JPH04149224A - Member for electric wire - Google Patents

Abstract

PURPOSE:To obtain the subject member, excellent in weather, heat distortion and cold resistances and useful as power cables, etc., by molding a specific vinyl chloride-based resin composition having a THF-insoluble content within a prescribed range. CONSTITUTION:The objective member is obtained by molding a vinyl chloride- based resin composition which is a vinyl chloride-based resin composition, prepared by thermally melt mixing vinyl chloride resin with a polymer polyol having >=2 hydroxyl groups and 300-10000, preferably 1000-5000 molecular weight (added in an amount of preferably 10-170 pts.wt. based on 100 pts.wt. vinyl chloride resin) and a compound such as trimer of 2,4-tolylene diisocyanate with >=3 isocyanate groups so as to provide preferably 0.3-1.3 ratio (NCO/OH) under shearing force and having 5-55wt.% THF-insoluble content thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a member for electric wires having excellent weather resistance, heat deformation resistance, and cold resistance.

[Prior art and problems to be solved by the invention] Vinyl chloride resin has been widely used for electric wire parts, but its weather resistance, heat deformation resistance, and cold resistance properties were poor, and improvements were needed. . In particular, heat deformation resistance and cold resistance are important because they relate to the shape retention of the molded product. This is because materials for electric wires are sometimes exposed to high temperatures due to heat generated by electrical resistance, so they need to have good heat deformation resistance, and because in cold regions they become more susceptible to impact fracture due to embrittlement, they need to have good cold resistance. By becoming.

Heat deformation resistance is achieved by reducing fluidity at high temperatures, so it is done in the same way as improving compression set, and methods for improving this include, for example, benzoyl peroxide, dicumyl peroxide, Organic peroxides such as t-butyl peroxide, diamine compounds such as 1,4-tetramethylene diamine and 1,6-hexamethylene diamine, sulfur compounds such as sulfur, tetramethylthuram disulfide, triazinedithiol, etc. Crosslinking of vinyl chloride resin with a compound, diallyl phthalate, crosslinking with components such as crosslinkable polyurethane or epoxy resin, and crosslinked vinyl chloride resin that has been crosslinked in advance during polymerization or crosslinked NBR1 that is highly compatible with vinyl chloride resin.
There are methods of blending crosslinked polyurethane etc. with vinyl chloride resin, and methods of using vinyl chloride resin having a reactive group such as a hydroxyl group to form a crosslinked product with diisocyanate or the like. In these methods, when crosslinking vinyl chloride resin, it is possible to easily obtain a composition with good heat deformation resistance, but on the other hand, there are problems: (1) poor thermal stability and coloring; (2) odor remains due to crosslinking agent residue; and (3) when the degree of crosslinking is increased, a large amount of plasticizer is required to achieve a desired hardness.

When a reactive plasticizer is used, the same problem as mentioned above occurs because it is often a radical reaction system.

When blending cross-linked vinyl chloride resin or cross-linked NBR with vinyl chloride resin, (1) physical properties such as tensile strength and elongation may significantly decrease due to their dispersibility in vinyl chloride resin (2) hardness (3) A large amount of plasticizer is required for the adjustment of (3) a decrease in impact resilience, (4) moldability deteriorates if added in a large amount, and (5) weather resistance is poor due to the butadiene component in crosslinked NBR.

Furthermore, a method in which a vinyl chloride resin having a reactive group such as a hydroxyl group is crosslinked with diisocyanate or the like has poor reactivity and therefore has little improvement effect.

In recent years, composites of vinyl chloride resin and polyurethane have attracted attention, and various methods have been proposed. For example, polyurethane is dissolved in vinyl chloride monomer (VCM) and VCM
A method for obtaining a composite of vinyl chloride resin and polyurethane by polymerization of polyol, a method for producing a hydroxyl group-containing vinyl chloride resin by polymerizing VCM in the presence of polyol, and a method for obtaining it by urethanization reaction, and a method for obtaining a composite of vinyl chloride resin and polyurethane. , a method of impregnating and reacting with isocyanate, a catalyst, etc.

