JP2016060819A - Flame retardant vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant vinyl chloride resin composition having less gum during molding, excellent in fire resistance, flexibility, tensile property and bleed out resistance, and therefore capable of providing a molded article such as a wire, a cable, a tube and a tape having high flame retardancy and excellent in handleability.SOLUTION: There is provided a flame retardant vinyl chloride resin composition containing 100 pts.mass of a component (a) vinyl chloride resin, 15 to 150 pts.mass of a component (b) cyclohexane-1,2-dicarboxylic di(isononyl)ester containing a cis isomer of 90 to 100 mol% and a tras isomer of 10 to 0 mol% obtained by hydrogenation of diisononyl phthalate ester of casNo.28553-12-0 and 1 to 150 pts.mass of a component (c) a flame retardant.SELECTED DRAWING: None

Description

The present invention relates to a vinyl chloride resin composition. More specifically, the present invention relates to a flame retardant vinyl chloride resin composition and an electric wire, cable, tube, packing or tape containing the resin composition.

Flame retardant vinyl chloride in which flame retardants such as antimony flame retardant, halogen flame retardant, metal hydroxide, zinc flame retardant, and phosphorus flame retardant are blended with vinyl chloride resin composition, especially vinyl chloride resin Since the resin composition is excellent in flame retardancy in addition to electrical characteristics and mechanical characteristics, it is frequently used as a coating material for electric wires and cables.

In recent years, due to increasing environmental problems in the world, there is an increasing demand for vinyl chloride resin compositions that do not contain a phthalic acid plasticizer as a main component for coating materials for electric wires and cables.

Therefore, the present inventor made an esterification reaction of “1,2-cyclohexanedicarboxylic acid or an anhydride thereof and an aliphatic monohydric mixed alcohol having 4 to 13 carbon atoms containing a branched alcohol having 9 carbon atoms as an essential component. 1,2-cyclohexanedicarboxylic acid diester obtained, wherein the content of branched-chain alcohols having 9 to 9 carbon atoms in the aliphatic monohydric mixed alcohol is 70 to 97% by weight, and branches having 9 carbon atoms A plasticizer for vinyl chloride resin containing 1,2-cyclohexanedicarboxylic acid diester, wherein the content of alcohol other than the chain alcohol is 3 to 30% by weight "(Patent Document 1). Thought. However, as a result of testing by the present inventor, the flame-retardant vinyl chloride resin composition using the plasticizer of Patent Document 1 as a plasticizer is prone to eye cracks at the time of molding, and the problem of insufficient bleed-out resistance is a problem. I found out.

JP 2001-207002 A

The problem of the present invention is that the wire, cable, tube, which has little flame at the time of molding, is excellent in flame retardancy, flexibility, tensile properties, and bleed-out resistance, and therefore has high flame retardancy and excellent handling properties. An object of the present invention is to provide a flame retardant vinyl chloride resin composition capable of obtaining molded articles such as packing and tape.

As a result of intensive studies, the present inventor has found that the above problems can be achieved by a vinyl chloride resin composition containing a specific plasticizer.

That is, the present invention
Component (a) 100 parts by mass of vinyl chloride resin;
Component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by mass; and component (c) flame retardant 1-150 parts by mass;
Is a flame retardant vinyl chloride resin composition.

2nd invention is an electric wire, a cable, a tube, packing, or a tape containing the resin composition as described in 1st invention.

A third invention is the electric wire or cable according to the second invention, characterized by conforming to the VW-1 combustion test of the UL1581 standard.

The flame-retardant vinyl chloride-based resin composition of the present invention has few eyes when molded, and is excellent in flame retardancy, flexibility, and bleed-out resistance. Therefore, using the flame-retardant vinyl chloride resin composition of the present invention, it is possible to obtain molded articles such as electric wires, cables, tubes, packings, and tapes having high flame retardancy and excellent handling properties.

