JPH09302243A - Flame-retardant thermosetting resin composition and flame-retardant molded item produced therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonhalogenous, water-insol. flame retardant which imparts strong flame-retardant properties to a thermosetting resin. SOLUTION: A compsn. comprising 100 pts.wt. melamine-deriv.-coated ammonium polyphosphate (contg. 0.5-20wt.% melamine units) and 0.1-30 pts.wt. triazine deriv. is reacted with a formaldehyde compd. to give a water-insol., triazine- deriv.-treated modified ammonium polyphosphate. The obtd. modified ammonium polyphosphate in an amount of 0.01-200 pts.wt. is compounded, together with a necessary curative, into 100 pts.wt. thermosetting resin prepolymer to give a flame-retardant thermosetting resin compsn. A test piece obtd. from the resultant compsn. exhibits a flame retardance (UL94V, 1.6mm-thick) of V-0, an oxygen index of 34.0, a surface electric resistance in the hot water immersion test of 4.0×10<16> Ω(initial) → 5.5×10<16> Ω (the first run) →5.3×10<16> Ω (the second run), and a bleeding resistance rated as 'exceleent'.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant thermosetting resin composition containing a non-halogen flame retardant as an active ingredient.
Specifically, it was treated with a triazine derivative obtained by reacting a specific triazine compound and formaldehyde as a non-halogen flame retardant with a melamine-coated ammonium polyphosphate (modified ammonium polyphosphate). A flame-retardant thermosetting resin that contains modified ammonium polyphosphate (sometimes referred to as "triazine-treated modified ammonium polyphosphate") as the main component of a flame retardant and has excellent water resistance and strong flame retardancy. The present invention relates to a composition and various flame-retardant molded articles molded from the flame-retardant thermoplastic resin composition.

[0002]

2. Description of the Related Art Conventionally, thermosetting resins typified by epoxy resins, urethane resins, phenol resins, etc., take advantage of their excellent heat resistance and / or mechanical strength to provide electric and electronic parts, civil engineering and building parts, In addition to being widely used as a molding material for automobile parts, it is also widely used as a raw material for manufacturing adhesives, sealing materials, synthetic resin-impregnated paper, and the like.

In order to achieve the purpose of making the thermosetting resin flame-retardant, a means such as blending a halogen-based organic compound or halogenating a part of the polymer chain has been generally used. It was However, a thermosetting resin composition containing the halogen-based organic compound has been regarded as a problem from the standpoint of environmental protection, in that a corrosive gas containing halogen is generated during combustion.

On the other hand, as a method of flame retarding without containing a halogen compound, the endothermic reaction at the combustion temperature of the resin can be used to cause decomposition and dehydration reaction of the additive to suppress the combustion of the resin. A method of blending a specific metal hydrate as an inorganic flame retardant has been proposed (JP-A-3-19).
0965).

However, since the flame retardancy-imparting effect of the metal hydrate is extremely weak, it is necessary to add a large amount of it in order to achieve the desired flame retardancy. As a result, there remain problems such as deterioration of resin moldability and deterioration of various properties such as mechanical strength of the obtained molded product.

[0006] A recently proposed measure to meet the above various requirements is to add ammonium polyphosphate, which is a phosphorus compound, to a thermosetting resin. However, another problem is that the ammonium polyphosphate is a compound which is very susceptible to hydrolysis due to its chemical structure. The problem is that the ammonium polyphosphate or a hydrolyzate of the ammonium polyphosphate elutes or bleeds out from the resin composition containing the ammonium polyphosphate in a hot and humid environment.

As another flame-retardant technique, Japanese Patent Laid-Open No. 1-
According to Japanese Patent No. 108261, a flame-retardant polymer composition containing ammonium polyphosphate coated with a synthetic resin, aluminum hydroxide and an organic nitrogen compound is disclosed. This measure succeeded in making ammonium polyphosphate hardly soluble in water by using ammonium polyphosphate coated with a synthetic resin.

However, due to the addition of the metal hydrate, the compatibility of the synthetic resin-coated ammonium polyphosphate with the thermosetting resin was lowered. As a result, there has been a problem that the mechanical strength of a molded article obtained by molding such a flame retardant composition is often lowered.

In order to solve these problems, the present inventors cross-link the surface of melamine-coated ammonium polyphosphate particles with a compound having a functional group reactive with active hydrogen belonging to an amino group in a melamine molecule. There has already been provided a thermosetting resin composition containing the water-insoluble ammonium polyphosphate particles thus obtained as a flame-retardant main agent (Japanese Patent Laid-Open No. Hei 7)
-268127 publication).

The water-insoluble ammonium polyphosphate particles described in the above-mentioned publicly known documents have a reduced hydrolyzability, whereby a flame-retardant thermosetting resin composition containing the insoluble ammonium polyphosphate as a flame retardant is obtained. Bleed-out of the flame retardant from the molded product obtained by using was eliminated.

However, since the water-insoluble resin layer used by the present inventors to coat the surface of the water-insoluble ammonium polyphosphate particles did not have sufficient flame retardancy, the molded article was further There is still room for improvement in order to be used in fields requiring high (strong) flame retardancy.

[0012]

Therefore, the present inventors have developed a coating which itself has strong flame retardancy and is excellent in hydrolysis suppressing ability, and thereby coats ammonium polyphosphate which is a flame retardant main agent. We have made intensive studies with the aim of establishing a policy to do so.

