JP4124949B2 - Flame retardant resin composition, prepreg and laminate using the same - Google Patents

Description

【００２０】
【表２】

【００２１】
表の注
（１）大日本インキ化学工業（株）製 エピクロンＮ−６９０、エポキシ当量＝２１０
（２）大日本インキ化学工業（株）製 エピクロンＮ−７７０、エポキシ当量＝１９０
（３）大日本インキ化学工業（株）製 ＬＡ−７０５４、水酸基当量＝１２５、窒素含有率＝１２重量％
（４）三井化学（株）性 ミレックスＸＬＣ−ＬＬ、水酸基当量＝１７５
（５）９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド
【００２２】
【発明の効果】
本発明の難燃性樹脂組成物、これを用いたプリプレグ及び積層板は、ハロゲン化合物を添加することなく高度な難燃性を有し、半田耐熱性等の特性も優れている。従って今後要求される非ハロゲン材料として新規で有用な熱硬化性樹脂組成物を提供するものである。[0001]
BACKGROUND 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 and the like are widely used for electrical and electronic equipment parts due to their excellent characteristics, and are often provided with flame retardancy to ensure safety against fire. Conventionally, flame retardants of these resins have been made using halogen-containing compounds such as brominated epoxy resins. Although these halogen-containing compounds have a high degree of flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by thermal decomposition, but also are highly toxic when decomposed in the presence of oxygen. May form bromodibenzofuran and polydibromobenzoxine. Also, it is extremely difficult to dispose of obsolete waste containing bromine. For these reasons, phosphorus compounds and nitrogen compounds have been studied as flame retardants to replace 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 and the phosphorus compound promote carbonization of the resin and prevent combustion. Various phosphorus compounds have been studied for flame retardancy, but in order not to impair the properties of thermosetting resins, it is necessary to incorporate phosphorus compounds into the resin skeleton by some chemical reaction with the resin. desirable.
[0004]
In order to incorporate a phosphorus compound into the epoxy resin skeleton, a phosphorus compound that reacts with an epoxy group may be used. Since such a phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide reacts with an epoxy group, it is useful as a flame retardant for epoxy resins. Triazine-modified novolak resins have a triazine ring in the molecule and are useful as nitrogen-based flame retardants.
[0005]
However, when 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triazine-modified novolak resin are used together and dissolved together with an epoxy resin to make a varnish, the usable time of the varnish is extremely short. There were drawbacks.
[0006]
[Problems to be solved by the invention]
The present invention has been made as a result of studies to solve such problems. By using a phenol compound having at least one electron-withdrawing group in the molecule, 9,10-dihydro-9- Resin composition and prepreg having sufficient flame retardancy even when oxa-10-phosphaphenanthrene-10-oxide and triazine-modified novolak resin are used in combination, and without using halogen And a laminate obtained from the prepreg.
[0007]
[Means for Solving the Problems]
The present invention includes (A) a non-halogenated epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent comprising a triazine-modified novolak resin, and (C) at least one electron withdrawing property in the molecule. A phenolic compound having a group, which is hydroxybenzaldehyde or salicylic acid or a salicylic acid ester , and (D) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as an essential component It is a flammable resin composition. And this invention is a prepreg characterized by making a base material impregnate the said flame-retardant resin composition, Furthermore, the said prepreg is formed by superposing one or more sheets and heating and pressurizing them. It is a flame retardant laminate or a copper clad laminate.
[0008]
As described above, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a phosphorus compound having a PH bond in the molecule, but the PH group is a weakly acidic group. Therefore, 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.
[0009]
In order to solve this problem, the present invention has 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a triazine-modified novolak resin, and at least one electron-withdrawing group in the molecule. Use phenolic compounds. Since the phenol compound having at least one electron-withdrawing group in the molecule is strongly acidic, it interacts with the amino group of the triazine-modified novolak resin faster and stronger than the PH group. There is little change in gel time during varnish preparation and use because varnish preparation occurs quickly. As a result, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triazine-modified novolak resin can be used simultaneously, and sufficient flame retardancy can be expected. Moreover, since the phenol compound which has at least 1 or more electron withdrawing group in a molecule | numerator reacts with an epoxy group, the characteristic of hardened | cured material is not deteriorated.
The resin composition of the present invention comprises 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a triazine-modified novolak resin, and a phenol compound having at least one electron-withdrawing group in the molecule. By using it, the technical essence is to develop sufficient flame retardancy using a halogen compound.
[0010]
Examples of the (A) component epoxy resin used in the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, tetrakis (glycidyloxyphenyl) ethane and the like. However, it is not limited to these, and several types may be used simultaneously. In view of heat resistance, novolac epoxy resins such as bisphenol A novolac epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin are preferable.
[0011]
Examples of the triazine-modified novolak resin (B) used in the present invention include melamine-modified novolak resin, benzoguanamine-modified novolak resin, and acetoguanamine-modified novolak resin. The blending amount of the triazine-modified novolak resin is preferably blended so that the nitrogen content is 0.5% to 2.5% with respect to the entire resin. If it is less than 0.5%, the flame retardancy becomes insufficient, and if it exceeds 2.5%, the water absorption rate is undesirably increased.
[0012]
The phenol compound having at least one electron withdrawing group in the molecule of the component (C) used in the present invention is hydroxybenzaldehyde, bisphenol S, salicylic acid, methyl salicylate, hydroxybenzonitrile, o-cresol-4-sulfonic acid. , Nitrophenol, dinitrophenol and the like, but are not limited thereto. Hydroxybenzaldehyde is preferable because the formyl group is not easily hydrolyzed and has excellent chemical resistance. Bisphenol S is preferred because it is bifunctional and does not reduce the crosslink density of the resin. Salicylic acid and salicylic acid esters are preferred because they are versatile and react easily because they are liquid.
[0013]
The flame retardant resin composition of the present invention includes the above-described epoxy resin, triazine-modified novolak resin, a phenol compound having at least one electron-withdrawing group in the molecule, and 9,10-dihydro-9-oxa-10-. Although it is contained as an essential component of phosphaphenanthrene-10-oxide, other resins, curing accelerators, coupling agents, and other components may be added within the range not departing from the object of the present invention. If a phenol aralkyl resin, a naphthalene aralkyl resin, or the like is used in combination as a curing agent, water absorption is preferably reduced.
[0014]
The flame retardant resin composition of the present invention is used in various forms. When impregnating a base material, it is usually used in the form of a varnish dissolved in a solvent. Although it is desirable that the solvent used has good solubility in the composition, a poor solvent may be used as long as it does not adversely affect the composition.
[0015]
A varnish obtained by dissolving the flame-retardant resin composition of the present invention in a solvent is coated and impregnated on a substrate such as a glass fabric, a glass fabric, or a fabric or fabric containing other than glass as a component. A prepreg can be obtained by drying at 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 a high degree of flame retardancy without containing a halogen compound, and is particularly suitable for use in laminated boards for printed wiring boards. It is.
[0016]
【Example】
(Example 1)
Cresol novolac epoxy resin (Epiclon N-690, manufactured by Dainippon Ink & Chemicals, Inc.), triazine-modified phenol novolak resin (LA-7054 manufactured by Dainippon Ink & Chemicals, Inc.), 26 parts by weight, p-hydroxybenzaldehyde 5.4 parts by weight, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 23.8 parts by weight and phenol aralkyl resin (Mitsui Chemicals Co., Ltd. Milex XLC-LL) 19.8 parts by weight Methyl cellosolve was added to the part, and the varnish was adjusted so that the non-volatile content concentration was 60% by weight. At this time, the phosphorus component was 1.9% by weight and the nitrogen component was 1.8% by weight with respect to the total of 100% by weight of the epoxy resin, the phosphorus compound, and the curing agent.
Using this varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of varnish solid, and dried in a dryer oven at 150 ° C. for 5 minutes to obtain a resin. A prepreg having a content of 44.4% was prepared.
6 sheets of the above prepregs, 35 μm thick electrolytic copper foils are stacked on the top and bottom, and heat-press molding is performed at a pressure of 40 kgf / cm ² and a temperature of 190 ° C. for 120 minutes. Got.
[0017]
(Examples 2-5 and Comparative Examples 1-2)
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except for the formulation shown in Tables 1 and 2.
[0018]
For the resin varnish, the time until gelation at 170 ° C. was measured immediately after adjustment and after standing at 23 ° C. for 7 days. 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 checking for abnormal appearance after immersion in a solder bath at 260 ° C. for 120 seconds after performing a moisture absorption treatment for 2 hours at boiling. Examined. The evaluation results are shown in Tables 1 and 2.
The copper clad laminates shown in the examples are all excellent in flame resistance and solder heat resistance. Moreover, it turns out that the time to gelation after leaving a resin varnish for 7 days at 23 degreeC does not change substantially immediately after adjustment, and the usable time is excellent.
[0019]
[Table 1]

