JPH06273930A - Curable resin composition and multilayer printed circuit board using the same and its manufacture - Google Patents

Abstract

(57) [Summary] [Structure] General formula (1) (wherein R ₁ is an organic residue containing an aromatic ring and having 6 to 15 carbon atoms, R ₂ is hydrogen, a phenyl group,
The alkoxyphenyl group, R ₃ , R ₄ and R ₅ represent hydrogen and an alkyl group having 9 or less carbon atoms, and at least two of R ₃ , R ₄ and R ₅ represent hydrogen. A curable resin composition containing 10 to 0.5 parts by weight of a photopolymerization initiator and / or a thermal polymerization initiator per 100 parts by weight of a copolymer having a repeating unit represented by Multilayer printed wiring board. [Chemical 21] [Effect] Having a polymaleimide skeleton and an unsaturated double bond in the side chain, the addition of a photopolymerization initiator gives a cured product with excellent photoreactivity and heat resistance after curing. Excellent as an insulating pattern.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention cures by heat and light,
The present invention relates to a curable resin composition that gives a cured product having excellent heat resistance and a multilayer printed wiring board using the same.

[0002]

2. Description of the Related Art With the increase in capacity and size of electronic computers, there is an increasing demand for higher density of printed wiring boards used therein. The high-density printed wiring board is manufactured by the full additive method including the basic steps shown in FIG.

(A) A step of providing a plating resist layer on a substrate.

(B) A step of exposing and developing to form a required relief pattern.

(C) A step of forming a wiring pattern by plating.

(D) A step of forming a multilayered printed wiring board.

It is desirable that the plating resist used in the above-mentioned full additive method finally becomes an insulating layer between wirings. As a result, it is possible to prevent the peeling of the wiring, the deviation of the wiring when the wiring is multi-layered, etc. Therefore, it is possible to multi-layer the printed wiring board having the wiring with a high aspect ratio.

The plating resist remaining in the printed wiring board as an insulating material is required to have excellent insulating properties and heat resistance. Furthermore, the low dielectric constant of the insulating layer is required to meet the demand for high density and miniaturization.

Conventionally, as a wiring board, there is known a prepreg in which a reinforcing material such as glass cloth is impregnated with a resin composition comprising a maleimide derivative and a styryl derivative (Japanese Patent Laid-Open No. 2-99545). This prepreg has excellent molding workability, and is known as a heat-resistant and flame-retardant laminated material for multilayer substrates.

[0010]

However, the inorganic reinforcing material such as glass cloth has a higher relative dielectric constant than the resin composition. Therefore, even if the relative permittivity of the resin composition is reduced, there is a limit in reducing the permittivity of the insulating plate reinforced with the glass cloth.

Further, since it is difficult to form a relief pattern using the resin composition comprising the maleimide derivative and the styryl derivative, a wiring pattern is formed on the substrate surface by using, for example, an acrylate resin resist. A multi-layer wiring board is produced by forming and adhering in multiple layers.

When an acrylate-based resist is used, the heat resistance of the relief pattern is low, so the relief pattern is peeled off after the pattern is formed and a new insulating layer is formed using another material. However, the surface of the substrate on which the wiring pattern has been once formed has irregularities due to the pattern, and there is a limit to increasing the density by multilayering.

An object of the present invention is to provide a resin composition capable of forming a relief pattern having heat resistance equivalent to that of a laminated material for a multilayer board.

Another object of the present invention is to provide a multilayer printed wiring board having no surface irregularities by using the above resin composition and a method for producing the same.

[0015]

Means for Solving the Problems The gist of the present invention for solving the above problems is as follows.

[1] General formula (1)

[0017]

[Chemical 7]

(In the formula, R ₁ has 6 carbon atoms including an aromatic ring.
To 15 organic residues, R ₂ represents hydrogen, a phenyl group, an alkoxyphenyl group, R ₃ , R ₄ and R ₅ represent hydrogen and an alkyl group having 9 or less carbon atoms, and at least R ₃ , R ₄ and R ₅ Two represent hydrogen. ) A curable resin composition comprising 10 to 0.5 parts by weight of a photopolymerization initiator and / or a thermal polymerization initiator with respect to 100 parts by weight of a copolymer having a repeating unit represented by the formula (1).

[2] General formula (2)

[0020]

[Chemical 8]

The curing according to the above [1], which contains a compound having a repeating unit represented by the formula (wherein R ₆ , R ₇ and R ₈ represent hydrogen and an organic residue having 1 to 20 carbon atoms). Resin composition.

