JP2003229647A - Prepreg for nonhalogen based printed wiring board and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a environment-friendly nonhalogen based prepreg for printed wiring board exhibiting excellent flame retardance, Tg, and substrate solder heat resistance, and its use. <P>SOLUTION: The glass basic material polyimide resin prepreg for printed wiring board is produced of thermosetting resin varnish not containing halogen element but containing (a) polyimide resin prepolymer, (b) aluminium hydroxide, and (c) organic silane having one or more functional group reacting on a hydroxy group at the terminal and having one or more aryl group of 6-12C as a hydrocarbon group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a non-halogen polyimide resin prepreg used for an electric insulating material such as a printed wiring board and its use.

[0002]

2. Description of the Related Art Generally, a polyimide resin laminated plate is manufactured by impregnating a glass cloth with a varnish solution of a polyimide resin composition, curing the varnish, and laminating B-staged prepregs, heating and pressurizing.

Since a polyimide resin has a higher glass transition temperature (hereinafter abbreviated as Tg) than an epoxy resin, a laminated board using the same has excellent through hole reliability and the like. On the other hand, the curing temperature at the time of stacking needs to be set higher than that of the epoxy resin system, and there is a drawback that the stacking work efficiency is poor. Also, because polyimide resin is hard and brittle,
Drill workability and the like tend to be inferior to those of a laminated board using an epoxy resin. Therefore, when a polyimide resin composition is used for a printed wiring board, an epoxy resin is often blended as a modifier to improve the stackability and drill workability.

Further, conventionally, a resin containing a halogen element such as bromine has been used in order to impart flame retardancy to the polyimide resin composition. In particular, since an epoxy resin is often blended as described above, a halogenated epoxy resin or a flame-retardant resin such as tetrabromobisphenol A or its glycidyl ether compound is often used.

However, the laminated board using the polyimide resin composition tends to have a higher water absorption rate during the moisture absorption treatment than the epoxy resin laminated board, and as a result, the solder heat resistance of the board becomes insufficient. In addition, the halogen element in the resin composition is one of the causes of lowering the electrical reliability such as migration and tracking properties, and in recent years, there has been a growing interest in environmental issues. There is a demand for a non-halogen-based material that does not contain a halogen element that causes the generation of the.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to use a prepreg for a polyimide resin-based printed wiring board which does not use a halogen element, has flame retardancy, has a high Tg, is excellent in heat resistance, and is environmentally friendly. And its use.

[0007]

The present invention is a prepreg for a printed wiring board, comprising: (a) a polyimide resin prepolymer; (b) aluminum hydroxide; and (c) a functional group reactive with a hydroxyl group at the terminal. A thermosetting resin varnish containing no halogen element, containing one or more and an organosilane having at least one aryl group having 6 to 12 carbon atoms as a hydrocarbon group,
The present invention relates to a glass-based polyimide resin prepreg for printed wiring boards.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (a) The polyimide resin prepolymer used in the present invention is obtained by reacting a tetracarboxylic acid anhydride, a diimide or a monoimide (hereinafter abbreviated as tetracarboxylic acid anhydride, etc.) with a diamine. Obtainable. The reaction can be carried out using a conventional method, and a commercially available product can also be used. Linear polyimide is preferred.
Examples of the tetracarboxylic acid anhydrides include maleic acid, trimellitic acid, pyromellitic acid, anhydrides such as bis (3,4-dicarboxyphenyl) ether, and diimides or monoimides. Tetracarboxylic acid diimides are preferred, and bismaleimides are particularly preferred.

The bismaleimide is not particularly limited as long as it is a compound containing two maleimide groups in the molecule and does not contain a halogen element. For example, maleic acid N, N′-ethylene-bisimide, maleic acid N,
N'-hexamethylene-bisimide, maleic acid N,
N'-metaphenylene-bisimide, maleic acid N,
N'-4,4'-diphenylmethane-bisimide (N,
N'-methylenebis (also referred to as -N-phenylmaleimide), maleic acid N, N'-4,4'-diphenylether-bisimide, maleic acid N, N'-4,4'-diphenylsulfone-bisimide, 4,4 '-Diamino-
3,3′-diethyl-5,5′-dimethyldiphenylmethane-bisimide, maleic acid 4,4′-methylene-di-2,6-diisopropylaniline-bisimide and the like are used, and these are used alone or in combination. be able to.

