JP2000309623A - Phosphorus-containing flame-retardant epoxy resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphorus-containing flame-retardant epoxy resin curable alone by using a hardener, capable of providing a flame-retardant synthetic resin composition having excellent characteristics including heat resistance by formulating the epoxy resin with another synthetic resin. SOLUTION: This phosphorus-containing flame-retardant epoxy resin is obtained by reacting an epoxy resin with a phosphorus compound of the formula in a molar ratio of 0.05-0.45 mol of the compound based on 1 mol of epoxy group and has 300 g/eq to 10,000 g/eq epoxy equivalent and 0.5-5% phosphorus content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phosphorus-containing flame-retardant which can be cured alone by using a curing agent, and which can be added and blended with other synthetic resins to impart flame retardancy. (Self-extinguishing) epoxy resin.

[0002]

2. Description of the Related Art In general, various synthetic resins are widely used in electric, electronic insulating materials, paints, composite materials, adhesives, etc. due to their excellent properties. For example, as a thermosetting resin, an epoxy resin, a phenol resin, an unsaturated polyester resin, a melamine resin, and the like are known. Usually, since these are flammable, they provide flame retardancy (self-extinguishing properties). Therefore, phosphorus-based flame retardants and halogen-based flame retardants are added.

[0003] These flame retardants are required to have heat resistance, strength, or water resistance that can withstand the heat received when molding a resin or when using a molded product. However, phosphorus-containing compounds that have been used as flame retardants are addition-type, so they do not contribute to improving the performance as a molded product, and addition-type phosphorus-based flame retardants after mixing with a synthetic resin There were problems with stability and water resistance.

[0004] On the other hand, the addition type halogen-based flame retardant has a large specific gravity, and therefore has a problem that it has poor compatibility with synthetic resins and is easily separated (bleed). It has also been known that the combined use of a phosphorus-containing compound and a bromine compound can further enhance the flame retardant effect. Did not contribute to the improvement.

[0005] The present invention, as described above, heat resistance and water resistance,
A new phosphorus-containing flame retardant that can provide a flame-retardant synthetic tree composition with excellent physical properties, including heat resistance more than conventional products, in place of the additive flame retardant, which has the problem of reduced performance in terms of bleeding. It is intended to provide a flame-retardant epoxy resin.

[0006]

The gist of the present invention is to react an epoxy resin with a phosphorus compound represented by the following formula (1) at a ratio of 0.05 to 0.45 mol per mol of epoxy group. Epoxy equivalent 300 g / eq-1
It is a phosphorus-containing flame-retardant epoxy resin represented by the following formula (2) having a phosphorus content of 0.5 to 5% at 000 g / eq.

[0007]

Embedded image

[0008]

Embedded image In the formula (2), Z ₁ and Z ₂ are each selected from any of the formulas (3), (4) and (5);
Is either formula (6) or formula (7), and a + d
Is the number of functional groups of Z ₁ , b is the number of functional groups of Z ₂ −1, and c represents an integer of 1 to 20.

[0009]

Embedded image Wherein (3), A _{is, -CH 2 -, - C (} CH 3) 2 -, -
SO ₂ — selected from any divalent group;
X represents either a halogen atom or a hydrogen atom, and e represents an integer of 0 or more. In this case, the number of functional groups is 2.

[0010]

Embedded image In the formula (4), R represents any of CH ₃ — and a hydrogen atom, and f represents an integer of 1 or more. In this case, the number of functional groups is f
+2.

[0011]

Embedded image In the formula (5), B is ₂ of any of —CH ₂ — and —SO ₂ —.
It is selected from valence groups. In this case, the number of functional groups is 4.

[0012]

Embedded image

[0013]

Embedded image

That is, the present invention provides a novel phosphorus compound obtained by reacting an epoxy group of an epoxy resin with a phenolic hydroxyl group (a hydroxyl group coordinated to an aromatic ring) of a phosphorus-containing compound represented by the formula (1). Contains flame-retardant epoxy resin. The phosphorus-containing flame-retardant epoxy resin obtained in the present invention imparts flame retardancy to various synthetic resin moldings and has a reactive functional group in a curing agent or the like in the synthetic resin or in these compositions. In this case, it is possible to improve the performance as a molded product by reacting this functional group with an epoxy group.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail.
The phosphorus-containing epoxy resin obtained in the present invention is a 10- (2,5-dihydroxyphene) represented by the formula (1).
yl) -10H-9-oxa-10-phosphap
It can be obtained by reacting a phosphorus compound of henanthrene-10-oxide with an epoxy resin at a predetermined molar ratio to introduce an epoxy group into the phosphorus compound.

