JPH0853533A - Brominated epoxy resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition excellent in flexibility and flame retardancy and useful for printed circuit laminate board. CONSTITUTION:This brominated epoxy resin composition for laminate contains (A) an epoxy resin synthesized by using (a) a tetrabrombisphenol A type epoxy resin having 330 to 500 epoxy equivalent, (b) another bisphenol A type epoxy resin having 170 to 300 epoxy equivalent and (c) a dimer acid of 180 to 200 acid value in a molar ratio of (0.3 to 0.6):(0.8 to 1.8):1 and conducting a thermal reaction of the resultant mixture and having <=0.3 acid value, (B) another thermosetting resin and (C) a flame retardant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brominated epoxy resin composition, which is suitable for adhesives, castings, paints, molding powders, etc.
In particular, the present invention relates to a resin composition for a printed wiring board, which has excellent compatibility with other thermosetting resins, flexibility and flame retardancy.

[0002]

2. Description of the Related Art As a base material for a laminated board, a conventional glass cloth,
Nonwoven glass and paper are generally used. The drilling of the laminated plate is usually done by drilling when the glass cloth is used as the base material, and punching is performed when the paper material is used as the base material, and the processing temperature gradually decreases from the viewpoint of productivity. There is.

When paper is used as a base material, a phenol resin is used as the resin impregnated in the paper, and a tung oil-modified phenol resin is generally used to obtain flexibility.

The oxygen index of phenolic resins is usually about 30.
It is higher than about 20 of ordinary non-flame-retardant epoxy resins and difficult to burn, but tung oil, which is a raw material of tung oil-modified phenol resin, is a yellow dry oil obtained from seeds of Cinnabaragiri. Although the phenol resin modified by (1) contributes to flexibility, it has a drawback that it is easy to burn.

As a technique for solving this problem, there is disclosed a resin varnish for producing a flame-resistant laminated board in which a reaction product of a halogenated bisphenol A diglycidyl ether and a dimer acid is added to a phenol resin (Japanese Patent Publication No. 60-173).
No. 40).

[0006]

However, although the brominated epoxy resin obtained by the above technique is effective in flame retardancy and punching processability (flexibility), it is incompatible with the phenol resin used in combination. It has a problem of solubility.

In view of this situation, the problem to be solved by the present invention is that it has excellent compatibility with other thermosetting resins typified by phenolic resins and epoxy resins in applications such as printed wiring boards and the resulting cured products. An object of the present invention is to provide an epoxy resin composition that has extremely excellent flexibility and contributes to flame retardancy.

[0008]

In view of the actual situation in the above-mentioned prior art, the present inventors have an excellent compatibility with other thermosetting resins represented by phenol resins and epoxy resins, and obtain a cured resin obtained. As a result of diligent studies to obtain an epoxy resin that has extremely excellent flexibility and contributes to flame retardancy, it can be obtained by reacting tetrabromobisphenol A type epoxy resin with bisphenol A type epoxy resin and dimer acid. The inventors have found that the above problems can be solved by using a brominated epoxy resin, and have completed the present invention.

That is, according to the present invention, the dimer is added to tetrabromobisphenol A type epoxy resin (a) 0.3 to 0.6 mol and other bisphenol A type epoxy resin (b) 0.8 to 1.8 mol. Laminate containing an epoxy resin (A) having an acid value of 0.3 or less obtained by blending 1 mol of the acid (c) and heating the mixture, another thermosetting resin (B) and a flame retardant (C) The present invention relates to a brominated epoxy resin composition for a board, preferably a brominated epoxy resin composition for a laminated board in which the tetrabromobisphenol A type epoxy resin (a) has an epoxy equivalent of 330 to 500 and a bromine content of 44 to 51%.