The diamine used in the present invention is not particularly limited as long as it is a compound containing two amino groups in the molecule and does not contain a halogen element. For example,
4,4'-diaminodicyclohexylmethane, 3,3 '
-Dimethyl-4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, bis (4-aminophenyl) propane, 4,4 '-Diaminodiphenyl sulfone, 1,
3-bis (2-p-anilinopropylidene) benzene,
1,4-bis (2-p-anilinopropylidene) benzene, 4,4'-diamino-3,3'-diethyl-5,
5'-dimethyldiphenylmethane, dicyandiamide,
Acetoguanamine, benzoguanamine, m-toluylenediamine, 2,4-diamino-6- (2'-undecylimidazolyl- (1 ')-) ethyl-S-triazine,
2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy)
Examples thereof include benzene, bis-4- (4-aminophenoxy) phenyl sulfone, and bis-4- (3-aminophenoxy) phenyl sulfone, and these can be used alone or in combination.

According to the present invention, when considering both the heat resistance after prepolymerization and curing and the Tg after curing, the diamine is used in an amount of 0.3 to 1. It is preferable to react with tetracarboxylic acid anhydride or the like at a ratio of 2 mol, and more preferable to react at a ratio of 0.5 to 1.0 mol.

(B) Aluminum hydroxide used in the present invention
Has the composition formula Al_TwoO_Three・ 3H_Two Gibusa represented by O
Ito, Bayer Light or Nord Strandite,
Or Al_TwoO_Three・ H_TwoBoehmite represented by O,
Any of the diaspores can be used. Also, this
It is also possible to use a mixture of one or more of these. Manufacturing
Considering the flame retardancy of strikes and printed wiring boards, crystal water
A gibbsite type having a large amount of γ in the molecule is preferable.

Further, the impurity Na contained in the component (b)
The content of ₂ O is preferably less than 0.2% by weight in consideration of heat resistance. The shape of the component (b) is not particularly limited. As the component (b), commercially available aluminum hydroxide can be used.

Further, in addition to the component (b), an inorganic filler can be optionally added. For example, boron, carbon, clay, glass, calcium carbonate, talc, alumina, silica, mica, titanium oxide, aluminum carbonate,
Examples thereof include magnesium silicate, aluminum silicate, aluminum borate, and silicon carbide. Beads, powder,
It can be used in the form of fibers, crushed products, whiskers, flakes and the like. Examples thereof include aluminum borate, silicon carbide whiskers, and glass single fibers.

The component (b) may be blended in an amount of 50 to 150 parts by weight per 100 parts by weight of the organic resin component in consideration of the expression of flame retardant effect, coating workability, moldability, heat resistance and peel strength. It is more preferable to add 70 to 130 parts by weight.

The (c) organosilane used in the present invention is
In addition to the surface treatment of the aluminum hydroxide (b), it can also be used for the surface treatment of an inorganic filler other than the component (b) which can be optionally blended. The component (c) does not contain a halogen element, has at least one functional group that reacts with a hydroxyl group at the terminal, and has at least one aryl group having 6 to 12 carbon atoms as a hydrocarbon group. However, the structure and the like are not particularly limited.

Examples of the functional group at the end of the component (c) of the present invention include hydroxyl groups of silanes, hydroxyl groups of alcohols, carboxyl groups of carboxylic acids, carbonyl groups of ketones and the like. Carbon number 1
Alternatively, an alkoxy group of 2, a silanol group and the like are preferable.

The hydrocarbon group in the molecule of component (c) preferably contains two or more aryl groups having 6 to 12 carbon atoms, and three aryl groups having 6 to 12 carbon atoms. Those contained above are more preferable. Here, the aryl group includes aralkyl and alkaryl. Examples thereof include phenyl, tolyl, naphthyl, benzyl, cumenyl, styryl, phenethyl, xylyl, mesityl, cinnamyl and the like. When the component (c) having at least one aryl group having a large molecular weight adheres to the surface of aluminum hydroxide as compared with an organic silane having only a hydrocarbon group such as a methyl group and an ethyl group, the water of crystallization of aluminum hydroxide is removed. As a result of an increase in the amount of heat energy required for dehydration, the dehydration temperature of aluminum hydroxide rises, and the heat resistance of aluminum hydroxide can be improved.

Since the component (c) is attached to the surface of the component (b), it is preferable that it is not in a gel state in consideration of heat resistance, and it is preferable that uneven attachment does not occur. The component (c) of the present invention may be blended with the component (b) and optionally (b).
The method of adhering to the surface of the inorganic filler other than the components is not particularly limited. A dry method in which the component (c) is directly added, a wet method using a treatment liquid diluted with an organic solvent, and the like are preferable.
The effect can also be obtained by blending in a thermosetting resin varnish and stirring.

