JPH10147696A - Flame retardant epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-smoking and flame retardant epoxy resin composition having a low bromine content and a low flame retardant content without containing antimony oxide. SOLUTION: (1) This flame retardant epoxy resin composition comprises an ammonium polyphosphate in an amount of 1-50 pts.wt. based on 100 pt.wt. bromine-based epoxy resin having 3-30wt.% bromine content or (2) the flame retardant epoxy resin comprises a composite flame retardant composed of the ammonium polyphosphate and red phosphorus at (75:25) to (96:4) weight ratio of the ammonium polyphosphate:red phosphorus in an amount of 1-50 pts.wt. based on 100 pts.wt. bromine-based epoxy resin having 3-30wt.% bromine content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition having excellent flame retardancy. More specifically, the present invention relates to a flame-retardant epoxy resin composition having a low bromine content, containing no antimony oxide, and having low smoke emission.

[0002]

2. Description of the Related Art Epoxy resin is one of the resins widely used in the fields of building materials, electric equipment, and the like. For example, reinforced epoxy resin reinforced with glass fiber or the like has chemical resistance and strength. Because of its excellent weather resistance and electrical characteristics, it is used as a structural material for building materials and transport parts such as aviation and vehicles, and as an electrical insulating material for laminated boards and molding materials. Epoxy resins used in such applications are required to have high flame retardancy from the viewpoint of fire safety.

[0003] In order to solve such problems, flame retardancy of plastics-low smoke emission and measures against harmful combustion gas-has been published by Nikkan Kogyo Shimbun on June 26, 1978. A method using a phosphoric acid ester such as tricresyl phosphate, a halogenated phosphoric acid ester such as tris (chloroethyl) phosphate, a halogenated phenyl compound including brominated phenyl or chlorinated phenyl, and a halogenated epoxy resin are described. ing. Japanese Patent Application Laid-Open No. 4-266940 is characterized in that it contains a halogenated phosphoric acid ester, a flame retardant such as antimony trioxide or a brominated epoxy resin, fine hollow spheres, a foaming agent, and an aromatic diamine. An epoxy resin composition for a composite material is disclosed. However, the fact is that phosphate esters are poorly used for imparting flame retardancy, and if added in large amounts for the purpose of enhancing flame retardancy, they may bleed on the surface of the epoxy resin, so that they are hardly used.

On the other hand, halogen-based flame retardants such as halogenated phosphoric acid esters, halogenated phenyl compounds and halogenated epoxy resins are used to impart high flame retardancy.
Often used with antimony oxide. The flame-retardant resin composition containing this halogen-based flame retardant may generate corrosive gas or toxic gas during a fire or incineration, and contains no halogen-based flame retardant or has a significant halogen content. There is a strong need for a suppressed epoxy resin composition.

[0005] Antimony oxide has been used as a synergistic effect agent for halogen-based flame retardants because it can impart a higher degree of flame retardancy. Therefore, its use is being suppressed.

As described above, there is a strong demand for an epoxy resin composition having a low halogen content, containing no antimony oxide, and having high flame retardancy and low smoke emission.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have been keen to obtain an epoxy resin composition having a low halogen content and containing no antimony oxide and having high flame retardancy and low smoke emission. Studied. As a result, an epoxy composition containing a bromine-containing epoxy resin and ammonium polyphosphate, a bromine-containing epoxy resin and ammonium polyphosphate and red phosphorus in a specific ratio has a high degree of flame retardancy while having a low halogen content. It was found that the composition was a composition, and based on this finding, the present invention was completed. As is clear from the above description, an object of the present invention is to provide a flame-retardant epoxy resin composition having a low bromine content, containing no antimony oxide, and having a low compounding amount of a flame retardant and low smoke emission. is there.