However, composites of vinyl chloride resin and polyurethane obtained by these methods have poor rubber elasticity and heat deformation resistance, and are not suitable for applications requiring these properties. In a method for producing such a composite, if a crosslinked urethane is produced using triisocyanate, the processability will be poor. In addition, as a commonly used composite method of vinyl chloride resin and polyurethane, roll or Banbury mixer
There is a method in which a vinyl chloride resin and a highly elastic polyurethane elastomer are blended into a polymer. Although the composite obtained by this method has excellent impact resilience, it has poor heat deformation resistance, so improvements are desired.

Cold resistance is achieved by keeping the glass transition temperature of the composition below the ambient temperature, since it means maintaining flexibility at low temperatures, that is, preventing embrittlement. Methods to improve this include, for example, the use of plasticizers with low molecular weight and high plasticization efficiency, polymer blending of elastomers such as polyurethane or polyester whose glass transition temperature is sufficiently lower than the outside temperature, and ethylene-vinyl acetate. -Methods using graft polymers such as vinyl chloride graft polymers and vinyl chloride-urethane copolymers can be mentioned.

However, when adding a plasticizer, the brittleness can be improved by using a plasticizer with a low molecular weight and high plasticizing efficiency, but if a composition with high hardness is required, the plasticizer to be added The amount is limited and the glass transition temperature cannot be lowered sufficiently. In addition, when using a low molecular weight plasticizer,
Since it has high volatility and good fluidity at high temperatures, it poses a problem in heat deformation resistance and cannot satisfy both cold resistance and cold resistance. Similarly, a method of polymer blending an elastomer such as polyurethane or polyester whose glass transition temperature is sufficiently lower than the outside temperature,
Even in methods using graft polymers such as vinyl acetate-vinyl chloride graft polymers and vinyl chloride-urethane copolymers, problems arise due to poor heat deformation resistance as described above.

[Means for Solving the Problems] In view of the above-mentioned current situation, the present inventors studied the components of polyurethane that forms a crosslinked body, and as a result, completed the present invention.

That is, the present invention provides a chlorinated resin obtained by heating and melt-mixing a vinyl chloride resin, a polymer polyol having two or more hydroxyl groups and a molecular weight of 300 to 10,000, and a compound having three or more isocyanate groups under shearing force. A vinyl resin composition comprising tetrahydrofuran (
The present invention relates to an electric wire member formed by molding a vinyl chloride resin composition having an insoluble content (THF) of 5 to 55% by weight.

The present invention will be explained in detail below.

The vinyl chloride resin used in the present invention may be obtained by a commonly used polymerization method. For example, suspension polymerization method,
There are bulk polymerization methods, solution polymerization methods, and emulsion polymerization methods.

Note that the vinyl chloride resin in the present invention refers to a vinyl chloride homopolymer and a vinyl chloride resin copolymerized with a monomer copolymerizable with vinyl chloride monomer.

In addition, the degree of polymerization of vinyl chloride resin is 800 to 8°000.
Preferably, those in the range of 1,000 to 5,000 are used.

Examples of monomers copolymerizable with vinyl chloride monomers include ethylene, propylene, butene, pentene-1, butadiene, styrene, α-methylstyrene, acrylonitrile, vinylidene chloride, vinylidene cyanide, alkyl vinyl ethers, Carboxylic acid vinyl esters, aryl ethers, dialkylmaleic acids, fumaric acid esters, N-vinylpyridone, vinylpyridine,
Examples include vinyl silanes, acrylic acid alkyl esters, methacrylic acid alkyl esters, and the like.

Further, the vinyl chloride resin may be a graft polymer such as an ethylene-vinyl acetate vinyl chloride graft polymer or a vinyl chloride-urethane copolymer. However, the vinyl chloride resin is not limited to these. Also used are crosslinked vinyl chloride resins obtained by adding a divinyl compound such as divinylbenzene during polymerization of these polymers.

Crosslinked vinyl chloride resin is tetrahydrofuran (THF)
The insoluble content is in the range of 0.1 to 25% by weight, and is used alone or in a blend with uncrosslinked vinyl chloride resin.