Component (a) “vinyl chloride resin”:
The vinyl chloride resin used as component (a) of the present invention refers to all polymers having a group represented by —CH ₂ —CHCl—, a vinyl chloride homopolymer; a vinyl chloride / vinyl acetate copolymer. , Vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / (meth) methyl acrylate copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, chloride Vinyl / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary Copolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer Copolymerized with vinyl chloride and vinyl chloride, such as vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymers, etc. Copolymers with other possible monomers; Post-chlorinated vinyl copolymers and other vinyl chloride homopolymers and modified vinyl chloride copolymers; and structurally vinyl chloride resins such as chlorinated polyethylene And similar chlorinated polyolefins.

The component (a) has a number average degree of polymerization of preferably 300 to 7000, more preferably 1000 to 2500, from the viewpoints of eye damage, bleed-out resistance, and tensile properties.

As the component (a), one or a mixture of two or more of these vinyl chloride resins can be used.

Component (b) “cyclohexane-1,2-dicarboxylic acid having 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer obtained by hydrogenation of diisononyl phthalate of cas No. 28553-12-0 Di (isononyl) ester ":
The vinyl chloride resin composition of the present invention comprises component (b) casNo. 28553-12-0 phthalic acid diisononyl ester (hereinafter sometimes abbreviated as DINP) obtained by hydrogenation of 90 to 100 mol% of cis isomer, 10 to 0 mol% of cyclohexane-1, 2-dicarboxylic acid di (isononyl) ester. Since the above component (b) is obtained by hydrogenating DINP, the resin composition of the present invention has little creaking during molding and is excellent in bleed-out resistance and flame retardancy.

The DINP is not particularly limited, and DINP synthesized by a known method can be used.

The component (b) is a mixture of 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer. For this reason, there is little discoloration at the time of molding, and the bleed-out resistance and flame retardancy are excellent. A mixture of 95 to 100 mol% of cis isomer and 5 to 0 mol% of trans isomer is preferable. Here, the sum of the cis isomer and the trans isomer is 100 mol%.

The mixture of the cis isomer and the trans isomer can be obtained by hydrogenating DINP by a known method (for example, a technique described in JP 2013-513477 A).

The ratio of the cis isomer to the trans isomer of the component (b) can be determined from a nuclear magnetic resonance spectrum of proton (hereinafter sometimes abbreviated as ¹ H-NMR). The methine proton of dialkyl hexahydrophthalate shows a signal at 2.5-3.0 ppm, of which 2.7-3.0 ppm is in the cis isomer and 2.5-2.7 ppm is in the trans isomer. Be attributed. Thus, the cis isomer ratio is 2.7-3.0 ppm integrated area to 2.5-3.0 ppm integrated area, and the trans isomer ratio is 2.5-3.0 ppm integrated area 2. It can be determined as an integrated area of 5 to 2.7 ppm. The measurement of ¹ H-NMR can be performed with reference to, for example, JP-T-2005-504119. It can also be done by requesting measurements from Mitsui Chemical Analysis Center.

The compounding amount of the component (b) is from 15 to 150 parts by mass of the component (b) with respect to 100 parts by mass of the component (a), from the viewpoint of eye discoloration, flame retardancy, flexibility, and bleed-out resistance. Preferably it is 20-120 mass parts.

In the resin composition of the present invention, the plasticizer other than the component (b), for example, cyclohexane-1, whose ratio of cis isomer to trans isomer is outside the specified range, is not limited to the object of the present invention. 2-dicarboxylic acid di (isononyl) ester, casNo. Cyclohexane-1,2-dicarboxylic acid di (isononyl) ester, phthalic acid ester, trimellitic acid ester, fatty acid dibasic ester, phosphoric acid ester obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester, One or more epoxy plasticizers and polyester plasticizers may be included.

Component (c) Flame retardant:
The component (c) is not particularly limited, and any flame retardant can be used, preferably a flame retardant usually used for vinyl chloride resins and resin compositions thereof.

