JP2002161197A - Flame resisting resin composition, prepreg and laminated sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition, a prepreg and a laminated sheet having an excellent flame resistance without using a halogenated flame retardant. SOLUTION: The flame resisting resin composition comprises (A) a non- halogenated epoxy resin having two or more epoxy groups in a molecule, (B) a curing agent consisting of a triazine modified novolac resin, (C) a carboxylic acid having two or more carbonyl groups in a molecule, and (D) 9, 10-dihydro-9- oxa-10-phosphaphenanthrene-10-oxide, as essential ingredients. The prepreg and the laminated sheet are prepared using the flame resisting resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition prepreg and a laminate having excellent flame retardancy without using a halogen-based flame retardant.

[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, disposal of aging waste material containing bromine is extremely difficult. 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 nitrogen compounds and phosphorus compounds promote carbonization of the resin and prevent combustion. Various phosphorus compounds have been studied as flame retardants.However, in order not to impair the properties of the thermosetting resin, it is necessary to incorporate the phosphorus compound into the resin skeleton by some kind of chemical reaction with the resin. desirable.

In order to incorporate a phosphorus compound into the epoxy resin skeleton, a phosphorus compound which reacts with an epoxy group may be used. 9,10-dihydro-9 which is a phosphorus compound
Since -oxa-10-phosphaphenanthrene-10-oxide reacts with an epoxy group, it is useful as a flame retardant for epoxy resins. Further, the triazine-modified novolak resin has a triazine ring in the molecule and is therefore useful as a nitrogen-based flame retardant.

However, 9,10-dihydro-9-oxa-
When 10-phosphaphenanthrene-10-oxide and a triazine-modified novolak resin are used in combination and dissolved together with an epoxy resin to form a varnish, there is a drawback that the usable time of the varnish becomes extremely short.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve such a problem, and the use of a carboxylic acid having two or more carboxyl groups in a molecule has resulted in 9,9. 10-dihydro-9-oxa-10-
Even when phosphaphenanthrene-10-oxide and a triazine-modified novolak resin are used in combination, the varnish has a sufficient usable time, and is obtained from a resin composition, prepreg and prepreg having sufficient flame retardancy without using halogen. To provide a laminated plate.

[0007]

The present invention provides (1) (A)
A non-halogenated epoxy resin having two or more epoxy groups in one molecule, a curing agent comprising (B) a triazine-modified novolak resin, (C) a carboxylic acid having two or more carboxyl groups in the molecule (D) 9 , 10-Dihydro-9-
Flame-retardant resin composition containing oxa-10-phosphaphenanthrene-10-oxide as an essential component, (2) Part or all of epoxy resin (A) is a novolak epoxy resin (1) wherein the carboxylic acid having two or more carboxyl groups in the molecule is itaconic acid or citraconic acid. Or, the base material is impregnated with the flame-retardant resin composition according to (2) or (4) the flame-retardant resin composition according to (1), (2) or (3). (5) A flame-retardant laminate or a copper-clad laminate obtained by laminating one or more of the prepregs described in (4) and heating and pressing.

As mentioned above, 9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide is a phosphorus compound having a P—H bond in the molecule,
Since the PH group is a weakly acidic group, it gradually interacts with the amino group of the triazine-modified novolak resin in the varnish.
For this reason, the gel time of the varnish gradually changes.

In the present invention, in order to solve this problem, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a triazine-modified novolak resin, and a compound having two or more carboxyl groups in the molecule. Use carboxylic acids. The carboxylic acid is strongly acidic and interacts with the amino group of the triazine-modified novolak resin faster and stronger than the PH group. Since the interaction occurs promptly during varnish preparation, there is little change in gel time between varnish preparation and use. Thereby, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a triazine-modified novolak resin can be used simultaneously, and sufficient flame retardancy can be obtained. In addition, a carboxylic acid having two or more carboxyl groups in a molecule reacts with an epoxy group and does not deteriorate the properties of a cured product because it is bifunctional.
Among carboxylic acids having two or more carboxyl groups in the molecule, itaconic acid or citraconic acid is particularly preferred.
Itaconic acid has a melting point of 167 ° C. and citraconic acid has a melting point of 91 ° C. and decomposes quickly upon melting. For this reason, itaconic acid and citraconic acid do not remain in the resin composition during prepreg coating and press molding, and do not lower the properties of the cured product. The resin composition of the present invention comprises 9,10-dihydro-9-
By using oxa-10-phosphaphenanthrene-10-oxide, a triazine-modified novolak resin and a carboxylic acid having two or more carboxyl groups in the molecule, sufficient flame retardancy is exhibited by using a halogen compound. The main point is to make it technical.

The epoxy resin of component (A) used in the present invention includes bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A novolak epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, tetrakis (glycidyloxyphenyl) ethane However, the present invention is not limited thereto, and several types may be used at the same time. Considering heat resistance, bisphenol A
Novolak epoxy resins such as novolak epoxy resin, phenol novolak epoxy resin and cresol novolak epoxy resin are preferred.

The triazine-modified phenol novolak resin (B) used in the present invention includes a melamine-modified novolak resin, a benzoguanamine-modified novolak resin,
Acetoguanamine-modified novolak resin and the like. The compounding amount of the triazine-modified novolak resin is preferably such that the nitrogen content is 0.5% to 2.5% based on the whole resin. If it is less than 0.5%, the flame retardancy becomes insufficient, and if it exceeds 2.5%, the water absorption increases, which is not preferable.

