TWI410430B - Phosphorus-containing benzoxazine-based bisphenols, derivatives thereof, and preparing method for the same - Google Patents

Abstract

Phosphorus-containing benzoxazine-based bisphenols and derivatives thereof are disclosed. The phosphorus-containing benzoxazine-based bisphenols are prepared by reacting DOPO with benzoxazine to form the phosphorus-containing benzoxazine-based bisphenols. The phosphorus-containing benzoxazine-based bisphenols can further to form advanced epoxy resins. The advanced epoxy resins can further be cured to form flame retardant epoxy thermosets.

Description

Phosphorus bisphenol derived from Benzoxazine, epoxy resin semi-cured product thereof, epoxy resin cured product thereof and method for producing same

The present invention relates to a phosphorus bisphenol compound, a derivative thereof, and a process for producing the same, and more particularly to a phosphorus bisphenol compound derived from Benzoxazine and a process for producing the same.

In the current printed circuit board epoxy resin, halogen and antimony trioxide are the main flame-resistant additives, for example, halogen-containing tetrabromopropanediol is the commonly used epoxy resin flame retardant.

However, the cured epoxy resin containing a halogen-containing flame retardant may generate a harmful carcinogenic gas such as dioxin or benzofuran in addition to corrosive gas during combustion. Therefore, the use of other elements to replace halogens to develop new halogen-free flame retardants is the main development direction today.

The flame retardant epoxy resin currently used in printed circuit boards has better properties and reliability with phosphorus-based bisphenol DOPOBQ and DOPONQ-derived phosphorus-containing epoxy resin materials. However, the above-mentioned phosphorus-containing epoxy resin material still has some problems in use, for example, its solubility is poor, and it can only be dissolved in a high-boiling solvent, so that the processing cost is too high, and its industrial application is also limited.

One aspect of the present invention provides a series of phosphorus bisphenol compounds synthesized from a Benzoxazine monomer and a phosphorus compound DOPO and a preparation thereof The method comprises the ring opening reaction of a benzoxazine monomer with DOPO to form a phosphorus bisphenol compound. The Benzoxazine monomer comprises a benzoxazine monomer derived from an aromatic bisamine or a benzoxazine monomer derived from a bisphenol.

According to an embodiment of the present invention, a phosphorus-based bisphenol compound (I) produced by an aromatic diamine-derived Benzoxazine monomer and a phosphorus-based compound DOPO has the following formula:

According to another embodiment of the present invention, a phosphorus-based bisphenol compound (II) produced by a bisphenol-derived benzoxazine monomer and a phosphorus-based compound DOPO has the following formula: Wherein R ₁ is selected from the group consisting of: R ₂ is selected from the group consisting of: X contains the following structure: n is an integer and 1≦n≦10.

According to an embodiment of the present invention, the flame-retardant phosphorus-based epoxy resin semi-cured (III) derived from the phosphorus-based bisphenol compound (I) has the following formula:

According to another embodiment of the present invention, the flame-retardant phosphorus-based epoxy resin semi-cured product (IV) derived from the phosphorus-based bisphenol compound (II) has a structure represented by the following formula:

Another aspect of the present invention provides a method for preparing a flame-retardant phosphorus-based epoxy resin, comprising a phosphorus-based bisphenol compound (I) or (II) and a compound (C) having an epoxy group structure, without a catalyst The chain extension reaction is carried out by raising the temperature in the presence of a small amount of a catalyst to obtain a flame retardant phosphorus epoxy resin semi-cured product. Flame retardant phosphorus The epoxy resin semi-cured material can be further cured to form a flame retardant phosphorus-based epoxy resin cured product.

Wherein the compound (C) has a structure represented by the following formula: Y is selected from the following groups: m is a number of 1≦m≦10, and P ₁ and Q ₁ are each selected from the group consisting of hydrogen, C1-C6 alkyl, CF ₃ , phenyl, and halogen.

According to the above, the embodiments of the present invention have the following technical advantages:

1. The embodiment of the present invention provides a novel route for synthesizing phosphorus bisphenol, and successfully introduces the phosphorus compound DOPO into the Benzoxazine monomer to form a phosphorus bisphenol compound having high reactivity, and also improves the flame resistance of the Benzoxazine resin. The problem.