The tetrabromobisphenol A type epoxy resin used in the present invention is a bisphenol A type epoxy resin in which four hydrogens in the phenyl group are replaced with bromine, and there is no particular limitation on the physical properties, but the epoxy equivalent is 33
Those of 0 to 500 are preferable, and those of 330 to 450 are particularly preferable. The bromine content is not particularly limited, but bromine is 44 to 51% from the viewpoint of the obtained resin characteristic value.
Those included are preferred. When it is 44% or less, the bromine content of the obtained resin becomes low, which is reflected in the compounded varnish,
When it is 51% or more, the obtained resin has a high molecular weight and thus the viscosity becomes high, which is not preferable.

The other bisphenol A type epoxy resin used in the present invention is a reaction product of epichlorohydrin and polyhydric phenol, and is generally called epi-bis type. There is no limitation on physical properties, but those having an epoxy equivalent of 170 to 300 are preferable, and 170 to 19 are particularly preferable.
0 is more preferable.

The dimer acid used in the present invention generally refers to a dimer of unsaturated fatty acid, and has a characteristic that it is remarkably different depending on the fatty acid as a raw material and the polymerization method. The dimer acid used for industrial products contains a trimer in addition to the dimer. As a manufacturing method, for example, linoleic acid such as tall oil fatty acid or unsaturated fatty acid having a high linolenic acid content is used in Diels Alde.
r) Obtained by polymerizing by reaction. In this case, the product has 36 carbon atoms and a carboxyl group, contains a dimer acid content of 70 to 98%, and has an acid value of 185 to 200 (KOHmg / g). Similarly, considering the molecular weight of the epoxy resin obtained by the reaction with other components used in the present invention, the acid value is 190 to 2
00 is preferable.

1 mol of dimer acid is reacted with 0.3 to 0.6 mol of the above tetrabromobisphenol A type epoxy resin and 0.8 to 1.8 mol of the other bisphenol A type epoxy resin. Thereby, the epoxy resin (A) of the present invention is obtained.

When the content of the tetrabromobisphenol A type epoxy resin is 0.3 mol or less, the bromine content of the invention resin becomes low, so that it is necessary to use other flame retardants in a large amount.
When it is 6 mol or more, the flame retardancy is advantageous, but on the other hand, there is a drawback that the compatibility with other thermosetting resins is deteriorated. In addition, other bisphenol A type epoxy resin,
When the amount is 8 mol or less, the obtained resin becomes a high molecular weight substance, so that the viscosity of the resin solution is high and the impregnation property to the substrate is deteriorated.
When the amount is 1.8 mol or more, a resin having a low molecular weight can be obtained, which is advantageous for impregnation, but the crosslink density increases, so that there is a problem in flexibility of the cured product. Thus, an effective resin can be obtained within the range of the number of moles of the above-mentioned two kinds of epoxy resins, but the sum of the number of moles of tetrabromobisphenol A type epoxy resin and bisphenol A type epoxy resin per 1 mole of dimer acid. When is less than or equal to 1, the composition has an equimolar amount with the acid or an acid excess, so that the epoxy equivalent becomes huge and deviates from the original concept of the epoxy resin. Further, in the case of excess acid, the acid value becomes 0.3 or more and the problems described later occur, which is not suitable.

In the above reaction, it is necessary to continue the reaction until the epoxy resin (A) obtained has an acid value of 0.3 or less. If the reaction is terminated at a stage where the acid value does not reach 0.3, the reactivity of the obtained epoxy resin is slow and
There is a problem that the obtained cured product has poor water resistance and the cured product is markedly colored depending on the type of curing agent used, which is not preferable. Further, the epoxy resin (A) is not particularly limited except for the acid value, but its epoxy equivalent is more preferably 560 to 1000 in consideration of the impregnation property into the base material.

A reaction catalyst can be used in the above reaction. Examples of the reaction catalyst include sodium hydroxide and potassium hydroxide as alkali metal hydroxides, tertiary amines such as triethylamine and benzyldimethylamine as organic amines, and quaternary ammonium salts such as tetramethylammonium chloride. Examples of phosphorus compounds include phosphonium compounds, phosphine compounds, and imidazole compounds.