[3] General formula (3)

[0023]

[Chemical 9]

(Wherein R ₈ is a phenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a benzoic acid residue,
Represents a pyrrolidone residue. The curable resin composition according to the above [1], which comprises a compound having a repeating unit represented by

[4] A resin composition containing 10 to 0.5 parts by weight of a photopolymerization initiator and / or a thermal polymerization initiator with respect to 100 parts by weight of the copolymer having the repeating unit represented by the general formula (1). A multilayer printed wiring board, wherein a wiring circuit is formed on at least one surface of a film made of a cured product, and the films on which the wiring circuit is formed are laminated and adhered.

[5] The multilayer printed wiring board according to the above [4], wherein the resin composition contains a compound having a repeating unit represented by the general formula (2).

[6] The multilayer printed wiring board according to [4], wherein the resin composition contains a compound having a repeating unit represented by the general formula (3).

[7] A film of a photocurable resin composition containing the general formula (1) and a photopolymerization initiator is formed on a substrate, and then exposed and developed to form a negative pattern of a circuit. A method of manufacturing a multilayer printed wiring board in which printed wiring boards having wiring circuits formed by plating are laminated and adhered to the circuit pattern portion where the coating is not formed to form a multilayer.

[8] A photocurable resin composition containing the general formula (1) and a photopolymerization initiator on a substrate made of a thermosetting resin composition containing the general formula (1) and a thermopolymerization initiator. After forming the coating film, it is exposed and developed to form the negative pattern of the circuit, and then the printed circuit board on which the wiring circuit is formed by plating is laminated and adhered to the circuit pattern part where the coating film is not formed to form a multilayer. Manufacturing method of multilayer printed wiring board.

Specific examples of the compound having the repeating unit represented by the general formula (1) include those represented by the following formulas 1 to 33 .

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

Specific examples of the compound having the repeating unit represented by the general formulas (2) and (3) include the following formula (a).
~ (N) are available.

[0041]

[Chemical 19]

[0042]

[Chemical 20]

Examples of the photopolymerization initiator include an azide compound having a chalcone structure. Further, as the radical polymerization initiator, for example, benzoyl peroxide,
Parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, dicumyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), 2 , 5-Dimethylhexane-2,5-dihydroperoxide, t-butylperbenzoate, 2,5-
Dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5- (t-butylperoxy) hexyne-3,2,5-dimethylhexyl-2,5-
Di (peroxybenzoate), cumene hydroperoxide, t-butylhydroperoxide, t-butyloxyacetate, t-butylperoxyoctate, t-butyloxyisobutyrate, dibenzyl peroxide,
Di-t-butyl peroxyphthalate and the like. One or more of these can be used.

[0044]

The resin composition of the present invention can improve the heat resistance of the cured product by containing the polymer of the maleimide derivative having a curable unsaturated double bond in the side chain. That is,
This is because the polymaleimide structure that is the main skeleton improves the glass transition temperature and the thermal decomposition temperature.

Further, a relief pattern can be easily formed by irradiation with light from a photopolymerization initiator that contains a functional group having an unsaturated bond in its side chain and is blended. Especially when an azide compound having a chalcone structure is used as a photopolymerization initiator,
The number of cross-linking points is increased by the highly reactive azido group, and the heat resistance is improved by the cross-linking point formed by ring opening of the chalcone structure.

Since the pattern thus formed has the same heat resistance as the substrate, it can be left as an insulating layer, and unevenness on the substrate surface due to conventional pattern removal can be eliminated.

[0047]

EXAMPLES The present invention will be specifically described with reference to examples.

Example 1 p-Aminostyrene 51.
4 g and 42.1 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) were put into 2 liters of diethyl ether and reacted at room temperature for 2 hours to obtain N- (p-vinylphenyl) maleanilic acid (yield 91.0 g). .

The above N- (p-vinylphenyl) maleanilic acid (10.9 g), acetic anhydride (200 ml) and sodium acetate (2 g) were reacted at 100 ° C. for 1 hour to give N- (p-
Vinylphenyl) maleimide was obtained (yield 4.2 g).

