JP2001049083A - Flame retardant resin composition, prepreg and laminate board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition having high flame retardancy without adding a halogen compound. SOLUTION: An epoxy resin composition comprises (A) an epoxy resin without containing a halogen atom within the molecule, (B) a compound having two or more secondary amino groups bound to an aromatic ring within the molecule which is represented by the following formula (wherein R1 and R2 are each an alkyl or an aryl group), (C) a curing agent comprising of a novolac resin and (D) a phosphorous atom-containing compound containing no halogen atom in its molecule, as essential components.

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 having excellent flame retardancy without using a halogen-based flame retardant, and a laminate or a copper-clad laminate.

[0002]

2. Description of the Related Art Thermosetting resins typified by epoxy resins are widely used for electric and electronic equipment parts due to their excellent properties, and are provided with flame retardancy to ensure fire safety. There are many cases. Conventionally, these resins have generally used a halogen-containing compound, particularly a bromine-containing compound such as a brominated epoxy resin. Although these bromine-containing compounds have a high degree of flame retardancy, they 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 dibromobenzooxin. Further, disposal of aging waste material containing bromine is extremely difficult. For these reasons, phosphorus compounds have been studied as flame retardants in place 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] As a curing agent for epoxy, novolak resin is preferable because it hardly burns and has high heat resistance. In particular, a compound having a large hydroxyl equivalent, such as a phenol aralkyl resin or a naphthalene aralkyl resin, is preferable because it does not easily burn. However, when a novolak resin is used as a curing agent, it is difficult to introduce a nitrogen source. Amine compounds are mainly used as a nitrogen source, but when these compounds are used in combination with a novolak compound, the usable time of the resin composition usually becomes extremely short, and the solder heat resistance also deteriorates remarkably.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve such a problem, and uses a compound having two or more secondary amino groups in a molecule to form a novolak resin as a curing agent. By doing so, the adhesive strength, heat resistance to moisture absorption solder and the service life of the resin composition are excellent, and by using a phosphorus atom-containing compound in combination, the flame retardancy is exhibited without using halogen due to the interaction between nitrogen and phosphorus. An object of the present invention is to provide a resin composition having high flame retardancy, a prepreg, and a laminate obtained from the prepreg.

[0006]

The present invention provides (A) an epoxy resin containing no halogen atom in the molecule, (B) a compound having two or more secondary amino groups bonded to an aromatic ring in the molecule, A flame-retardant resin composition comprising (C) a curing agent composed of a novolak resin, and (D) a phosphorus atom-containing compound containing no halogen molecule in the molecule as essential components. Further, a prepreg characterized by impregnating a base material with the flame-retardant resin composition, wherein one or more of the prepregs are laminated and heated and pressurized. It is a copper-clad laminate.

[0007] Epoxy resin is a resin that easily burns,
The flammable sites are the glycidyl ring-opened structure and the alkyl group, and the flammable sites are the benzene ring. 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.

When a novolak compound is used as a curing agent for epoxy, it is difficult to introduce a nitrogen source. As the nitrogen source, amine compounds are mainly used. The novolak compound is an acidic compound, and the amine compound is a basic compound. The amine compound exerts a catalytic action on each other, so that the usable time of the resin composition is extremely shortened, and the solder heat resistance is significantly deteriorated.

Generally, aromatic amines are less basic than alkylamines. Further, secondary amines have lower reactivity with epoxy than primary amines due to steric hindrance, but react with epoxy groups. Therefore, even when a compound having a secondary amino group bonded to an aromatic ring is used in combination with a novolak resin as a curing agent for an epoxy resin, the usable time of the resin composition is not shortened and the solder heat resistance does not deteriorate. Further, a compound having only one secondary amino group bonded to an aromatic ring in a molecule lowers the crosslinking density of epoxy and lowers heat resistance, whereas a compound having two or more epoxy resins has a lower epoxy group. Since it is incorporated in a crosslinked structure, it does not lower heat resistance. Therefore, in a system using a novolak resin as a curing agent for an epoxy resin, if a nitrogen source is introduced by a compound having two or more secondary amino groups bonded to an aromatic ring in a molecule,
Improved flame resistance. In the present invention, as a curing agent for the epoxy resin, a novolak resin and a compound having two or more secondary amino groups bonded to an aromatic ring for introducing a nitrogen source are used to improve heat resistance, and The technical gist of the present invention is to use a phosphorus compound in combination to express flame retardancy with non-halogen by the interaction between nitrogen and phosphorus.