That is, the epoxy group 1 in the epoxy resin
The phosphorus compound represented by the formula (1) is used in an amount of 0.0
5 to 0.45 mole ratio, more preferably 0.08 to 0.
It is obtained by reacting at 39 mol. The amount of the phosphorus compound is 0.1 to 1 mol of the epoxy group in the epoxy resin.
If the amount is less than 05 mol, the flame retardancy is not sufficiently improved, and if the amount is 0.45 mol or more, the flame retardancy can be expected to be improved, but the viscosity is too high and the dispersion in the synthetic resin is difficult, which is not preferable.

The reaction between the phosphorus compound represented by the formula (1) and the epoxy resin may be performed by a known method. For example, metal oxides, inorganic salts, organic bases and salts thereof, and so-called onium compounds may be used. There is a method using a catalyst.

Epoxy resins used for the reaction include glycidyl ethers represented by bisphenol A, bisphenol F, bisphenol S, phenol novolak and orthocresol novolac, and halogenated compounds represented by tetrabromobisphenol A and tetrabromobisphenol F. Known epoxy equivalents such as glycidyl ethers, glycidylamines represented by tetraglycidylaminodiphenylmethane and tetraglycidylaminodiphenylsulfone are 130 g / eq to 1,500.
g / eq epoxy resin can be used alone or in combination.

The phosphorus-containing flame-retardant epoxy resin of the present invention comprises
It can be cured using a curing agent. As the curing agent to be used, any of acid anhydrides, polyamine compounds, phenol compounds and other commonly used curing agents can be used. When the phosphorus-containing flame-retardant epoxy resin of the present invention alone is cured using a curing agent, the amount of the curing agent is 0.5 to 1.2 with respect to 1 equivalent of the epoxy group of the phosphorus-containing flame-retardant epoxy resin. Is equivalent. In addition, the phosphorus-containing flame-retardant epoxy resin of the present invention may contain commonly used additives according to the purpose. For example, quartz powder,
A commonly used filler such as titanium oxide, alumina, or the like, or a pigment, a colorant, or the like is added as necessary.

The phosphorus-containing flame-retardant epoxy resin of the present invention can be used by being blended with various synthetic resins. Examples of the synthetic resin used include an epoxy resin, a phenol resin, a melamine resin, and an unsaturated polyester resin, and the most preferred resin is an epoxy resin. That is, when the synthetic resin used is an epoxy resin, the phosphorus-containing flame-retardant epoxy resin of the present invention is obtained by reacting the phosphorus compound represented by the formula (1) with the epoxy resin at a specific ratio. It is a phosphorus-containing flame-retardant compound having a group, and the phosphorus-containing flame-retardant compound has one epoxy group, thereby constituting one component of an epoxy resin as a thermosetting resin composition. Therefore, also in this case, it can be cured by using a curing agent. As the curing agent to be used, a conventional amount of any of acid anhydrides, polyamine compounds, phenol compounds, and other commonly used curing agents is used.

Further, when the phosphorus-containing flame-retardant epoxy resin of the present invention is used by being mixed with various synthetic resins, commonly used additives can be added according to the purpose. For example, a commonly used filler such as quartz powder, titanium oxide, alumina, or the like, or a pigment, a colorant, or the like is added as necessary.

[0022]

Examples and Comparative Examples Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The physical properties of the cured products in the examples were measured by the following measurement methods. Tg: Viscoelastic spectrometer DMA manufactured by DuPont
980, measured at a heating rate of 2 ° C./min,
The value at tan δ is shown. Boiling water absorption: Water absorption when immersed at 100 ° C. for 1 hour. Water absorption under pressure: Water absorption when water is absorbed by a forced moisture absorption test at 120 ° C. × 1 hr. Flame resistance, flexural strength and flexural modulus: JIS K 691
Measured value measured according to 1. With respect to the flame retardancy, the measured value of 1 or less means that the framing time was 1 second or less for both the two-time flame contact of the test piece. The two numbers indicate the framing time of the first and second flame contacts.