Next, a copolymer obtained by anionic polymerization of the above N- (p-vinylphenyl) maleimide and N-phenylmaleimide was obtained. The reaction conditions are: t-butoxypotassium (manufactured by Kanto Chemical Co., Ltd.) 0.2 mmol, N- (p-vinylphenyl) maleimide 2.0 mmol, N-phenylmaleimide 3.0 mmol, tetrahydrofuran solution totaling 15 m.
1 was reacted under nitrogen at 0 ° C. for 24 hours. Polymer yield is about 60 mol%, styrene equivalent number average molecular weight (GPC)
Was about 8000.

To a 20% by weight solution of the above-mentioned copolymer of N- (vinylphenyl) maleimide and N-phenylmaleimide (molar ratio 2: 3), 4,4'-diene was added to 100 parts by weight of the polymer component. 10 parts by weight of azidochalcone (manufactured by Shinko Giken) was added.

This tetrahydrofuran solution was applied onto a glass plate and dried to form a film having a thickness of about 10 μm.

The above film was prepared by using a high pressure mercury lamp.
It was exposed to 00 mJ. The exposed film was immersed in tetrahydrofuran for 1 minute, but no change was observed in the film.

Thermal properties of similarly exposed polymers were investigated.
When a 5% weight loss temperature under nitrogen was observed at a temperature rising rate of 5 ° C./minute, decomposition occurred at about 400 ° C. Further, as a result of differential scanning calorimetry, exothermic heat due to the thermal crosslinking reaction was recognized at about 160 ° C (heating rate 10 ° C / min).

Comparative Example 1 N- (p-obtained in Example 1)
A 20 wt% tetrahydrofuran solution of only a copolymer obtained by anionic polymerization of vinylphenyl) maleimide and N-phenylmaleimide was applied on a glass plate and dried to form a film having a thickness of about 10 μm.

The above film was exposed in the same manner as in Example 1 and then immersed in tetrahydrofuran for 1 minute to completely dissolve it.

Similarly, the thermal properties of the exposed polymer were decomposed at about 420 ° C. when observed at a 5% weight loss temperature under nitrogen at a heating rate of 5 ° C./min. Further, as a result of differential scanning calorimetry, exothermic heat due to the thermal crosslinking reaction was recognized at about 160 ° C (heating rate 10 ° C / min).

Example 2 20% by weight of a copolymer of N- (vinylphenyl) maleimide and N-phenylmaleimide prepared in the same manner as in Example 1 (molar ratio 4: 1).
To the solution was added 10 parts by weight of 4,4'-diazidochalcone per 100 parts by weight of the polymer component.

A glass plate was used to form a film having a thickness of about 10 μm from the above solution in the same manner as in Example 1, and the film was exposed. This was immersed in tetrahydrofuran for 1 minute, but no change occurred in the film. Similarly, the temperature rise rate of exposed polymer is 5 ℃
When a 5% weight loss temperature under nitrogen was observed at 1 / min, it decomposed at about 400 ° C. Further, as a result of differential scanning calorimetry, an exotherm of about 170 ° C. due to the thermal crosslinking reaction was recognized (heating rate 10 ° C./min).

Example 3 With respect to the maleimide copolymer shown in Table 1, 4,4′-diazidochalcone was added in the same manner as in Example 1, and exposure and development were carried out. It was confirmed that all the copolymers in Table 1 were photocrosslinked.

[0061]

[Table 1]

Example 4 A glass cloth was impregnated with 2,2 ′-[bis (N-phenylmaleimide)] propane, which was then pressed and heated to prepare a substrate. This was treated with an HS10SB solution manufactured by Hitachi Chemical Co., Ltd. to deposit a plating catalyst on the surface. After drying, the photosensitive resin solution prepared in Example 2 was applied and dried to form a coating film having a film thickness of about 10 μm.
A simulated pattern having a line / space of 100 μm / 100 μm was exposed to this (exposure amount: 500 mJ), and then developed with dichloromethane to obtain a relief pattern.

The substrate on which the relief pattern is formed is 2
After heating at 00 ° C for 20 minutes, copper sulfate 0.04 mol / l, ethylenediaminetetraacetic acid 0.08 mol / l, formaldehyde 0.03 mol / l, 2,2-dipyridyl 30 mg
/ L, polyethylene glycol 10 g / l and sodium hydroxide were mixed to adjust the pH to 12.6, and copper was plated by a dipping method to form a wiring pattern (plating condition: 70 ° C., 3 hours).

The obtained simulated printed wiring board was set to 2,2'-
[Bis (N-phenylmaleimide)] Propane impregnated with propane is laminated and adhered through a prepreg.
A multilayer printed wiring board of layers was prepared.

