C10) carbon atoms per alkyl chain. It is. If it is less than C8, it is difficult to obtain necessary heat resistance. This is because the smaller the number of alkyl chain carbon atoms, that is, the lower the molecular weight, the more the volatilization of the plasticizer by heating is promoted and the vinyl chloride resin composition is cured. On the other hand, when it is C11 or more, it is difficult to obtain an alcohol necessary for ester synthesis of the plasticizer, and the cost becomes high, so the practicality is low, and C10 or less is preferable.

  The alkyl chain of the terephthalic acid ester may have a straight chain structure or a branched chain structure, but is preferably a branched chain structure. Specifically, di-2-ethylhexyl terephthalate (DOTP) as C8, diisononyl terephthalate (DINTP) as C9, and diisodecyl terephthalate (DIDTP) as C10 are not limited thereto.

  In embodiment of this invention, the addition amount of the said terephthalic acid ester shall be 100 mass parts or less with respect to 100 mass parts of vinyl chloride resins. It is preferable to add 10 parts by mass or more. Addition of silicone oil is effective for adding terephthalic acid ester. However, when the addition amount of terephthalic acid ester exceeds 100 parts by mass, the plasticizer itself bleeds and stickiness occurs on the surface.

(Silicone oil)
As the silicone oil used in the vinyl chloride resin composition according to the embodiment of the present invention, for example, dimethyl silicone oil, methyl hydrogen silicone oil, and methylphenyl silicone oil are suitable. The silicone oil is not limited to straight silicone oil, and may be modified silicone oil.

  In the embodiment of the present invention, the amount of the silicone oil added is required to be 0.1 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. If the amount added is less than 0.1 parts by mass, the required weather resistance cannot be obtained. Moreover, it is preferable that the addition amount is 2.5 parts by mass or less. When it exceeds 2.5 parts by mass, a problem is likely to occur in workability.

(Adipic acid ester)
As the adipic acid ester used in the vinyl chloride resin composition according to the embodiment of the present invention, an adipic acid ester having 8 to 10 (C8 to C10) carbon atoms per alkyl chain is suitable.

  The alkyl chain of the adipic acid ester may be a straight chain structure or a branched chain structure, but is preferably a branched chain structure. Specific examples include di-2-ethylhexyl adipate (DOA) as C8, diisononyl adipate (DINA) as C9, and diisodecyl adipate (DIDA) as C10.

  In embodiment of this invention, the addition amount of the said adipic acid ester is 1 mass part or more with respect to 100 mass parts of vinyl chloride resins. If the addition amount is less than 1 part by mass, bleeding of silicone oil cannot be suppressed. Moreover, it is preferable that the addition amount is 30 parts by mass or less. When it exceeds 30 parts by mass, a problem is likely to occur in workability.

(Vinyl chloride resin)
Examples of the vinyl chloride resin include vinyl chloride homopolymers (that is, polyvinyl chloride), copolymers of vinyl chloride and other copolymerizable monomers, and mixtures thereof. Examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, (meth) acrylic acid, acrylonitrile and the like.

  It is preferable to use a vinyl chloride resin having an average degree of polymerization of 1000 to 2500. Those having an average degree of polymerization of 1000 to 2000 are more preferred in terms of heat resistance, cold resistance and moldability. When the degree of polymerization is lowered, moldability is improved, but heat resistance and cold resistance are lowered. Conversely, when the degree of polymerization is increased, heat resistance and cold resistance are improved, but moldability is deteriorated.

  If necessary, two or more types of vinyl chloride resins having different degrees of polymerization may be blended and used.

(Other ingredients)
In the embodiment of the present invention, as long as the effects of the present invention are exhibited, in addition to the above components, polymers other than PVC, inorganic fillers, stabilizers, antioxidants, plasticizers, lubricants, colorants, UV absorbers, Various additives such as a light stabilizer, a crosslinking agent, and a crosslinking assistant can be blended.

  For example, if you want to improve heat resistance, cold resistance, insulation, etc., other plasticizers such as phthalic acid ester, isophthalic acid ester, trimellitic acid ester, pyromellitic acid ester, epoxidized soybean oil as needed May be used in a blend.

〔Electrical wire〕
The electric wire which concerns on embodiment of this invention was equipped with the conductor and the insulating layer which consists of the said vinyl chloride resin composition concerning embodiment of this invention coat | covered on the outer periphery of the conductor, It is characterized by the above-mentioned.

FIG. 1 is a cross-sectional view schematically showing an example of an electric wire according to an embodiment of the present invention.
As shown in FIG. 1, the electric wire 10 according to the present embodiment includes a conductor 1 and an insulating layer 2 covered on the outer periphery of the conductor 1. As the conductor 1 to be coated, for example, a conductor having an outer diameter of about 0.15 to 7 mmφ can be used. Although the conductor etc. which twisted the tin plating annealed copper wire can be used conveniently, it is not limited to this. The number of conductors 1 is not limited to one as shown in FIG. 1, and a plurality of conductors may be used.

