JPS58101128A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved flame retardnace and low smoking properties without damaging electrical characteristics, heat resistance, etc., comprising a uniform mixture of synthetic resin, antimony trioxide, halogen- containing organic compound, and adducts of melamine with various kinds of acids. CONSTITUTION:A synthetic resin (e.g., epoxy resin, etc.) is blended with preferably 1-6wt% based on total organic substances in the composition of antimony trioxide, 1-6wt% based on total organic substances in the composition of a halogen-containing organic compound (e.g., bromobenzene, etc.), 1-6wt% based on total organic substances in the composition of an adduct of melamine with phosphoric acid, 2-15wt% based on total organic substances in the composition of melamine-cyanuric acid adduct and 2-15wt% melamine-molybdic acid, and, if necessary, an inorganic filler, a diluent, a colorant, etc., to give the desired flame-retardant resin composition. EFFECT:No reduction in mechanical strength and gloss. Having improved water resistance.

Description

[Detailed Description of the Invention] Technical Summary of the Invention The present invention relates to (1) a flammable resin composition, and more specifically,
The present invention relates to a resin composition that has excellent flammability and low smoke generation properties without impairing the electrical properties, heat resistance, and mechanical properties of a cured synthetic resin product.

Technical background of the invention and its problems Conventionally, insulating materials made of resin compositions used in electrical equipment, etc. have been made with very low flammability in order to prevent the occurrence of fires and improve safety. High performance is required, and research and development on flammability of various resin compositions is progressing.

However, among insulating materials that use synthetic resins, systems that use synthetic resins and phenolic resins, which have excellent electrical insulation and heat resistance, as resin compositions are approximately 6N class resins described below. Only the composition is known. That is, (1) Phosphorus atoms are 5 to 5 to the total amount of organic matter in the composition.
6 weight amount of the resin composition.

Mountain) Chlorine atoms are 26 to 3 with respect to the total amount of organic matter in the composition
A resin composition comprising an amount of 0 weight arc.

(C) Bromine atom is 1 relative to the total amount of organic matter in the composition
A resin composition containing 3 to 50 parts by weight.

(d) A resin composition containing chlorine atoms and bromine atoms in amounts of 2% by weight and 6% by weight, respectively, based on the total amount of organic substances in the composition.

(e) A resin composition containing phosphorus atoms and bromine atoms in amounts of 2% by weight and 5% by weight, respectively, based on the total amount of organic substances in the composition.

(f) A resin composition comprising antimony trioxide and bromine atoms in amounts of 3% by weight and 5% by weight, respectively, based on the total amount of organic matter in the composition.

By the way, in (1) among the nine compositions described above, the phosphorus atoms contained are usually blended in the best form of phosphoric ester. However, since phosphoric acid esters are generally liquid at room temperature, when flame retardation is attempted using such compounds, the phosphoric acid esters gradually bleed out from the cured resin, resulting in a permanent flame retardant effect. There is a drawback that it cannot be expected.

On the other hand, when a halogen compound is blended as in (d), the amount added is large, and the resin tends to undergo phase separation, making it impossible to obtain a cured resin product with a uniform composition. In addition to being difficult to obtain, there is a drawback that the mechanical strength of the cured resin product and the gloss of its surface are reduced.

In addition, in order to eliminate the disadvantages of using halogen compounds, we reduced the amount of halogen compounds added and added phosphorus atom-containing compounds such as phosphoric acid esters to achieve flame retardancy through their synergistic effect. However, since a tetraphosphate ester is used in the case of kerosene, there is a drawback that a permanent flame release effect cannot be expected.

On the other hand, (f) is the most commonly used flammable resin composition today. However, the degree of flammability required for haze-flammable resin compositions used for insulating materials, etc. is increasing day by day, and the degree of flammability required for the above-mentioned (f) composition is increasing day by day. It is not always possible to satisfy the flammability of L tons, but there is a demand for a tortoise with an even higher flammability.

On the other hand, since many cured flame-retardant resins generate a large amount of smoke when thermally decomposed, there is a strong desire to develop flame-retardant materials with low smoke-emitting properties.

Examples of materials aimed at reducing smoke emissions include:
It has been proposed to further add hydrated alcohol or molybdenum fluoride to the composition (f). However, although these compositions have some effect of reducing smoke emission, when actually used in electrical equipment, etc., the effect is negligible), and flame retardancy is hardly improved. It does not satisfy the required performance.

OBJECT OF THE INVENTION The purpose of the present invention is to improve the above-mentioned conventional drawbacks and to provide a cured synthetic resin with significantly superior Ita properties and An object of the present invention is to provide a resin composition having low smoke emission properties.

Summary of the Invention As a result of intensive research into flame retardants, the present inventor discovered that the above object could be achieved by adding melamine and various alcohol adducts, and was able to complete the present invention.

That is, the S-flammable resin composition of the present invention comprises a synthetic resin, antimony iodide, an organic compound having a herogen atom, a melamine-cyanuric acid adduct, a melamine-phosphorous stirrup adduct, and a melamine-molybdenum adduct. It is characterized by consisting of a homogeneous mixture of.

The present invention will be explained in more detail below.

The adduct of melamine and acid used in the present invention has the following formula CI) M.