Example 1 Brominated epoxy resin, Epototo YDB-400 (manufactured by Toto Kasei Co., Ltd., tetrabromobisphenol A type diglycidyl ether, epoxy equivalent (hereinafter referred to as EEW.) 400 g / eq, bromine content 49. 0%) 442 g
And 10- (2,5-Dihydroxyphenyl)
-10H-9-oxa-10-phosphaphen
anthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd., hereinafter referred to as HCA-HQ, molecular weight 324.3)
104.5 g as an aqueous solution using 0.5 g of tetramethylammonium chloride as a reaction catalyst, and HCA
-HQ to epoxy group molar ratio (hereinafter referred to as P / E)
The reaction was carried out at a temperature of 100 to 180 ° C. for 5 hours at 292/1, and EEW. 1,190 g / eq, phosphorus content 1.8
% And a bromine content of 39.6%. Resin A5
4.6 g of Epotote YD-128 (bisphenol A)
Diglycidyl ether, EEW. 187 g / eq) 4
To 5.4 g of the mixture, methylated tetrahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd .;
48 g) as a curing accelerator, and
0.1 g of ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd .; hereinafter, referred to as 2E4MZ) is blended, and 12
The composition was cured by heating at 0 ° C. for 1 hour, 150 ° C. for 1 hour, and 170 ° C. for 1 hour. The phosphorus content, bromine content and physical properties of the cured product in the obtained cured product were measured, and the results are shown in Table 1.

Example 2 Epotote YDB-400 (described above) 442 g, Epotote YD-128 (described above) 453.5 g, HCA-HQ
(P / E = 0.091 / 1) under the same conditions as in Example 1 (P / E = 0.091 / 1). 350g / e
q, Resin B having a phosphorus content of 1.0% and a bromine content of 21.7% was obtained. To 100 g of the resin B thus obtained, 47 g of HN-2200 (described above) as a curing agent and 0.1 g of 2E4MZ (described above) as a curing accelerator were blended and cured under the same curing conditions as in Example 1. The physical properties of the cured product were measured, and the results are shown in Table 1.

Example 3 453.5 g of Epotote YD-128 (described above), HCA
-HQ (described above) was reacted under the same conditions as in Example 1 (P / E = 0.133 / 1), and EEW. 313g /
eq, a resin C having a phosphorus content of 1.8% and a bromine content of 0%. To a mixture of 55.8 g of the resin C thus obtained and 44.2 g of Epototo YDB-400 (described above), 47 g of HN-2200 (described above) as a curing agent and 0.1 g of 2E4MZ (described above) as a curing accelerator were blended. The composition was cured under the same curing conditions as in Example 1, and the physical properties of the obtained cured product were measured. The results are shown in Table 1.

Comparative Example 1 Epotote YDB-400 (described above) 442 g, Epotote YD-128 (described above) 244 g, Epotote YD-0
11 (bisphenol A type diglycidyl ether manufactured by Tobu Kasei Co., Ltd., EEW.475 g / eq) 214 g / e
q, 100 g of triphenyl phosphite (trade name TP-1, phosphorus content 10%, manufactured by Daihachi Chemical Industry Co., Ltd.)
Is stirred and mixed at 100 to 120 ° C., and EEW. 350g /
eq. A resin D having a phosphorus content of 1.0% and a bromine content of 21.7% was obtained. 48 g of HN-2200 (described above) as a curing agent and 0.1 g of 2E4MZ (described above) as a curing accelerator were mixed with 100 g of the resin D thus obtained.
The composition was cured under the same curing conditions as described above, and the physical properties of the obtained cured product were measured. The results are shown in Table 1.

Comparative Example 2 Epotote YDB-400 (described above) 44.2 g, Epotote YD-128 (described above) 17.9 g, and Epotote YD
-011 (described above), 37.9 g of a mixture, 48 g of HN-2200 (described above) as a curing agent, and 2 g of a curing accelerator.
0.1 g of E4MZ (described above) was blended and cured under the same curing conditions as in Example 1, and the physical properties of the resulting cured product were measured.
The results are shown in Table 1.