Second, the phosphorus bisphenol compound synthesized in the embodiment of the invention can be combined with an epoxy tree The fat is subjected to an advancement reaction to synthesize a flame-retardant phosphorus-based epoxy resin semi-cured product, and it is not necessary to add a catalyst during the synthesis, and the synthesis step is simple. The synthetic flame retardant phosphorus epoxy resin semi-cured product has excellent solubility and low viscosity characteristics, and has the advantages of convenient processing and mass production.

3. The flame retardant phosphorus epoxy resin semi-cured material according to the embodiment of the present invention, the cured product retains excellent toughness, and has good flame retardant properties and thermal stability.

The present invention provides a series of phosphorus bisphenol compounds, derivatives thereof, and processes for their preparation. The phosphorus-based bisphenol compound is produced by ring-opening reaction of a Benzoxazine monomer having a difunctional group with a phosphorus-based compound DOPO.

DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide) is a phosphorus-based compound having an active hydrogen atom reactive with an electron-deficient compound. Benzoxazine (oxobenzobenzocyclohexane) is a compound having a benzene ring-bonded nitrogen-containing heterocyclic ring structure, and a nitrogen-oxygen heterocyclic ring can be subjected to ring-opening polymerization to form a polymer upon heating. The Benzoxazine monomer used in the practice of the present invention is a Benzoxazine monomer having a bifunctional group, and is generally formed by condensation condensation of a bisphenol or an aromatic bisamine with an aldehyde and an aniline, but is not limited to the above method.

According to one embodiment of the present invention, the phosphorus bisphenol compound (I) is produced by mixing a phosphorus compound (DOPO) and a benzoxazine monomer (A) in a solvent, and ring-opening the benzoxazine (A) by heating.

According to another embodiment of the present invention, the synthesis of the phosphorus bisphenol compound (II) is carried out by the above method, and the difference is that the benzoxazine monomer (B) is taken. The benzoxazine monomer (A) is produced by subjecting a phosphorus compound (DOPO) to ring opening of benzoxazine (B).

The structures of the phosphorus compound (DOPO), the benzoxazine monomer (A), and the benzoxazine monomer (B) are as follows:

According to an embodiment of the present invention, the above phosphorus bisphenol compounds (I) and (II) may be further subjected to a chain extension reaction with a compound (C) having an epoxy group structure to synthesize a semi-cured flame retardant phosphorus epoxy resin. Compounds (III) and (IV) wherein compound (C) has the structure shown by the formula:

The flame-retardant phosphorus-based epoxy resin semi-cured products (III) and (IV) have the following structures: According to an embodiment of the present invention, after the flame-retardant phosphorus-based epoxy resin semi-cured (III) or (IV) is reacted with a curing agent, a flame-retardant epoxy resin cured product can be formed.

Embodiment 1: Synthesis of phosphorus bisphenol compound (I):

According to an embodiment of the present invention, a phosphorus bisphenol compound (I) can be synthesized by mixing and heating DOPO with a benzoxazine monomer (A) in a solvent, and the reaction formula is as follows: Wherein R ₁ is selected from the group consisting of: X contains the structure shown below: Where n is an integer and 1≦n≦10.

Phosphorus-based bisphenol compound (I)-derived flame-retardant phosphorus-based epoxy resin semi-cured product (III):

The phosphorus-based bisphenol compound (I) can be further subjected to a chain extension reaction with a compound having an epoxy group structure to synthesize a flame-retardant phosphorus-based epoxy resin semi-cured product (III). The compound having an epoxy group structure may be any suitable epoxy resin, such as bisphenol A resin, bisphenol F resin, bisphenol S resin, biphenol. A difunctional epoxy compound such as a resin.

According to an embodiment of the present embodiment, the epoxy resin having the compound (C) structure can be subjected to a chain extension reaction with a phosphorus bisphenol compound (I) at 100 to 200 ° C to synthesize a flame retardant phosphorus epoxy resin semi-cured product. (III), the reaction is as follows: Wherein m is a number of 1≦m≦10, and Y is selected from the following groups: , P ₁ and Q ₁ are each selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, CF ₃ , phenyl, and halogen.

