JP4055049B2 - Pre-preg for non-halogen printed wiring board and its use - Google Patents

Description

【００４２】
表１から明らかなように、本発明のプリプレグを用いた金属張り積層板は、ハロゲン元素を用いずにＵＬ−９４耐熱性試験においてＶ−０を達成した。また、ＴｇもＤＶＥ法で２３０℃以上の高Ｔｇを有し、基板はんだ耐熱性も良好であった。一方、比較例では、水酸化アルミニウムの配合量を有機樹脂固形分１００重量部当たり５０重量部未満とした比較例１、及び全有機樹脂固形分中の窒素含有率を５重量％未満に低くした比較例３は、耐熱性試験でＶ−０を達成できなかった。更に、（ｃ）成分を使用しなかった比較例２は、耐熱性試験はＶ−０であったが、基板はんだ耐熱性が劣り、所望の性能を達成し得なかった。
【００４３】
【発明の効果】
本発明によるプリプレグは、ハロゲン元素を用いず、難燃性を有し、Ｔｇが高く、基板はんだ耐熱性に優れており、これを用いることにより、プリント配線板用金属張り積層板を得ることができる。また、この積層板は優れた難燃性を示すと同時に、燃焼時にダイオキシン等の有害物質を発生する原因となるハロゲン元素成分を実質的に含有せず、環境問題に対応した金属張り積層板である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a non-halogen polyimide resin prepreg used for an electrical insulating material such as a printed wiring board and its use.
[0002]
[Prior art]
In general, a polyimide resin laminate is manufactured by impregnating a glass cloth with a varnish solution of a polyimide resin composition, laminating a prepreg which has been cured to form a B stage, and heating and pressing.
[0003]
Since the polyimide resin has a higher glass transition temperature (hereinafter abbreviated as Tg) than the epoxy resin, a laminate using the polyimide resin has excellent through-hole reliability and the like. On the other hand, it is necessary to set the curing temperature at the time of lamination higher than that of the epoxy resin system, and there is a drawback that the lamination work efficiency is poor. In addition, since the polyimide resin is hard and brittle, the drillability and the like tend to be inferior compared to a laminated board using an epoxy resin. Therefore, when using a polyimide resin composition for a printed wiring board, an epoxy resin is often blended as a modifier to improve the laminating property and drill workability.
[0004]
Conventionally, in order to impart flame retardancy to a polyimide resin composition, a resin containing a halogen element such as bromine has been used. In particular, since epoxy resins are often blended as described above, halogenated epoxy resins or flame retardant resins such as tetrabromobisphenol A and glycidyl ethers thereof are often used.
[0005]
However, a laminate using a polyimide resin composition tends to have a higher water absorption rate during moisture absorption treatment than an epoxy resin laminate, resulting in insufficient substrate solder heat resistance. In addition, the halogen element in the resin composition is a cause of lowering electrical reliability such as migration and tracking properties, and in recent years there has been increased interest in environmental problems, and harmful substances such as dioxins during combustion. There is a demand for a non-halogen material that does not contain a halogen element that causes the generation of oxygen.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a prepreg for a polyimide resin-based printed wiring board and a use thereof that does not use a halogen element, has flame retardancy, has high Tg, is excellent in heat resistance, and copes with environmental problems. .
[0007]
[Means for Solving the Problems]
The present invention is a prepreg for a printed wiring board, comprising: (a) a polyimide resin prepolymer; (b) 50 to 150 parts by weight of aluminum hydroxide per 100 parts by weight of organic resin solids ; the reaction functional groups having one or more, and at least one organic silane organic resin solids 0.005 parts viewed contains per 100 parts by weight having more aryl group having 6 to 12 carbon atoms as the hydrocarbon group The present invention relates to a glass substrate polyimide resin prepreg for a printed wiring board, characterized in that it is obtained from a thermosetting resin varnish having a nitrogen content in the total organic resin solid content of 5% by weight or more and containing no halogen element. .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The (a) polyimide resin prepolymer used in the present invention can be obtained by reacting a tetracarboxylic acid anhydride, diimide or monoimide (hereinafter abbreviated as tetracarboxylic acid anhydride) with a diamine. The reaction can be carried out using conventional methods, and commercially available products can also be used. Linear polyimide is preferred. Examples of tetracarboxylic acid anhydrides include anhydrides such as maleic acid, trimellitic acid, pyromellitic acid, and bis (3,4-dicarboxyphenyl) ether, diimides, and monoimides. Tetracarboxylic acid diimide is preferred, and bismaleimide is particularly preferred.
[0009]
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 (also referred to as N, N'-methylenebis (-N-phenylmaleimide), maleic acid N, N'-4,4'-diphenyl ether-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, etc. These can be used alone or in combination.
