JPS6316422B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flame-retardant and smoke-inhibiting flexible thermoplastic resin composition. Characterized by its chlorine content and therefore low flammability, as well as its excellent mechanical properties, polyvinyl chloride, in addition to its versatile formulation versatility, can be used, for example, in structural components, decorative textiles, etc. Polyvinyl chloride is widely used commercially in the production of films, wire coverings, floor coverings, etc., but as is well known, polyvinyl chloride requires the inclusion of large amounts of thermoplastics to provide flexibility. Formulations containing flammable plasticizers thus have reduced flame retardancy and, when exposed to elevated temperatures in a flame, have an increased tendency to smoke and are often dangerous. This poses a greater danger to those caught in the flames than the flames themselves. Especially generated HCl
Because gas causes poisoning accidents in the event of a fire due to its corrosive nature and toxicity, reducing this gas is an important issue when making polyvinyl chloride flame retardant. In addition, the temperature is not as high as in a flame, but at 200 to 300 degrees Celsius, where almost no hydrochloric acid gas is generated from polyvinyl chloride.
Even within this range, the contained plasticizer gas is generated, and if it comes into contact with another flame, it will easily ignite and transfer to nearby combustible materials such as dust, which may cause a fire. In order to solve these problems, the present inventors (1) developed a flexible polyvinyl chloride resin that does not require the inclusion of a liquid plasticizer, and (2) developed a suitable material for the above flexible polyvinyl chloride resin. As a result of intensive research into the formulation of flame retardants, the present invention was completed. That is, the present invention uses an aliphatic diisocyanate which is soluble in vinyl chloride monomer and has a softening point of 20 to 100°C, and which is soluble in the monomer or monomer mixture described below.
20 to 150 per 100 parts by weight (hereinafter simply referred to as parts)
In the coexistence of a thermoplastic polyurethane elastomer, vinyl chloride monomer alone or vinyl chloride monomer and a monomer that can be copolymerized with vinyl chloride monomer and give a homopolymer with a glass transition temperature lower than 30°C. 1 to 50 parts of a flame retardant and 5 to 50 parts of a filler per 100 parts of a soft thermoplastic resin obtained by polymerizing a polymer mixture in an aqueous medium.
This is a flame-retardant soft thermoplastic resin composition containing 100 parts of The main feature of the present invention is the use of a soft thermoplastic resin having the following features (1) to (3). (1) It has flexibility even if it does not contain plasticity. (2) Flame retardant. (3) Less amount of hydrochloric acid gas generated at high temperatures (800℃). In developing a flame-retardant resin composition, the present inventors focused on flame-retardant polyvinyl chloride, and succeeded in producing a flexible polyvinyl chloride resin that does not require the inclusion of a plasticizer. However, it was surprisingly discovered that the amount of hydrochloric acid gas generated by this resin at high temperatures is extremely small compared to a soft polyvinyl chloride composition containing a plasticizer. Furthermore, a composition that satisfies the flame retardancy and smoke suppression properties by adding 1 to 50 parts of a flame retardant and 5 to 100 parts of a filler to 100 parts of the above resin having flame retardancy and hydrochloric acid gas suppression properties. was found to be obtained. The soft thermoplastic resin used in the present invention can be produced by the following method. That is, vinyl chloride monomer (hereinafter referred to as MVC)
Or, 100 parts of a monomer mixture of MVC and a monomer that can be copolymerized with it and whose homopolymer has a glass transition temperature lower than 30°C (hereinafter collectively referred to as MVC monomers), Soluble in and has a softening point of 20~
Thermoplastic polyurethane elastomer (hereinafter referred to as
It is produced by polymerizing in the presence of 20 to 150 parts of MVC (abbreviated as soluble TPU), an aqueous medium, a suspending agent, and an oil-soluble polymerization initiator. MVC soluble type in the production of soft thermoplastics
TPU is a substance that substantially dissolves in the MVC monomer under the polymerization conditions for manufacturing the above-mentioned flexible thermoplastic resin, and has a softening point of 100° to 20°C, preferably 60° to 30°C. be. What is the softening point here?