According to one or more embodiments of the present embodiment, the phosphorus content of the flame-retardant phosphorus-based epoxy resin semi-cured (III) may be from 0.5 to 4 wt%.

According to one or more embodiments of the present embodiment, the ratio of the epoxy equivalent of the compound (C) to the phenol group equivalent ratio of the phosphorus bisphenol compound (I) may be from 1:1 to 10:1.

According to the present embodiment, the chain extension reaction can be carried out without a catalyst. However, it can also be carried out in the presence of a very small amount of catalyst to accelerate the reaction. The catalyst may be phenylimidazole, dimethylimidazole, triphenylphosphine, a quaternary phosphonium compound or a quaternary ammonium compound.

Curing of flame retardant phosphorus epoxy resin semi-cured (III):

The flame-retardant phosphorus-based epoxy resin semi-cured product (III) can be cured by a curing agent to form a flame-retardant phosphorus-based epoxy resin cured product.

According to an embodiment of the present invention, the curing agent may be a phenol novolac resin, a dicyandiamide, a diaminodiphenyl methane, a diaminodiphenyl sulfone, or a hydrazine. Phthalic anhydride or hexahydrophthalic anhydride.

Embodiment 2: Phosphorus bisphenol compound (II):

According to the present embodiment, the benzoxazine monomer (B) and DOPO are mixed and heated in a solvent to synthesize the phosphorus-based bisphenol compound (II), and the reaction formula is as follows: Wherein R ₂ is selected from the group consisting of: X may include, but is not limited to, the structure shown below: Where n is an integer of 1≦n≦10.

Synthesis of flame retardant phosphorus epoxy resin semi-cured product (IV) with phosphorus bisphenol compound (II):

The phosphorus-based bisphenol compound (II) can be subjected to a chain extension reaction at 100 to 200 ° C with a compound (C) having an epoxy group structure in the same manner as in the first embodiment to synthesize a flame-retardant phosphorus-based epoxy resin semi-cured. (IV), the reaction is as follows: Wherein m is a number of 1≦m≦10, and Y is selected from the group as shown in the first embodiment.

According to one or more embodiments of the present embodiment, the phosphorus content of the flame-retardant phosphorus-based epoxy resin semi-cured (IV) may be from 0.5 to 4 wt%.

According to one or more embodiments of the present embodiment, the ratio of the epoxy equivalent of the compound (C) to the phenol group equivalent ratio of the phosphorus bisphenol compound (II) may be from 1:1 to 10:1.

Curing of flame retardant phosphorus epoxy resin semi-cured (IV):

The flame-retardant phosphorus-based epoxy resin semi-cured product (IV) may be cured by a curing agent as shown in the first embodiment to form a flame-retardant phosphorus-based epoxy resin cured product.

Synthesis Example 1-1: Preparation of phosphorus bisphenol compound (I-a)

According to the structure of the phosphorus-based bisphenol compound (I), a phosphorus-based bisphenol compound (Ia) wherein X is CH ₂ can be synthesized, and has the following structure:

The phosphorus bisphenol compound (Ia) is synthesized by taking 0.2 mol (86.9 g) of Benzoxazine resin Pd derived from an aromatic bisamine 4,4'-diaminodiphenylmethan (DDM) (commercially available Benzoxazine resin Pd, available from Shikoku Chemicals Corporation and 0.4 mol (86.46 g) of DOPO were added to a 500 ml single port round bottom reactor containing 200 ml of tetrahydrofuran (THF). After reacting at room temperature for 1 hour and completely dissolving, the temperature was raised to reflux temperature, and the reaction was continued for 12 hours. After completion of the reaction, it was directly poured into 1000 ml of deionized water for precipitation and washing, washed into a powder, and then filtered by an air suction filter. The resulting filter cake was dried using a vacuum oven at 110 ° C to give 164.7 g of product as a yellow powder, yield 95%, mp. Fig. ^{1 is a 1} H NMR spectrum of a phosphorus-based bisphenol compound (Ia).