The 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, and tetrakis (glycidyloxyphenyl).
Ethane and the like can be mentioned, but it is not limited to these, and several kinds may be used at the same time.

The component (B) used in the present invention is a compound having two or more secondary amino groups bonded to an aromatic ring in the molecule, and is typically a compound represented by the general formula (1). is there.

Embedded image Specifically, N, N'-diphenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-phenyl-N 'included in the general formula (1)
-Isopropyl-p-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, or p- (p-toluenesulfonylamide) diphenylamine, N-phenyl-N'-( 3
-Methacryloyloxy-2-hydroxypropyl)-
Examples thereof include p-phenylenediamine. N, N'-diphenyl-p-phenylenediamine is preferred from the viewpoint of versatility and the like. The amount of the component (B) is preferably 5 to 20 parts by weight per 100 parts by weight of the component (A). If the amount is less than 5 parts by weight, the flame retardancy becomes insufficient because the nitrogen content decreases, which is not preferable. If the amount exceeds 20 parts by weight, the crosslinking density is lowered, and the heat resistance becomes insufficient.

The component (C) used in the present invention is exemplified by phenol novolak resin, cresol novolak resin, phenol aralkyl resin, naphthalene aralkyl resin and the like. Considering to increase 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 component (A). If it is less than 30 parts by weight or exceeds 150 parts by weight, heat resistance is undesirably reduced.

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 and crexylenyl phosphate. Zirdiphenyl phosphate,
Phosphoric acid esters such as xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate and resorcinol diphenyl phosphate, and condensed phosphoric acid esters such as dialkylhydroxymethyl phosphonate are exemplified. However, the present invention is not limited to this. In order not to impair the excellent properties of the epoxy resin, those which react with the epoxy resin are desirable, and in particular, because of its good reactivity with the epoxy resin and flame retardancy, 9,10-dihydro-9-oxa is preferred. -10-phosphaphenanthrene-10
-Oxides are preferred. In order to achieve V-0 in the flame retardancy test (UL-94), the compounding amount of the component (D) is preferably 1.5% by weight or more as the phosphorus content of the entire composition. Below this, V-0 may not be achieved in some cases. The upper limit of the amount of the component (D) is sufficient if the component (B) and the component (C) are relatively incombustible, so that 2.0% by weight is sufficient.

The flame-retardant resin composition of the present invention is, as described above, an epoxy resin containing no halogen atom in the molecule, a novolak resin as a curing agent, and a secondary amino group bonded to an aromatic ring in the molecule. A curing agent comprising a compound having two or more groups and a phosphorus atom-containing compound containing no halogen atom in the molecule as a flame retardant are essential components, but other curing agents and curing agents may be used within a range not contrary to the object of the present invention. Accelerators, coupling agents and other components can be added.

Although the flame-retardant resin composition of the present invention is used in various forms, it is usually used as a varnish dissolved in a solvent in order to obtain a prepreg by impregnating a substrate. The solvent used must have 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 on a substrate such as a glass woven fabric, a glass non-woven paper, or a cloth containing a component other than glass. Prepreg can be obtained by drying at 200 ° C. The prepreg is used for producing a laminate or a copper-clad laminate suitable for a printed wiring board by heating and pressing. The flame-retardant resin composition of the present invention is a thermosetting resin composition having high flame retardancy without adding a halogen compound, and is suitable for flame-retardant laminates or copper-clad laminates and other uses. It is used for

【Example】

Hereinafter, the present invention will be described with reference to examples.
“Parts” indicates “parts by weight” and “%” indicates “% by weight”.