[0010]
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′-diaminodiphenylsulfone, 1,3-bis (2-p-anilinopropylidene) benzene, 1,4-bis (2-p-anilinopro) Pyridene) 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) benzene, bis-4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) phenylsulfone, etc. These can be used alone or in combination.
[0011]
According to the present invention, the diamine has 0.3 to 1.2 moles of diamine per mole of tetracarboxylic acid anhydride and the like, considering both the heat resistance after prepolymerization and curing and the Tg after curing. It is preferable to make it react with a tetracarboxylic anhydride etc. by a ratio, and it is more preferable to make it react by the ratio of 0.5-1.0 mol.
[0012]
(B) Aluminum hydroxide used in the present invention has a composition formula of Al ₂ O ₃ ・ 3H ₂ Gibbsite represented by O, Bayerite or Nordstrandite, or Al ₂ O ₃ ・ H ₂ Either boehmite represented by O or diaspore can be used. Also, one or more of these can be mixed and used. In consideration of the manufacturing cost and the flame retardancy of the printed wiring board, the gibbsite type having a large amount of crystal water in the molecule is preferable.
[0013]
Further, the impurity Na ₂ contained in the component (b) The content of O is preferably less than 0.2% by weight in consideration of heat resistance. The component (b) is not particularly limited regarding the shape. As the component (b), commercially available aluminum hydroxide can be used.
[0014]
In addition to the component (b), an inorganic filler can be optionally added. Examples thereof include boron, carbon, clay, glass, calcium carbonate, talc, alumina, silica, mica, titanium oxide, aluminum carbonate, magnesium silicate, aluminum silicate, aluminum borate, and silicon carbide. It can be used in the form of beads, powder, fibers, pulverized products, whiskers, flakes and the like. For example, aluminum borate, silicon carbide whisker, glass single fiber, and the like can be given.
[0015]
The component (b) is preferably 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 retardancy and coating workability, moldability, heat resistance, and peel strength. It is more preferable to blend ~ 130 parts by weight.
[0016]
The (c) organosilane used in the present invention can also be used for surface treatment of inorganic fillers other than the component (b) that can be optionally blended, in addition to (b) surface treatment of aluminum hydroxide. 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. In addition, the structure and the like are not particularly limited.
[0017]
Examples of the functional group at the end of the component (c) of the present invention include a hydroxyl group of silanes, a hydroxyl group of alcohols, a carboxyl group of carboxylic acids, and a carbonyl group of ketones. An alkoxy group having 1 or 2 carbon atoms or a silanol group is preferable.
[0018]
Further, the hydrocarbon group in the component (c) molecule preferably includes two or more aryl groups having 6 to 12 carbon atoms, and includes three or more aryl groups having 6 to 12 carbon atoms. It is 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 one or more aryl groups having a large molecular weight adheres to the surface of the aluminum hydroxide as compared with the organic silane having only a hydrocarbon group such as a methyl group or an ethyl group, As a result of the increase in the amount of heat energy required for dehydration, the dehydration temperature of aluminum hydroxide increases, and the heat resistance of aluminum hydroxide can be improved.
[0019]
Since the component (c) is attached to the surface of the component (b), it is preferable that the component is not in a gel state in consideration of heat resistance, and a state in which uneven adhesion does not occur is preferable. The method of adhering the component (c) of the present invention to the surface of the inorganic filler other than the component (b) and the component (b) that can be optionally blended 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, or the like is preferable. The effect can also be obtained by mixing in a thermosetting resin varnish and stirring.
[0020]
The amount of component (c) is preferably 0.01 to 10 parts by weight, preferably 1 to 7 parts by weight, based on the total weight of component (b) and other fillers, considering both interfacial adhesion and heat resistance. Is more preferable. Moreover, 0.005-15 weight part is preferable per 100 weight part of organic resin solid content, and 0.5-10.5 weight part is more preferable.
[0021]
According to the present invention, it is preferable to blend (d) a non-halogen epoxy resin as a modifier for the laminate properties. 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 does not substantially contain a halide such as an organic bromine compound, an organic chlorine compound, or an inorganic chlorine compound. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, glycidyl etherified product of polyfunctional phenol, glycidyl etherified product of polyfunctional alcohol, hydrogen of these An additive etc. are mentioned. One or more of these may be used in combination.
[0022]
According to the present invention, it is preferable to use a glycidyl etherified product of a polycondensate of phenols and formaldehyde for the component (d) in order to improve Tg and heat resistance after curing of the resin varnish. Examples of such resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins and the like, and these can be used alone or in combination.
[0023]
The blending amount of the component (d) of 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) considering both drill workability, Tg and heat resistance. preferable.
[0024]
In addition to the above components (a), (b), (c) and (d), a curing accelerator, a filler other than aluminum hydroxide, a colorant, an oxidation, as long as the object of the present invention is not impaired An inhibitor, a reducing agent, an ultraviolet opaque agent and the like can be added. In particular, inorganic fillers are effective in improving flame retardancy. These may be used alone or in combination of two or more.