[0020]
[Table 2]

[0021]
Notes to Table (1) Daikoku Ink Chemical Industries, Ltd. Epicron N-690, Epoxy Equivalent = 210
(2) manufactured by Dainippon Ink & Chemicals, Inc. Epicron N-770, epoxy equivalent = 190
(3) Dainippon Ink & Chemicals, Inc. LA-7054, hydroxyl group equivalent = 125, nitrogen content = 12% by weight
(4) Mitsui Chemicals Co., Ltd. Millex XLC-LL, hydroxyl group equivalent = 175
(5) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
【The invention's effect】
The flame retardant resin composition of the present invention, a prepreg and a laminate using the flame retardant resin composition have high flame retardancy without adding a halogen compound, and are excellent in properties such as solder heat resistance. Accordingly, the present invention provides a novel and useful thermosetting resin composition as a non-halogen material required in the future.

Claims (4)

(A) a non-halogenated epoxy resin having two or more epoxy groups in one molecule;
(B) a curing agent comprising a triazine-modified novolak resin,
(C) a phenol compound having at least one electron-withdrawing group in the molecule , which is hydroxybenzaldehyde represented by the following general formula (1) or salicylic acid or salicylic acid ester represented by the following general formula (3) ;
(D) A flame retardant resin composition comprising 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as an essential component.

  The flame-retardant resin composition according to claim 1, wherein a part or all of the epoxy resin as the component (A) is a novolac epoxy resin. A prepreg obtained by impregnating a base material with the flame retardant resin composition according to claim 1 . A flame-retardant laminate or a copper-clad laminate obtained by superposing one or more prepregs according to claim 3 and heating and pressing them.