[0008]

[Means for Solving the Problems]

(1) Ammonium polyphosphate is added in an amount of 1 to 100 parts by weight of a bromine-based epoxy resin having a bromine content of 3 to 30% by weight.
A flame-retardant epoxy resin composition containing 50 parts by weight. (2) Ammonium polyphosphate having a ratio (weight ratio) of ammonium polyphosphate: red phosphorus of 75:25 to 96: 4 to 100 parts by weight of a bromine-based epoxy resin having a bromine content of 3 to 30% by weight. The compound flame retardant consisting of red phosphorus
A flame-retardant epoxy resin composition containing 50 parts by weight. (3) The flame-retardant epoxy resin composition according to any one of the above (1) or (2), wherein the brominated epoxy resin is a brominated epoxy resin or a mixed resin of an epoxy resin and a brominated epoxy resin. (4) The flame retardancy according to any one of (1) to (3) above, wherein the ammonium polyphosphate is ammonium polyphosphate, melamine-modified ammonium polyphosphate, coated ammonium polyphosphate, or a mixture of one or more thereof. Epoxy resin composition. (5) The flame-retardant epoxy resin composition according to any one of the above (1) or (3), wherein the red phosphorus is red phosphorus or coated red phosphorus. (6) A carbon fiber or a glass fiber is further added to the flame-retardant epoxy resin composition according to any one of the above items 1 to 3, in an amount of 1 part by weight to 100 parts by weight of the brominated epoxy resin. A flame-retardant epoxy resin composition containing 65 parts by weight.

As the ammonium polyphosphate constituting the flame-retardant epoxy resin composition of the present invention, ammonium polyphosphate, melamine-modified ammonium polyphosphate, carbamyl polyphosphate or coated ammonium polyphosphate can be used. Ammonium polyphosphate is preferably used because it has water insolubility.
Here, the coated ammonium polyphosphate is obtained by coating or microencapsulating ammonium polyphosphate with a thermosetting resin, and the water solubility of these ammonium polyphosphate is 0.5% by weight or less at 25 ° C. As a resin that can be used for microencapsulation, a thermosetting resin which hardly transmits water and forms a film having excellent water resistance is preferable, for example, alkyd resin, allyl resin, urea resin, melamine resin, epoxy resin, Phenolic resin, unsaturated polyester resin, silicone resin,
Urethane resin, xylene resin, thermosetting resin such as furan resin, or a modified type thereof, anion,
At least one selected from those ion-modified with cations or the like, those specially modified with a high condensation type or the like and those modified with other substances (specifically describe what has been modified) can be selected. Among these resins, melamine resin, urea resin, urea resin, urethane resin, and phenol resin are preferably used from the viewpoints of water resistance of the resin, strength of the coating, and more dense coating.

When the ammonium polyphosphate is coated with a thermosetting resin, it is particularly preferable to select a resin which is close to the polarity (solubility parameter, SP value) of the epoxy resin. In other words, by bringing the polarity of the ammonium polyphosphate surface closer to the epoxy resin, the dispersibility in the epoxy resin is increased, and the synergistic effect with the combined use flame retardant during combustion can be further enhanced.

As the ammonium polyphosphate, commercially available ones can be usually used. Examples of the commercially available products include Sumisafe P (trade name, manufactured by Sumitomo Chemical Co., Ltd.),
Sumisafe PM (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Terage C60 (trade name, manufactured by Chisso Corporation), Terage C70 (trade name, manufactured by Chisso Corporation), Nonenen W-3
(Trade name, manufactured by Marubishi Yuka Kogyo Co., Ltd.), Hoscheck P /
30 (trade name, manufactured by Monsanto), Hoscheck P / 3
0 (trade name, manufactured by Monsanto), Hostafraam AP4
62 (trade name, manufactured by Hoechst) and the like.

As the red phosphorus used in the present invention, untreated red phosphorus or one that has been surface-treated with an inorganic substance and / or an organic substance (hereinafter referred to as coated red phosphorus) is used. In particular, coated red phosphorus can be suitably used in view of safety and ease of handling. Commercial products of the coated red phosphorus include Hishigard CP-A15 (trade name, manufactured by Nippon Chemical Industry Co., Ltd.),
Novaled 120UF (trade name, Rin Chemical Co., Ltd.)
And Nova Excel 140 (trade name, manufactured by Rin Kagaku Kogyo Co., Ltd.).

