JP2001072833A - 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 resing composition of which cured material is excellent in heat resistance, and useful for an insulating material and a build-up printed circuit board by incorporating a specific epoxy resin, an epoxy resin curing agent and a polyether sulfon. SOLUTION: This resin composition contains (A) 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], (B) an epoxy resin curing agent (e.g.; a phenol novolak) and (C) a polyether sulfon having preferably phenolic hydroxyl groups at both terminal ends 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 a curing catalyst (e.g.; triphenylphosphine) and an inorganic filler (e.g.; a silica) may be 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 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 heat resistance.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition for a build-up method, the cured product of which is excellent in heat resistance, and a resin composition for a build-up method using the resin composition. And to provide a build-up printed wiring board using the insulating material.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a resin composition containing a specific epoxy resin, an epoxy resin curing agent, and polyether sulfone has been developed. The inventors have found that the above objects have been achieved, and have completed the present invention. That is, the present invention relates to (I). (A) an epoxy resin represented by the following general formula (1), (B) an epoxy resin curing agent, and (C)
The present invention relates to a resin composition for a build-up method containing polyether sulfone.

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 addition, the present invention relates to (II). The present invention relates to an insulating material for a build-up method using the resin composition described in the above (I). Further, the present invention provides (III). The above (I
The present invention relates to a build-up printed wiring board using the insulating material described in I).

[0006]

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, comprising (A) an epoxy resin represented by the general formula (1), (B) an epoxy resin curing agent, and (C) a polyether sulfone. contains.

In the present invention, the following general formula (1), which is the component (A), is used.

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 formula, from the viewpoint of curability, R is preferably a methyl group, an ethyl group, a propyl group (including isomers), a butyl group (including isomers), a hexyl group ( Isomer), a cyclopentyl group or a cyclohexyl group, and i is 0
And n is the number of repetitions of 1 to 5. More preferably, R is a methyl group, an ethyl group, or a t-butyl group, i is a number of 0 to 2, and n is a repeating number of 1 to 3. If necessary, two or more epoxy resins can be used.

The amount of the component (A) can be appropriately selected according to the relationship with the other components, and is usually 1% by weight or more, preferably 1% by weight, based on the total amount of the resin composition of the present invention. 8
0% by weight.

As the method for producing the component (A), a known method can be adopted. For example, a polycondensate of a phenol and an aldehyde is reacted with epihalohydrin in the presence of an alkali such as caustic soda. And the like.

In the present invention, as the epoxy resin curing agent as the component (B), known epoxy resin curing agents can be used. For example, polyphenol-based epoxy resins such as phenol novolak, cresol novolak, and phenol-modified polybutadiene can be used. Resin curing agent; amine epoxy resin curing agent such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone; acid anhydride epoxy resin such as pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, etc. And a curing agent; if necessary, two or more of them can be used. Among them, a polyphenol-based epoxy resin curing agent such as phenol novolak is preferred from the viewpoint of low water absorption of the cured product.

The amount of the component (B) can be usually 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 component (B), the epoxy equivalent of the component (A) and the hydroxyl equivalent of the component (B) are usually 1:
0.8 to 1: 1.2, preferably 1: 1.

In the present invention, known polyether sulfones can be used as the component (C). 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 heat resistance of the cured product, a halogen atom is preferable, and the solvent resistance of the cured product is preferable. From the viewpoint of toughness, a phenolic hydroxyl group is preferable, and in that case, it is preferable that both ends are phenolic hydroxyl groups. In the polyether sulfone molecule,
The structural units other than both ends are not particularly limited.

The amount of the component (C) used is usually 10 to 70% by weight based on the whole resin composition of the present invention. 10
If the amount is less than 70% 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 the method for producing the component (C), known methods can be employed. Examples of commercially available products include:
Sumitomo Chemical Co., Ltd., trade name: SUMIKAEXCEL, Amoco Co., trade name: REDEL, and the like.

The resin composition of the present invention may contain (D) a curing catalyst for the purpose of accelerating the curing reaction. As the component (D), known components can be used.
Triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-
Organic phosphine compounds such as 2-cyanoethylphosphine and triphenylborane complexes thereof; quaternary phosphonium salts such as tetraphenylphosphonium tetrafluoroborate and tetrabutylphosphonium tetraphenylborate; tributylamine, triethylamine and 1,8-
Tertiary amines such as diazabicyclo (5,4,0) undecene-7 and triamylamine; quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate; 2-ethylimidazole , 2-ethyl-
Imidazoles such as 4-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 component (D) 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.
It is preferably 1 minute to 15 minutes in the range of 250 ° C.

The resin composition of the present invention may contain (E) an inorganic filler from the viewpoint of low thermal expansion and low water absorption of the cured product. Examples of the component (E) include silica, titanium oxide, and alumina, and two or more of them can be used as needed. (E) The type of component is
It can be appropriately selected depending on the purpose to be contained,
For example, when the resin-containing layer obtained by curing the resin composition of the present invention, silica is preferred when emphasis is given to imparting low dielectric property, and when emphasis is given to imparting heat dissipation, alumina is preferred. preferable. Usually, silica is preferably used from the viewpoint of the former.

Regarding the particle size of the component (E), the thickness of the resin-containing layer in the insulating material (generally, 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 size before the component (E) is blended can be appropriately selected. For example, when the thickness of the resin-containing layer in a desired insulating material is 50 μm per layer, the maximum particle size before blending of the component (E) may be 30 μm or less from the viewpoint of strength and smoothness of the insulating material. Preferably 10μ
m is more preferable.