The carboxylic acid having two or more carboxyl groups in the molecule of the component (C) used in the present invention includes adipic acid, itaconic acid, citraconic acid, oxalic acid, tartaric acid, fumaric acid, malonic acid, maleic acid, and the like. Examples include, but are not limited to, phthalic acid and terephthalic acid. Among them, itaconic acid or citraconic acid is preferable because it has a high rate of decomposition during molding and the amount remaining on the laminate is reduced. When itaconic acid or citraconic acid is used in the present invention, 9,10-dihydro-9-
0.5 parts by weight to 3 parts by weight is preferable for 10 parts by weight of oxa-10-phosphaphenanthrene-10-oxide. If the amount is less than 0.5 part by weight, the varnish preservability becomes insufficient, and if it exceeds 3 parts by weight, curing inhibition is caused, which is not preferable.

The flame-retardant resin composition of the present invention comprises the epoxy resin described above, a triazine-modified novolak resin, a carboxylic acid having two or more carboxyl groups in the molecule,
Although it is contained as an essential component of 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, other resins, curing accelerators, coupling agents, and other components may be used within a range not inconsistent with the object of the present invention. It can be added. It is preferable to use a phenol aralkyl resin, a naphthalene aralkyl resin, or the like as a curing agent in combination, since water absorption is low.

The flame-retardant resin composition of the present invention is used in various forms. When impregnating a substrate, it is usually used in the form of a varnish dissolved in a solvent. It is desirable that the solvent used has good solubility in the composition, but a poor solvent may be used as long as it does not adversely affect the composition.

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 glass woven cloth, glass non-woven cloth, or woven cloth or non-woven cloth containing components other than glass. The prepreg can be obtained by drying at 80 to 200 ° C. Such a prepreg is used for producing a laminate or a copper-clad laminate by heating and pressing. The flame-retardant resin composition of the present invention is a thermosetting resin composition having high flame retardancy even without containing a halogen compound, and is particularly preferably used for a laminated board for printed wiring boards and the like. It is.

[0016]

(Example 1) Cresol novolak epoxy resin (Epiclon N-6 manufactured by Dainippon Ink and Chemicals, Inc.)
90) 100 parts by weight of triazine-modified phenol novolak resin (LA-705 manufactured by Dainippon Ink and Chemicals, Inc.)
4) 26 parts by weight, adipic acid 3.3 parts by weight, 9,10-
22.5 parts by weight of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and phenol aralkyl resin (Mirex XLC-LL manufactured by Mitsui Chemicals, Inc.)
Methylcellosolve was added to 20.8 parts by weight, and the varnish was adjusted so that the nonvolatile content concentration was 60% by weight. At this time, the phosphorus component was 1.9% by weight and the nitrogen component was 1.8% based on 100% by weight of the total of the epoxy resin, the phosphorus compound and the curing agent.
% By weight. Using this varnish, 100 parts by weight of glass fiber cloth (0.18 mm thick, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of varnish solids, dried in a dryer oven at 150 ° C. for 5 minutes, and dried. A prepreg having a content of 44.4% was prepared. Stack the 6 prepregs above and 3
5μm electrolytic copper foil is overlaid, pressure 40kgf / cm ² ,
Heat and pressure molding was performed at a temperature of 190 ° C. for 120 minutes, and the thickness was 1.
A 2 mm double-sided copper-clad laminate was obtained.

(Examples 2 to 8, and Comparative Examples 1 and 2)
And the formulation shown in Table 2 except that
A double-sided copper-clad laminate was prepared in the same manner as described above.

For the resin varnish, immediately after adjustment and at 23 ° C.
And the time until gelation at 170 ° C. after standing for 7 days was measured. The obtained copper-clad laminate was measured for flame retardancy, solder heat resistance and peel strength. Flame retardancy was evaluated by the vertical method according to the UL-94 standard. Solder heat resistance and peel strength were measured in accordance with JIS C 6481. 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 for abnormal appearance. Examined. The evaluation results are shown in Tables 1 and 2. All of the copper-clad laminates shown in Examples have excellent flame resistance and solder heat resistance. In addition, the time until gelling after the resin varnish was left at 23 ° C. for 7 days did not substantially change from that immediately after the adjustment, indicating that the usable time was excellent.

[0019]

[Table 1]

[0020]

[Table 2]

Notes to Table (1) Epicron N- manufactured by Dainippon Ink and Chemicals, Inc.
690, epoxy equivalent = 210 (2) Epicron N- manufactured by Dainippon Ink and Chemicals, Inc.
770, epoxy equivalent = 190 (3) LA-705 manufactured by Dainippon Ink and Chemicals, Inc.
4. Hydroxyl equivalent = 125, nitrogen content = 12% by weight (4) Mitsui Chemicals, Inc. MILEX XLC-LL, hydroxyl equivalent = 175 (5) 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide

[0022]

The flame-retardant resin composition of the present invention, the prepreg and the laminate using the same, have high flame retardancy without adding a halogen compound, and have excellent properties such as solder heat resistance. I have. Accordingly, the present invention provides a novel and useful thermosetting resin composition as a non-halogen material required in the future.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05K 1/03 610 H05K 1/03 610L

Claims (5)

[Claims] 1. A non-halogenated epoxy resin having two or more epoxy groups in one molecule; (B) a curing agent comprising a triazine-modified novolak resin;
A carboxylic acid (D) having at least two carboxyl groups,
A flame-retardant resin composition comprising 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as an essential component. 2. The flame-retardant resin composition according to claim 1, wherein part or all of the epoxy resin (A) is a novolak epoxy resin. 3. The flame-retardant resin composition according to claim 1, wherein (C) the carboxylic acid having two or more carboxyl groups in the molecule is itaconic acid or citraconic acid. 4. A prepreg comprising a substrate impregnated with the flame-retardant resin composition according to claim 1, 2 or 3. 5. One or two prepregs according to claim 4,
A flame-retardant laminate or a copper-clad laminate, characterized by being laminated and heated and pressed.