The resulting flame-retardant base agent does not cause elution from the flame-retardant composition in which it is incorporated, nor bleed-out due to its hydrolysis, and is free from the generation of halogen. Reached Moreover, the flame retardant composition itself or the flame retardant composition comprising the flame retardant auxiliary agent and the flame retardant aid depending on the case may exhibit a high degree of flame retardance even in a flame retardant compound added at a low concentration. The object of the present invention is sufficiently met in the point of forming a flammable thermosetting resin composition.
In addition to the above, an object of the present invention is to provide various flame-retardant molded articles molded from the above flame-retardant thermoplastic resin composition.

[0014]

As means for forming a flame-retardant thermosetting resin composition capable of exhibiting the above-mentioned high flame retardancy, the present inventors have found that a specific triazine compound and formaldehyde (the present invention Is a general term for "multimers including oligomers such as formaldehyde monomer and its dimer, dioxane, and trimer, trioxane"), and reacting a melamine-coated ammonium polyphosphate with a triazine derivative It was found that the above-mentioned problems can be solved by using the water-insoluble modified ammonium polyphosphate obtained as a main component of a flame retardant,
As a result of further research based on this finding, the present invention has been completed.

As is apparent from the above, the object of the present invention is suitable for the fields of sealing materials, adhesives, synthetic resin-impregnated paper, etc., as well as providing electric and electronic parts materials, civil engineering building materials, automobile parts materials. A thermosetting resin composition having excellent hydrolysis resistance and flame retardancy that can be used for

The present invention has its main points in that it exerts its effects by combining the following constituents: 1) A thermosetting resin contains modified ammonium polyphosphate treated with a triazine derivative as an active ingredient. Flame-retardant thermosetting resin composition. 2) A group of triazine derivatives represented by the following general formula (1) with respect to 100 parts by weight of melamine-coated ammonium polyphosphate in which the modified ammonium polyphosphate treated with triazine derivative contains 0.5 to 20% by weight of melamine based on the melamine unit. One or a mixture of two or more selected from 0.1
The flame-retardant thermosetting resin composition according to item 1, which is a modified ammonium polyphosphate obtained by reacting formaldehyde with a composition containing 30 to 30 parts by weight:

[0017]

[Chemical 7]

[Wherein R ¹ is a methyl group, a phenyl group or any group represented by the following general formula (2) or general formula (3)],

[0019]

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[0020]

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[Wherein R ² is a phenyl group or a carbon number of 1
A 12 linear alkyl group or branched alkyl group, R ³ is hydrogen or a methyl radical. 3) Modified ammonium polyphosphate treated with triazine derivative gives melamine 0.5-based on melamine monomer.
0.1 to 30 parts by weight of a mixture of one or two or more kinds selected from the group of triazine derivatives represented by the following general formula (1) and melamine per 100 parts by weight of melamine-coated ammonium polyphosphate containing 20% by weight. And C ₃ H _6-n
0.1 to 30 parts by weight of one or more melamines selected from methylolmelamine having 4 to 9 carbon atoms represented by N ₆ (CH ₂ OH) _n (where n is a number of 1 to 6). Item 3. The flame-retardant thermosetting resin composition according to Item 1 or 2, which is a water-insoluble modified ammonium polyphosphate obtained by reacting formaldehyde with the contained composition:

[0022]

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[Wherein R ¹ is one or more selected from a methyl group, a phenyl group, or a group represented by the following general formula (2) or general formula (3)],

[0024]

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[0025]

[Chemical 12]

[In the above general formula (2) or general formula (3), R ² is a phenyl group or a linear or branched alkyl group having 1 to 12 carbon atoms, and R ³ is a hydrogen atom or a methyl group. 1 or more types selected]. 4) The modified ammonium polyphosphate treated with the triazine derivative is added in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the thermosetting resin.
The flame-retardant thermosetting resin composition according to any one of 1 to 3. 5) Thermosetting resin is composed of alkyd resin, epoxy resin, hard urethane resin, soft urethane resin, phenol resin, melamine resin, guanamine resin, xylene-formaldehyde resin, urea resin, unsaturated polyester resin, allyl resin and polyimide resin. Item 5. The flame-retardant thermosetting resin composition according to any one of Items 1 to 4, which is one or more selected from the group consisting of: 6) Flame-retardant thermosetting molded from a flame-retardant thermosetting resin composition in which the flame-retardant composition according to any one of items 1 to 5 is added as an active ingredient to the thermosetting resin. Resin molded products.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The modified triazine derivative-treated ammonium polyphosphate, which is one of the constituents of the flame-retardant thermosetting resin composition of the present invention, is a melamine-coated ammonium polyphosphate (modified ammonium polyphosphate). Amino group of melamine present in the coating layer, melamine or carbon number 4
1 to 8 selected from the amino group present in methylolmelamine and the amino group present in a specific triazine compound 1
It is considered to be obtained by reacting both the above-mentioned active hydrogen of amino group and formaldehyde.

That is, it was concluded that the triazine derivative-treated modified ammonium polyphosphate obtained by the above treatment with a triazine derivative is a modified ammonium polyphosphate having a crosslinked structure formed by the triazine derivative on its surface. This triazine derivative-treated modified ammonium polyphosphate can be obtained, for example, by the following method: <Example of manufacturing method of triazine derivative-treated modified ammonium polyphosphate><Example of melamine-coated methylol> Heat stirring or heat kneading function 100 parts by weight of melamine-coated ammonium polyphosphate and melamine-coated ammonium polyphosphate having a melamine content of 0.5 to 20% by weight, preferably 2 to 10% by weight, more preferably 3 to 7% by weight contained in a reaction vessel. 0. 0 with respect to the number of moles of melamine units contained in 100 parts by weight (based on the number of moles of melamine monomer).
An aqueous solution of formaldehyde corresponding to 5 to 6 equivalent times, preferably 1 to 3 equivalent times is charged, and the inside of the reactor is stirred and mixed.