Examples of the component (c) include antimony flame retardants, halogen flame retardants, metal hydroxides, zinc flame retardants, phosphorus flame retardants, and nitrogen-containing flame retardants.

Examples of the antimony flame retardant include antimony trioxide, antimony pentoxide, antimony trichloride, antimony borate, and antimony molybdate.

Examples of the halogen flame retardant include 1,2-bis (pentabromophenyl) ethane, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, and bis (tetrabromophthalimide). Brominated flame retardants such as ethane, poly (dibromopropyl ether), tetrabromobisphenol A carbonate oligomer, tetrabromobisphenol epoxy oligomer, tetrabromobisphenol A-bis (dibromopropyl ether), brominated polystyrene, and hexabromobenzene; chlorine Chlorinated flame retardants such as chlorinated paraffin, chlorinated polyphenyl, and perchlorpentacyclodecane.

Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.

Examples of the zinc flame retardant include zinc stannate and zinc borate.

Examples of the phosphorus flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, trineopentyl phosphate, tri (2-ethylhexyl) phosphate, tri (butylated) Organophosphate flame retardants such as phenyl) phosphate, tri (isopropylated phenyl) phosphate, triphenyl phosphate, trixylenyl phosphate, t-butyldiphenyl phosphate; two or three organic phosphate esters of one or more Condensed organophosphate flame retardants composed mainly of compounds in which molecules or more are condensed; a compound in which one or more hydrogen atoms of an organophosphate or condensed organophosphate are substituted with bromine atoms Brominated organophosphate flame retardants such as tris (tribromoneopentyl) phosphate; compounds in which one or more hydrogen atoms of an organophosphate ester or condensed organophosphate ester are replaced by chlorine atoms, eg tris Examples include chlorinated organic phosphate ester flame retardants such as (2,3-dichloropropyl) phosphate; ammonium polyphosphate flame retardants; and inorganic phosphorus flame retardants such as red phosphorus.

Examples of the nitrogen-containing flame retardant include cyanurate flame retardants such as melamine cyanurate, tris (2-vidoxyethyl) isocyanurate, and tris (2,3-epoxypropyl) isocyanurate; triazine flame retardants; and Examples include guanidine flame retardants.

As said component (c), 1 or more types of these can be used.

The compounding amount of the component (c) is from 1 to 150 parts by mass of the component (b) with respect to 100 parts by mass of the component (a), from the viewpoint of eye discoloration, flame retardancy, flexibility, and bleed-out resistance. Preferably it is 2-120 mass parts.

The resin composition of the present invention may further contain a vinyl chloride resin and a stabilizer usually used for the resin composition. Examples of the stabilizer include organotin compound-based, barium-zinc-based, calcium-zinc-based, and lead-based stabilizers. Among these, from the viewpoint of environmental problems, organotin compound-based, barium-zinc-based, and calcium-zinc-based stabilizers are preferable. As a stabilizer, these 1 type, or 2 or more types of mixtures can be used. As for the compounding quantity of a stabilizer, 0.1-10 mass parts is preferable with respect to 100 mass parts of said components (a).

The resin composition of the present invention may further contain various metal soaps, fatty acids, and lubricants such as polyethylene wax. The blending amount of the lubricant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a).

In the resin composition of the present invention, the vinyl chloride resin and various additives usually used in the resin composition (for example, heat stabilizer, filler, lubricant, Foaming agents, pigments, ultraviolet absorbers, etc.) and various fillers (for example, calcium carbonate, clay, talc, etc.) can be further included.