When carrying out the reaction, an organic solvent may be used if necessary.

The other thermosetting resin used in combination with the epoxy resin of the present invention is liquefied to show fluidity when heated to a high temperature, or softened to show plasticity, and at the same time, the intermolecular reaction is caused by a chemical reaction. A resin that can be three-dimensionally crosslinked and hardened to become insoluble and infusible, and specific examples thereof include a phenol resin, an epoxy resin, an amino resin, and an unsaturated polyester resin. Among these, phenol resin, when considering the purpose of use and emphasizing resin compatibility,
Epoxy resins are preferred.

The ratio of the above-mentioned epoxy resin to the other thermosetting resin is preferably 250 to 600 parts by weight based on 100 parts by weight of the other thermosetting resin. If it is less than 250 parts by weight, the viscosity of the compounded varnish is high and impregnating property becomes a problem.

The flame retardant which can be used in combination with the resin of the present invention is not particularly limited as long as the target flame retardancy can be obtained in the resin composition system containing the resin of the present invention. Examples of flame retardants that can be used in combination include, for example, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate,
Phosphorus compounds such as triphenyl phosphite, brominated epoxy resins, halogenated compounds such as brominated epoxy oligomers, metal oxides such as aluminum hydroxide, etc. may be mentioned, and one or a mixture of two or more thereof may be used. It Among these, phosphorus compounds such as tricresylphosphate, and the properties of the cured product are maintained and the flame retardancy of the brominated epoxy resin which is the resin of the present invention and high synergistic effect are obtained. A brominated epoxy resin and a brominated epoxy oligomer having a high content are preferable.

The curing agent used in the present invention is not particularly limited, and a known and commonly used compound is appropriately selected and used in a combination system with another thermosetting resin used in combination, depending on the purpose of use. be able to. Examples of the curing agent include amino curing agents, acid anhydride curing agents, and oligomer curing agents. Amine-based curing agents are preferable because of their excellent intermediate curing characteristics.

Specifically, first, as the amine curing agent, for example, diethylenetriamine, triethylenetetramine, tetraethylpentamine, dipropylenetriamine, bis (hexamethylene) triamine, 1,3,6-
Polyamines such as trisaminomethylhexane, trimethylhexamethylenediamine, polyetherdiamine, polyethylenediamine such as diethylaminopropylamine, mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N
An aliphatic polyamine such as aminoethylpiperazine, an aliphatic primary amine such as an aliphatic amine containing an aromatic ring such as metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
Aromatic diamine eutectic mixture, aromatic primary amines such as other aromatic diamines, spiro such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane Ring-containing diamines, hydanto ring-containing diamines, imide ring-containing diamines, di-triamines having an ether bond in the main chain, polyoxyethylene chain diamines, main chain silicone diamines, polyamine epoxy resin adducts, polyamine- Ethylene oxide adduct, polyamine-propylene oxide adduct,
Modified amines such as cyanoethylated polyamines, ketimines, etc., long chain diamines, long chain tertiary amines, trimethylguanidine, guanidine derivatives, alkyl tert monoamines,
Triethanolamine, piperidine, N, N'-dimethylpiperazine, 1,4-diazadicyclo (2,2,2)
Octane, pyridine, picoline, 1,8-diazabicycloundecane (DBU), benzyldimethylamine, 2
-(Dimethylaminomethyl) phenol, 2,4,6-
Tris (dimethylaminomethyl) phenol, 2,4
Tertiary and secondary amines such as tri-2-ethylhexylate of 6-tris (dimethylaminomethyl) phenol,
As polyamino resin, polyamide adduct, and imidazoles, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl body , 1-cyanoethyl compound / trimellitic acid salt, azine compound, quaternary salt, isocyanuric acid salt, hydroxymethyl compound, etc., and other potential amine curing agents such as boron trifluoride-amine complex (complex) and dicyandiamide Derivatives Organic acid hydrazide, diaminomaleonitrile and its derivatives. Examples include melamine and its derivatives, amine imides, polyamine salts and the like.

