JP2001072834A - Resin composition for build-up process, insulating material for build-up process and build-up printed circuit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition of which cured material is excellent in a specific low water-absorption property, toughness or a low heat expansion property, and useful for an insulating material and a build-up printed circuit board by incorporating a specific epoxy resin, epoxy resin curing agent and a polyether sulfon. SOLUTION: This resin composition contains (A) preferably an epoxy resin of the formula [Gly is glycidyl; R is a 1-10C alkyl or the like; (i) is 0-4; (n) is 1-10] and having >=2 glycidyl groups, (B) a polyhydric phenol-based epoxy resin curing agent (e.g.; a phenol novolak) and (C) preferably a polyether sulfon having a phenolic hydroxyl group at the terminal of its molecule. It is preferable that the using amount of the component A is 1-80 wt.% and that of the component C is 10-70 wt.%. The ratio of the epoxy equivalent of the component A to the hydroxyl group equivalent of the component B is preferably (1:0.8)-(1:1.2). In this composition, further 10-80 wt.% inorganic filler (e.g.; a silica) is preferably incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition for a build-up method. Specifically, the present invention relates to a resin composition containing an epoxy resin, an epoxy resin curing agent, and polyether sulfone. Further, the present invention relates to an insulating material for a build-up method using the resin composition, and a build-up printed wiring board.

[0002]

2. Description of the Related Art In recent years, the miniaturization of electronic devices,
As the thickness and weight are reduced, high-density mounting is required. For this reason, in printed wiring boards, it is necessary to reduce the diameters of through holes and via holes and to employ blind via holes as well as to make circuit patterns finer. In order to satisfy these requirements, attention has been paid to build-up printed wiring boards obtained by a build-up method. Insulating material for build-up printed wiring boards is a photosensitive resin type that has the merit that many via holes can be formed at once by exposure and development processes, and a finer via hole is formed by using a laser process. A thermosetting resin type is used, which makes it possible. Generally, a photosensitive resin type insulating material must impart photosensitivity to a resin composition to be used, and there are restrictions on resin selection, and a very large amount of know-how is included in an exposure and development process. Therefore, much attention is now focused on thermosetting resin type insulating materials.

A resin composition used for a thermosetting resin-type insulating material contains not only a thermosetting resin such as an epoxy resin or a phenoxy resin as a resin component, but also a thermosetting resin and a thermoplastic resin. Some have been proposed. For example, a resin composition containing an epoxy resin and polyether sulfone is described in JP-A-7-33991 and JP-A-7-34048. However, when a conventional resin composition is used, it has been difficult to obtain an insulating material for a build-up method that is satisfactory in terms of low water absorption, toughness, or low thermal expansion.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cured product which is excellent in low water absorption, toughness or low thermal expansion.
To provide a resin composition for a build-up method, to provide an insulating material for a build-up method using the resin composition, and to provide a build-up printed wiring board using the insulating material. That is.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that an epoxy resin having two or more glycidyl groups, a specific epoxy resin curing agent, and a specific polyether The present inventors have found that a resin composition containing a sulfone or an inorganic filler meets the above object, and have completed the present invention.

That is, the present invention relates to (I). The present invention relates to a resin composition for a build-up method containing an epoxy resin having two or more glycidyl groups, a polyhydric phenol-based epoxy resin curing agent, and polyether sulfone. Further, the present invention provides (II). The present invention relates to a resin composition for a build-up method containing an epoxy resin having two or more glycidyl groups, an epoxy resin curing agent, and a polyether sulfone having a phenolic hydroxyl group at a terminal. Further, the present invention provides (III). An epoxy resin having two or more glycidyl groups, an epoxy resin curing agent,
The present invention relates to a resin composition for a build-up method containing polyether sulfone and an inorganic filler. Further, the present invention provides (IV). The present invention relates to an insulating material for a build-up method using the resin composition according to any one of the above (I) to (III). Further, the present invention provides
(V). The present invention relates to a build-up printed wiring board using the insulating material described in the above (IV).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin composition of the present invention is a resin composition for a build-up method, and contains an epoxy resin having two or more glycidyl groups, an epoxy resin curing agent, a polyether sulfone, and optionally an inorganic filler. I do.