  The insulating layer 2 is comprised from said vinyl chloride resin composition which concerns on embodiment of this invention. The electric wire 10 can be obtained by coating as an insulating layer by a molding means such as extrusion coating. If necessary, the crosslinking treatment may be performed by a method such as electron beam irradiation.

  In the present embodiment, the insulating layer is constituted by a single layer as shown in FIG. 1, but it may be a multilayer structure. In this case, at least the outermost layer is formed using the vinyl chloride resin composition.

〔cable〕
A cable according to an embodiment of the present invention is characterized by using the above-described vinyl chloride resin composition according to an embodiment of the present invention as a coating material (sheath or insulating layer and sheath).

FIG. 2 is a cross-sectional view schematically showing an example of the cable according to the embodiment of the present invention.
As shown in FIG. 2, the cable 20 according to the present embodiment is obtained by twisting together three wires 10 according to the embodiment of the present invention in which a conductor 1 is coated with an insulating layer 2 together with an intervening 3 such as paper. A three-strand stranded wire, a presser tape 4 wound around the outer periphery thereof, and a sheath 5 that is extrusion-coated on the outer periphery thereof. It is not limited to a three-core stranded wire, but may be one electric wire (single core) or a multi-core stranded wire other than a three-core stranded wire. The presser tape 4 can be omitted or replaced with a braid.

  The sheath 5 is comprised from said vinyl chloride resin composition which concerns on embodiment of this invention. In the present embodiment, the insulating layer 2 is also composed of the above vinyl chloride resin composition, but is not limited to this, and other insulating layer resin compositions (non-halogen flame retardant resin compositions) May be preferable). The sheath 5 may be subjected to a crosslinking treatment by a method such as electron beam irradiation as necessary.

  In the present embodiment, the sheath is composed of a single layer as shown in FIG. 2, but it may be a multilayer structure. In this case, at least the outermost layer is formed using the vinyl chloride resin composition.

  Hereinafter, the present invention will be described more specifically with reference to examples. Note that the present invention is not limited in any way by the following examples.

  Tables 1 and 2 show examples, and Table 3 shows conventional examples and comparative examples.

<Method for producing test piece (sheet)>
With respect to 100 parts by mass of PVC having an average degree of polymerization of 1300, plasticizer, silicone oil, calcium-zinc non-lead stabilizer as a stabilizer, and calcium carbonate as a filler were mixed in the proportions shown in Tables 1 to 3. Thereafter, a sheet having a thickness of 1 mm was formed by kneading (roll temperature 160 ° C., 5 minutes) and pressing (press temperature 180 ° C., preheating 3 minutes, pressure 10 MPa for 2 minutes). Since the plasticizer needs to be added in an amount of 40 parts by mass or more as a roll kneadable amount, in the example of the terephthalic acid ester addition amount of 10 parts by mass, it was prepared by blending 30 parts by mass of DINP (diisononyl phthalate).

The following materials were used in Tables 1-3.
(1) Vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: TK-1300)
(2) Plasticizer / terephthalic acid ester DOTP (di-2-ethylhexyl terephthalate)
DINTP (Diisononyl terephthalate)
DIDTP (Diisodecyl terephthalate)
・ Phthalic acid ester DINP (diisononyl phthalate)
DOP (di-2-ethylhexyl phthalate)
Adipic acid ester DOA (di-2-ethylhexyl adipate)
DINA (Diisononyl Adipate)
DIDA (diisodecyl adipate),
(3) Silicone oil (made by Shin-Etsu Silicone, trade name: KF-96-100cs)
(4) Stabilizer: Ca-Zn lead-free stabilizer (5) Filler: Calcium carbonate (Maruto Co., Ltd., trade name: Softon 1500)

<Test method>
The weather resistance was evaluated with a metal halide lamp weather resistance acceleration tester M6T manufactured by Suga Test Instruments. Irradiation under conditions of sample surface irradiance 1.5 kw / m ² , temperature 60 ° C., humidity 50%, light source-sample distance 350 mm, irradiation time 72 hours (3 minutes water spray +117 minutes irradiation 120 minutes cycle × 36 times) Then, the elongation residual ratio of the tensile test after irradiation / before irradiation and the appearance after irradiation were evaluated. The tensile test was performed according to JISK6723. In the evaluation of the residual elongation rate, 60% or more was accepted (◯), and less than 60% was rejected (x). Moreover, the evaluation evaluation of an external appearance made the pass ((circle)) the case where there is no crack (crack) on the sample surface after irradiation, and made the disqualification (x) the case where there exists. In the weather resistance determination, the case of the residual elongation rate ○ and the appearance ○ was determined to be acceptable (◯), and if any of the results was ×, it was determined to be unacceptable (×). The results are shown in Tables 1-3.