The reaction temperature is 10 to 120 ° C., preferably 20 to 90 ° C., which is the temperature at which the amino group of the melamine monomer contained in the melamine-coated ammonium polyphosphate easily reacts with the formaldehyde to form a methylol group.
The temperature is set to 0 ° C. and the reaction is performed at the same temperature for 1 min to 48 hours to obtain a product in which the melamine molecules contained in the melamine-coated ammonium polyphosphate are sufficiently methylated.

Attention should be paid to the following points in this reaction. That is, at a reaction temperature higher than 120 ° C., dehydration condensation of the methylol group occurs violently. On the other hand, at a reaction temperature of less than 10 ° C, the methylolation reaction becomes very slow.

On the other hand, melamines in an amount of 0.1 to 30 parts by weight, preferably 1 to 10 parts by weight, and the triazine represented by the above general formula (1) are placed in another reaction vessel having a heating and stirring function or a heating and kneading function. 1 or 2 selected from the group of derivatives
0.1 to 30 parts by weight, 5 to 15 parts by weight of the mixture of at least one species (the sum of the amounts of both triazine derivatives in the mixture) is charged. Then, an aqueous solution of formaldehyde is charged by 0.1 to 10 equivalent times, preferably 0.5 to 8 equivalent times with respect to the sum of active hydrogen equivalents of amino groups contained in the added triazine derivative and the like. , Mix well in the reactor.

In this reaction, when the amount of the aqueous formaldehyde solution charged is less than 0.1 equivalent times, the effect of improving the hydrolyzability is not sufficiently exhibited, and conversely, it exceeds 10 equivalent times. In this case, the residual amount of unreacted formaldehydes also increases.

After the above reaction, the reaction temperature is 10 to 120 ° C., preferably 20 to 90, which is the temperature at which formaldehydes easily react with an amino group to form a methylol group.
The temperature is set to 0 ° C. and the reaction is carried out at the same temperature for 1 min to 48 hours to prepare an aqueous solution of the methylolated triazine derivative or a suspension slurry thereof.

In the above reaction, that is, each of the methylolation reaction of the melamine-coated ammonium polyphosphate and the triazine derivative, an arbitrary amount of a basic compound can be optionally added as a catalyst.

The above basic compound means the p of the aqueous solution.
H is usually 7.2 or more, preferably 8 or more, or any of the substances capable of reacting with an acidic substance to form a salt. This type of basic substance can be roughly classified into an inorganic substance and an organic substance.

Examples of the inorganic basic substance include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide and strontium hydroxide. Etc .; alkali metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate (sodium bicarbonate), potassium hydrogen carbonate and the like.

As the organic basic substance, organic amines,
Examples thereof include organic oximes. Examples of organic amines include the following: ◆ Aliphatic (mono / poly) amines such as alkyl (mono) amines and alkylenediamines, among them polyalkylenepolyamines such as diethylenetriamine, hexaethylenetetramine, cycloalkyl (Mono / poly) amine For example, cyclopentylamine, cyclohexylamine, decahydronaphthylamine, norbornylamine, etc., cyclohexylenediamine, etc .; Organic oximes include the following: ◆ Alkylaldoximes, benzald Examples thereof include oximes, dialkyl ketoxime, alkylaryl ketoxime, and diaryl ketoxime. Alkylaldoximes include acetoaldoxime, propoaldoxime, butoaldoxime, and hexaldoxime.Dialkylaldoximes include acetoxime, diethylketoxime, methylethylketoxime, methylisobutylketoxime, and alkylarylketoxime. Is acetophenoxime, acetotoloxime and the like, and diarylketoxime is diphenylketoxime, ditolylketoxime and the like.

<Example of Derivatization of Methylolated Melamine with Triazine> An aqueous solution or suspension of a mixture of the methylolated melamine-coated ammonium polyphosphate, the melamines and the methylolated triazine derivative obtained as described above is heated with a stirring device or heated. It is charged in a reaction vessel equipped with a kneading device, and the temperature is 50 to 15 at which the condensation reaction can easily occur.
Warm at 0 ° C., preferably 70-120 ° C. for 10 min-10 h. The considerations for this reaction step are the same as those described above.

In this condensation reaction, a single solvent composed of water and / or an organic solvent or a mixed solvent can be used as a liquid medium, and for example, a water / alcohol mixed solvent is preferable. Further, in the condensation reaction, an optional amount of acidic compound can be added as a catalyst at any time.

By such a method, the modified ammonium polyphosphate treated with the triazine derivative can be obtained. In order to obtain the modified ammonium polyphosphate treated with the triazine derivative, it is possible to adopt other production methods.As described above, the raw materials are each methylolated and then mixed and co-condensed. The triazine derivative-treated modified ammonium polyphosphate can also be produced by a method of mixing at a ratio of 1: 1 and adding a predetermined amount of formaldehyde to carry out a methylolation reaction and a cocondensation reaction.

Examples of the above-mentioned triazine derivative include acetoguanamine, benzoguanamine, succinylguanamine, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4. , 8,10-Tetraoxaspiro [5.5]
Undecane, 2,4-diamino-6- [2'-methylimidazolyl
-(1 ')]-Ethyl-1,3,5-triazine, 2,4-diamino-6-
[2'-Ethylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-propylimidazolyl-
(1 ')]-Ethyl-1,3,5-triazine, 2,4-diamino-6-
[2'-Butylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-pentylimidazolyl-
(1 ')]-Ethyl-1,3,5-triazine, 2,4-diamino-6-
[2'-Hexylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-heptylimidazolyl-
(1 ')]-Ethyl-1,3,5-triazine, 2,4-diamino-6-
[2'-Octylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-nonylimidazolyl-
(1 ')]-Ethyl-1,3,5-triazine, 2,4-diamino-6-
[2'-decylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-1,3 , 5-triazine, 2,4-diamino-6-
[2'-Phenylimidazolyl- (1 ')]-ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl -1,3,5-triazine, 2,4-diamino-6- [2'-phenyl-4'-methylimidazolyl- (1 ')]
-Ethyl-1,3,5-triazine, 2,4-diamino-6- [2'-undecyl-4'-methylimidazolyl- (1 ')]-ethyl-1,3,5-
Examples thereof include triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-1,3,5-triazine / isocyanuric acid adduct.

