JP2001200032A - Flame retardant resin composition, prepreg and laminated board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly flame-retardant resin composition without adding a halogenide compound thereto. SOLUTION: The flame-retardant composition comprises (A) an epoxy resin containing no halogen atom in the molecule; (B) an epoxy resin having 2 or more functionalities wherein the resin contains no halogen atom, but contains nitrogen atoms in the molecule; (C) a curing agent comprising a novolac resin; and (D) a phosphorus-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition prepreg having excellent flame retardancy without using a halogen-based flame retardant, and a laminate.

[0002] Thermosetting resins represented by epoxy resins are widely used for electric and electronic equipment parts due to their excellent characteristics, and are provided with flame retardancy to ensure fire safety. There are many. Conventionally, these resins have generally used a halogen-containing compound such as a brominated epoxy resin. Although these halogen-containing compounds have high flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by thermal decomposition, but also have high toxicity when decomposed in the presence of oxygen. May form bromodibenzofuran and polydibromobenzooxin. Further, it is extremely difficult to treat aging waste materials and refuse containing bromine. For these reasons, phosphorus compounds and nitrogen compounds have been studied as flame retardants instead of bromine-containing flame retardants.

[0003] As described above, flame retardancy can be realized by a phosphorus compound and a nitrogen compound. The mechanism is that the nitrogen compound promotes the decomposition of the phosphorus compound and the production of polyphosphoric acid by thermal condensation, and the polyphosphoric acid forms a film on the surface of the epoxy resin, which has an insulating effect and an oxygen blocking effect, and as a result, combustion It is to prevent.

[0004] Epoxy resin is a resin that easily burns,
The sites that are easily combustible are the structural sites in which the glycidyl group is opened, and the sites that are difficult to burn are the benzene ring portions. In addition, the alkyl group is a structural portion that is easily combustible. Since amine-based curing agents generally have a small curing agent equivalent, when an amine compound is used as an epoxy curing agent, the number of ring-opening sites of the epoxy group in the resin increases and the resin is easily burned. For this reason, as a curing agent for the epoxy resin, a novolak compound is more preferable than an amine-based curing agent. Novolak compounds are not easily burned and have high heat resistance, but when used as a curing agent, it is difficult to introduce a nitrogen source.

[0005]

SUMMARY OF THE INVENTION The present invention has been made as a result of studying to solve such a problem. That is, nitrogen is introduced by using a nitrogen atom-containing epoxy resin,
By using in combination with a phosphorus atom-containing compound to express flame retardancy without using halogens due to the interaction of nitrogen and phosphorus,
A resin composition having high flame retardancy, a prepreg, and a laminate or a copper-clad laminate obtained from the prepreg, which is intended to develop excellent moisture absorption solder heat resistance due to novolak curing. Is what you do.

[0006]

The present invention provides (A) an epoxy resin containing no halogen atom in the molecule, and (B) a bifunctional or more epoxy resin containing no halogen atom in the molecule and containing a nitrogen atom. , (C) a curing agent comprising a novolak resin, and (D) a phosphorus atom-containing compound containing no halogen atom in the molecule as essential components. A prepreg obtained by impregnating a base material with a flame-retardant resin composition, wherein one or more of the prepregs are stacked and heated and pressed to obtain a flame-retardant laminate or copper. It is a laminated board.

[0007] Epoxy resin is a resin that easily burns,
The sites that are easily combustible are the structural sites in which the glycidyl group is opened, and the sites that are difficult to burn are the benzene ring portions. In addition, the alkyl group is a structural portion that is easily combustible. Since amine-based curing agents generally have a small curing agent equivalent, when an amine compound is used as an epoxy curing agent, the number of ring-opening sites of the epoxy group in the resin increases and the resin is easily burned. For this reason, as a curing agent for the epoxy resin, a novolak compound is more preferable than an amine-based curing agent.

As described above, the epoxy resin is a resin which easily burns, but if a nitrogen atom-containing epoxy resin is used, a nitrogen source can be introduced into the novolak resin curing system,
Improved flame resistance. In the present invention, by using a nitrogen atom-containing epoxy resin, a nitrogen source is introduced into the novolak resin curing system to improve heat resistance, and when a phosphorus component is used in combination, non-halogen flame-retardant due to the interaction between nitrogen and phosphorus. The main point of the technology is to express the nature.

The component (A) used in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolak type epoxy resin,
Examples thereof include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and tetrakis (glycidyloxyphenyl) ethane, but are not limited thereto, and a plurality of types may be used in combination.

The component (B) used in the present invention includes, for example, glycidylamine-type epoxy resins such as N, N'-tetraglycidyl-diaminodiphenylmethane, but is not limited thereto. You can use them together. The amount of the component (B) is (A)
10 to 10 parts by weight of the total amount of the component and the component (B)
50 parts by weight are preferred. If the amount is less than 10 parts by weight, good flame retardancy cannot be obtained.

As the component (C) used in the present invention, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, naphthalene aralkyl resin and the like are exemplified. Considering to improve the properties, those having a large hydroxyl equivalent are preferred, and phenol aralkyl resins,
Naphthalene aralkyl resins are preferred. The amount of the component (C) is preferably 30 to 150 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount is less than 30 parts by weight or exceeds 150 parts by weight, the heat resistance will decrease.

