JPS6311372B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flame retardant additive for cellulose acetate that is used when melt molding cellulose acetate resin and can impart flame retardancy to molded products. More specifically, the first aspect of the present invention is aromatic phosphoric acid and phosphorous acid ester compounds (A), aliphatic phosphoric esters, halogenated aliphatic phosphoric esters, or condensates thereof (B) and an epoxy group-containing compound (C), the second one is the flame retardant additive for cellulose acetate that contains (A), (B), and (C) in the first invention. 3
The present invention relates to a flame retardant additive for cellulose acetate, which further includes an ester plasticizer that does not contain phosphorus as an essential component. Due to its excellent physical properties, cellulose acetate resin has traditionally been applied and used in a wide variety of ways as molded products and fibers, but recently as its use has diversified, it has been used as a material similar to other synthetic polymer materials. The flammability of cellulose acetate resin has attracted attention as one of its major drawbacks.
At present, there is a strong demand for flame retardancy. Many proposals have been made to make synthetic polymer materials flame retardant using various methods such as copolymerization, kneading, and surface treatment. Most of the flame retardants proposed in these proposals consist of three groups of basic elements: halogen compounds, phosphorous compounds, and inorganic salts. Alternatively, a combination of two or more types is usually selected. However, flame retardant technology to provide the desired flame retardancy is
Strength of synthetic polymer materials by using flame retardants,
There are many problems, such as a decline in physical properties such as hue and light resistance, complicated manufacturing techniques, and an increase in the price of the product due to the use of flame retardants, etc., and despite many proposals, it is extremely difficult to put it into practical use. Have difficulty. As with other polymer materials, there are many proposals for cellulose acetate resin, such as those mentioned above.
Among these, in oxygen-containing polymeric materials such as the resins, it is known that phosphorus, a group of compounds containing phosphorus and halogens are effective in imparting flame retardance. In addition, it is clear that the kneading type is advantageous for the flame retardant method of cellulose acetate due to the characteristics of the resin, and there have been many proposals for this method, especially when the resin uses a plasticizer in the molding process. Because of this, there are proposals to impart flame retardancy by using flame-retardant plasticizers. The method of using this plasticizer is an excellent method from a practical standpoint, but in that case, the additive must have many advanced properties such as plasticity, flame retardance, thermal stability, and compatibility. This is what is required. Although many flame-retardant plasticizers that have been proposed to date have flame retardancy,
Most of them have some kind of drawback such as insufficient compatibility or thermal stability, and at present they are not yet fully satisfactory for practical use. In view of the above-mentioned circumstances, the present inventors conducted intensive studies to obtain a practical additive that can impart flame retardancy to cellulose acetate molded products, and as a result they have developed the following invention. Reached. The first invention is (A) one or more than one selected from aromatic phosphate esters and aromatic phosphite esters.
-70% by weight (B) 25-60% by weight of one or more selected from aliphatic phosphoric acid esters, halogenated aliphatic phosphoric esters, or condensates thereof (C) epoxy group-containing compounds A flame retardant additive for cellulose acetate characterized by consisting of 5 to 15% by weight of one or more of the above three components (A), (B) and (C), and the second flame retardant additive of the present invention. The invention is based on (A) one or more aromatic phosphoric acid esters selected from aromatic phosphoric acid esters and aromatic phosphite esters.
~65% by weight (B) 20~55% by weight of one or more selected from aliphatic phosphate esters, halogenated aliphatic phosphates, or condensates thereof (C) Epoxy group-containing compound (D) 5-15% by weight of one or more phosphorus-free ester plasticizers (A), (B), (C) and (D) A flame retardant additive for cellulose acetate. That is, the present inventors found that although the thermal stability is good for cellulose acetate, the compatibility is insufficient.