The melamine-coated ammonium polyphosphate used as a raw material in the present invention sublimates the melamine monomer to add and / or add to the surface of the ammonium polyphosphate particles.
Alternatively, it may be a melamine-coated ammonium polyphosphate obtained by adhering it, and can also be obtained by the following method, for example.

That is, the temperature is 350 ° C. or lower, preferably 20.
Ammonium polyphosphate is charged in a heating and kneading device such as a kneader heated to 0 to 300 ° C., and melamine is added and heated to add and / or attach melamine to the surface of the ammonium polyphosphate particles. The above temperature range is a temperature at which the ammonium polyphosphate does not melt, the ammonia added to the ammonium polyphosphate easily desorbs, and melamine can sublime.

The proportion of the melamines added in the melamine addition and / or adhesion reaction is 0.5 to 20% by weight, preferably 2-1 to the ammonium polyphosphate.
It is sufficient to set it to 5% by weight, and when the melamine-coated ammonium polyphosphate is produced by the above method, most of the added melamines are added and / or attached to the surface of the ammonium polyphosphate. A coated ammonium polyphosphate is obtained.

Here, the addition means a state in which melamine is chemically bonded to a hydroxyl group on the surface in a state where ammonia is desorbed from ammonium polyphosphate, the added melamine is stable even when heated, and is removed again. There is no separation.
On the other hand, “adhesion” means a state in which melamines are adsorbed on the surface of ammonium polyphosphate particles, and melamines repeat sublimation and adsorption on the surface of ammonium polyphosphate particles as heating continues.

As the raw material of the melamine-coated ammonium polyphosphate, ammonium polyphosphate may be a commercially available product or one obtained by a known method, and as the commercially available product, a trade name (trademark registration pending) "Terrage ( (TERRAJU)
S10 "(manufactured by Chisso), trade name (trademark registration pending)," TERRAJU S20 "(manufactured by Chisso), trade name" Sumisafe-P "(manufactured by Sumitomo Chemical Co., Ltd.), trade name" Exolit " -422 "(made by Hoechst), product name" Phos-chek P / 30 "(made by Monsanto), product name" Phos-chek P / 40 "(made by Monsanto), etc. Can be mentioned.

As a known method for producing a known ammonium polyphosphate, for example, approximately equimolar amounts of ammonium orthophosphate and phosphorus pentoxide are present in the presence of gaseous ammonia and under the simultaneous motion of the reactants, for example, with stirring. Temperature 170 ~
Heating to 350 ° C., preferably 250 to 300 ° C. can be mentioned.

As the melamines, commercially available products can be used, and methylolmelamine having a carbon number of 4 to 9 [general formula C ₃ H _6-n N ₆ (CH ₂ OH) _n (where n = 1 to 6) is used. Can be obtained by reacting 1 to 6 moles of formaldehyde with 1 mole of the melamine, or a commercially available product may be used.

The amount of ammonium polyphosphate treated with triazine derivative added to the thermosetting resin composition is 10% by weight of the resin.
0.1 to 200 parts by weight, preferably 1 to 0 parts by weight
To 100 parts by weight, more preferably 3 to 50 parts by weight. When the amount of the ammonium polyphosphate added is too small, the flame retardant effect is not sufficiently exerted, and when it is added in an excessively large amount, the moldability of the composition and the machine of a molded article obtained therefrom are obtained. Strength decreases.

<Thermosetting Resin> Suitable examples of the thermosetting resin as the base material of the flame-retardant thermosetting resin composition of the present invention include alkyd resin, epoxy resin and hard urethane resin. , Soft urethane resin, phenol resin, melamine resin, guanamine resin, xylene-formaldehyde resin, urea resin (urea resin) and unsaturated polyester resin, allyl resin (arlyl resin), and polyimide resin.

The above-mentioned alkyd resin is generally a resin obtained by the condensation of a polyhydric alcohol and a polycarboxylic acid, and its representative is the trade name “Glyptal resin (Glyptal resin) by condensation of glycerol (glycerin) and phthalic acid. Glypta
l Resin) ”.

The above-mentioned unsaturated polyester resin is generally an unsaturated polyester having a relatively low molecular weight obtained by a polycondensation reaction of an unsaturated dicarboxylic acid and a glycol, which is a resin crosslinked by copolymerization with a vinyl monomer. Including both. The raw material compounds that constitute these unsaturated polyester resins are as follows: ◆ Unsaturated dicarboxylic acids often used are (anhydrous) maleic acid and / or fumaric acid; ◆ Adjust the amount of double bonds For example, those which are co-condensed are, for example, phthalic anhydride, adipic acid and the like; ◆ Those which are frequently used as glycols are, for example, ethylene glycol, diethylene glycol, triethylene glycol or propylene glycol; ◆ Those which are frequently used as vinyl monomers Is, for example, styrene, vinyltoluene, chlorostyrene, vinyl acetate,
(Meth) acrylic acid ester [methyl (meth) acrylate, etc.] and the like. The above-mentioned allyl resin (allyl resin is a resin obtained from an allyl alcohol derivative, for example, diethylene glycol bisallyl carbonate is used for casting, a copolymer of diallyl phenylphosphonate and methyl methacrylate is used for glass fiber laminates. .