Examples of acid anhydride type curing agents include phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), pyromellitic dianhydride, Aromatic acid anhydrides such as 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, alkenyl anhydride Succinic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methyl ester / triglyceride and anhydride of adduct of linoleic acid / linolenic acid / eleostearic acid with maleic anhydride Cycloaliphatic compounds such as adducts with maleic acid Anhydride, polyadipic acid anhydride,
Examples thereof include aliphatic acid anhydrides such as polyazelaic acid anhydride and polysebacic acid anhydride, halogenated acid anhydrides such as chlorendic acid anhydride and tetrabromophthalic anhydride.

As the oligomer curing agent, for example, phenol novolac resin, cresol novolac resin, BPA
Examples thereof include novolac resins, biphenol novolac resins, and halogen-substituted novolac resins, such as novolac-type phenol resins, amino resins, resole-type phenol resins, aniline-formalin resins, and polyvinylphenol resins.

Other curing agents include light / ultraviolet curing agents such as aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, triallyl selenium salts, acridine orange, benzoflavin, and cetoflavin T, polymercaptans, polysulfide resins. Examples include polymercaptan type curing agents and the like.

Among these curing agents, as described above,
Amine-based curing agents are preferred, but for laminate applications, varnish stability (latent curing), workability, mechanical properties, thermal properties,
Dicyandiamide is preferable from the viewpoint of the balance of electric properties. When using the above oligomer curing agent,
It is preferably used in combination with other curing agents such as amine curing agents.

The above-mentioned curing agents may of course be used alone or in combination of two or more kinds. These curing agents may be simply mixed with another resin system containing the resin of the present invention, or the molecular sieve may be impregnated with the curing agent or used in the form of microcapsules.

If necessary, a curing accelerator may be used. As the curing accelerator, any conventionally known one can be used, and examples thereof include tertiary amines such as benzyldimethylamine, quaternary ammonium salts, imidazole, organic acid metal salts, Lewis acids, amine complex salts, and the like. These may be used alone or in combination of two or more. Also,
Although its use ratio is not particularly limited,
Usually, the range of 0.1 to 5% by weight in the composition is mentioned.

The curing accelerator can be used by simple mixing, molecular sieve impregnation, or microencapsulation, as in the case of the curing agent.

In the brominated epoxy resin composition for laminated boards of the present invention, a solvent may be further used in combination. The solvent is not particularly limited, and various solvents can be used as necessary. For example, acetone, methyl ethyl ketone, toluene,
Xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, methanol, ethanol and the like can be mentioned, and it is also possible to appropriately use two or more kinds of them as a mixed solvent.

The proportion of the solvent used is not particularly limited. For example, in the matrix resin composition for printed wiring board, the nonvolatile content is, for example, 10 to 90% by weight, and particularly 40 to 80% by weight from the viewpoint of varnish formation. It is preferable to use it within the following range.

The brominated epoxy resin composition for laminates of the present invention is extremely useful for laminates as described above, but when combined with a curing agent, for example, adhesives, castings, paints, molding powders, etc. It can be used for various purposes.

As a method for producing a laminated board from the brominated epoxy resin composition for laminated boards of the present invention, a known and commonly used method can be used. For example, a tung oil-modified phenol resin is used as another thermosetting resin in combination with the brominated epoxy resin of the present invention, and a flame retardant is added to obtain a flame retardant suitable for the purpose, to form a varnish. Paper as a base material is impregnated with this varnish at a resin content of 30 to 70% by weight to prepare a prepreg.
Examples include a method in which 10 to 10 sheets are set with a copper foil with an adhesive and heated and pressed, and the like.

Needless to say, the varnish according to the present invention can also be used by impregnating it in a paper substrate which has been previously treated with a water-soluble melamine-modified phenol resin or a water-soluble phenol resin and drying it.