In the resin composition of the present invention, the above component (a), the above component (b), and an optional component used as desired can be mixed with any melt kneader (for example, a single screw extruder, a twin screw extruder, a roll, It can be obtained by melt-kneading using a mixer and various kneaders. Preferably, it can be obtained by melt kneading at a resin temperature of 150 to 180 ° C. using a pressure kneader.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Raw materials used Component (a):
(A-1) A vinyl chloride homopolymer having a number average degree of polymerization P = 1050.
(A-2) Vinyl chloride homopolymer having a number average degree of polymerization P = 1400.
(A-3) Vinyl chloride homopolymer having a number average polymerization degree P = 1700.
(A-4) A vinyl chloride homopolymer having a number average polymerization degree P = 2000.
(A-5) A vinyl chloride homopolymer having a number average degree of polymerization P = 2500.

Component (b):
(B-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 92 mol% of cis isomer and 8 mol% of trans isomer obtained by hydrogenating DINP.
(B-2) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 100 mol% of cis isomer and 0 mol% of trans isomer obtained by hydrogenating DINP.

Comparative component (b ′):
(B′-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 85 mol% of cis isomer and 15 mol% of trans isomer obtained by hydrogenating DINP.
(B′-2) casNo. A diisononylcyclohexane-1,2-dicarboxylate plasticizer containing 95 mol% of cis isomer and 5 mol% of trans isomer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester.

Component (c):
Component (c-1) Aluminum hydroxide “Hijilite H42M (trade name)” from Showa Denko KK
Component (c-2) Fatty acid-treated magnesium hydroxide “Kisuma 5B (trade name)” manufactured by Kyowa Chemical Industry Co., Ltd.
Component (c-3) Zinc borate “HA-1 (trade name)” by Sakai Chemical Industry Co., Ltd.
Component (c-4) Antimony trioxide “PATOX-M (trade name)” manufactured by Nippon Seiko Co., Ltd.

Optional component (d):
(D-1) Dioctyl tin mercapto stabilizer “ADEKA STAB 465 (trade name)” by ADEKA Corporation.
(D-2) Barium-zinc composite stability of ADEKA Corporation.
(D-3) A polyethylene wax lubricant “High Wax 4202E (trade name)” manufactured by Mitsui Chemicals, Inc.

Test method (1) Eye distortion during cable forming:
Using a twisting machine, twist three wires corresponding to UL style 1015 of conductor size AWG20, wrap a shield tape on the outside so that the inner diameter (diameter) of the tape shield layer is 6.0 mm, and A braided shield layer was provided on the outside using a braiding machine. Furthermore, a cable was formed on the outer side of the braided shield layer by using a wire extrusion molding machine having a diameter of 65 mm and covering the flame-retardant vinyl chloride resin composition with a thickness of 0.8 mm for 4 hours. The die exit was visually observed and evaluated according to the following criteria.
◯: No eye discoloration even after 4 hours.
Δ: There is no discoloration before 1 hour. After 1 hour, eyes will be recognized 4 hours later.
×: Eye discoloration is recognized before 1 hour.

(2) Bleed-out resistance:
The cable obtained in (1) above was exposed to an environment at a temperature of 70 ° C. and a relative humidity of 95% for 7 days, and then the surface of the cable was visually observed and evaluated according to the following criteria.
○: No change from before test.
(Triangle | delta): There exists some cloudiness on the cable surface compared with before a test. However, no bleed out is allowed.
X: Bleed out is observed on the cable surface.

(3) Flame retardancy test:
The cable obtained in the above (1) was subjected to UL 1581 standard VW-1 combustion test.
○: Passed.
X: Fail.

(4) Hardness:
In accordance with JIS K7215: 1986, a 6 mm thick press sheet was used as a test piece, and a durometer hardness (type A) of 15 seconds or a durometer hardness (type D) of 5 seconds was measured. The table shows 60A if the durometer hardness (type A) 15 second value is 60 degrees, and 45D if the durometer hardness (type D) 5 second value is 45 degrees.

(5) Tensile strength and tensile elongation:
Based on JIS K6723-1995, a dumbbell No. 2 test piece punched from a 1.0 mm thick press sheet was used and measured at a tensile speed of 200 mm / min.