The component (D) used in the present invention includes trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Zirdiphenyl phosphate,
Phosphate esters such as xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate and resorcinol diphenyl phosphate, condensed phosphate esters such as dialkylhydroxymethyl phosphonate, and phosphine oxides such as triphenyl phosphine oxide And the like, but are not particularly limited thereto, and several types may be used in combination. In order not to impair the excellent properties of the epoxy resin, those which react with the epoxy resin are desirable, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is particularly desirable. The compounding amount of the component (D) is determined by the flame retardancy test (UL-
In order to achieve V-0 in 94), the phosphorus content is preferably 1.5% by weight or more of the whole composition. Below this, V-0 may not be achieved in some cases. Also (D)
It is sufficient that the upper limit of the compounding amount is 2.0% by weight.

The flame-retardant resin composition of the present invention is an epoxy resin having no halogen atom in the molecule or a bifunctional or higher epoxy resin having no halogen atom and containing a nitrogen atom. As a resin and a flame retardant, a phosphorus atom-containing compound containing no halogen atom in the molecule is used as an essential component, but other curing agents, curing accelerators, coupling agents, and other components within a range not inconsistent with the object of the present invention. Can be added. When a novolak resin having a large hydroxyl equivalent such as a phenol aralkyl resin or a naphthalene aralkyl resin is used in combination as a curing agent, flame retardancy and solder heat resistance are improved.

Although the flame-retardant resin composition of the present invention is used in various forms, a solvent is usually used when impregnating the substrate. It is desirable that the solvent used has good solubility in the composition, but a poor solvent may be used as long as the solvent is not adversely affected.

The varnish obtained by dissolving the flame-retardant resin composition of the present invention in a solvent is applied and impregnated to a substrate such as a glass woven fabric, a glass non-woven paper, or a cloth having a component other than glass. By drying at ℃, a prepreg suitable for a laminate for a printed wiring board can be obtained.
Prepreg is used to produce a laminate by heating and pressing, the flame retardant resin composition of the present invention is a thermosetting resin composition having a high degree of flame retardancy without adding a halogen compound, It is preferably used for a laminated board or the like.

[0016]

EXAMPLES (Example 1) Cresol novolak type epoxy resin (Epiclon N-69 manufactured by Dainippon Ink and Chemicals, Inc.)
0) and 19 parts of glycidylamine type epoxy resin (Epiclon 430 manufactured by Dainippon Ink and Chemicals, Inc.).
81 parts by weight of phenol aralkyl resin (Mirex XLC-LL manufactured by Mitsui Chemicals, Inc.)
7.5 parts by weight of epoxy resin (BPS-N manufactured by Nikka Chemical Co., Ltd.), 24 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 11 parts by weight of triphenylphosphine oxide Was dissolved in methylcellosolve, and the varnish was adjusted so that the nonvolatile content concentration became 60%. At this time, the phosphorus component was 1.93% and the nitrogen component was 0.52% with respect to the whole composition excluding the solvent.

Using this varnish, 100 parts of glass cloth (0.18 mm thick, manufactured by Nitto Boseki Co., Ltd.) is impregnated with 80 parts of a varnish solid, and dried in a dryer oven at 150 ° C. for 5 minutes. A prepreg having a resin content of 44.4% was produced. Six pieces of the above prepreg are stacked, and the thickness is 35 μm
Of electrolytic copper foil, pressure 40kgf / cm ² , temperature 1
Heat-press molding at 90 ° C for 120 minutes, thickness 1.2mm
Was obtained.

(Example 2 and Comparative Examples 1 and 2) A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except that the composition was as shown in Tables 1 and 2.

The following characteristics were evaluated for the obtained laminate. Flame retardancy was evaluated by the vertical method according to the UL-94 standard. JIS for solder heat resistance and peel strength
It measured according to C6481. The solder heat resistance was determined by performing a moisture absorption treatment for 2 hours after boiling and then immersing in a solder bath at 260 ° C. for 120 seconds to check for abnormal appearance. The formulations and evaluation results are shown in Tables 1 and 2. All of the laminates obtained in the examples are excellent in flame resistance and heat resistance to moisture absorption soldering.

[0020]

[Table 1]

[0021]

[Table 2]

Notes to Table (1) Epicron N-69 manufactured by Dainippon Ink and Chemicals, Inc.
0, epoxy equivalent 210 (2) Epicron 430 manufactured by Dainippon Ink and Chemicals, Inc.
Epoxy equivalent 120 (3) Mirex XLC-LL, manufactured by Mitsui Chemicals, Inc., hydroxyl equivalent 175 (4) BPS-N, manufactured by Nichika Chemical, epoxy equivalent 125 (5) 9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide (6) Triphenylphosphine oxide

[0023]

The flame-retardant resin composition of the present invention has a high degree of flame retardancy without adding a halogen compound, and provides a novel thermosetting resin composition as a non-halogen material required in the future. It is.

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Claims (4)

[Claims] (1) an epoxy resin containing no halogen atom in the molecule; (B) an epoxy resin containing no halogen atom in the molecule;
And a bifunctional or more epoxy resin containing a nitrogen atom, (C)
A flame-retardant resin composition comprising, as essential components, a curing agent comprising a novolak resin and (D) a phosphorus atom-containing compound having no halogen atom in the molecule. 2. The flame-retardant resin composition according to claim 1, which contains 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as the phosphorus atom-containing compound as the component (D). 3. A prepreg obtained by impregnating a substrate with the flame-retardant resin composition according to claim 1. 4. A flame-retardant laminate or a copper-clad laminate, wherein at least one prepreg according to claim 3 is overlaid and heated and pressed.