Considering both interfacial adhesion and heat resistance, the blending amount of component (c) is preferably 0.01 to 10 parts by weight, based on the total weight of component (b) and other fillers,
7 parts by weight is more preferred. In addition, organic resin solid content 100
0.005 to 15 parts by weight is preferable per part by weight,
0.5 to 10.5 parts by weight is more preferable.

According to the present invention, it is preferable to add (d) a non-halogen type epoxy resin as a modifier for the properties of the laminate. The component (d) of the present invention is a resin that has two or more epoxy groups in the molecule and is not halogenated. It is substantially free of halides such as organic bromine compounds, organic chlorine compounds, or inorganic chlorine compounds. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
Examples thereof include a biphenyl type epoxy resin, an alicyclic epoxy resin, a polyfunctional phenol glycidyl ether compound, a polyfunctional alcohol glycidyl ether compound, and hydrogenated products thereof. One or more of these may be used in combination.

According to the present invention, the component (d) includes
In order to improve the Tg and heat resistance of the resin varnish after curing,
It is preferable to use a glycidyl ether compound of a polycondensation product of phenols and formaldehyde. Examples of such a resin include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and a bisphenol A novolac type epoxy resin. These can be used alone or in combination.

The amount of the component (d) used in the present invention is preferably 30 to 150 parts by weight, preferably 50 to 100 parts by weight, per 100 parts by weight of the component (a), in consideration of both drill workability, Tg and heat resistance. Parts by weight are preferred.

In addition to the above-mentioned components (a), (b), (c) and (d), a curing accelerator, a filler other than aluminum hydroxide, and a coloring agent may be optionally used as long as the object of the present invention is not impaired. Agents, antioxidants, reducing agents, UV opaque agents and the like can be added. In particular, the inorganic filler is effective in improving flame retardancy. These may be used alone or in combination of two or more.

In the present invention, considering the flame retardancy, the nitrogen content, which is the content of nitrogen element, is preferably 5% by weight or more based on the weight of the total solid content of the organic resin. The total organic resin solid content is the total amount of (a) the polyimide resin prepolymer, (d) the non-halogen-based epoxy resin, and the weight of the organic resin blended with the other. The nitrogen content is the content of elemental nitrogen with respect to the total amount.

According to the present invention, the above (a), (b),
A prepreg can be obtained by impregnating a glass substrate with a polyimide resin varnish obtained by blending (c) and optionally component (d) in a solvent and drying. Conventional prepreg manufacturing methods can be used. The type of glass substrate used here is not particularly limited. For example, glass woven cloth, glass non-woven cloth and the like can be mentioned. Thickness 0.02
Those having a thickness of up to 0.4 mm can be used depending on the thickness of the target prepreg or laminate. Here, the impregnated amount is shown as a resin content, and the resin content is a ratio of a total weight part of the organic resin solid content and the inorganic filler to the total weight of the prepreg. The impregnation amount or resin content is 30 to 8
It is preferably 0% by weight, more preferably 40 to 70% by weight. The resin content can be appropriately determined according to the performance of the desired prepreg and the thickness of the insulating layer after lamination. The drying conditions for producing the prepreg are a drying temperature of 60 to 200 ° C. and a drying time of 1 to 30 minutes.
It can be freely selected according to the desired prepreg characteristics.

The prepreg obtained according to the desired thickness of the laminated plate is laminated, one side or both sides of the prepreg are laminated, and heated and pressed to produce a laminated plate. Copper foil or aluminum foil is mainly used as the metal foil, but other metal foils can also be used. The thickness of the metal foil is usually preferably 3 to 200 μm. The heating temperature at the time of manufacturing the laminated plate is 130 to 25
0 degreeC is preferable and 160-200 degreeC is more preferable. The pressure is preferably 0.5 to 10 MPa, more preferably 1 to 4 MPa. It can be appropriately determined depending on the prepreg characteristics, the ability of the press, the desired thickness of the laminate, and the like.