This refers to the softening temperature determined by the temperature increase method using a Shimadzu Koka flow tester under the following conditions. Measurement conditions for Shimadzu Koka flow tester Nozzle dimensions: 1mmφ x 2mmL Load: 30Kg Heating rate: 3℃/min Materials with a softening point of over 100℃ will be difficult to dissolve in the MVC monomer, and at 20℃ If it is less than 20%, the resulting polymer will have poor tensile strength and heat resistance. or
MVC-soluble TPU is preferably a non-yellowing type that uses aliphatic diisocyanate as a raw material. While the non-yellowing type has good UV stability,
In the case of non-yellowing types, the resulting polymer obtained after polymerization tends to be colored. Effective for the present invention
A suitable example of MVC soluble TPU is Pantex T manufactured by Dainippon Ink and Chemicals Co., Ltd.
-5265, Pantex T-525, etc. The softening points are 53°C and 47°C, respectively. In the production of soft thermoplastic resin, MVC-soluble TPU starts polymerization at 20 to 150 parts per 100 parts of MVC or MVC monomer at the time of preparation. For 100 parts of MVC or MVC monomer,
If the amount of MVC-soluble TPU is less than 20 parts, the resulting polymer will not have satisfactory softness;
If it exceeds 150 parts, the polymerization rate may become slow, which is not preferable. In soft thermoplastic resins, the
A good MVC soluble TPU content is 17-65% by weight. 17
If it is less than % by weight, it is difficult to obtain satisfactory softness. On the other hand, if it exceeds 65% by weight, flame retardancy decreases and costs increase, making it economically unfavorable. In the production of soft thermoplastic resins, it is possible to copolymerize with MVC, and the glass transition temperature of the homopolymer is
Monomers with temperatures lower than 30℃ include olefins such as ethylene and propylene, vinylidene halides such as vinylidene chloride, vinyl esters such as vinyl acetate, vinyl ethers such as n-butyl vinyl ether, butyl acrylate, and acrylic. Examples include acrylic esters such as 2-ethylhexyl acid, methacrylic esters such as 2-ethylhexyl methacrylate, and the like. The amount used is preferably 50% by weight or less, more preferably 30% by weight or less in the MVC monomer. This is because if the amount exceeds 50% by weight, the processability, heat resistance, etc. of the resulting polymer deteriorate. The polymerization method employed in the production of the soft thermoplastic resin may be either a suspension polymerization method or an emulsion polymerization method, and the suspending agent used in the suspension polymerization method may be any known suspending agent. For example, partially saponified polyvinyl alcohol, methylcellulose, ethylcellulose, hydroxymethylcellulose, polyacrylic acid, vinyl ether-maleic anhydride copolymer, gelatin, etc. are used, and these may be used alone or in combination. In addition, the amount of these used is 0.01 to 0.01 to aqueous medium.
It is about 2% by weight. The oil-soluble polymerization initiator used in the production of the soft thermoplastic resin may be any known polymerization initiator.
For example, azo compounds such as azobisisobutylvaleronitrile, lauryl peroxide, di-2
Ethylhexyl peroxydicarbonate, t-
There are organic peroxides such as butyl peroxypivalate. The amount used is about 0.01 to 2% by weight based on the MVC monomer at the time of preparation. Aqueous media in the production of soft thermoplastic resins/
The charging ratio of (MVC soluble TPU + MVC monomer) is preferably 1/1 to 3/1. This is because if the ratio is less than 1/1, polymerization becomes unstable, and if the ratio exceeds 3/1, it is not economically advantageous. The polymerization temperature is 30° to 70°C, preferably 40° to 60°C. This is not industrially advantageous since the polymerization rate tends to slow down below 30°C. Moreover, if the temperature exceeds 70°C, the heat resistance etc. of the resulting polymer tends to deteriorate, which is not preferable. Next, the flame retardant is specifically one or more selected from the group consisting of antimony trioxide, zinc borate, molybdenum oxide, ammonium molybdate, zirconium oxide, and ferrocene; The filler is one or more selected from the group consisting of calcium carbonate, basic magnesium carbonate, magnesium hydroxide, hydrotalcite, magnesium oxide, sodium hydrogen carbonate, and aluminum hydroxide. Preferred flame retardants are antimony trioxide, zinc borate, and ferrocene; preferred fillers are calcium carbonate, hydrotalcite, and aluminum hydroxide. The proportion of flame retardant and filler used is 1 to 50 parts and 5 to 100 parts, respectively, per 100 parts of soft thermoplastic resin.