Example 1 Cresol novolak epoxy resin (Epiclon N-69 manufactured by Dainippon Ink and Chemicals, Inc.)
0), 54.7 parts of a phenol aralkyl resin (Mirex XLC-LL manufactured by Mitsui Chemicals, Inc.), N, N '
7.7 parts of -diphenyl-p-phenylenediamine,
Methylcellosolve was added to 22.5 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the varnish was adjusted to a non-volatile content of 60%. At this time, the total of the epoxy resin and the curing agent is 100
Parts, the phosphorus component is 1.78% and the nitrogen component is 0.45%
%.

Using this varnish, 100 parts of a 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 prepared. Six pieces of the above prepreg are stacked, and the thickness is 35 μm
Of electrolytic copper foil, pressure 40kgf / cm2, temperature 1
Heat-press molding at 90 ° C for 120 minutes, thickness 1.2mm
Was obtained.

(Examples 2 to 4 and Comparative Examples 1 to 4) Table 1
And the formulation shown in Table 2 except that
A double-sided copper-clad laminate was prepared in the same manner as described above.

The resulting double-sided laminate was measured for flame retardancy, solder heat resistance, and peel strength. In addition, the varnish gel time retention was measured in order to check the preservability of the varnish. Tables 1 and 2 show these results. All of the laminates having the formulations shown in the examples have excellent flame resistance and heat resistance to moisture absorption soldering, and also have good varnish preservability.

(Measurement method) Flame retardancy: Evaluated vertically according to UL-94 standard. 2. Solder heat resistance: Measured according to JIS C6481. After performing the moisture absorption treatment for 2 hours in boiling, it was examined whether there was any abnormality in the appearance after immersion in a solder bath at 260 ° C. for 120 seconds. 3. Peel strength: Measured according to JIS C6481. 4. Varnish gel time retention: The varnish was allowed to stand at 23 ° C. for 3 days, and the gel time of the varnish before and after the varnish was measured to determine the varnish gel time retention. Varnish gel time retention (%) = (gel time after standing / gel time before standing) × 100

[0023]

[Table 1]

[0024]

[Table 2]

Notes to Table (1) Epicron N-69 manufactured by Dainippon Ink and Chemicals, Inc.
0, epoxy equivalent 190 (2) Mirex XLC-LL manufactured by Mitsui Chemicals, hydroxyl equivalent 175 (3) SN-170 manufactured by Nippon Steel Chemical, hydroxyl equivalent 190 (4) N, N'-diphenyl-p-phenylenediamine (5) ) N-Phenyl-N′-isopropyl-p-phenylenediamine (6) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide

[0026]

The flame-retardant resin composition of the present invention has a high 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.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F072 AA07 AB09 AB29 AD14 AD15 AD23 AD27 AE02 AE04 AE07 AF28 AG03 AH02 AJ04 AK02 AL13 4F100 AB17B AB33B AG00 AH03A AH10A AK33A AK53A AR00A BA02 CA02A EJ11 CC03 002 CD061 CD071 CE002 EN036 EW047 EW147 FD137 FD142 FD146 GQ00 4J036 AC03 AD08 AF06 AF08 DC04 DC10 FA12 FB08 JA07 JA11

Claims (5)

[Claims] 1. Curing comprising (A) an epoxy resin containing no halogen atom in the molecule, (B) a compound having two or more secondary amino groups bonded to an aromatic ring in the molecule, and (C) a novolak resin. A flame-retardant resin composition comprising, as essential components, an agent and (D) a phosphorus atom-containing compound containing no halogen atom in the molecule. 2. The method according to claim 1, wherein the component (D) contains a phosphorus atom-containing compound.
The flame-retardant resin composition according to claim 1, which is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. 3. The flame-retardant resin composition according to claim 1, wherein the novolak resin (C) is a phenol aralkyl resin and / or a naphthalene aralkyl resin. 4. A prepreg comprising a substrate impregnated with the flame-retardant resin composition according to claim 1, 2 or 3. 5. A flame-retardant laminate or a copper-clad laminate, wherein at least one prepreg according to claim 4 is superposed and heated and pressed.