[0028]

EXAMPLES The present invention will now be described in more detail based on examples. These examples do not limit the invention in any way. In the examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 100 parts of maleic acid N, N'-4,4'-diphenylmethane-bisimide and 30 parts of 4,4'-diaminodiphenylmethane were mixed with 1 part of ethylene glycol monomethyl ether.
It was put in 50 parts and heated at 125 ° C. for 90 minutes under reflux with stirring. After that, the liquid temperature is cooled to 80 ° C., and o-
130 parts of cresol novolac type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name: YDCN-703S) was added, and the mixture was further stirred for 60 minutes and then cooled to 30 ° C.
Next, 6 parts of dicyandiamide and an imidazole curing accelerator (manufactured by Shikoku Kasei Co., Ltd., trade name: Curezol C ₁₁
0.3 part, methoxy monophenylsilane 16 parts, aluminum hydroxide (gibbsite type) 32
0 parts and ethylene glycol monomethyl ether 10
8.1 parts were added and stirred to prepare a resin varnish having a nonvolatile content of 70% by weight and a nitrogen content of 6.0% by weight. A 100 μm glass woven fabric (IPC product number # 2116 type) was impregnated with this varnish and dried in a dryer at 180 ° C. for 6 minutes to obtain a prepreg in a B-stage state having a resin content of 60%.

Example 2 In the same manner as in Example 1 except that 9.6 parts of monohydroxytriphenylsilane was used instead of trimethoxymonophenylsilane, the nonvolatile content was 70% by weight and the nitrogen content was the same. A resin varnish of 6.0% by weight was obtained. The varnish thus obtained was treated in the same manner as in Example 1 to obtain B having a resin content of 60%.
-A stage prepreg is obtained.

Preparation of solution of organosilane treatment A In a glass flask equipped with a stirrer, trimethoxymonophenylsilane and ethylene glycol monomethyl ether were placed, and 10 parts of trimethoxymonophenylsilane was added.
A wt% solution was made. Furthermore, while continuing stirring,
Aluminum hydroxide (gibbsite type) for 1 part of solution
An organic silane-treated A solution was prepared by adding 2 parts.

EXAMPLE 3 In Example 1, trimethoxymonophenylsilane 1
Nonvolatile content 67% by weight in the same manner as in Example 1 except that 480 parts of organosilane-treated A solution was used instead of 6 parts, 320 parts of aluminum hydroxide (gibbsite type) and 108.1 parts of ethylene glycol monomethyl ether. A resin varnish having a nitrogen content of 6.0% by weight was obtained. The obtained varnish was treated in the same manner as in Example 1 to obtain a prepreg in a B-stage state having a resin content of 60%.

Example 4 100 parts of N, N'-4,4'-diphenylmethane-bisimide maleate and 50 parts of 2,2-bis (4- (4-aminophenoxy) phenyl) propane were added to 150 parts of ethylene glycol monomethyl ether. Throw in 125
The mixture was heated at reflux at 90 ° C. for 90 minutes and stirred. After cooling to a liquid temperature of 100 ° C., 20 parts of benzoguanamine and a phenol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name:
YDPN-638P is used) 110 parts are added, and further 90
After stirring for minutes, at room temperature, 8 parts of dimethoxydiphenylsilane, 200 parts of aluminum hydroxide (gibbsite type) and 90 parts of ethylene glycol monomethyl ether were added and stirred to give a nonvolatile content of 67% by weight and a nitrogen content of 6.7% by weight. % Resin varnish was prepared. This varnish is impregnated into a 50 μm glass woven cloth (IPC product number # 1080 type),
After drying for 7 minutes in a dryer at 170 ° C, B containing 70% resin
-A stage prepreg is obtained.

Example 5 In the same manner as in Example 4 except that 6 parts of monohydroxytriphenylsilane was used instead of dimethoxydiphenylsilane, the nonvolatile content was 67% by weight and the nitrogen content was 6.7% by weight. % Resin varnish was obtained. The varnish obtained was treated in the same manner as in Example 4 to obtain a prepreg in a B-stage state having a resin content of 70%.

Comparative Example 1 In Example 4, the compounding amount of aluminum hydroxide was 12
A resin varnish having a nonvolatile content of 63% by weight and a nitrogen content of 6.7% by weight was obtained in the same manner as in Example 4 except that the content was 0 part. Using this varnish, a prepreg in a B-stage state having a resin content of 68% was obtained in the same manner as in Example 4.

Comparative Example 2 A varnish was synthesized in the same manner as in Example 1 except that trimethoxymonophenylsilane in Example 1 was not used and the amount of ethylene glycol monomethyl ether was changed to 100 parts. A 60% B-stage prepreg was obtained.

Comparative Example 3 In Example 1, except that the content of 4,4'-diaminodiphenylmethane was 20 parts, the content of o-cresol novolac type epoxy resin was 175 parts, and the content of dicyandiamide was 5 parts. In the same manner as in Example 1, a resin varnish having a nonvolatile content of 71% by weight and a nitrogen content of 4.7% by weight was obtained. Using this varnish, a prepreg in a B-stage state having a resin content of 59% was obtained in the same manner as in Example 1.