In the present invention, as the epoxy resin having two or more glycidyl groups, known resins can be used. For example, bisphenol A, bisphenol F, tetrabromobisphenol A, bisphenol S, dihydroxybiphenyl, dihydroxynaphthalene Epoxy resins derived from dihydric phenols such as dihydroxystilbene and alkyl-substituted hydroquinone; novolak epoxy resins derived from novolaks such as phenol novolak, cresol novolak, naphthol novolak, bisphenol A novolak; phenol , Alkyl-substituted phenols, naphthols, and other phenols with benzaldehyde, hydroxybenzaldehyde, terephthalaldehyde, alkyl-substituted terephthalaldehyde Polyfunctional epoxy resins derived from polycondensates with aldehydes such as phenols and the like; epoxy resins derived from polyadducts of phenols with cyclopentadiene; and the like, and if necessary, two or more thereof. Can also be used.

The type of epoxy resin is appropriately selected according to the purpose. From the viewpoint of reactivity and compatibility with polyethersulfone, epoxy resin derived from bisphenol A and epoxy resin derived from bisphenol F are used. A resin, an epoxy resin derived from phenol novolak, and an epoxy resin derived from cresol novolak are preferable, and an epoxy resin derived from cresol novolak is more preferable.

On the other hand, from the viewpoint of the balance between reactivity, low water absorption of the cured product, heat resistance, and the like, an epoxy resin derived from phenol novolak, an epoxy resin derived from cresol novolak, represented by the following general formula (1): An epoxy resin represented by the following general formula (1) is particularly preferable.

Embedded image (In the formula, Gly represents a glycidyl group, and R is each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a carbon number containing a cycloalkyl group having 5 to 7 carbon atoms. Represents a hydrocarbon group of 6 to 20, i is independently a number of 0 to 4, and when i is 2 or more, R may be the same or different, and n is 1 to 10
Is the number of repetitions of )

In the epoxy resin represented by the general formula (1), from the viewpoint of curability, preferably,
Represents a methyl group, an ethyl group, a propyl group (including isomers),
A butyl group (including isomers), a hexyl group (including isomers), a cyclopentyl group, or a cyclohexyl group, i is a number of 0 to 3, and n is a repeating number of 1 to 5; More preferably, R is a methyl, ethyl, or t-butyl group, i is a number from 0 to 2, and n is 1
3 is the number of repetitions.

The amount of the epoxy resin to be used can be appropriately selected depending on the relationship with other components, and is usually 1% by weight or more, preferably 1 to 3% by weight, based on the total amount of the resin composition of the present invention.
80% by weight.

As a method for producing the epoxy resin, a known method can be employed. For example, a method of reacting a phenol or a derivative thereof with epihalohydrin in the presence of an alkali such as caustic soda and the like can be mentioned.

In the present invention, known epoxy resin curing agents can be employed, such as phenol novolak, cresol novolak, tris (hydroxyphenyl) alkanes, phenol modified polybutadiene, phenol aralkyl resins, Polyhydric phenol-based epoxy resin curing agents such as polyadducts of phenols and dicyclopentadiene; amine-based epoxy resin curing agents such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone; pyromellitic anhydride, trimellitic anhydride Acid anhydride-based epoxy resin curing agents such as acid and benzophenonetetracarboxylic dianhydride; and two or more of them can be used as necessary. Among them, from the viewpoint of low water absorption of the cured product, a polyphenol-based epoxy resin curing agent is preferable, and phenol novolak is particularly preferable.

The amount of the epoxy resin curing agent used can usually be set so that the cured product obtained from the resin composition of the present invention has a high glass transition temperature. For example, when phenol novolak is used as the epoxy resin curing agent, the epoxy equivalent of the epoxy resin and the hydroxyl equivalent of the epoxy resin curing agent are usually 1: 0.8 to 1: 1.2, preferably 1: 1.

In the present invention, known polyether sulfones can be employed. Examples of the terminal group of the polyethersulfone molecule include, for example, a halogen atom, an alkoxy group, a phenolic hydroxyl group, and the like.From the viewpoint of solvent resistance and toughness of the cured product, a phenolic hydroxyl group is preferable. It is preferred that both ends are phenolic hydroxyl groups. In the polyethersulfone molecule, structural units other than both ends are not particularly limited.

The amount of polyether sulfone used is usually
It is 10 to 70% by weight based on the whole resin composition of the present invention. If the amount is less than 10% by weight, the toughness of the cured product may decrease. If the amount exceeds 70% by weight, the processability of the composition may decrease or the water absorption of the cured product may increase.

As a method for producing polyethersulfone, known methods can be employed. Examples of commercially available products include Sumitomo Chemical Co., Ltd., trade names: Sumika Excel, Amoco, and commercial products. Name: REDEL, etc.