[0035]

EXAMPLES Next, the present invention will be specifically described with reference to Reference Examples, Examples and Comparative Examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.

Reference Example 1 <Synthesis of Thermosetting Resin (Phenolic Resin)> A mixture of 1200 parts of m, p-cresol, 800 parts of tung oil and 2 parts of paratoluenesulfonic acid was reacted at 80 ° C. for 3 hours and then 80%. Paraformaldehyde (540 parts) is added and reacted at 90 ° C. for 4 hours. Then, 700 parts of toluene and 700 parts of methyl alcohol were added thereto to obtain a tung oil-modified phenol resin (hereinafter referred to as reference resin) having a solid content of 60%.

Reference Example 2 <Synthesis of Brominated Epoxy Resin> Tetrabromobisphenol A type epoxy resin (epoxy equivalent 350, bromine content: 47.5%) 0.51 mol,
Bisphenol A type epoxy resin (epoxy equivalent 18
6) 1.43 mol of dimer acid (acid value 190) 1.
Benzyldimethylamine 0.007
Moles were mixed and reacted at 100 ° C. for 5 hours. The obtained brominated epoxy resin had an epoxy equivalent of 790 and an acid value of 0.1.
1. The bromine content was 11.4%. (Hereinafter resin A-1
Say)

Reference Example 3 <Synthesis of brominated epoxy resin> Tetrabromobisphenol A type epoxy resin (epoxy equivalent 410, bromine content: 48.2%) 0.50 mol,
Bisphenol A type epoxy resin (epoxy equivalent 18
0) 1.68 mol of dimer acid (acid number 196) 1.
Benzyldimethylamine 0.007
Moles were mixed and reacted at 100 ° C. for 5 hours. The obtained brominated epoxy resin has an epoxy equivalent of 673 and an acid value of 0.1.
Below, the bromine content was 12.5%. (Hereinafter referred to as Resin A-2)

Reference Example 4 <Synthesis of Brominated Epoxy Resin> Tetrabromobisphenol A type epoxy resin (epoxy equivalent 450, bromine content: 50.0%) 0.35 mol bisphenol A type epoxy resin (epoxy equivalent 240)
With respect to 0.90 mol, dimer acid (acid value 192) was 1.00
1 mole of benzyldimethylamine was added, and the mixture was reacted at 100 ° C. for 5 hours. The obtained brominated epoxy resin had an epoxy equivalent of 2670, an acid value of 0.1 or less, and a bromine content of 11.8%. (Hereinafter resin A-3
Say)

Reference Example 5 <Synthesis of Brominated Epoxy Resin> Tetrabromobisphenol A type epoxy resin (epoxy equivalent: 350, bromine content: 47.5%) 0.55 mol,
Bisphenol A type epoxy resin (epoxy equivalent 17
0) 1.70 mol of dimer acid (acid value 185) 1.
Benzyldimethylamine 0.007
Moles were mixed and reacted at 100 ° C. for 5 hours. The obtained brominated epoxy resin has an epoxy equivalent of 630 and an acid value of 0.1.
Below, the bromine content was 11.6%. (Hereinafter referred to as Resin A-4)

Reference Example 6 <Synthesis of Brominated Epoxy Resin> Tetrabromobisphenol A type epoxy resin (epoxy equivalent 360, bromine content: 47.0%) 1.00 mol,
Bisphenol A type epoxy resin (epoxy equivalent 19
0) 0.80 mol of dimer acid (acid value 194) 1.
Benzyldimethylamine 0.007
Moles were mixed and reacted at 100 ° C. for 5 hours. The obtained brominated epoxy resin has an epoxy equivalent of 1005 and an acid value of 0.1.
The bromine content was 1 or less and 21.6%. (Hereinafter resin B
-1)