The above-mentioned multilayer printed wiring board can be miniaturized by the full-additive method, has a flat surface, is excellent in insulating properties and heat resistance, and can have a low relative dielectric constant. It was

[0066]

The curable resin composition of the present invention has an unsaturated double bond such as a vinyl group in the side chain in the polymaleimide skeleton which is excellent in heat resistance, is excellent in solubility, and initiates photopolymerization. By adding an azide compound having a chalcone structure as an agent, a cured product having excellent photoreactivity and excellent heat resistance after curing is provided. Therefore, it is excellent as an insulating pattern of a printed wiring board.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a manufacturing process of a multilayer printed wiring board by a full additive method.

[Explanation of symbols]

1 ... Plating resist, 2 ... Substrate, 3 ... Wiring, 4 ... Adhesive layer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location G03F 7/027 514 H01L 23/29 23/31 H05K 1/03 D 7011-4E 3/46 T 6921 −4E (72) Inventor Yuichi Sado, 7-1, 1-1 Omika-cho, Hitachi, Hitachi, Ltd. Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor, Takao Miwa 7, 1-1, Omika-cho, Hitachi, Ibaraki Inside the Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Akio Takahashi 7-1-1 Omika-cho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Research Laboratory, Hitachi Ltd.

Claims (8)

[Claims] 1. A compound represented by the general formula (1): (However, in the formula, R ₁ is an organic residue having an aromatic ring and having 6 to 15 carbon atoms, R ₂ is hydrogen, a phenyl group, an alkoxyphenyl group, R ₃ , R ₄ , and R ₅ are hydrogen and have 9 or less carbon atoms. A copolymer 100 having a repeating unit represented by an alkyl group and at least two of R ₃ , R ₄ and R ₅ represent hydrogen.
A curable resin composition comprising 0.5 to 10 parts by weight of each of a photopolymerization initiator and / or a thermal polymerization initiator with respect to parts by weight. 2. A general formula (2): The curable resin composition according to claim 1, comprising a compound having a repeating unit represented by the formula (wherein R ₆ , R ₇ and R ₈ represent hydrogen and an organic residue having 1 to 20 carbon atoms). . 3. A compound represented by the general formula (3): (Wherein R ₈ represents a phenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a benzoic acid residue, a pyrrolidone residue), and the curable resin according to claim 1 containing a repeating unit. Composition. 4. A compound represented by the general formula (1): (However, in the formula, R ₁ is an organic residue having an aromatic ring and having 6 to 15 carbon atoms, R ₂ is hydrogen, a phenyl group, an alkoxyphenyl group, R ₃ , R ₄ , and R ₅ are hydrogen and have 9 or less carbon atoms. A copolymer 100 having a repeating unit represented by an alkyl group and at least two of R ₃ , R ₄ and R ₅ represent hydrogen.
A wiring circuit is formed on at least one side of a film made of a cured product of a resin composition containing 0.5 to 10 parts by weight of each of a photopolymerization initiator and / or a thermal polymerization initiator, relative to parts by weight. A multilayer printed wiring board, characterized in that films having wiring circuits are laminated and adhered. 5. The resin composition has the general formula (2): The multilayer printed wiring board according to claim 4, comprising a compound having a repeating unit represented by the formula (wherein R ₆ , R ₇ and R ₈ represent hydrogen and an organic residue having 1 to 20 carbon atoms). 6. The resin composition has the general formula (3): (Wherein R ₈ represents a phenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a benzoic acid residue, or a pyrrolidone residue). The multilayer printed wiring according to claim 4 containing a compound having a repeating unit. Board. 7. A film of a photocurable resin composition containing the general formula (1) and a photopolymerization initiator is formed on a substrate, exposed and developed to form a negative pattern of a circuit, and then the film is formed. A method for producing a multilayer printed wiring board, comprising: laminating and adhering a printed wiring board on which a wiring circuit is formed by plating on a circuit pattern portion where no wiring is formed, to form a multilayer. 8. A photocurable resin composition containing the general formula (1) and a photopolymerization initiator on a substrate made of a thermosetting resin composition containing the general formula (1) and a thermopolymerization initiator. After forming a coating, it is exposed and developed to form a negative pattern of the circuit, and then a printed wiring board having a wiring circuit formed by plating on the circuit pattern portion where the coating is not formed is laminated and adhered to form a multilayer. A method for manufacturing a multilayer printed wiring board, which is characterized in that