Department. If the flame retardant content is less than 1 part, the effective oxygen index will be insufficient, and if it exceeds 50 parts, the mechanical properties will deteriorate and the cost will also increase, which is not preferable. Furthermore, if the amount of the filler is less than 5 parts, the hydrochloric acid gas suppressing property will be insufficient, and if it exceeds 100 parts, the mechanical properties will be significantly deteriorated, which is undesirable. The above-mentioned flame retardants and fillers exhibit different effects and therefore require some consideration when actually used. For example, to achieve the same flame retardant effect, antimony trioxide needs to be used in a smaller amount than zinc borate, and when both are used together, they have a synergistic effect, so the amount used can be reduced compared to using them alone. . The amounts of the flame retardants used are preferably 1 to 20 parts for antimony trioxide and zinc borate, and 1 to 5 parts for ferrocene. The amounts of the fillers used are preferably 10 to 50 parts for calcium carbonate and aluminum hydroxide, and 5 to 25 parts for hydrotalcite. These may be blended individually or in combination of two or more. The composition of the present invention may further contain additives of a type and amount that do not adversely affect the effects of the present invention. Examples of such additives include heat stabilizers, lubricants, antioxidants, ultraviolet absorbers, etc. that are commonly used in polyvinyl chloride. The soft thermoplastic resin, flame retardant, and filler used in the present invention may be mixed by adding them at the same time or in any order, and the mixer may be a Banbury mixer, a kneader blender, Hensiel mixer, ribbon blender,
An extruder or other suitable mixer can be used. The method for molding the composition in the present invention includes processing methods used in the field of processing polyvinyl chloride;
For example, calendering, extrusion molding, injection molding, press molding, etc. can be employed. The molded product obtained from the composition of the present invention has excellent flame retardancy and hydrochloric acid gas suppression properties, and is flexible without containing a plasticizer, so it has excellent heat resistance, oil resistance, and stain resistance. Furthermore, it has excellent mechanical properties, cold resistance, and weather resistance, so it is suitable as a material for structural components, electric wire coverings, floor coverings, etc. Specifically, the soft thermoplastic resin composition obtained by the present invention has flame retardancy with an oxygen index of 30 or more, which is a measure of the flammability of a substance, and smoke suppression with an amount of hydrochloric acid gas generated during smoke generation. It is 150 mg/g or less according to the test method of the Japan Electric Cable Industry Standard.
Therefore, a molded article using the resin composition of the present invention has high safety against fire and the like. Next, the present invention will be explained in more detail with reference to Examples. The physical properties were measured according to the following method. Brittleness temperature JIS K6301 Tensile test JIS K6723 Flame retardancy test JIS K7201 Hydrochloric acid gas generation JCSC No. 53 Example 1 In a stainless steel autoclave with an internal volume of 10
40 parts of MVC soluble TPU (Pandex T-5265 manufactured by Dainippon Ink and Chemicals Co., Ltd.), 200 parts of pure water, 0.8 parts of partially saponified polyvinyl alcohol (Gosenol KH-17 manufactured by Nippon Gosei Co., Ltd.), di- After charging 0.05 part of 2-ethylhexyl peroxydicarbonate and replacing the internal air with N ₂ , 60 parts of MVC was charged. After reacting at 58° C. for 15 hours, unreacted monomers were removed and this was dehydrated and dried to obtain 90 parts of a powdery polymer. 5 parts of antimony trioxide, 30 parts of soft calcium carbonate, 1.5 parts of barium stearate, and 0.5 parts of zinc stearate were mixed with 100 parts of the obtained polymer, and the mixture was kneaded at 170°C using an 8-inch roll. A composition was obtained. Next, this composition was molded at 180°C using a press molding machine.