The polymer polyol used in the present invention has two or more hydroxyl groups and a molecular ff of 1300 to 10°OOO, preferably 1,000 to 5,000. Such a polymer polyol has, for example, a carbon number of 4
It can be obtained by condensation polymerization of ~10 aliphatic dicarboxylic acids and glycols having 5 or less repeating units obtained by ring-opening polymerization of aliphatic glycols having 2 to 10 carbon atoms and/or epoxy groups.

In addition, the molecular weight as used in the present invention refers to the number average molecular weight, which is determined by gel permeation chromatography (G
It can be measured by PC), etc.

2 to 10 carbon atoms used in the production of polymer polyols
The aliphatic glycols include, for example, 1°2-ethanediol, 1,2-propanediol, 1,4-butanediol, butynediol, 3-methyl-1,5-bentanediol, 16-hexanediol, Examples include 1,10-decamethylene diol, 2,5-dimethyl-2,5-hexanediol, neopentyl glycol, and 1,4-cyclohexane dimetatool.

On the other hand, examples of compounds having epoxy groups include ethylene oxide, propylene oxide, tetrahydrofuran (TH
Examples include cyclic ethers such as F). These can also be ring-opening polymerized to form glycols with 5 or less repeating units.
It is suitably used as the glycol of the present invention. One or more of these may be used.

4 to 10 carbon atoms used in the production of polymer polyols
Examples of the aliphatic dicarboxylic acids include succinic acid, geltaric acid, adipic acid, azelaic acid, and sebacic acid, and one or more of these may be used. Such polymer polyols are commercially available from Nippon Polyurethane Co., Ltd. under the trade name Niraporan.

The amount of polymer polyol added is vinyl chloride resin 100%
It is preferably 10 to 170 parts by weight. If it is less than 10 parts by weight, the rubber elasticity will not be improved, and if it exceeds 170 parts by weight, processing will not be possible.

The compounds having three or more isocyanate groups used in the present invention include, for example, 2,4- and 2,6-tolylene diisocyanate, m- and p-phenylene diisocyanate, ]-]chlorophenylene-2.4- Diisocyanates 1,5-naphthalene diisocyanate, methylenebisphenylene 4,4'-diisocyanate, m- and p-
Diisocyanate trimers such as xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,6,1,1-undecane triisocyanate, lysine Triisocyanates such as ester triisocyanate, 4-isocyanate methyl-1,8-octamethyl diisocyanate,
Alternatively, polyfunctional incyanates such as polyphenylmethane polyisocyanate may be used, and one or more of these may be used. It is also possible to use the above diisocyanates in combination.

However, it is desirable that the number of moles of NCO groups in the triisocyanate is 0.25 or more relative to the number of moles of NCO groups in all isocyanates. If it is less than 0.25, sufficient performance cannot be exhibited due to insufficient crosslinking density.

Further, the NGO10H ratio is preferably in the range of 0.3 to 1.3. If it is less than 0.3, even if only triisocyanate is used as the isocyanate, sufficient performance cannot be exhibited due to insufficient crosslinking density. If it exceeds 1.3, processing cannot be performed.

There are no restrictions on the use of plasticizers in the present invention. Examples of plasticizers that can be used in the present invention include di-n-butyl phthalate, di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisooctyl phthalate, octyldecyl phthalate, and phthalate. Phthalic acid plasticizers such as diisodecyl acid, butyl benzyl phthalate, di-2-ethylhexyl isophthalate, di-2-ethylhexyl adipate (DOA), di-n-denle adipate, diisodecyl adipate, dibutyl sebacate, di-sebacate Aliphatic ester plasticizers such as 2-ethylhexyl, trimellitic acid plasticizers such as trioctyl trimellitate and tridecyl trimellitate, pyromellitic acid plasticizers such as tetraoctyl pyromellitate, tributyl phosphate, phosphoric acid Phosphate ester plasticizers such as tri-2-ethylhexyl, 2-ethylhexyldiphenyl phosphate, and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil; and adipic acid or sebacic acid and glycol. Polymer plasticizers with an average molecular weight ff of 1,500 to 1,000 obtained by condensation polymerization of 1,500 to 1,000, and the like are used, and one or more of these may be used.