The following formula (II
) to (IV) (IF) Cyanuric acid (If) and phosphoric acid (I
II) or molybdenum III (IV) and heating. At this time, it is preferable to carry out the reaction in equimolar amounts, and this can be accomplished by heating the mixture to 7.degree. and 100.degree. C. to add melamine and acid, cooling, filtering, and drying by heating.

When adding the melamine-acid adduct obtained by the above treatment, the amount of melamine-phosphorus adduct is 1 to 6% by weight based on the total amount of organic matter in the composition. Preferably, each adduct is blended in an amount of 2 to 15 weight by weight.

The antimony trioxide used in the present invention is not particularly limited as long as it is a powdery granule that can be kneaded and dispersed with a synthetic resin. It is preferred to use the following:

The amount of fukaru antimony trioxide to be added is preferably one weight or more relative to the total amount of organic matter in the composition. Although there is no problem with adding a large amount of antimony, it is practically preferable to add antimony in an amount of 1 to 6 times.

Any organic compound having a halogen atom used in the present invention can be used as long as it has good thermal stability and does not impair the heat resistance of the Wa cured product. It is preferable to use an organic compound containing . These include, for example, bromine compounds such as bromobenzene, bromophenol, brominated epoxy resins, decabromobiphenyl and 2,3-dibromopropyl-tetrabromophenyl ether, and dichlorane (trade name, 7tsuriki-+ manufactured by Mikal). ), and one or more chlorine compounds selected from the group consisting of these are used.

The amount of the organic compound having a halogen atom added is preferably in the range of 5 to 7 times the total weight of the melamine-phosphorus adduct and antimony trioxide.

The synthetic resin used in the present invention may be any resin that is normally used as an insulating material in electrical equipment, etc., and examples thereof include epoxy resin, phenolic resin, thermosetting polyester, etc. Examples include resins and polyurethane resins, and one or more selected from the group consisting of these resins are used.

In addition to the above-mentioned materials, the combustible resin composition of the present invention may further contain various additives such as inorganic fillers such as silica powder and alumina powder, flexibility imparting agents, diluents, coloring agents, and mold release agents. There is no problem even if it contains an agent.

Effects of the Invention The material obtained by curing the resin composition of the present invention not only has an excellent firefighting effect but also has low smoke generation. In addition, it has excellent heat resistance and water resistance, and because the flame retardant is extremely well dispersed in the resin composition,
Since it is well dispersed, there is no problem such as a decrease in gloss on the surface of the cured product, and there is no decrease in mechanical strength, electrical properties, etc.

In the following, examples are drawn to further explain the invention.

Examples 1 to 4 Epicote 828 (trade name, manufactured by Shell Chemical Co., Ltd.), which is a bisphenol diglycidyl type epoxy resin, was used as the epoxy resin, and HN-2200 (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is methyltetrahydrophthalic anhydride, was used as the curing agent. BROC (trade name, manufactured by Hitachi Chemical Co., Ltd., bromine content: 513% by weight), which is a brominated epoxy resin, was used on an organic compound having a halogen atom, and in addition, antimony trioxide and melamine Using a nuric acid adduct, a melamine-phosphorus ant adduct, and a melamine-molybdenum adduct, and further adding silica powder, each was blended in the proportions (parts by weight) shown in the table to obtain the anti-retardant properties of the present invention. Four types of w fat compositions were prepared. Each of the resin compositions was stirred at room temperature using a kneader for 6 hours or more, then molded and heated in a tzsr for 48 hours to obtain a cured product.

Comparative Examples 1 to 5 At the same time, five types of comparative examples were prepared, including those without the addition of melamine-floor adducts and those with melamine or molybdenum oxide added alone, and cured products of each were prepared in the same manner as in the examples. Obtained. Their composition is also shown in the table.

The cross-flammability and smoke-emitting properties of each of the cured products obtained by the above-mentioned operations were examined by the following method.

llI flammability test: test piece (127XIZ7X2111)
is vertically fixed in a glass cylinder with a diameter of 10011B, and a mixed gas of oxygen and nitrogen is flowed from the bottom of the cylinder.

The upper end of the test piece is heated with a gas burner. 3 minutes when heated and ignited Oxygen and nitrogen when extinguishing within Measure the flow rate of the acid, and use the following formula to calculate the acid flow rate. Find the prime index (0■).

Then, the generated smoke is poured into a certain volume of a passenger container. from one point in the container. Find the transmittance of the light using the following formula. Ru.

I Cs Tomi-Su. -(m-1) L I.

(In the formula, C3: smoke emitting property, L: distance (m) between the light source and receiver, I: light transmittance before the test, and Io: light transmittance during the test.) These results showed that Kameoka sometimes listed in the table. As is clear from the table, it was confirmed that the cured product obtained by the 11 flammable resin composition of the present invention has excellent flame retardancy, and has low paper-making and smoke-emitting properties. On the other hand, when melamine or molybdenum oxide is used alone instead of the melamine-adduct, good m
No flammability was obtained, and a cured resin product with degraded electrical properties due to melamine absorbing moisture was obtained.

Claims (1)

[Claims] Synthetic resin, antimony trioxide, organic compound with halogen atom, melamine-cyanuric acid adduct, melamine-
(1) A flammable resin composition comprising a homogeneous mixture of a phosphoric acid adduct and a melamine-molybdic acid adduct.