The material was made into a sheet and subjected to physical property tests, flame retardancy tests, and measurements of the amount of hydrochloric acid gas generated. The results are shown in Table-1. In the following Examples 2 to 11, the operating conditions for producing the compositions were the same as in Example 1, so only the blended amounts of each substance are shown, and the results are summarized in Table 1. Example 2 Polymer (Example 1) 100 Antimony trioxide 5 Heavy calcium carbonate 30 Barium stearate 1.5 Zinc 0.5 Example 3 Polymer (Example 1) 100 Antimony trioxide 5 Aluminum hydroxide 30 Barium stearate 1.5 〃 Zinc 0.5 Example 4 Polymer (Example 1) 100 Antimony trioxide 5 Zinc borate 5 Light calcium carbonate 30 Barium stearate 1.5 〃 Zinc 0.5 Example 5 Polymer (Example 1) 100 Antimony trioxide 5 Molybdic acid Ammonium 5 Light calcium carbonate 30 Barium stearate 1.5 Zinc 0.5 Example 6 Polymer (Example 1) 100 Antimony trioxide 5 Ferrocene 2 Light calcium carbonate 30 Barium stearate 1.5 Zinc 0.5 Example 7 Polymer (Example 1) ) 100 Antimony trioxide 5 Light calcium carbonate 30 Hydrotalcite 10 Barium stearate 1.5 Zinc 0.5 Example 8 Polymer (Example 1) 100 Antimony trioxide 5 Zinc borate 5 Light calcium carbonate 30 Aluminum hydroxide 10 Stearic acid Barium 1.5 Zinc 0.5 Example 9 Polymer (Example 1) 100 Antimony trioxide 5 Zinc borate 5 Heavy calcium carbonate 30 Hydrotalcite 10 Barium stearate 1.5 Zinc 0.5 Example 10 Polymer (Example 1) 100 Antimony trioxide 10 Light calcium carbonate 30 Barium stearate 1.5 〃 Zinc 0.5 Example 11 Polymer (Example 1) 100 Antimony trioxide 5 Light calcium carbonate 50 Barium stearate 1.5 〃 Zinc 0.5 Example 12 Stainless steel with an internal volume of 100 made in an autoclave
30 parts of MVC soluble TPU (Pandex T-5265 manufactured by Dainippon Ink and Chemicals Co., Ltd.), 200 parts of pure water, 0.8 parts of partially saponified polyvinyl alcohol (Gosenol KH-17 manufactured by Nippon Gosei Co., Ltd.), After charging 0.05 part of 2-ethylhexyl peroxydicarbonate and replacing the air inside with N ₂ , 70 parts of MVC was charged. After reacting at 58° C. for 15 hours, unreacted monomers were removed and this was dehydrated and dried to obtain 90 parts of a powdery polymer. To 100 parts of the obtained polymer, 5 parts of antimony trioxide, 30 parts of light calcium carbonate, 1.5 parts of barium stearate, and 0.5 parts of zinc stearate were mixed and kneaded at 180°C using a 40φmm extruder. It was then pelletized to obtain a composition. Next, this composition was formed into a sheet at 180° C. using an extruder equipped with a T die, and a physical property test, a flame retardance test, and a measurement of the amount of hydrochloric acid gas generated were performed. Display the results -
Shown in 2. In Examples 13 to 16 below, the operating conditions for producing the compositions were the same as in Example 12, so only the blended amounts of each substance are shown, and the results are summarized in Table 2. Example 13 Polymer (Example 12) 100 Antimony trioxide 3 Light calcium carbonate 30 Barium stearate 1.5 Zinc 0.5 Example 14 Polymer (Example 12) 100 Antimony trioxide 5 Light calcium carbonate 30 Hydrotalcite 10 Stearin Barium acid 1.5 Zinc 0.5 Example 15 Polymer (Example 12) 100 Molybdenum oxide 5 Light calcium carbonate 30 Hydrotalcite 10 Barium stearate 1.5 Zinc 0.5 Example 16 Polymer (Example 12) 100 Antimony trioxide 5 Heavy calcium carbonate 30 Hydrotalcite 10 Barium stearate 1.5 Zinc 0.5 Comparative example 1 1.5 parts of barium stearate and 0.5 parts of zinc stearate were blended with 100 parts of the polymer produced in Example 1. A sheet was prepared in the same manner as above, and physical property tests, flame retardancy tests, and hydrochloric acid gas generation measurements were conducted. The results are shown in Table-1. Comparative Example 2 Polyvinyl chloride [Aron manufactured by Toagosei Chemical Industry Co., Ltd.