Since the volatility and plasticizability of the plasticizer are important for the electric wire member of the present invention, the plasticizer to be used must be selected depending on its intended use and test items. For example, if heat deformation resistance and cold resistance are required at the same time, the use of low molecular weight plasticizers such as DOP should be avoided. plasticizer. Furthermore, if only cold resistance is required, all plasticizers can be used.

Catalysts may be used in preparing the compositions of the invention.

Although the reaction proceeds without using a catalyst, it is preferable to use a catalyst because the reaction proceeds more uniformly.

Such a catalyst may be any catalyst used in general urethanization reactions, such as triethylamine,
Examples include amine catalysts such as triethylenediamine and N-methylmorpholine, and tin catalysts such as tetramethyltin, tetraoctyltin, dimethyldioctyltin, triethyltin chloride, dibutyltin diacetate, and dibutyltin dilaurate.

In the present invention, stabilizers can also be added to the vinyl chloride resin. As a stabilizer, for example, lead stearate,
Examples include metal soap stabilizers such as calcium stearate, barium stearate, zinc stearate, and cadmium stearate, and epoxy stabilizers such as epoxidized soybean oil and epoxidized linseed oil.

Further, if necessary, commonly used ultraviolet absorbers, antioxidants, anti-aging agents, processing aids, fillers, etc. can be added. However, in the present invention, if a tin-based stabilizer is used, it becomes a hydrolysis catalyst for the ester-based polymer polyol, so it is better to avoid using it.

The composition of the present invention is prepared in a kneading machine capable of shearing and melting resin, such as a roll molding machine, a twin-screw kneader, an extruder, or a Banbury mixer. For more details, for example:
Taking the Banbury mixer as an example, first, under a casing temperature of 100 to 200°C, vinyl chloride resin and, if necessary, commonly used ultraviolet absorbers, antioxidants, anti-aging agents, processing aids, fillers, etc. are added. Add and mix. Next, the polyol, plasticizer, incyanate, and catalyst, which had been kept at a temperature of 50 to 80 DEG C., are weighed and mixed and charged through the inlet of a Banbury mixer. While applying shear force, 1
The temperature was set to 00 to 200°C, and further heated and mixed, followed by melting and urethanization reaction of the vinyl chloride resin, and the temperature was 3 to 60°C.
Take it out after a minute.

The resin composition thus obtained can be formed into a sheet by applying it to a roll molding machine.

The THF-insoluble content of the composition of the present invention is required to be 5 to 55% by weight. When the insoluble content is less than 5% by weight, sufficient compression set cannot be imparted, and when it exceeds 55% by weight, molding becomes difficult.

The method for measuring this THF-insoluble content is as follows. That is, a roll sheet with a thickness of 1.0 ± 0.1 mm is
Cut into 1.5 mm squares and weigh 1.0 g. 30 of this
Place in a 0cc beaker and stir in 200ml THF for 2 hours using a stirrer.

The sample, which swells with THF, is filtered through a 300-mesh sieve, crushed with a glass rod, etc., and the filtrate is further stirred in 200 ml of THF with a stirrer for 4 hours. This solution was passed through a pre-weighed filter paper to separate the insoluble matter, and the insoluble matter and the filter paper were placed in a petri dish for 40 minutes.
After drying in an oven at °C for 5 hours, the weight is measured.

The weight percent of the THF insoluble matter is determined from the weight of the insoluble matter obtained by this method.

In the present invention, the electric wire members include general electric cables and communication cables, as well as computers, OA equipment, and VTRs.
, appliance wires used in televisions, etc., and general insulated wires used in other fields, and are used for the insulator portion that covers these conductors and the sheath material that protects the insulator.