In order to cross-link the copolymer with the vinyl monomer, an organic peroxide, an azo compound or the like is used as a radical polymerization initiator and a curing accelerator. There are various types of the above-mentioned polyimide resins, and among them, the one called polybismaleimide is often used for the purpose of requiring high heat resistance.

In the flame-retardant thermosetting resin composition of the present invention, various additives usually added as necessary, for example, curing agents, curing accelerators, other flame retardants, flame retarding aids, Colorants,
A surfactant, an antistatic agent, an oxidation stabilizer, a heat stabilizer, a plasticizer, a light resistance stabilizer, a pigment, a solvent and the like can be appropriately used in combination.

<Flame-Resistant Thermosetting Resin Molded Product> The flame-retardant composition of the present invention is effective amount, preferably 0.1 to 200 parts by weight per 100 parts by weight of the base polymer thermosetting resin prepolymer.
More preferably 1 to 100 parts by weight, most preferably 3 to
If necessary, a predetermined amount of a curing agent is added to a prepolymer of 50 parts by weight of a flame-retardant thermosetting resin, and an uncured composition is cured simultaneously with shaping (molding) or after shaping (molding). The above is the flame-retardant thermosetting resin molded product of the present invention. There are various shapes of molded products, but most are flat, cylindrical, etc.
Relatively simple.

Among the molded products, 1 is the most frequently used one, a domestic bathtub (commonly called poly bath etc.), and the other 1 is a substrate for mounting parts of electric equipment, a wiring substrate, especially a printed wiring substrate, an insulating plate, a solenoid coil. Bobbins, switchboard boards for variable output voltage transformers (terminal boards), non-fuse breakers, flyback transformers, heat insulation bulkheads, etc. Even if exposed to high temperatures for a long time, not only deterioration and destruction, but also slight deformation is allowed. Equipment used for applications that are not used, such as coreless motor parts, parts, etc., such as automobile parts, such as trunk floor coverings and bulkheads between the rear seats and the trunk, steering wheel, shift lever grips, wood grain dashboard, etc. The equipment accompanied by, and another molded article is the hull itself of a small boat, its members or parts, and the like.

[0057]

EFFECTS OF THE INVENTION The flame-retardant thermosetting resin composition of the present invention has the following effects: (1) Triazine derivative treatment Modified ammonium polyphosphate Despite its relatively small amount, it is highly advanced. Excellent flame retardancy; (2) Halogen-containing gas is not generated, elution and bleed-out of the ammonium polyphosphate hardly occur; (3) As a molding material for electric and electronic parts, for civil engineering,
It can be suitably used for a wide range of applications such as for automobile parts, adhesives, synthetic resin impregnated papers, and the like.

[0058]

EXAMPLES The present invention will be specifically described below based on Examples with reference to Comparative Examples when it is more useful, but the present invention is not limited thereto. The evaluations in Examples and Comparative Examples were carried out by the following methods. (1) Flame retardance: UL94V UL Subject 94 (Underwriter Laboratories, Inc.) “Vertical combustion test prescribed in“ Combustion test of plastic material for parts of equipment ”. Thickness of test piece: 1.6 mm (1/16 inch) (2) Flame retardance: Oxygen index (O.I.) In accordance with JIS K7201 (combustion test method for polymer materials by oxygen index method). (3) Evaluation of hot water immersion test A test piece (length 100 mm x width 100 mm x thickness 2 mm) is molded by hot pressing, and the surface electric resistance value of the test piece is measured by a vibration capacitance type micro-current / electrometer (Takeda Riken). It was measured at. Then, the test piece was immersed in hot water (temperature: 95 ° C.) for 2 hours and then taken out, water drops adhering to the test piece were wiped off, and the surface electric resistance value of the test piece was measured (first time).

A test piece whose surface electric resistance value significantly decreased after one immersion in hot water was rated as a bleed resistance rank "x (impossible)". The test piece was again immersed in hot water at a temperature of 95 ° C. for 2 hours, then taken out, the water droplets adhering to the test piece were wiped off, and the surface electric resistance value of the test piece was measured (second time).

A test piece whose surface electric resistance value was significantly reduced in the second hot water immersion test was evaluated as a bleed resistance rank "△".
(Inferior), and a test piece that showed little decrease in surface electric resistance even in the two tests was ranked as bleeding resistance rank "○ (good)".

The various melamine-coated ammonium polyphosphate intermediates used in each of the examples of the present invention were obtained by the following methods: Kneader preheated to 270 to 300 ° C. (content of 5 liters) ) Was charged with 2000 parts by weight of ammonium polyphosphate [trade name: TERRAJU (trademark registration pending) S20 (manufactured by Chisso Corporation)].
When the temperature of the ammonium polyphosphate reached 250 to 280 ° C, a predetermined amount of melamine was added and mixing was continued while heating for 6 hours to obtain a melamine-coated ammonium polyphosphate.

As a result of observing the obtained melamine-coated ammonium polyphosphate with an electron microscope, it was confirmed that the surface of the ammonium polyphosphate particles was uniformly coated with melamine, and as a result of the elemental analysis, most of melamine was found to be present. It was confirmed that it was added to ammonium polyphosphate.

[0063]

Example 1 Mixer of 100 parts by weight of melamine-coated ammonium polyphosphate (content of melamine unit: 5% by weight) and 3.4 parts by weight of formaldehyde aqueous solution (concentration: 35%) [trade name: Kenmix mixer (Aikosha Seisakusho Co., Ltd. Made)]
And stirred at room temperature for 5 minutes. It was placed in a polyethylene bag, sealed, and reacted in an oven (maintained at 28 ° C) for 24 hours.