By using an additive consisting of component (A), component (B) which has good compatibility but insufficient thermal stability, and component (C) which is effective in improving thermal stability,
By using a four-component additive consisting of these three components and a well-compatible phosphorus-free component (D), plasticity and thermal stability that cannot be expected from additives made from each individual component can be achieved. The present invention was achieved based on the discovery that excellent properties can be achieved in terms of properties, compatibility, and flame retardancy. More specifically, the additive of the present invention can be used when melt-molding cellulose acetate resin to impart flame retardancy to the molded product, and the additives used in the blended (A) and (B)
The three components (C) and the four components (A), (B), (C), and (D) provide an unprecedented flame retardant additive for cellulose acetate that is highly practical and highly practical. . Each of the individual components constituting the additive of the present invention is already known, but in the present invention, a synergistic effect can be exerted by appropriately blending the three or four components. It satisfies all of the various properties required as a flame retardant additive for cellulose acetate, has outstanding performance, and can bring about effects that cannot be matched by conventional products. The purpose of the present invention is to make effective use of the excellent thermal stability of component (A), the excellent compatibility and plasticity of component (B), and the excellent thermal stability imparting properties of component (C). By compensating for the drawbacks of the components and further imparting a higher degree of plasticity with component (D), the flame retardant properties of components (A) and (B) can be fully demonstrated in practical use, and the resin can be made flame retardant. It is an object of the present invention to provide an additive that imparts excellent flame retardancy to cellulose acetate molded products in terms of workability such as ease of process and good workability during chemical treatment. The aromatic phosphoric acid ester which is the component (A) in the first invention is triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tricylenyl phosphate, diphenyl monoorthoxenyl. phosphate, octyl diphenyl phosphate, phenylchloropropyl phosphate, or substituted phenol alkylene oxide adduct phosphate esters, and aromatic phosphite esters include triphenyl phosphite, tri(nonylphenyl) phosphite, and diphenyl phosphite. Examples include enyldecyl phosphite, diphenylhydrodiene phosphite, phenyl diisooctyl phosphite, phenyl dilauryl dithiophosphite, diphenyl lauryl monothiophosphite, and one or more of them. are used in combination. Examples of the aliphatic phosphoric acid ester which is component (B) in the present invention include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, and trilauryl phosphate, and butyl acid. Alkyl or dialkyl acid phosphates such as phosphate, dibutyl acid phosphate, octyl acid phosphate, didecyl acid phosphate, and similar compounds in which these alkyls are replaced with alkyl alkylene oxide adducts, as well as acid phosphates. alkylene oxide adducts. Examples of halogenated aliphatic phosphoric acid esters include tris(dichloropropyl) phosphate, trichloroethyl phosphate, trichloropropyl phosphate, etc., and condensates thereof, and one or more of these may be used. are used in combination. Furthermore, as the epoxy group-containing compound which is component (C) in the present invention, ethyl glycidyl ether, phenyl glycidyl ether, lauryl glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, bisphenol A- diglycidyl ether, or
There are epoxidized soybean oil, epoxidized polybutadiene, etc., and one or more of them are used in combination. Phosphorus-free ester plasticizers, which are component (D) of the second invention, include aliphatic carboxylic acid esters and aromatic carboxylic acid esters, specifically dimethyl phthalate, diethyl phthalate, and methyl phthalyl. Examples include ethylene glycolate, dicarbitol phthalate, dibutyl phthalate, diamyl phthalate, dibutyl sebatate, and one or more of them are used in combination. Although specific examples have been given for each component used in the above invention, the invention is not limited to these examples. As mentioned above, the purpose of the present invention is achieved by using a mixture of the three components (A), (B), and (C) or the four components, (A), (B), (C, and D). The mixing ratio of each component is also important in order for the additive to fully satisfy all of the above-mentioned properties, including flame retardancy, compatibility, heat resistance, and plasticity. In order to fully satisfy the required properties of the additive consisting of three components (A), (B), and (C), which is the first invention, the mixing ratio of each component is 20 to 80%.
(same below weight%), preferably 30 to 70%, component (B)
is 20-70%, preferably 25-60%, and component (C) is 5-70%.
It is in the range of 20%, preferably 5-15%. In addition, the mixing ratio of each component of the additive consisting of four components (A), (B), (C), and (D), which is the second invention, is 20 to 75%.