When ammonium polyphosphate and red phosphorus are used in combination, the ratio (weight ratio) of ammonium polyphosphate to red phosphorus is 75 per 100 parts by weight of the brominated epoxy resin or the mixture of the brominated epoxy resin and the epoxy resin. : 2
5 to 96: 4, preferably 80:20 to 92: 8, a composite flame retardant of ammonium polyphosphate and red phosphorus,
The composition contains 0 parts by weight, preferably 15 to 35 parts by weight. If the proportion is 1 part by weight or less, sufficient flame retardancy cannot be obtained, and if it exceeds 50 parts by weight, the reduction in resin physical properties becomes larger than the effect of improving flame retardancy obtained.

The epoxy resin in the present invention refers to a thermosetting epoxy resin which is cured by adding a curing agent and heating, and the epoxy resin is divided into an epoxidized olefin product group and a glycidyl ether group. Can be used, but there are no particular restrictions on use. However, the most important and most popular epoxy resins include glycidyl ether compounds such as phenol novolak type and cresol novolak type based on aliphatic polyalcohol or novolak, and 2,2.
-Bis (4-hydroxyphenyl) -propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) -methane (bisphenol F), 2,2-bis (4
-Hydroxyphenyl) -ethane (bisphenol A)
D), a glycidyl ether compound obtained from 2,2-bis (4-hydroxyphenyl) -butane and the like. The compound is produced, for example, by reacting bisphenol A with epichlorohydrin in the presence of an alkali,
At that time, by changing the molar ratio, one having a low viscosity or a high viscosity can be obtained.

The brominated epoxy resin is a compound in which active hydrogen in the above epoxy resin is substituted with bromine, and a commercially available product can be used sufficiently. The brominated epoxy resin generally has a higher crystallinity than that of a bromine-free epoxy resin and has a
It is a solid resin having a melting point of 0 ° C. It can be adjusted in bromine content and viscosity by melt-mixing with other epoxy resins. Commercially available brominated epoxy resins include DER-542 and DER-511 (trade names, Dow-
Chemical Japan Co., Ltd.), Epototo YDB340 (trade name, manufactured by Toto Kasei Co., Ltd.) and the like.

The brominated epoxy resin of the present invention is a brominated epoxy resin or a mixture of a brominated epoxy resin and an epoxy resin, and has a bromine content of 3 to 30% by weight. When the bromine content is 3% by weight or less, the amount of ammonium polyphosphate or red phosphorus to be contained in order to obtain the desired flame retardancy becomes large, and the decrease in resin properties is more than the effect of improving the flame retardancy obtained. Become. When the bromine content is more than 30% by weight, the desired flame retardancy can be obtained, but the composition contains a large amount of bromine, so that the smoke generating property and the corrosive gas concentration at the time of combustion increase, and the present invention has It will not fulfill its purpose.

As the curing agent used for curing the epoxy resin, ethylenediamine, hexamethylenediamine,
Amine curing agents such as diethylenetriamine and triethylenetetramine; polyaminoamide curing agents; acids such as phthalic anhydride and trimellitic anhydride; and acid anhydride curing agents; polymercaptan curing agents; dicyandiamide; and bases such as organic acid dihydrazide. An active hydrogen compound or the like is used.

The carbon fiber and glass fiber used in the present invention not only supplement the strength of the resin molded product reduced by the addition of the filler, but also reinforce the carbonized layer when the resin is carbonized by polyphosphoric acid in a fire. It works as an agent. Therefore, the amount of the reinforcing agent added is the compounding amount of the filler,
Although it depends on the desired strength, it is desirable to use it in the range of 1 to 40% by weight based on the total amount of the epoxy resin molded product.

The epoxy resin composition of the present invention can appropriately use a plasticizer, a stabilizer, an additive and the like. The additives are pigments, dyes, antibacterial agents and the like, are not particularly limited, and can be added as needed. These compounds can be generally added in a small amount, for example, 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin.

[0020]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which by no means limit the scope of the present invention. The evaluation in Examples and Comparative Examples was performed by the following method.