3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) as a triazine derivative was placed in a reaction vessel (capacity: stirrer, thermometer, inlet and condenser) having a capacity of 500 ml. Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 5.3 parts by weight, formaldehyde aqueous solution (concentration 35%) 10.5 parts by weight, hexamethylenetetramine (trade name "urotropin") as a catalyst 0 .2 parts by weight and 10 parts by weight of water were added, and the temperature was adjusted to 80 to 90 ° C for 10
After heating and stirring for min, an aqueous solution of the triazine derivative was obtained.

Ammonium polyphosphate coated with the above methylolated melamine and a water / methanol mixed solution (a mixed solution of 135 parts by weight of water / 20 parts by weight of methanol) as a solvent were introduced into the reactor through an inlet, and the reactor was The contents were heated and stirred, and the pH of the liquid phase was adjusted to 3 to 4, and the reaction was carried out at the reflux temperature for 1.5 hours. After the reaction is completed, the inside of the reactor is 25 to 3
The mixture was rapidly cooled to 0 ° C., filtered under reduced pressure, washed with water and methanol, and dried in an oven at 100 ° C. for 2 h, and then treated with a triazine derivative-modified ammonium polyphosphate (A) 10
5 parts by weight were obtained.

As an epoxy resin, 100 parts by weight of a bisphenol A type epoxy resin [trade name: Epicoat 828 (manufactured by Yuka Shell Epoxy Co.)], 20 parts by weight of the modified triazine derivative-treated ammonium polyphosphate and 10 parts of talc were used.
1 part by weight of diethylenetriamine was added as a curing agent, and further mixed.

After deaeration under reduced pressure, the mixture was heated at 30 ° C. for 60 minutes and then hot press molded at 100 ° C. for 15 minutes to prepare a flat plate. A test piece having a predetermined shape was cut out from the obtained flat plate (hereinafter referred to as "test piece A"). Using the obtained test piece A, its flame retardancy measurement, oxygen index measurement, and hot water immersion test (hot water resistance measurement) were performed. Table 1 shows the measurement results.

[0068]

Example 2 A reaction vessel having a capacity of 500 ml (installed with a stirrer, a thermometer, an inlet and a condenser), 100 parts by weight of melamine-coated ammonium polyphosphate (content of melamine unit: 3% by weight), and a triazine derivative of 3,9- Bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 15 parts by weight, aqueous formaldehyde solution (concentration 35%) Three
0 parts by weight and a water / methanol mixed solution (water 1
35 parts by weight / mixed solution of 20 parts by weight of methanol) was charged, and the liquid phase in the reactor was gradually heated and stirred, and
The mixture was reacted at reflux temperature for 1.5 hours while adjusting the pH to 3-4.

After the completion of the reaction, the inside of the reactor was rapidly cooled to 25 to 30 ° C., filtered under reduced pressure, washed with water and methanol, and dried in an oven at 100 ° C. for 2 hours to obtain a triazine derivative-treated modified ammonium polyphosphate (B). ) 110 parts by weight were obtained.

A flat plate was prepared in the same manner as in Example 1 except that the above-mentioned modified ammonium polyphosphate treated with triazine derivative was used. A test piece having a predetermined shape was cut out from the obtained flat plate (hereinafter referred to as "test piece B"). Using the obtained test piece B, flame retardancy measurement, oxygen index measurement, and hot water immersion measurement test were performed. Table 1 shows the measurement results.

[0071]

Example 3 In a reaction vessel (equipped with a stirrer, a thermometer, an inlet and a condenser) having a capacity of 500 ml, 100 parts by weight of melamine-coated ammonium polyphosphate (content of melamine unit: 10% by weight), 3,9- Bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 3 parts by weight, aqueous formaldehyde solution (concentration 35%) 26
Water / methanol mixed solution (water 13
A mixed solution of 5 parts by weight / 20 parts by weight of methanol) was added, and the mixture was heated and stirred to adjust the pH of the solution to 3 to 4 and reacted at the reflux temperature for 1.5 hours.

After the completion of the reaction, the inside of the reactor was rapidly cooled to 25 to 30 ° C., filtered under reduced pressure, washed with water and methanol, dried in an oven at 100 ° C. for 2 hours, and modified polyphosphoric acid treated with a triazine derivative. Ammonium (C) 10
3 parts by weight were obtained.

Polyisocyanate [trade name: DN-98
51 parts by weight of 0S (manufactured by Dainippon Ink and Chemicals), 49 parts by weight of polyester polyol [trade name: D-220 (manufactured by Dainippon Ink and Chemicals)] and 10 parts by weight of triazine derivative-treated modified ammonium polyphosphate. Disperse and mix,
Then, after degassing, the mixture was heated at 150 ° C. for 30 minutes.
Hot pressing was performed to obtain a flat plate. A test piece having a predetermined shape was cut out from the obtained flat plate (hereinafter referred to as "test piece C"). Using the obtained test piece C, its flame retardancy measurement, oxygen index measurement, and hot water immersion test were performed. Table 1 shows the measurement results.