In the present invention, examples of the inorganic filler include silica, titanium oxide, and alumina.
If necessary, two or more of these can be used. The type of the inorganic filler can be appropriately selected according to the purpose to be contained, for example, emphasis is placed on providing a low dielectric property to a resin-containing layer obtained by curing the resin composition of the present invention. In such a case, silica is preferred, and when emphasis is placed on imparting heat dissipation, alumina is preferred. Usually, silica is preferably used from the viewpoint of the former.

Regarding the particle size of the inorganic filler, the thickness of the resin-containing layer in the insulating material (usually 10 to 30 per layer)
Depending on the via diameter (about 0 μm) and the via diameter (generally about 30 to 150 μm), the maximum particle diameter before blending the inorganic filler can be appropriately selected. For example, when the thickness of the resin-containing layer in the desired insulating material is 50 μm per layer, the maximum particle size before blending the inorganic filler is preferably 30 μm or less from the viewpoint of strength and smoothness of the insulating material. , 10μ
m is more preferable.

The content ratio of the inorganic filler is usually from 10 to 80% by weight based on the whole resin composition. When the amount is less than 10% by weight, the effect of low water absorption and low coefficient of thermal expansion of the cured product may be reduced. On the other hand, when the amount exceeds 80% by weight, laser processability may be reduced. In order to achieve a low coefficient of thermal expansion equivalent to that of a general glass cloth substrate laminate, silica is usually 50% by weight or more, preferably 70% by weight or more.

The resin composition of the present invention may contain a curing catalyst for the purpose of accelerating the curing reaction. Known curing catalysts can be used, for example, triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, Organic phosphine compounds and their triphenylborane complexes; quaternary phosphonium salts such as tetraphenylphosphonium tetrafluoroborate and tetrabutylphosphonium tetraphenylborate; tributylamine, triethylamine, 1,8-diazabicyclo (5,4,0) Undecene-7, triamylamine,
Quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate, etc .; 2-ethylimidazole, 2-ethyl-4
Imidazoles such as -methylimidazole; and the like, and if necessary, two or more of them can be used. Among them, organic phosphine compounds and imidazoles are preferable.

The amount of the curing catalyst used can be appropriately selected so that the gel time of the resin composition of the present invention becomes a desired value. Usually, the gel time of the resin composition is from 80 ° C to 2 ° C.
It is preferable that the heating time is 1 minute to 15 minutes in the range of 50 ° C.

The resin composition of the present invention may contain a thermosetting resin other than an epoxy resin, if necessary. For example, cyanate resins, bismaleimides,
Addition polymer of bismaleimides and diamines, alkenyl aryl ethers such as bisvinyl benzyl ether of bisphenol A, alkenyl amine resins such as vinyl benzyl of diaminodiphenylmethane, alkynyl ethers such as dipropargyl ether of bisphenol A, diaminodiphenylmethane Alkynylamine resins, phenolic resins, resole resins, allyl ether compounds, allylamine compounds, isocyanates, triallyl isocyanurates, triallyl cyanurates, vinyl group-containing polyolefin compounds, and the like.

Further, the resin composition of the present invention may contain a thermoplastic resin other than polyether sulfone, if necessary. Examples thereof include polysulfone, polyetherimide, polyphenylene ether, polystyrene, polyethylene, polybutadiene, polyimide, polycarbonate, polyacrylate, polymethacrylate, terminal amine and terminal carboxyl group-modified polybutadiene-acrylonitrile rubber, and modified products thereof.

Further, the resin composition of the present invention may be provided with photocurability, if necessary, and may contain, for example, acrylates, methacrylates, styrenes and the like.

The resin composition of the present invention may further contain, if necessary, a bromo-containing polycarbonate, a bromo-containing polyphenylene oxide, a bromo-containing polyacrylate,
Organic flame retardants such as bromo-containing polystyrene; inorganic flame retardants such as antimony trioxide, aluminum hydroxide and red phosphorus; release agents such as waxes and zinc stearate;
Surface treatment agents such as silane coupling agents; organic fillers such as epoxy resin powder, melamine resin powder, urea resin powder, guanamine resin powder, polyester resin powder;
Known additives may be contained.

The cured product of the resin composition of the present invention is excellent in low water absorption, toughness or low thermal expansion, and is suitably used as a resin composition for a build-up method. Specifically, it is mainly used as an insulating material for a build-up method, a resin component such as an ink-like material, a copper foil with resin, a resin layer, and the like. Here, the ink-like material means that the resin composition of the present invention is mixed with a solvent to form an ink, and the resin-coated copper foil is obtained by mixing the resin composition of the present invention with a solvent,
After coating on a copper foil, the solvent is evaporated and semi-cured. Usually, the ink-like material is prepared and used by the following method (i), and the copper foil with resin is prepared and used by the following method (ii).