(1) Flame retardancy: Oxygen index (O.I.) Based on Japanese Industrial Standard JIS K7201 (combustion test method for polymer materials by oxygen index method).

(2) Flame retardancy: V-0, V-0, in accordance with the vertical flame test specified in "flame test of plastic materials for equipment parts" of UL94V UL Subject (Underwriters Laboratories, Inc.) Grades V-1 and V-2 were given. However,
Burning (not applicable) was evaluated as x. Test specimen thickness: 1.6
mm or 3 mm.

(3) Flexural strength The flexural strength was based on Japanese Industrial Standard JIS K7203 (bending test for hard plastic). However, the shape of the test piece is 10
0 mm, width 25 mm, and thickness 2 mm.

(4) Measurement of Smoke Amount The concentration (%) of carbon dioxide and carbon monoxide 4 minutes after combustion in an NBS smoke chamber was measured with a gas detector tube. The reduction rate of the gas concentration calculated from the total concentration (%) of carbon dioxide and carbon monoxide generated when only the resin is burned, and the total concentration (%) of carbon dioxide and carbon monoxide after burning the test piece The smoke emission reduction rate (%) was evaluated as follows.

(Preparation of epoxy resin having a bromine content of 12% by weight) Bisphenol A type epoxy resin Epicoat 82
8 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) was heated to 70 ° C., and brominated epoxy resin D.I. E. FIG. R.
(Dow epoxy resin) 542 (trade name, bromine content 4
8% by weight and 25 parts by weight of Dow Chemical Japan Co., Ltd. were added and melt-mixed. This was filtered while heating, and cooled to room temperature.

Examples 1-4 Based on 100 parts by weight of an epoxy resin having a bromine content of 12% by weight, the amount (parts by weight) of ammonium polyphosphate (Terage C60, trade name, manufactured by Chisso Corporation) shown in Table 1 )
Was mixed well beforehand, and 11 parts by weight of diethylenetriamine was added as a curing agent, followed by further mixing. After degassing, the mixture was heated at 40 ° C. for 60 minutes,
Press molding was performed at 0 ° C. for 15 minutes to produce a flat plate. The obtained flat plate was cut into a predetermined shape to prepare a test piece.
Using the obtained test pieces, UL-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed. The results are shown in Table 1.

Examples 5 to 10 With respect to 100 parts by weight of an epoxy resin having a bromine content of 12% by weight, ammonium polyphosphate (Terage C60, trade name, manufactured by Chisso Corporation) in the amount (parts by weight) shown in Table 2 )
A flat plate was prepared according to Example 1, except that Nova Excel 140 (trade name, manufactured by Rin Kagaku Kogyo KK) was added as red phosphorus. A predetermined test piece was prepared using the obtained flat plate, and UL-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed using the test piece. The results are shown in Table 2.

Comparative Examples 1-3 Ammonium polyphosphate (Terage C60, trade name, manufactured by Chisso Corporation) in the amount (parts by weight) shown in Table 2 with respect to 100 parts by weight of an epoxy resin having a bromine content of 12% by weight. )
A flat plate was prepared according to Example 1, except that Nova Excel 140 (trade name, manufactured by Rin Kagaku Kogyo KK) was added as red phosphorus. A predetermined test piece was prepared using the obtained flat plate, and UL-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed using the test piece. The results are shown in Table 2.

(Preparation of epoxy resin having a bromine content of 6% by weight) Bisphenol A type epoxy resin Epicoat 828
87.5 parts by weight (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) were heated to 70 ° C., and brominated epoxy resin D.I. E. FIG.
R. (Dow epoxy resin) 542 (trade name, bromine content: 48 wt%, manufactured by Dow Chemical Japan Co., Ltd.) 12.5
Parts by weight were added and melt mixed. This was filtered while heating, and cooled to room temperature.