[0025]
In the present invention, when flame retardancy is considered with respect to the weight of the total organic resin solid content, the nitrogen content, which is the content of nitrogen element, is preferably 5% by weight or more. The total organic resin solid content is the total amount of (a) polyimide resin prepolymer, (d) non-halogen epoxy resin, and other organic resin weights blended with others. The nitrogen content is the content of nitrogen element relative to the total amount.
[0026]
According to the present invention, a glass substrate is impregnated with a polyimide resin varnish obtained by blending the components (a), (b), (c) and optionally (d) in a solvent, and then dried. A prepreg can be obtained. Conventional prepreg manufacturing methods can be used. The kind of glass substrate used here is not particularly limited. For example, a glass woven fabric, a glass nonwoven fabric, etc. are mentioned. The thing of thickness 0.02-0.4mm can be used according to the thickness of the target prepreg or laminated board. Here, the impregnation amount is shown as a resin content, and the resin content is a ratio of the 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 preferably 30 to 80% by weight, and more preferably 40 to 70% by weight. The resin content can be appropriately determined according to the performance of the target prepreg and the thickness of the insulating layer after lamination. The drying conditions for producing the prepreg can be freely selected according to the desired prepreg characteristics in the range of a drying temperature of 60 to 200 ° C. and a drying time of 1 to 30 minutes.
[0027]
A prepreg obtained according to the thickness of the target laminate is laminated, a metal foil is laminated on one side or both sides, and heated and pressed to produce a laminate. As the metal foil, copper foil or aluminum foil is mainly used, but other metal foils can also be used. The thickness of the metal foil is usually preferably 3 to 200 μm. 130-250 degreeC is preferable and the heating temperature at the time of laminated board manufacture has more preferable 160-200 degreeC. 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 capacity of the press, the thickness of the target laminate, and the like.
[0028]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. These examples do not limit the invention in any way. In addition, unless otherwise indicated in an Example, a part means a weight part.
[0029]
Example 1
100 parts of maleic acid N, N′-4,4′-diphenylmethane-bisimide and 30 parts of 4,4′-diaminodiphenylmethane are placed in 150 parts of ethylene glycol monomethyl ether and heated at 125 ° C. for 90 minutes under reflux. did. Thereafter, the liquid temperature was cooled to 80 ° C., 130 parts of o-cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: YDCN-703S) was added, stirred for another 60 minutes, and then cooled to 30 ° C. did. Subsequently, 6 parts of dicyandiamide, 0.3 part of imidazole curing accelerator (trade name: Curesol C ₁₁ ZA used, manufactured by Shikoku Kasei Co., Ltd.), 16 parts of trimethoxymonophenylsilane, aluminum hydroxide (gibbsite type) 320 And 108.1 parts of ethylene glycol monomethyl ether 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. This varnish was impregnated into a 100 μm glass woven fabric (IPC product number # 2116 type) and dried in a dryer at 180 ° C. for 6 minutes to obtain a B-stage prepreg having a resin content of 60%.
[0030]
Example 2
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 6.0% by weight. A resin varnish was obtained.
The obtained varnish was treated in the same manner as in Example 1 to obtain a B-stage prepreg having a resin content of 60%.
[0031]
Trisilane monophenylsilane and ethylene glycol monomethyl ether were placed in a glass flask equipped with an apparatus for adjusting and stirring the organosilane treatment A solution to prepare a 10 wt% solution of trimethoxymonophenylsilane. Further, while continuing stirring, 2 parts of aluminum hydroxide (gibbsite type) was added to 1 part of the solution to prepare an organosilane-treated A solution.
[0032]
Example 3
In Example 1, except that 16 parts of trimethoxymonophenylsilane, 320 parts of aluminum hydroxide (gibbsite type) and 108.1 parts of ethylene glycol monomethyl ether were used, 480 parts of the organosilane-treated A solution were used. In the same manner as in Example 1, a resin varnish having a nonvolatile content of 67% by weight and 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 B-stage prepreg having a resin content of 60%.
[0033]
Example 4
100 parts of maleic acid N, N′-4,4′-diphenylmethane-bisimide and 50 parts of 2,2-bis (4- (4-aminophenoxy) phenyl) propane are introduced into 150 parts of ethylene glycol monomethyl ether, and 125 parts. 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 110 parts of a phenol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: YDPN-638P are used) are added, and the mixture is further stirred for 90 minutes. 8 parts of dimethoxydiphenylsilane, 200 parts of aluminum hydroxide (gibbsite type) and 90 parts of ethylene glycol monomethyl ether were added and stirred to prepare a resin varnish having a nonvolatile content of 67% by weight and a nitrogen content of 6.7% by weight. The varnish was impregnated into a 50 μm glass woven fabric (IPC product number # 1080 type) and dried in a dryer at 170 ° C. for 7 minutes to obtain a B-stage prepreg having a resin content of 70%.