%, preferably 30-65%, component (B) 20-60%, preferably 20-55%, component (C) 5-20%, preferably 5-15%, component (D) 5-5%. 20%, preferably 5~
It is in the range of 15%. Furthermore, the content of phosphorus contained in the additives in the first and second aspects of the present invention must be 5% or more, preferably 7% by weight or more, in order to impart flame retardancy. In the present invention, by using each component together within the above blending ratio range, the characteristics of each individual component are synergistically exhibited, and the resulting additive has the required characteristics. All of them will be satisfied. The amount of the additive according to the invention used to impart flame retardancy to cellulose acetate ranges from 15 to 65%, preferably from 25 to 50%. There are no particular limitations on the method of putting the additive of the present invention into practical use; for example, the individual components may be mixed separately with cellulose acetate, or some or all of the components may be mixed in advance with the additive. Possible methods include mixing the filtrate with cellulose acetate. Further, when carrying out the present invention, there is no problem in adding components other than the additives of the present invention for other purposes as long as the effects of the present invention are not impaired. Hereinafter, examples of the present invention will be given and the effects thereof will be described, but of course the present invention is not limited to these examples. First, the test methods performed on the examples and comparative examples of the present invention will be described below. Compatibility test: Put 9 g of cellulose acetate resin and 1 g of the additives of Examples and Comparative Examples shown in the table into a hard glass test tube with a capacity of 20 ml.
The resulting mixture was immersed in an oil bath at 0.degree. C. and removed after 1 hour and evaluated by visual observation according to the standards shown below. 〇...The entire pellet is dissolved uniformly and transparently △...Heterogeneity such as particulate matter is present in some parts ×...There is a lot of insoluble matter or there is layer separation Heat resistance test; Sample pellets of Examples and Comparative Examples 10
Take g in a hard glass test tube with a capacity of 20ml,
After being left at 200° C. for 1 hour, the degree of coloring was evaluated by visual observation according to the standard shown below. 〇...The whole is colorless or light yellow △...The whole or a part is yellow or brown ×...The whole or a part is brown or dark Cellulose board" 7
-6 test pieces were prepared and used for testing. A Bunsen burner with a flame approximately 15 mm long was placed on this test piece for 5 minutes.
The combustion condition after the flame was removed was determined according to the standard shown below. 〇…Burning speed is less than 5 mm per second and from the ignition end
Flame extinguished within 96 mm △...Burning speed was 12 mm per second or less ×...Other than the above Example 1 2000 g of cellulose acetate, 400 g of triphenyl phosphate, 50 g of triphenyl phosphite
g, tri(2-chloroethyl) phosphate 400
g and 150 g of epoxidized soybean oil were mixed well at 80 to 90°C to evenly adhere the whole mixture, and then mixed with 25 g of epoxidized soybean oil
The sample was extruded into a rod shape at 200°C to 220°C using a 2.0 mm extruder, cooled, and then pelletized. Examples 2 to 8 and Comparative Examples 1 to 5 Samples were prepared in the same manner as in Example 1 using the additives shown in the following table, and were subjected to testing. The ingredients of the additive of the present invention and the comparative examples and the test results conducted on them are as shown in the following table. It is clear from the evaluation results shown in the table that the effects of the additive of the present invention are remarkable.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) 30 to 70% by weight of one or more selected from aromatic phosphoric esters and aromatic phosphites; (B) aliphatic phosphoric esters and halogens; 25 to 60% by weight of one or more selected from aliphatic phosphoric acid esters or condensates thereof; (C) 5 to 15% by weight of one or more epoxy group-containing compounds; A flame retardant additive for cellulose acetate, characterized in that it consists of each of the three components shown in (A), (B) and (C) in respective weight percentages. 2 (A) 30 to 65% by weight of one or more selected from aromatic phosphoric acid esters and aromatic phosphite esters, (B) aliphatic phosphoric acid esters and halogenated aliphatic phosphoric esters or 20 to 55% by weight of one or more types selected from these condensates, (C) 5 to 15% by weight of one or more epoxy group-containing compounds, (D) Contains phosphorus. 5 to 15% by weight of one or more ester plasticizers and each of the four components shown in (A), (B), (C) and (D) above. Flame retardant additive for cellulose acetate.