The content ratio of the component (E) is usually 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 obtain a low coefficient of thermal expansion equivalent to that of a general glass cloth substrate laminate, silica is usually required to be 50% by weight or more, preferably 70% by weight or more.

The resin composition of the present invention may contain a thermosetting resin other than the component (A), if necessary. For example, epoxy resins other than the component (A), cyanate resins, bismaleimides, addition polymers of bismaleimides and diamines, alkenyl aryl ethers such as bisvinylbenzyl etherified bisphenol A, and vinylbenzylated diaminodiphenylmethane Such as alkenylamine resins, alkynyl ethers such as dipropargyl ether of bisphenol A, alkynylamine resins such as propargylated diaminodiphenylmethane, phenolic resins, resole resins, allyl ether compounds, allylamine compounds, isocyanates,
Triallyl isocyanurate, triallyl cyanurate, vinyl group-containing polyolefin compounds, and the like.

The epoxy resin other than the component (A) includes:
For example, bifunctional epoxy resins derived from dihydric phenols such as bisphenol A, bisphenol F, tetrabromobisphenol A, bisphenol S, dihydroxybiphenyl, dihydroxynaphthalene, dihydroxystilbene, and alkyl-substituted hydroquinone; phenol novolak, cresol novolak, Novolak-type epoxy resins derived from novolaks such as naphthol novolak, bisphenol A novolak, etc .; Polyfunctional epoxy resins derived from condensates; epoxy resins derived from polyadducts of phenols and cyclopentadiene; and the like. That.

Further, the resin composition of the present invention may contain, if necessary, a thermoplastic resin other than the component (C). 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.

Further, the resin composition of the present invention may 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 has excellent heat resistance 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 a resin composition of the present invention mixed with a solvent to form an ink, and a resin-coated copper foil is a mixture of the resin composition of the present invention with a solvent and copper. After coating on 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 and semi-curing the solvent are appropriately selected depending on the components of the resin composition 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 heat resistance, a build-up printed wiring board having the cured product as an insulating layer is useful. The thickness of one insulating layer is usually in the range of 10 to 300 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.

[0032]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Examples 1 and 2 Each component and the solvent described in Table 1 were mixed with the composition (parts by weight) described in Table 1, and the resulting mixture was placed on a Teflon sheet to a thickness of about 200 microns. I laid it down. 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. About the obtained hardened | cured material, the glass transition temperature (Tg) and the coefficient of thermal expansion were measured by the following methods. Table 1 shows the results. -Glass transition temperature (Tg): Seiko Electronic Industry Co., Ltd.
Was measured using a thermal analyzer TMA120. -Thermal expansion coefficient: manufactured by Seiko Electronic Industry Co., Ltd., thermal analyzer T
The measurement was performed in the range of 50 to 100 ° C. using MA120.

[0033]

[Table 1] Epoxy resin-1: an epoxy resin derived from a polycondensation product of 2-t-butyl-5-methylphenol and 4-hydroxybenzaldehyde (Japanese Patent Publication No. 7-121979)
No. 4, pp. 139-334, 1988. Epoxy resin-2: epoxy resin derived from cresol novolak (manufactured by Sumitomo Chemical Co., Ltd.) Phenol novolak: manufactured by Arakawa Chemical Co., Ltd. PES4800P: terminal Cl -Type polyether sulfone (Sumitomo Chemical Industries, Ltd., trade name: Sumika Excel 4800P)-PES5003P: terminal phenolic hydroxyl group type polyether sulfone (Sumitomo Chemical Industries, Ltd., trade name: Sumika Excel 5003P) 2E4MZ: 2-ethyl-4-methylimidazole SO-C1: silica (trade name, manufactured by Admatechs Co., Ltd.)
Admafine SO-C1)

[0034]

The resin composition for a build-up method of the present invention has a cured product having excellent heat resistance, and by using the composition, a useful insulating material for a build-up method and further a build-up print. A wiring board is provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/14 H05K 3/46 T H05K 3/46 H01L 23/14 R (72) Inventor Noriaki Saito Ibaraki 6 Kitahara, Tsukuba Sumitomo Chemical Co., Ltd. F-term (reference) 4J002 BB20X CC04X CD07W CN03Y DE138 DE148 DJ018 EF116 EN027 EN036 EN047 EU117 EW137 EW177 FD018 FD02X FD026 FD207 GQ01 4J036 AF36 DB22 DC05 DC05 DC07 DC06 DC05 FB08 FB15 GA02 GA06 GA23 JA01 JA05 JA06 JA08 5E346 AA12 AA15 AA32 BB01 CC08 CC09 CC16 CC31 DD02 DD12 DD32 EE31 GG02 GG22 GG28 HH18

Claims (7)

[Claims] 1. A resin composition for a build-up method, comprising (A) an epoxy resin represented by the following general formula (1), (B) an epoxy resin curing agent, and (C) polyether sulfone. object. 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 ) 2. The resin composition according to claim 1, wherein the component (B) is a polyphenol-based epoxy resin curing agent. 3. The resin composition according to claim 1, wherein the component (C) is a polyether sulfone having a phenolic hydroxyl group at a terminal. 4. The method according to claim 1, further comprising (D) a curing catalyst.
4. The resin composition according to any one of items 1 to 3. 5. The resin composition according to claim 1, further comprising (E) an inorganic filler. 6. An insulating material for a build-up method, characterized by using the resin composition according to claim 1. 7. A build-up printed wiring board using the insulating material for a build-up method according to claim 6.