Reference Example 7 <Synthesis of Brominated Epoxy Resin> Tetrabromobisphenol A type epoxy resin (epoxy equivalent 400, bromine content: 48.0%) 0.80 mol,
Bisphenol A type epoxy resin (epoxy equivalent 19
0) 1.50 mol of dimer acid (acid value 190) 1.
Benzyldimethylamine 0.007
Moles were mixed and reacted at 100 ° C. for 5 hours. The obtained brominated epoxy resin has an epoxy equivalent of 693 and an acid value of 0.1.
Hereafter, the bromine content was 17%. (Hereinafter referred to as Resin B-2)

Examples 1 to 4 and Comparative Example 1 Each of the resins (A-1) obtained in Reference Examples 2 to 6
(A-4) and (B-1) to (B-2) were individually dissolved with methyl ethyl ketone and then mixed with (reference resin) obtained in Reference Example 1 to examine compatibility ( Tables 1 and 2). Next, varnishes were prepared according to the formulations shown in Tables 3 and 4, and a mixed solution having a nonvolatile content (NV) of 45% was prepared with toluene / methyl alcohol (= 1/1).

After that, a primary treated product having a resin impregnation ratio of 9%, which had been previously impregnated with a water-soluble phenolic resin into a paper substrate AKP [manufactured by Nippon Paper Industries Co., Ltd.], was selected from (A-1) to (A).
-4) and each of the mixed solutions of (B-1) to (B-2) were used to produce a prepreg with a resin impregnation ratio of 49%. Eight sheets of this prepreg were stacked, a 35 μm thick copper foil with an adhesive was set on one side, and heat and pressure were applied to laminate molding to produce a 1.6 mm-thick single-sided copper-clad laminate.

Each of the obtained single-sided copper-clad laminates was tested for workability, flame retardancy, water absorption, and physical properties. The results are shown in Tables 3 and 4.

[0046]

[Table 1]

[0047]

[Table 2] [Criteria] O: Compatible. … Transparent.

Δ: Slightly compatible ... Slightly cloudy x: Incompatible. … Muddy.

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is excellent in flexibility and flame retardancy and is useful for printed wiring laminates.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C08L 63/00 NJW

Claims (11)

[Claims] 1. A tetrabromobisphenol A type epoxy resin (a) in an amount of 0.3 to 0.6 mol and other bisphenol A.
Epoxy resin (A) having an acid value of 0.3 or less obtained by blending 1 mol of dimer acid (c) with 0.8 to 1.8 mol of epoxy resin (b) of type epoxy resin, and heat curing A brominated epoxy resin composition for laminates, which comprises a resin (B) and a flame retardant (C). 2. The composition according to claim 1, wherein the tetrabromobisphenol A type epoxy resin (a) has an epoxy equivalent of 330 to 500. 3. The composition according to claim 1 or 2, wherein the tetrabromobisphenol A type epoxy resin (a) has a bromine content of 44 to 51%. 4. The composition according to any one of claims 1 to 3, wherein the other bisphenol A type epoxy resin (b) has an epoxy equivalent of 170 to 300. 5. The dimer acid (c) has an acid value of 180 to 200.
And the dimer acid content is 70 to 98%, and the composition according to any one of claims 1 to 4. 6. The epoxy equivalent of the epoxy resin (A) is 5
The composition according to any one of claims 1 to 5, which is 60 to 3000. 7. The composition according to claim 1, wherein the other thermosetting resin (B) is a tung oil-modified phenol resin. 8. The flame retardant (C) is one or more selected from the group consisting of phosphorus compounds, brominated epoxy resins and brominated epoxy oligomers, according to claim 1 to 7. The composition according to claim 1. 9. The method according to claim 1, further comprising a curing agent.
The composition according to any one of 1. 10. The composition according to claim 9, wherein the curing agent is dicyandiamide and / or a novolac resin. 11. The thermosetting resin (B) according to any one of claims 1 to 10, wherein the amount of the other thermosetting resin (B) is 250 to 600 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Composition.