Example 4 Resin B (described above) was dissolved in methyl ethyl ketone to obtain 200 g of a 50% nonvolatile (hereinafter referred to as NV) methyl ethyl ketone solution. As a curing agent, a phenol novolak resin (manufactured by Toto Kasei Co., Ltd.) Softening point: 98 ° C., hereinafter referred to as DC-5) in methyl ethyl ketone (N
V. 50%) 2E4MZ as a curing accelerator
(Described above) was used as a resin varnish using 0.1 g each,
Glass cloth (WEA-18K-105BZ _2, manufactured by Nitto Boseki Co., Ltd.) was impregnated into and dried 5 minutes in a 0.99 ° C. oven B- after staged, and below the Puriburegu 8 plies obtained copper foil ( 3EC, thickness 35μ, manufactured by Mitsui Kinzoku Mining Co., Ltd.), and 20 kgf / cm 2 × 1
Heat and pressure cure under the curing condition of 70 ° C. × 2 hours.
A laminate having a thickness of 6 mm and a resin content of about 42% was obtained. Table 2 shows the physical property values of the obtained laminate.

Example 5 108.5 g of YD-128 (described above) and 66.5 g of HCA-HQ (described above) were reacted under the same conditions as in Example 1 (P / E).
= 0.353 / 1), EEW. A resin E having 1,035 g / eq, a phosphorus content of 3.6% and a bromine content of 0% was obtained. A solution of the resin E thus obtained in dimethylformamide (N
V. 50%) as a curing agent, and 20 g of a solution of DC-5 (described above) in methyl ethyl ketone (NV. 50%).
Was used as a resin varnish using 0.1 g of 2E4MZ (described above) as a curing accelerator, and a laminate was obtained in the same manner as in Example 4. Table 2 shows the physical property values of the obtained laminate.

Comparative Example 3 A solution of resin D (described above) in methyl ethyl ketone (NV. 50)
%), A resin varnish was prepared by using 60 g of a methyl ethyl ketone solution (NV. 50%) of DC-5 (described above) as a curing agent and 0.1 g of 2E4MZ (described above) as a curing accelerator. A laminate was obtained in the same manner as in. Table 2 shows the physical property values of the obtained laminate.

Comparative Example 4 YD-128 (described above) 62 g and HCA-HQ (described above) 3
8 g was dissolved in dimethylformamide, and NV. The resin varnish was prepared by using 20 g of a methyl ethyl ketone solution (NV. 50%) of DC-5 (described above) as a curing agent and 0.1 g of 2E4MZ (described above) as a curing accelerator. A laminate was obtained by the same operation. Table 2 shows the physical property values of the obtained laminate.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

From the above results, the novel phosphorus-containing epoxy resin of the present invention is useful as a flame retardant, and even if it is used for another synthetic resin, it has good flame retardancy without deterioration in physical properties. A flammable synthetic resin composition can be obtained. Further, it is possible to simultaneously introduce phosphorus and halogen into the skeleton in one molecule, and it is also possible to use it in various synthetic resins in combination with a halogen-based flame retardant, which is very useful for the industrial world. is there.

[0035]

[Brief description of the drawings]

FIG. 1 is a GPC chart of the phosphorus-containing flame-retardant epoxy resin obtained in Example 1.

FIG. 2 is a GPC chart of the phosphorus-containing flame-retardant epoxy resin obtained in Example 3.

FIG. 3 is an IR spectrum of the phosphorus-containing flame-retardant epoxy resin obtained in Example 1.

FIG. 4 is an IR spectrum of the phosphorus-containing flame-retardant epoxy resin obtained in Example 3.

Claims (1)

[Claims] 1. An epoxy resin containing a phosphorus compound represented by the following formula (1) in an amount of from 0.05 to 0.
A phosphorus-containing flame-retardant epoxy resin represented by the following formula (2) having an epoxy equivalent of 300 g / eq to 10,000 g / eq and a phosphorus content of 0.5 to 5% obtained by reacting at a ratio of 45 mol. . Embedded image Embedded image In the formula (2), Z ₁ and Z ₂ are each selected from any of the formulas (3), (4) and (5);
Is either formula (6) or formula (7), and a + d
Is the number of functional groups of Z ₁ , b is the number of functional groups of Z ₂ −1, and c represents an integer of 1 to 20. Embedded image Wherein (3), A _{is, -CH 2 -, - C (} CH 3) 2 -, -
SO ₂ — selected from any divalent group;
X represents either a halogen atom or a hydrogen atom, and e represents an integer of 0 or more. In this case, the number of functional groups is 2. Embedded image In the formula (4), R represents any of CH ₃ — and a hydrogen atom, and f represents an integer of 1 or more. In this case, the number of functional groups is f
+2. Embedded image In the formula (5), B is ₂ of any of —CH ₂ — and —SO ₂ —.
It is selected from valence groups. In this case, the number of functional groups is 4. Embedded image Embedded image