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 Vinyl chloride resin (manufactured by Tosoh Corporation, trade name: Ryuron E-2800) obtained by suspension polymerization in a Banbury mixer with an internal volume of 1,700 cc and a casing temperature of 150°C.
, average degree of polymerization 2800) as a stabilizer, barium stearate 12g, zinc stearate 6g1 as an amine scavenger Nissan Ferro Organic Chemical Co., Ltd. cleavage product name B
9 g of P-331 was charged and stirred at a constant rotational speed. Separately, 240 g of a polymer polyol (manufactured by Nippon Polyurethane Co., Ltd., trade name Niraporan 4067, number average molecular weight 2,000), which had been kept at 70°C in advance, and trioctyl trimellitate (TOTM) 42 as a plasticizer were added.
0.0 g of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Co., Ltd., part name Coronate EH) 39.8 g (NGO10H ratio -1) 0.03 g of dibutyltin dilaurate was added as a catalyst and mixed for 1 minute. The mixture was then poured into the Banbury mixer through the inlet.

The reaction and mixing time was then 15 minutes.

After the reaction was completed, the resulting composite was formed into a sheet using a roll molding machine, which was then press molded and evaluated for each item according to the evaluation method described below.

Evaluation method (1,)li! 2 degrees J I 5K6301 Spring type hardness tester (A type)
It was measured by

(2) Heat deformation resistance The heat deformation rate was measured according to J　5K6723.

(3) Cold resistance The embrittlement temperature was measured according to JISK6723.

(4) Weather Resistance The appearance of the sample after 3000 hours of irradiation was visually observed using a Sunshine Weatherometer (manufactured by Suga Test Instruments Co., Ltd.) and evaluated as follows.

○: No change ×, cracks and/or color deterioration △, intermediate state between ○ and × Weather resistance test conditions Ultraviolet irradiation blank using carbon arc Valor temperature: 63℃ Water injection time: 18m1n/120m1n Injection pressure +0
．． 8-1.3 kg/cm2 test time + 3000 hours results are shown in Table 1.

Example 2 Adipic acid polyester plasticizer (manufactured by Adeka Argus Chemical Co., Ltd., trade name: Adeka Sizer PN-28) as a plasticizer
The sample was manufactured and evaluated in the same manner as in Example 1, except that 420 g of the sample (average molecular weight ji 2,000) was used.

The results are shown in Table 1.

Comparative Example 1 Put 1 kg of the vinyl chloride resin used in Example 1, 20 g of barium stearate, 10 g of zinc stearate, and 1 kg of TOTMl into a Henschel mixer, heat and stir, and dry up at 120°C to obtain vinyl chloride. The resin composition was kneaded with a roll at 150°C for 5 minutes. Evaluation was conducted in the same manner as in Example 1 using this.

The results are shown in Table 1.

Comparative Example 2 Adipic acid polyester plasticizer PN280 was used as a plasticizer.
1. , IKg was used, and the same manner as in Comparative Example 1 was used.

The results are shown in Table 1.

Comparative Example 3 In Example 2, triisocyanate (Coronate EH
) instead of hexamethylene diisocyanate 19
．． 8g (NGO, 10H ratio -1) was used, and everything else was produced and evaluated in the same manner as in Example 2.

The results are shown in Table 1.

Comparative Example 4 In Comparative Example 2, polymerization was carried out using a crosslinking agent by a normal suspension polymerization method, and the resulting resin had a TI (F insoluble content of Q, 7
It was produced and evaluated in the same manner as in Comparative Example 2, except that 1 kg of vinyl chloride resin (TE (average degree of polymerization of F solubles: 2,000)) was used.

The results, Table 1 This is shown.

[Effects of the Invention] As is clear from the above description, the vinyl chloride resin composite obtained by the present invention has high flexibility and easy moldability. It is also characterized by good heat deformation resistance, cold resistance, and weather resistance, and is suitable for use as a material for electric wires.

Claims (1)

[Claims] (1) Vinyl chloride resin, a vinyl chloride obtained by heating and melt-mixing a polymer polyol having two or more hydroxyl groups and a molecular weight of 300 to 10,000 and a compound having three or more isocyanate groups under shearing force. type resin composition, wherein the composition has a tetrahydrofuran insoluble content of 5 to 5.
An electric wire member formed by molding a vinyl chloride resin composition containing 55% by weight.