Manufacturing Method of Metal-clad Laminated Plates In Examples 1, 2 and 3 and Comparative Examples 1 and 2, four prepregs obtained in the above steps were stacked and a copper foil having a thickness of 18 μm was arranged on the outside thereof. Then, it was heated and pressed at a pressure of 3 MPa and a temperature of 200 ° C for 80 minutes to obtain a double-sided copper clad laminate. For Examples 4 and 5 and Comparative Example 3, the obtained prepreg 8
The sheets were stacked and a double-sided copper clad laminate was obtained by the same laminating method.

After etching the copper foil of the obtained double-sided copper-clad laminate, UL-94 heat resistance test, Tg measurement and substrate solder heat resistance test were conducted. The results are shown in Table 1.

The Tg was measured using a Rheogel E-4000 viscoelasticity measuring device manufactured by UBM Co., Ltd. Further, the soldering heat resistance of the substrate was evaluated by observing the substrate immersed in a solder bath at 288 ° C. for 20 seconds after the moisture absorption treatment shown in Table 1. Each symbol is
◯: No change, Δ: occurrence of measling, ×: occurrence of blister.

[0041]

[Table 1]

As is clear from Table 1, the metal-clad laminate using the prepreg of the present invention achieved V-0 in the UL-94 heat resistance test without using a halogen element. Further, Tg also had a high Tg of 230 ° C. or higher by the DVE method, and the substrate soldering heat resistance was also good. On the other hand, in Comparative Examples, the content of aluminum hydroxide was less than 50 parts by weight per 100 parts by weight of the organic resin solids, and the nitrogen content in the total organic resin solids was reduced to less than 5% by weight. Comparative Example 3 could not achieve V-0 in the heat resistance test. Further, in Comparative Example 2 in which the component (c) was not used, the heat resistance test was V-0, but the solder heat resistance of the substrate was poor and the desired performance could not be achieved.

[0043]

EFFECTS OF THE INVENTION The prepreg according to the present invention does not use a halogen element, has flame retardancy, has a high Tg, and is excellent in heat resistance to soldering on a substrate. By using this, a metal-clad laminate for a printed wiring board is obtained. The board can be obtained. In addition, this laminated plate shows excellent flame retardancy, and at the same time, it does not substantially contain halogen element components that cause harmful substances such as dioxins during combustion, and is a metal-clad laminated plate that is environmentally friendly. is there.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 79/08 A 79/08 C08K 5/54 F term (reference) 4F072 AA05 AA07 AA09 AD27 AD45 AE07 AF03 AF21 AG03 AG19 AH02 AJ04 AK02 AL13 4F100 AA19A AB01B AB01C AB17 AB33B AB33C AH06A AK01A AK49A AK53A AK54A AL05A BA02 BA03 BA07 BA10 B07 CD10 EX0G0 CD02 CD047CD02Q2 CD43 J2J040CD2 J4160 001

Claims (8)

[Claims] 1. A prepreg for a printed wiring board, comprising:
(A) a polyimide resin prepolymer; (b) aluminum hydroxide; and (c) having at least one functional group that reacts with a hydroxyl group at the terminal and having 6 to 1 carbon atoms as a hydrocarbon group.
A glass-based polyimide resin prepreg for a printed wiring board, which is obtained from a thermosetting resin varnish containing no halogen element, which contains an organic silane having at least one aryl group of 2. 2. A thermosetting resin varnish comprises 100 parts by weight of an organic resin solid content in the component (a) and 50 to 15 parts of the component (b).
The prepreg according to claim 1, comprising 0 part by weight and 0.005 to 15 parts by weight of the component (c). 3. The thermosetting resin varnish further comprises (d) 1
The prepreg according to claim 1 or 2, comprising a non-halogen epoxy resin having at least two epoxy groups in the molecule. 4. The prepreg according to claim 1, 2 or 3, wherein the component (c) contains two or more aryl groups having 6 to 12 carbon atoms as hydrocarbon groups. 5. The prepreg according to claim 1, wherein the component (c) contains three or more aryl groups having 6 to 12 carbon atoms. 6. The nitrogen content in the total organic resin solids content of the varnish is 5% by weight or more, 1).
The prepreg described in the item. 7. The component (d) is a glycidyl ether compound of a polycondensation product of phenols and formaldehyde.
The prepreg according to any one of claims 1 to 6. 8. A metal-clad laminate obtained by laminating at least one prepreg according to any one of claims 1 to 7 and arranging a metal foil on one side or both sides of the prepreg and heat-pressing.