(I) Each component of the resin composition of the present invention is represented by γ
-Butyrolactone, dimethylformamide (DMF),
Mixed with a solvent such as N-methylpyrrolidone (NMP),
Use ink-like material. This ink-like material is directly applied onto a core substrate using a roll coater, a table coater, or the like, and after distilling off the solvent, is heated and cured to form an insulating layer. Thereafter, via formation and wiring layer formation are performed through laser processing and a plating process, and these steps are repeated to produce a build-up printed wiring board.

(Ii) Each component of the resin composition of the present invention is
γ-butyrolactone, dimethylformamide (DM
F), mixed with a solvent such as N-methylpyrrolidone (NMP), etc. to form a varnish, and then coated on a copper foil using a table coater or the like, thinned, evaporated, and semi-cured. To make a copper foil with resin. After laminating the copper foil with resin on the core substrate and press-molding, the copper foil is etched to form a circuit. By repeating this, a build-up printed wiring board is manufactured.

In the above method (i), the conditions for distilling off the solvent are appropriately selected according to the components of the resin composition to be used and the type and amount of the solvent used.
C, in the range of 1 minute to 30 minutes. The conditions for heat curing are usually in a hot air oven at 60 ° C. to 200 ° C. for 30 minutes to 5 hours.

On the other hand, in the above method (ii), the conditions for distilling off the solvent and semi-curing are appropriately selected depending on the components of the resin composition to be used and the type and amount of the solvent used.
The temperature ranges from 60 ° C to 200 ° C for 1 minute to 30 minutes. Also,
The conditions for press-molding copper foil with resin are a molding pressure of 10 kg.
/ Cm ² -100 kg / cm ² , 80 ° C.-250 ° C., 20
Minutes to 300 minutes.

In the production of a build-up printed wiring board, a method using an ink-like material as described in the above (i),
It is preferable because the thickness can be easily controlled and a fine pattern can be formed because an electroless plating process is used for forming the wiring layer. On the other hand, the method using the resin-coated copper foil as in the above (ii) has an advantage that handling is easy.

Since the cured product of the resin composition of the present invention is excellent in low water absorption, toughness or low thermal expansion, a build-up printed wiring board having the cured product as an insulating layer is useful. The thickness of one insulating layer is usually 10 to 3
It is in the range of 00 μm. Other uses of the resin composition of the present invention include insulating materials other than build-up printed wiring boards such as glass-based printed wiring boards, composite materials, adhesive materials, paint materials, and the like.

[0035]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1, Comparative Examples 1 and 2 Each component and solvent described in Table 1 were mixed with the composition (parts by weight) described in Table 1, and the resulting mixture was formed on a Teflon sheet to a thickness of about 200 microns. Laid. This was vacuum-dried at 100 ° C. for 10 minutes to obtain a semi-cured state. This semi-cured product was hot-pressed at 50 kg / cm ^{2 under} the curing conditions shown in Table 1 to obtain a cured product. The selected cured product was allowed to absorb water at 85 ° C./85%, and the water absorption was determined from the weight change after 24 hours. Table 1 shows the results.

Examples 2 to 5 The components and solvents shown in Table 2 were mixed with the compositions (parts by weight) shown in Table 2, and the resulting mixture was adjusted to a thickness of about 150 microns on a glass substrate. Was applied. This glass substrate was cured in a vacuum oven at 160 ° C. for 15 minutes and dried under vacuum to produce a semi-cured product. The obtained semi-cured product was further heated and cured in a hot-air oven at 180 ° C. × 2 h, to produce a cured film of about 100 μm on a glass substrate. Using the cured film obtained, ASTM
The cured film was subjected to a tensile test according to D-638. Table 2 shows the elongation at break obtained from the results of the tensile test.

Examples 6 to 9 and Comparative Example 3 The components and solvents shown in Table 3 were mixed with the compositions (parts by weight) shown in Table 3, and kneaded in a roll. The obtained roll kneaded material was spread on a Teflon sheet so as to have a thickness of about 200 μm. This was vacuum-dried at 100 ° C. for 5 minutes to obtain a semi-cured state. 50 kg / c of this semi-cured product
It was hot pressed at 175 ° C. for 2 hours at m ² to obtain a cured product.
About the obtained hardened | cured material, the coefficient of thermal expansion and the water absorption were measured by the following methods. Table 3 shows the results. Thermal expansion coefficient: Measured in the range of 50 to 100 ° C. using a thermal analyzer TMA120 manufactured by Seiko Electronic Industry Co., Ltd.・ Water absorption: 85
Water was absorbed under the condition of ° C./85%, and was determined from the weight change after 24 hours. Further, as an evaluation of workability, the roll kneaded material obtained above was formed into a sheet having a thickness of about 100 μm on a copper foil of 18 μm using a doctor blade.
After drying in a vacuum for 5 minutes to obtain a semi-cured state, the obtained resin-coated copper foil was wound around a cylinder having a diameter of 8 cm with the insulating layer facing downward, and the resin layer was examined for cracks. When no cracks were generated, the result was evaluated as 、, and when it was generated, as ×,
It is shown in Table 3.