[0074]

Example 4 Example 3 was repeated except that the modified ammonium polyphosphate treated with the triazine derivative was obtained according to Example 2.
A flat plate was prepared according to the above. The obtained flat plate was cut out to prepare a test piece having a predetermined shape (hereinafter referred to as "test piece D").
That). Using the obtained test piece D, flame retardancy measurement, hot water immersion test and oxygen index measurement were performed. Table 1 shows the measurement results
Shown in

[0075]

Example 5 100 parts by weight of melamine-coated ammonium phosphate polyphosphate (content of melamine unit: 7% by weight) and concentration: 35%
Put 7.2 parts by weight of formaldehyde solution in a polyethylene bag and rub it by hand. It was sealed and allowed to react for 36 h in an oven (maintained at 28 ° C.) to give a methylolated melamine coated ammonium polyphosphate.
500 ml reaction vessel (stirrer, thermometer,
Equipped with an inlet and a condenser), 2,4-diamino-6- [2'-methyl-imidazolyl-
(1 ′)]-Ethyl-S-triazine (5.3 parts by weight), formaldehyde aqueous solution (concentration 35%) (4.3 parts by weight) and water (10 parts by weight) were added, and the mixture was heated and stirred at 80 to 90 ° C. for 30 minutes to prepare a triazine derivative. An aqueous solution of

The above methylolated melamine-coated ammonium polyphosphate and a water / methanol mixed solution as a solvent (135 parts by weight water / 20 parts by weight methanol)
Was charged into the reactor through the inlet, heated and stirred to react at reflux temperature for 5 hours. After the reaction is completed, the inside of the reactor is 25-30
The mixture was rapidly cooled to 0 ° C., filtered under reduced pressure, further washed with methanol, and dried in an oven (105 ° C.) for 2 hours to obtain 100 parts by weight of modified ammonium polyphosphate treated with a triazine derivative.

100 parts by weight of melamine resin [containing cellulose powder (manufactured by Fuji Kasei)] for molding material and 10 parts by weight of modified ammonium polyphosphate treated with triazine derivative are mixed well and subjected to hot press molding at 165 ° C. for 4 minutes to obtain a flat plate. Got A predetermined test piece (this is called "test piece E") was cut out from the obtained flat plate. Using the obtained test piece E, its flame retardancy measurement, hot water immersion test and oxygen index measurement were performed. Table 1 shows the results.

[0078]

Example 6 In obtaining an aqueous solution of a triazine derivative, 2,
11 parts by weight of 4-diamino-6- [2'-methyl-imidazolyl- (1 ')]-ethyl-S-triazine, 8.9 parts by weight of formaldehyde aqueous solution (concentration 35% by weight), carbonic acid as a catalyst The procedure of Example 5 was repeated except that 5 ml of an aqueous sodium solution (concentration: 1%) was added, to obtain 110 parts by weight of a modified ammonium polyphosphate treated with a triazine derivative.

100 parts by weight of a phenol resin for a molding material [containing cellulose powder (manufactured by Fudo Co.)] and 10 parts by weight of a modified ammonium polyphosphate treated with a triazine derivative were sufficiently mixed and subjected to hot press molding at 170 ° C. for 4 minutes to obtain a flat plate. Got A predetermined test piece (this is called "test piece F") was cut out from the obtained flat plate. Using the obtained test piece F, flame retardancy measurement, hot water immersion test and oxygen index measurement were performed. Table 1 shows the results.

[0080]

[Comparative Example 1] In place of the modified polyammonium phosphate treated with a triazine derivative, ammonium polyphosphate microcapsulated with a melamine / formaldehyde resin [trade name: Exolit-462 (manufactured by Hoechst)] was used. A flat plate was obtained according to Example 1, and each test piece (hereinafter referred to as "test piece G") was produced using the obtained flat plate. Using the obtained test piece G, flame retardancy measurement, hot water immersion test and oxygen index measurement were performed. Table 1 shows the results.
Shown in

[0081]

[Comparative Example 2] A flat plate was prepared according to Example 3 except that untreated ammonium polyphosphate [trade name: Sumisafe-P (manufactured by Sumitomo Chemical Co., Ltd.)] was used instead of the triazine derivative-treated ammonium polyphosphate. Each test piece (hereinafter referred to as "test piece H") was cut out from the obtained flat plate. Using the obtained test piece H, flame retardancy measurement, hot water immersion measurement and oxygen index measurement were performed. Table 1 shows the results.

[0082]

[Comparative Example 3] Mixer of 100 parts by weight of melamine-coated ammonium polyphosphate (content of melamine unit: 5% by weight) and 3.4 parts by weight of formaldehyde aqueous solution (concentration: 35%) [trade name: Kenmix mixer (Aikosha Seisakusho Co., Ltd. Made)]
And stirred at room temperature for 5 minutes. It was put in a polyethylene bag, sealed, and allowed to react in an oven (held at 28 ° C.) for 24 hours to obtain a methylolated melamine-coated ammonium polyphosphate.

A reaction vessel having a capacity of 500 ml (installed with a stirrer, a thermometer, an inlet, and a condenser) was methylolated melamine-coated ammonium polyphosphate and a water / methanol mixed solution as a solvent (a mixed solution of 135 parts by weight of water / 20 parts by weight of methanol). ) Was charged and the pH of the liquid phase in the reactor was adjusted to 3 to 4 by heating and stirring, and the reaction was carried out at the reflux temperature for 1.5 hours.

After completion of the reaction, the inside of the reactor was rapidly cooled to 25 to 30 ° C., filtered under reduced pressure, washed with water and methanol, and dried in an oven (set at 100 ° C.) for 2 hours to obtain 99 weight parts of water-insoluble ammonium polyphosphate. I got a part.

A flat plate was obtained according to Example 5 except that the water-insoluble ammonium polyphosphate was used in place of the triazine-treated modified ammonium polyphosphate, and each test piece (hereinafter referred to as " Test piece I ") was cut out. Using the obtained test piece I, flame retardancy measurement, hot water immersion test and oxygen index measurement were performed. Table 1 shows the results.