  Bleed resistance was evaluated in a constant temperature and humidity chamber having a temperature of 70 ° C. and a humidity of 90%. After leaving for 72 hours and taking out, the case where there was no stickiness on the surface was regarded as acceptable (◯), and the case where it was present was regarded as unacceptable (x). The results are shown in Tables 1-3.

  In the conventional examples 1 and 2 using DOP or DINP performed as a reference, both weather resistance and bleed resistance were acceptable.

  In Example 1 and Comparative Example 1, 10 parts by weight of DOTP was added, but in Example 1 in which 0.1 part by weight of silicone oil and 1 part by weight of DIDA were added, both weather resistance and bleed resistance were acceptable. However, in Comparative Example 1 in which silicone oil and DIDA were not added, cracks occurred after the weather resistance test, and the appearance was unacceptable, so the weather resistance was not acceptable.

  Examples 2 and 3 and Comparative Examples 2 and 3 are cases in which the amount of DOTP added is 40,100 parts by mass, but Example 2 in which 0.1 part by mass of silicone oil and 1 part by mass of DIDA were added. 3 was acceptable as in Example 1, while Comparative Examples 2 and 3 in which no silicone oil and DIDA were added failed in appearance as in Comparative Example 1, and also had no residual elongation. Since it was acceptable, the weather resistance was not acceptable.

  From the above, it was shown that 0.1 part by mass or more of silicone oil and 1 part by mass or more of adipic acid ester such as DIDA are necessary for achieving both weather resistance and bleed resistance.

  In Examples 4 to 6 in which 1 part by mass of silicone oil and 15 parts by mass of DIDA were added, both weather resistance and bleed resistance were acceptable. This is because bleeding of silicone oil can be suppressed by adding adipic acid ester such as DIDA. On the other hand, in Comparative Examples 4 to 6 in which only 1 part by mass of silicone oil was added and DIDA was not added, the weather resistance was improved, but stickiness to the surface due to bleeding occurred. From this, it was confirmed that the improvement in weather resistance and the suppression of bleeding were not compatible without the addition of both silicone oil and adipic acid ester such as DIDA.

  From Example 6 and Comparative Example 7, it can be seen that when DOTP exceeds 100 parts by mass, DOTP itself bleeds, and the amount of DOTP added is 100 parts by mass.

  From Examples 7 to 9, it can be seen that both weather resistance and bleed resistance can be achieved even when 2.5 parts by mass of silicone oil is added. In addition, Example 10 shows that both weather resistance and bleed resistance can be achieved even when 30 parts by mass of DIDA is added.

  In addition, Examples 11 to 16 and Comparative Examples 8 and 9 showed that the alkyl chain carbon number C8 to C10 of the terephthalic acid ester had the same tendency as the above results. Further, Examples 5, 17, and 18 showed that the same tendency was observed in the C8 to C10 alkyl chain carbon number of the adipic acid ester.

  In addition, this invention is not limited to the said embodiment and Example, A various deformation | transformation implementation is possible.

1: Conductor, 2: Insulating layer, 3: Intervening, 4: Pressing tape, 5: Sheath 10: Electric wire, 20: Cable

Claims (8)

A vinyl chloride resin composition containing terephthalic acid ester as a plasticizer,
A vinyl chloride resin composition comprising 100 parts by mass or less of the terephthalic acid ester, 0.1 parts by mass or more of silicone oil, and 1 part by mass or more of adipic acid ester with respect to 100 parts by mass of the vinyl chloride resin.   The vinyl chloride resin composition according to claim 1, comprising 0.1 to 2.5 parts by mass of the silicone oil and 1 to 30 parts by mass of an adipic acid ester with respect to 100 parts by mass of the vinyl chloride resin.   The vinyl chloride resin composition according to claim 1 or 2, comprising 10 to 100 parts by mass of the terephthalic acid ester with respect to 100 parts by mass of the vinyl chloride resin.   The vinyl chloride resin composition according to any one of claims 1 to 3, wherein the terephthalic acid ester is a terephthalic acid ester having 8 to 10 carbon atoms in an alkyl chain.   The vinyl chloride resin composition according to any one of claims 1 to 4, wherein the adipic acid ester is an adipic acid ester having 8 to 10 carbon atoms per alkyl chain.   A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein the terephthalic acid ester is 100 parts by mass or less, the silicone oil is 0.1 part by mass or more, and adipic acid with respect to 100 parts by mass of the vinyl chloride resin. The electric wire provided with the insulating layer which consists of a vinyl chloride resin composition containing 1 mass part or more of ester.   A vinyl chloride resin composition containing a terephthalic acid ester as a plasticizer, wherein the terephthalic acid ester is 100 parts by mass or less, the silicone oil is 0.1 part by mass or more, and adipic acid with respect to 100 parts by mass of the vinyl chloride resin. A cable including a sheath made of a vinyl chloride resin composition containing 1 part by mass or more of an ester.   The cable according to claim 7, comprising the electric wire according to claim 6.

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