[0038]

[Table 1] -Epoxy resin-1: Epoxy resin derived from cresol novolak (manufactured by Sumitomo Chemical Co., Ltd.)-Phenol novolak: manufactured by Arakawa Chemical Co., Ltd.-PES4800P: polyether sulfone (manufactured by Sumitomo Chemical Co., Ltd.) (Name: Sumika Excel 4800P, terminal Cl type) 2E4MZ: 2-ethyl-4-methylimidazole

[0039]

[Table 2] Epoxy resin-1: an epoxy resin derived from cresol novolak (manufactured by Sumitomo Chemical Co., Ltd.) Epoxy resin-2: from a polycondensate of 2-t-butyl-5-methylphenol and 4-hydroxybenzaldehyde Derived epoxy resin (Japanese Patent Publication No. 7-121979)
Phenol novolak: manufactured by Arakawa Chemical Industries, Ltd. PES5003P: polyether sulfone of phenolic hydroxyl group type (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumika Excel 5003P) -PES4800P: polyether sulfone of Cl terminal type (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumika Excel 4800P)-2E4MZ: 2-ethyl-4-methylimidazole

[0040]

[Table 3] ・ Epoxy resin-1: Epoxy resin derived from cresol novolak (manufactured by Sumitomo Chemical Co., Ltd.) ・ Phenol novolak: manufactured by Arakawa Chemical Co., Ltd. ・ PES5003P: polyether sulfone (manufactured by Sumitomo Chemical Co., Ltd.) Name: Sumika Excel 5003P, terminal phenolic hydroxyl group type) ・ TSS-4: Silica (Tatsumori Co., Ltd., maximum particle size 20 μm)
m) ・ Benzoguanamine: heat-resistant resin powder (Nippon Shokubai Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole

[0041]

According to the resin composition for a build-up method of the present invention, the cured product obtained is excellent in low water absorbency, toughness or low thermal expansion property. And a build-up printed wiring board.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) H05K 3/46 H05K 3/46 T (31) Priority claim number Japanese Patent Application No. 11-188980 (32) Priority date July 2, 1999 (7.2 July 1999) (33) Priority Country Japan (JP) (72) Inventor Noriaki Saito 6 Kitahara, Tsukuba, Ibaraki Prefecture F-term in Sumitomo Chemical Co., Ltd. 4J002 CC03X CD04W CD05W CD061 CD181 CE00X CN03Y DE137 DE147 DJ017 EF126 EJ046 EN076 ER026 EV216 FD010 FD017 FD130 FD146 4J036 AD08 AD09 AD14 AD21 AE02 AE07 AF01 AF05 AF06 AF07 AF15 AF19 DA01 DB06 FA01 FA05 CC01 GA02 GA02 FB07 GA08

Claims (10)

[Claims] 1. A resin composition for a build-up method, comprising an epoxy resin having two or more glycidyl groups, a polyhydric phenol-based epoxy resin curing agent, and polyether sulfone. 2. A resin composition for a build-up method comprising an epoxy resin having two or more glycidyl groups, an epoxy resin curing agent and a polyether sulfone having a phenolic hydroxyl group at a terminal. 3. A resin composition for a build-up method, comprising an epoxy resin having two or more glycidyl groups, an epoxy resin curing agent, polyether sulfone, and an inorganic filler. 4. The resin composition according to claim 2, wherein the epoxy resin curing agent is a polyphenol-based epoxy resin curing agent. 5. The method according to claim 1, further comprising an inorganic filler.
Or the resin composition according to 4. 6. The resin composition according to claim 3, wherein the inorganic filler is silica. 7. The resin composition according to claim 3, wherein the content of the inorganic filler is 10 to 80% by weight based on the whole resin composition.
3. The resin composition according to item 1. 8. The resin composition according to claim 1, further comprising a curing catalyst. 9. An insulating material for a build-up method comprising using the resin composition according to claim 1. 10. A build-up printed wiring board comprising the insulating material for a build-up method according to claim 9.