[0086]

Comparative Example 4 A flat plate was obtained in the same manner as in Example 6 except that untreated ammonium polyphosphate [trade name: Sumisafe-P (manufactured by Sumitomo Chemical Co., Ltd.)] was used in place of the triazine-treated ammonium polyphosphate. Each test piece (hereinafter referred to as "test piece J") was cut out from the obtained flat plate. Using the obtained test piece J, its flame retardancy measurement, hot water immersion measurement, and oxygen index measurement were performed. Table 1 shows the results.

[0087]

Example 7 <Preparation of Sealant Composition> 100 parts by weight (pbw) of an oxypropylene ether polymer having a silyl group at the terminal (reaction product of an oxypropylene polymer and methyldimethoxysilane) was treated with a triazine derivative. As the ammonium polyphosphate, 90 parts by weight of the same material as in Example 1, 20 parts by weight of dipentaerythritol as a carbon forming agent, and 20 parts by weight of calcium carbonate as a filler were uniformly mixed. Next, 2 parts by weight of tin octylate (2-ethylcaproic acid) and 1 part by weight of laurylamine were added to this mixture as a curing agent to obtain a sealant composition.

<Preparation of Fireproof Seal Joint> Two gypsum boards (length 100 mm × width 45 mm × thickness 12 mm) were cut out, and both were placed at a position where the largest faces face each other with a gap of 10 mm to form joints. It was An uncured sealant composition is used as a sealing material for the joints, and the length is 100 mm and the width is 45 mm.
× Inserted to have a thickness of 12 mm. The gypsum board with joints thus obtained was cured while being left still so that the joints were horizontal (25 ° C; humidity 65% RH; 10 days).

<Fire Resistance Test and Evaluation of Fire Resistance of Joints After Curing> After the joints were cured, the state of the foamed carbonized layer was visually inspected after applying a Bunsen burner flame to the center of the joint from below for 30 minutes of combustion. The results were evaluated by observing and observing the observation results with respect to the size of foaming and the hardness of the carbonized layer. The rating of the visual result is as follows: ◆ "Excellent fire resistance" when the foam is large and the carbonized layer is hard; "Carbonized whether the foamed is small or the carbonized layer is large""Fire resistance is good" when the layer is brittle; ◆ "Poor fire resistance" when the foaming is small and the carbonized layer is brittle.

[0090]

[Comparative Example 5] Instead of triazine derivative-treated modified ammonium polyphosphate, trade name "Sumisafe" was used as melamine-treated ammonium polyphosphate that was not treated with triazine.
Example 7 except that the same amount of "-PM (Sumitomo Chemical Co., Ltd.)" was used.
To obtain a composition corresponding to the sealant composition.
This composition was inserted into joints formed between gypsum boards as in Example 7 and subjected to a fire resistance test. The visual observation result of the test joint was rated "poor".

[0091]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 9/04 KCN C08K 9/04 KCN C08L 61/00 C08L 61/00 63/00 NLD 63/00 NLD 67/06 MSK 67/06 MSK 75/00 MGE 75/00 MGE 79/08 LRB 79/08 LRB E04B 1/74 E04B 1/74 1/94 1/94 T

Claims (6)

[Claims] 1. A flame-retardant thermosetting resin composition containing, as an active ingredient, a modified ammonium polyphosphate treated with a triazine derivative with respect to a thermosetting resin. 2. The modified ammonium polyphosphate treated with a triazine derivative has a melamine content of 0.5 to 2 on a melamine unit basis.
0.1 to 30 parts by weight of a mixture of one or two or more kinds selected from the group of triazine derivatives represented by the following general formula (1) per 100 parts by weight of melamine-coated ammonium polyphosphate containing 0% by weight. The flame-retardant thermosetting resin composition according to claim 1, which is a modified ammonium polyphosphate obtained by reacting formaldehyde with respect to the composition described above: [Wherein R ¹ is a methyl group, a phenyl group or any group represented by the following general formula (2) or general formula (3)], Embedded image [Here, R ² is a phenyl group or a linear or branched alkyl group having 1 to 12 carbon atoms, and R ³ is hydrogen or a methyl group]. 3. The modified general ammonium polyphosphate treated with a triazine derivative is represented by the following general formula (1) with respect to 100 parts by weight of melamine-coated ammonium polyphosphate containing 0.5 to 20% by weight of melamine based on melamine monomer. in one or more mixtures of 0.1 to 30 parts by weight and melamine is selected from triazine derivatives group represented and _{C 3 H 6-n n 6} (CH 2 OH) carbon atoms represented by _n 4 to 9
Obtained by reacting formaldehydes with a composition containing 0.1 to 30 parts by weight of one or more melamines selected from methylolmelamine (where n is a number of 1 to 6). The flame-retardant thermosetting resin composition according to claim 1 or 2, which is a modified ammonium polyphosphate. [Wherein R ¹ is a methyl group, a phenyl group or the following general formula:
1 selected from the groups represented by (2) or the general formula (3)
More than one species], [Chemical 6] [In the above general formula (2) or general formula (3), R ² is a phenyl group, a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group, and R ³ is 1 selected from hydrogen or a methyl group. More than seeds]. 4. The addition amount of the modified ammonium polyphosphate treated with the triazine derivative is 0.1 to 200 parts by weight with respect to 100 parts by weight of the thermosetting resin. The flame-retardant thermosetting resin composition described in 1. 5. The thermosetting resin is an alkyd resin, epoxy resin, hard urethane resin, soft urethane resin, phenol resin, melamine resin, guanamine resin, xylene-formaldehyde resin, urea resin, unsaturated polyester resin, allyl resin and polyimide. The flame-retardant thermosetting resin composition according to claim 1, which is one or more selected from the group consisting of resins. 6. A flame-retardant molded from a flame-retardant thermosetting resin composition, wherein the flame-retardant composition according to claim 1 is added to a thermosetting resin as an active ingredient. Thermosetting resin moldings.