Examples 11 to 13 With respect to 100 parts by weight of an epoxy resin having a bromine content of 6% by weight, ammonium polyphosphate (Terage C60, trade name, manufactured by Chisso Corporation) in the amount (parts by weight) shown in Table 3 )), A flat plate was obtained in accordance with Example 1, and a predetermined test piece was prepared using the obtained flat plate.
-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed. Table 3 shows the results.

(Preparation of epoxy resin having a bromine content of 24% by weight) Bisphenol A type epoxy resin Epicoat 82
8 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) was heated to 70 ° C., and brominated epoxy resin D.I. E. FIG. R.
(Dow epoxy resin) 542 (trade name, bromine content 4
8 wt%, 50 parts by weight of Dow Chemical Japan Co., Ltd.) were added and melt-mixed. This was filtered while heating, and cooled to room temperature.

Examples 14 to 16 Ammonium polyphosphate (Terage C60, trade name, manufactured by Chisso Corporation) in an amount (parts by weight) shown in Table 3 with respect to 100 parts by weight of an epoxy resin having a bromine content of 24% by weight. )
Was mixed well beforehand, and 11 parts by weight of diethylenetriamine was added as a curing agent, followed by further mixing. After degassing, the mixture was heated at 40 ° C. for 60 minutes,
Press molding was performed at 0 ° C. for 15 minutes to produce a flat plate. The obtained flat plate was cut into a predetermined shape to prepare a test piece.
Using the obtained test pieces, UL-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed. Table 3 shows the results.

Comparative Examples 4 to 7 Flat plates were prepared in accordance with Example 1 except that only the epoxy resin having a bromine content of 6, 12, 24 or 48% by weight without a flame retardant was used. A predetermined test piece was prepared using the obtained flat plate, and UL-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed using the test piece. Table 4 shows the results.

Comparative Examples 8 to 11 The procedure of Example 1 was repeated except that Atox-S (trade name, manufactured by Nippon Seimitsu Co., Ltd.) was blended as antimony trioxide in the amount (parts by weight) shown in Table 5. A flat plate was prepared. A predetermined test piece is prepared using the obtained flat plate, and UL
-94V evaluation, measurement of oxygen index, bending strength and smoke emission test were performed. Table 5 shows the results.

[0035]

The composition of the present invention is a flame-retardant epoxy resin composition which has a low bromine content, does not contain antimony oxide, has a high flame retardancy and a low smoke emission while containing a low amount of a flame retardant. is there. Therefore, the properties of the obtained epoxy resin molded product are also good. Thus, the composition comprises
It is possible to provide materials more suitable for a wide range of fields, such as civil engineering building materials, automotive parts materials, paints, adhesives, synthetic resin impregnated papers, and the like.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 9/00 C08K 9/00

Claims (6)

[Claims] 1. A flame-retardant epoxy resin composition containing 1 to 50 parts by weight of ammonium polyphosphate based on 100 parts by weight of a bromine-based epoxy resin having a bromine content of 3 to 30% by weight. 2. A polyphosphoric acid having a ratio (weight ratio) of ammonium polyphosphate: red phosphorus of 75:25 to 96: 4 with respect to 100 parts by weight of a bromine-based epoxy resin having a bromine content of 3 to 30% by weight. A flame-retardant epoxy resin composition containing a composite flame retardant comprising ammonium and red phosphorus in a proportion of 1 to 50 parts by weight. 3. The flame-retardant epoxy resin composition according to claim 1, wherein the brominated epoxy resin is a brominated epoxy resin or a mixed resin of an epoxy resin and a brominated epoxy resin. 4. The flame-retardant epoxy according to claim 1, wherein the ammonium polyphosphate is ammonium polyphosphate, melamine-modified ammonium polyphosphate, coated ammonium polyphosphate or a mixture of at least one of these. Resin composition. 5. The flame-retardant epoxy resin composition according to claim 1, wherein the red phosphorus is red phosphorus or coated red phosphorus. 6. The flame-retardant epoxy resin composition according to any one of claims 1 to 3, further comprising carbon fiber or glass fiber in an amount of 1 to 65 parts by weight based on 100 parts by weight of the brominated epoxy resin. A flame-retardant epoxy resin composition contained in parts by weight.