Synthesis Example 1-2: Preparation of phosphorus bisphenol compound (I-b)

According to the structure of the phosphorus-based bisphenol compound (I), a phosphorus-based bisphenol compound (Ib) wherein X is -O- can be synthesized, and has the following structure:

The phosphorus bisphenol compound (Ib) is synthesized by taking 0.2 mol (87.3 g) of Benzoxazine resin ODABZ derived from an aromatic bisamine 4,4-oxydianiline (ODA), and a commercially available Benzoxazine resin ODABZ is commercially available from Shikoku Chemicals. The compound of the phosphorus bisphenol compound (Ib) was prepared by the procedure shown in Synthesis Example 1-1 to give a yellow powder product (166.7 g, yield: 95%, melting point: 110 ° C).

Synthesis Example 1-3 :

The flame retardant phosphorus epoxy resin semi-cured system utilizes a phosphorus bisphenol compound (Ia) or (Ib) as an epoxy resin modifier, and a diglycidyl ether of bisphenol A (DGEBA), double Phenol F epoxy tree Synthesis of diglycidyl ether of bisphenol F (DGEBF) or cyclopentadiene epoxy (Dicyclopentadiene epoxy).

The method for preparing epoxy resin semi-cured materials with different phosphorus contents is to add 10 g of epoxy resin (for example, bisphenol A epoxy resin, bisphenol F epoxy resin or cyclopentadiene epoxy resin) to 100 ml three-necked circle. In the bottom reactor, the reactor interface was externally connected with nitrogen and a condenser, stirred using a heating stirrer and heated to 150 ° C in an oil bath. A desired amount of the phosphorus bisphenol compound (I-a) was added to the above reactor for 1.5 hours to obtain a transparent viscous liquid, which was cooled to obtain a liquid epoxy resin.

The flame-retardant phosphorus-based epoxy resin semi-cured product (III-a) synthesized using the phosphorus bisphenol compound (Ia) as an epoxy resin modifier has the following general formula:

The flame-retardant phosphorus-based epoxy resin semi-cured product (III-b) synthesized by using a phosphorus bisphenol compound (Ib) as an epoxy resin modifier has the following general formula:

Depending on the reactants used (phosphorus bisphenol compound and epoxy resin) and the phosphorus content to be synthesized, a flame retardant phosphorus epoxy resin semi-cured product and a cured product having different properties can be synthesized, and the reactants thereof The parameters of the product are summarized in Table 1 below, and the properties of the cured product are summarized in Table 2 below.

Synthesis Example 2-1: Preparation of phosphorus bisphenol compound (II-a)

According to the structure of the phosphorus-based bisphenol compound (II), a phosphorus-based bisphenol compound (II-a) wherein X is CH ₂ can be synthesized, and has the following structure:

The phosphorus bisphenol compound (II-a) is synthesized by taking 0.2 mol (86.9 g) of bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazinyl)methane benzoxazine derived from bisphenol. For example, a commercially available Benzoxazine resin Fa, available from Shikoku Chemicals Corporation and 0.4 mol (86.46 g) of DOPO, in the same manner as in the synthesis of the phosphorus bisphenol compound (Ia) shown in the first embodiment, is used to synthesize a phosphorus bisphenol compound. (II-a), a yellow powder product of 162.9 g,yield: 94%, m.p.

Synthesis Example 2-2 Preparation of phosphorus bisphenol compound (II-b)

According to the structure of the phosphorus-based bisphenol compound (II), a phosphorus-based bisphenol compound (II-b) wherein X is -C(C ₂ H ₃ ) ₂ - can be synthesized, and has the following structure:

The phosphorus bisphenol compound (II-b) was synthesized by taking 0.2 mol (92.51 g) of Benzoxazine resin derived from bisphenol A (commercially available Ba from Shikoku Chemicals Corporation) and 0.4 mol (86.46 g). DOPO, a phosphorus bisphenol compound (II-b) was synthesized in the same manner as in the synthesis of the phosphorus bisphenol compound (Ia) shown in the first embodiment, to obtain a yellow powder product of 170.1 g, a yield of 95%, and a melting point of 118. °C.