Examples 1 to 10, Comparative Examples 1 and 2
The components (parts by mass) shown in Table 1 or 2 were melt-kneaded using a pressure kneader at a resin temperature at discharge of 160 ° C. to obtain a flame retardant vinyl chloride resin composition. The above evaluations (1) to (5) were performed. The results are shown in Table 1 or 2.

(6) Spear when forming UL insulated wire:
Using a flame-retardant vinyl chloride resin composition, using an φ40 mm wire extrusion molding machine, a wire corresponding to UL style 1007 having a conductor size of AWG26 was molded continuously for 4 hours. The die exit was visually observed and evaluated according to the following criteria.
◯: No eye discoloration even after 4 hours.
Δ: There is no discoloration before 1 hour. After 1 hour, eyes will be recognized 4 hours later.
×: Eye discoloration is recognized before 1 hour.

(7) Bleed-out resistance 2:
Evaluation was performed in the same manner as in the above (2) except that the electric wire obtained in (6) was used.

(8) Flame retardancy test 2:
About the electric wire obtained by said (6), the VW-1 combustion test of UL1581 specification was done.
○: Passed.
X: Fail.

Examples 11-13
The components (parts by mass) shown in Table 3 were melt-kneaded using a pressure kneader under the condition of a resin temperature at discharge of 160 ° C. to obtain a flame retardant vinyl chloride resin composition. Evaluation of said (4)-(8) was performed. The results are shown in Table 3.

(9) Eye distortion when forming tubes:
Using a flame retardant vinyl chloride resin composition, using a φ40 mm extrusion tube molding machine, the resin temperature at the spiral die outlet is 170 ° C., the cooling water temperature is 15 ° C., the take-up speed is 10 m / min, and the vacuum degree of the vacuum water tank is −7. Under a condition of 0.0 KPa, a tube having an inner diameter of 2.1 mm and an outer diameter of 3.3 mm was extruded continuously for 4 hours. The die exit was visually observed and evaluated according to the following criteria.
◯: No eye discoloration even after 4 hours.
Δ: There is no discoloration before 1 hour. After 1 hour, eyes will be recognized 4 hours later.
×: Eye discoloration is recognized before 1 hour.

(10) Bleed-out resistance 3:
Evaluation was performed in the same manner as in (2) above, except that the tube obtained in (9) above was used.

Examples 14 and 15, Comparative Examples 3 and 4
The components (parts by mass) shown in Table 3 were melt-kneaded using a pressure kneader under the condition of a resin temperature at discharge of 160 ° C. to obtain a flame retardant vinyl chloride resin composition. The evaluations of (4), (5), (9), and (10) were performed. The results are shown in Table 3.

The flame-retardant vinyl chloride resin composition of the present invention has little eye-crack at the time of molding, and is excellent in flexibility, tensile properties, and bleed-out resistance. Therefore, it was possible to obtain cables and electric wires with high flame retardancy and excellent handling properties. Moreover, the tube excellent in handling property was able to be obtained.

On the other hand, instead of component (b), Comparative Examples 1 and 3 using a plasticizer having a cis / trans ratio outside the specified range, Component (b) (DINP (casson. 28553-12-0 phthalate diisononyl ester) Instead of a plasticizer obtained by hydrogenation of casNo. In Comparative Examples 2 and 4 using a plasticizer obtained by hydrogenation of 68515-48-0 phthalic acid diisononyl ester, glazing occurred during molding and the bleed-out resistance was insufficient.

Claims (3)

Component (a) 100 parts by mass of vinyl chloride resin;
Component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by mass; and component (c) flame retardant 1-150 parts by mass;
A flame retardant vinyl chloride resin composition comprising:
An electric wire, cable, tube, packing, or tape containing the resin composition according to claim 1.
The electric wire or cable according to claim 2, which conforms to a UL 1581 standard VW-1 combustion test.