[0034]
Example 5
A resin varnish having a nonvolatile content of 67% by weight and a nitrogen content of 6.7% by weight was obtained in the same manner as in Example 4 except that 6 parts of monohydroxytriphenylsilane was used instead of dimethoxydiphenylsilane. It was. The obtained varnish was treated in the same manner as in Example 4 to obtain a B-stage prepreg having a resin content of 70%.
[0035]
Comparative Example 1
In Example 4, 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 amount of aluminum hydroxide was changed to 120 parts. Using this varnish, a B-stage prepreg having a resin content of 68% was obtained in the same manner as in Example 4.
[0036]
Comparative Example 2
A varnish was synthesized in the same manner as in Example 1 except that the amount of ethylene glycol monomethyl ether was changed to 100 parts without using trimethoxymonophenylsilane in Example 1, and a B-stage having a resin content of 60%. A prepreg in state was obtained.
[0037]
Comparative Example 3
The same as Example 1 except that the amount of 4,4′-diaminodiphenylmethane in Example 1 was 20 parts, the amount of o-cresol novolac epoxy resin was 175 parts, and the amount of dicyandiamide was 5 parts. Thus, 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 B-stage prepreg having a resin content of 59% was obtained in the same manner as in Example 1.
[0038]
Manufacturing method Examples 1, 2, 3 and Comparative Examples 1 and 2 of metal-clad laminates Overlap the four prepregs obtained in the above steps, and arrange a copper foil with a thickness of 18 μm on the outside, pressure A double-sided copper-clad laminate was obtained by heating and pressing at 3 MPa and a temperature of 200 ° C. for 80 minutes.
For Examples 4 and 5 and Comparative Example 3, 8 prepregs obtained were stacked, and a double-sided copper-clad laminate was obtained by the same lamination method.
[0039]
After etching the copper foil of the obtained double-sided copper-clad laminate, UL-94 heat resistance test, Tg measurement, and board solder heat resistance test were performed.
The results are shown in Table 1.
[0040]
The Tg was measured using a Rheogel E-4000 type viscoelasticity measuring device manufactured by UBM Co., Ltd.
The substrate solder heat resistance was evaluated by observing a base material immersed in a solder bath at 288 ° C. for 20 seconds after the moisture absorption treatment described in Table 1. Each symbol means ◯: no change, Δ: occurrence of mesuring, and x: occurrence of blistering.
[0041]
[Table 1]

[0042]
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. Tg also had a high Tg of 230 ° C. or higher by the DVE method, and the substrate solder heat resistance was also good. On the other hand, in the comparative example, the amount 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. In Comparative Example 3, V-0 could not be achieved 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 substrate solder heat resistance was poor and the desired performance could not be achieved.
[0043]
【The invention's effect】
The prepreg according to the present invention does not use a halogen element, has flame retardancy, has a high Tg, and has excellent substrate solder heat resistance. By using this, a metal-clad laminate for a printed wiring board can be obtained. it can. In addition, this laminate has excellent flame retardancy, and at the same time, does not contain a halogen element component that causes generation of harmful substances such as dioxin at the time of combustion, and is a metal-clad laminate that responds to environmental problems. is there.

Claims (6)

A printed wiring board prepreg, comprising: (a) a polyimide resin prepolymer; (b) 50 to 150 parts by weight of aluminum hydroxide per 100 parts by weight of organic resin solids ; and (c) a functional group that reacts with a hydroxyl group at the terminal. based on having one or more, and at least one organic silane organic resin solids 0.005 parts viewed contains per 100 parts by weight having more aryl group having 6 to 12 carbon atoms as the hydrocarbon group, the total organic A glass substrate polyimide resin prepreg for a printed wiring board, which is obtained from a thermosetting resin varnish having a nitrogen content in a resin solid content of 5% by weight or more and containing no halogen element. The prepreg according to claim 1, wherein the thermosetting resin varnish further comprises (d) a non-halogen epoxy resin having at least two epoxy groups in one molecule. The prepreg according to claim 1 or 2 , wherein the component (c) contains two or more aryl groups having 6 to 12 carbon atoms as hydrocarbon groups. The prepreg according to claim 1 or 2 , wherein the component (c) contains 3 or more aryl groups having 6 to 12 carbon atoms. The prepreg according to any one of claims 2 to 4 , wherein the component (d) is a glycidyl etherified product of a polycondensate of phenols and formaldehyde.   A metal-clad laminate obtained by laminating at least one prepreg according to any one of claims 1 to 5 and arranging a metal foil on one side or both sides thereof, followed by heating and pressing.