Synthesis Example 2-3 :

The phosphorus bisphenol compound (II-a) or (II-b) is used as an epoxy resin modifier to react with bisphenol A epoxy resin, bisphenol F epoxy resin or cyclopentadiene epoxy resin. Synthesis of a flame retardant phosphorus epoxy resin semi-cured product.

The flame-retardant phosphorus-based epoxy resin semi-cured product (IV-a) synthesized by using the phosphorus bisphenol compound (II-a) as an epoxy resin modifier has the following general formula:

The flame-retardant phosphorus-based epoxy resin semi-cured product (IV-b) synthesized by using the phosphorus bisphenol compound (II-b) as an epoxy resin modifier has the following formula:

Depending on the reactants used (phosphorus bisphenol compound and epoxy resin) and the phosphorus content to be synthesized, a flame retardant phosphorus epoxy resin semi-cured product and a cured product having different properties can be synthesized, and the reactants thereof The parameters of the product are summarized in Table 1. The properties of the cured product are summarized in Table 2.

Synthesis Example 3: Preparation of cured epoxy resin

The resin semi-cured material is heated to 150 ° C to be in a molten state, and the hardener 4,4-diamino diphenyl sulfone (DDS) is added to an equivalent amount of the above epoxy. The resin semi-cured material was uniformly stirred, and then hardened in an oven. The curing conditions were 2 hours at 180 ° C, 2 hours at 200 ° C, and 2 hours at 220 ° C.

Table 2 shows the thermal property analysis data of the cured product of the examples of the present invention, which are the results of the glass transition temperature (Tg) and the UL-94 flame resistance test of the cured epoxy resin obtained by the above synthesis examples. The UL-94 flame test is a test for the flame resistance of plastic materials in equipment and equipment.

As can be seen from Table 2, when the phosphorus bisphenol compound and the ring of the embodiment of the present invention After the semi-curing reaction of the oxygen resin, the original flammable resin (bisphenol A epoxy resin semi-cured material) can meet the V-0 rating of the UL-94 flame resistance test, and also has excellent glass transition temperature, for example, a synthesis example. The (III-aa-1.5)/DDS cured product of 1-3 (phosphorus content: 1.23%) has a glass transition temperature of 189 °C.

Fig. 2 is a graph showing the analysis of dynamic mechanical properties of the compound (III-aa-1.5)/DDS cured product. The curve above the second graph is the storage modulus of each sample (corresponding to the vertical axis on the left side of the figure), which means that each sample can bear at different temperatures. Subject to stress. The lower peak in Figure 2 is the softened glass transition temperature of each sample (corresponding to the vertical axis on the right side of the figure). The significance is the softening temperature of each sample. The higher the temperature, the higher the operating temperature that can be withstood.

As is apparent from Fig. 2, the flame-retardant phosphorus-based epoxy resin cured product of the embodiment of the present invention has an appropriate glass transition temperature and can be operated at a high temperature of about 150 to 200 °C. In addition, the storage modulus of the modified epoxy resin is higher than that of the unmodified resin. For example, the storage modulus (3.1 GPa) of the (III-aa-1.5)/DDS cured product at 50 ° C is higher than that of the unmodified. Quality bisphenol A epoxy resin / DDS cured product (2.5 GPa). As can be seen from the graph in Fig. 2, the modified (added phosphorus) epoxy resin cured product (III- compared to the unmodified epoxy resin cured product (bisphenol A epoxy resin/DDS) Although aa-1.5)/DDS slightly reduces the maximum bearing capacity at high temperatures, it still has good mechanical properties; therefore, under the premise that mechanical properties can still be considered, it is more important that the addition of phosphorus completely improves the incombustibility of Benzoxazine resin. The problem.

Figure 3 is a thermogravimetric analysis of the III-aa/DDS cured product with different phosphorus contents. It can be known from the residual ratio of the compound of FIG. 3 at a high temperature that the flame-retardant phosphorus-based epoxy resin of the present invention has good thermal stability, is very stable before 350 ° C, and with the phosphorus content of the compound itself. The higher the higher the residual ratio, and the unmodified (phosphorus-free) bisphenol A epoxy resin/DDS cured product, the residual rate at high temperature is significantly lower than the flame retardant phosphorus epoxy resin of the present invention. . Figure 3 shows that the addition of phosphorus does help to provide thermal stability and protects resin molecules from thermal decomposition.