TS-1100, = 1050] per 100 parts, 55 parts of dioctyl phthalate, 1.5 parts of barium stearate,
A sheet was prepared by adding 0.5 part of zinc stearate in the same manner as in Example 1, and was subjected to physical property tests, flame retardancy tests,
The amount of hydrochloric acid gas generated was measured. The results are shown in Table-1. Comparative Example 3 1.5 parts of barium stearate and 0.5 parts of zinc stearate were blended with 100 parts of the polymer produced in Example 12, a sheet was prepared in the same manner as in Example 12, and the material was tested for physical properties and flame retardancy. The amount of hydrochloric acid gas generated was measured. The results are shown in Table-2. Comparative Example 4 0.5 parts of antimony trioxide, 3 parts of light calcium carbonate, 1.5 parts of barium stearate, and 0.5 parts of zinc stearate were added to 100 parts of the polymer produced in Example 12, and the same method as in Example 12 was carried out. A sheet was prepared, and physical property tests, flame retardancy tests, and hydrochloric acid gas generation measurements were conducted. The results are shown in Table-2. Comparative Example 5 Polyvinyl chloride [Aron manufactured by Toagosei Chemical Industry Co., Ltd.
TS-1100, = 1050] 40 parts of dioctyl phthalate, 1.5 parts of barium stearate per 100 parts,
A sheet was prepared in the same manner as in Example 12 by adding 0.5 part of zinc stearate, and a physical property test, a flame retardance test, and a measurement of the amount of hydrochloric acid gas generated were performed. Display the results -
Shown in 2. Comparative Example 6 Polyvinyl chloride [Aron manufactured by Toagosei Kagaku Kogyo Co., Ltd.
TS-1100, = 1050] For 100 parts, 40 parts of dioctyl phthalate, 5 parts of antimony trioxide, 30 parts of light calcium carbonate, and 1.5 parts of barium stearate.
Example 12
A sheet was prepared in the same manner as above, and physical property tests, flame retardance tests, and hydrochloric acid gas generation amount measurements were performed. The results are shown in Table-2.

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Claims (1)

[Claims] 1 Soluble in vinyl chloride monomer and has a softening point of 20
~100℃ and using an aliphatic diisocyanate per 100 parts by weight of the monomer or monomer mixture described below.
In the coexistence of 20 to 150 parts by weight of a thermoplastic polyurethane elastomer, vinyl chloride monomer alone or vinyl chloride monomer and a monopolymer that can be copolymerized therewith and has a glass transition temperature lower than 30°C can be obtained. 1 to 50 parts by weight of a flame retardant per 100 parts by weight of a soft thermoplastic resin obtained by polymerizing a monomer mixture with a flame retardant in an aqueous medium.
A flame-retardant flexible thermoplastic resin composition comprising 5 to 100 parts by weight of a filler and a filler.