From the above, it is understood that the flame-retardant phosphorus-based epoxy resin cured product of the embodiment of the present invention is suitably applied to a circuit board substrate, a semiconductor packaging material, and other related fields having a flame retardant demand.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt;</RTI><RTIgt^{;</RTI><RTIgt;</RTI><RTIgt;} H NMR spectrum.

Figure 2 is a graph showing the dynamic mechanical properties of a series of (III-aa)/DDS cured products with different phosphorus contents.

Figure 3 is a thermogravimetric analysis of a series of (III-aa)/DDS cured products with different phosphorus contents.

Claims (14)

A phosphorus-based bisphenol compound (II) having a structure represented by the following formula: Wherein R ₂ is selected from the group consisting of: X contains the following structure: , n is an integer and 1≦n≦10. A flame-retardant phosphorus-based epoxy resin semi-cured product (IV) derived from the phosphorus-based bisphenol compound (II) according to claim 1 and having a structure represented by the following formula: Among them, Y is selected from the following groups: m is a number of 1≦m≦10, and P ₁ and Q ₁ are each selected from the group consisting of hydrogen, C1-C6 alkyl, CF ₃ , phenyl, and halogen. A method for preparing a phosphorus bisphenol compound, comprising: adding a phosphorus compound (DOPO) and a Benzoxazine monomer to an organic solvent and reacting at room temperature until completely dissolved, and then raising the temperature to a reflux temperature to synthesize a phosphorus A bisphenol compound, wherein the phosphorus compound (DOPO) has the structure of the formula: The Benzoxazine monomer has the structure shown by the monomer (B): Wherein R ₂ is selected from the group consisting of: X contains the following structure: , n is an integer and 1≦n≦10. A method for producing a flame-retardant phosphorus-based epoxy resin comprising: subjecting a phosphorus-based bisphenol compound prepared according to the method of claim 3 to a chain extension reaction of a compound (C) having an epoxy group structure to synthesize a flame retardant A phosphorus-based epoxy resin semi-cured product in which the compound (C) has the structure of the following formula: Among them, Y is selected from the following groups: , P ₁ and Q ₁ are each selected from the group consisting of hydrogen, C1-C6 alkyl, CF ₃ , phenyl and halogen. The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 4, wherein the chain extension reaction is carried out at 100 to 200 ° C without adding a catalyst. The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 4, wherein the chain extension reaction is carried out at 100 to 200 ° C, and the chain extension reaction is carried out in the presence of a very small amount of a catalyst, and the catalyst is a phenyl group. Imidazole, dimethylimidazole, triphenylphosphine, a quaternary phosphonium compound or a quaternary ammonium compound. The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 4, wherein the flame-retardant phosphorus-based epoxy resin semi-cured material has a phosphorus content of 0.5 to 4% by weight. The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 4, wherein the ratio of the epoxy group equivalent of the compound (C) to the phenol group equivalent ratio of the phosphorus-based bisphenol compound is from 1:1 to 10 :1. The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 4, wherein the phosphorus-based bisphenol compound (II-a) has the following structure: The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 9, wherein the phosphorus-based bisphenol compound (II-a) is subjected to a chain extension reaction with the compound (C), and the compound (C) Y-system From the following (a), (b) and (c): A method of producing a flame-retardant phosphorus-based epoxy resin according to claim 4, wherein the phosphorus-based bisphenol compound (II-b) has the following structure: The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 11, wherein the phosphorus-based bisphenol compound (II-b) undergoes a chain extension reaction with the compound (C), and the compound (C) Y-system From the following (a), (b) and (c): The method for preparing a flame-retardant phosphorus-based epoxy resin according to claim 4, further comprising curing the flame-retardant phosphorus-based epoxy resin semi-cured product with a curing agent to form a phosphorus-containing flame-resistant epoxy resin cured product. The method for producing a flame-retardant phosphorus-based epoxy resin according to claim 13, wherein the curing agent is a phenol resin, dicyandiamide, methylbisphenylamine, bisaminobisbenzoquinone, phthalic anhydride or hexahydrohydride. Anthraquinone anhydride.