JPH11147996A - Resin composition for laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the UV-intercepting capability of a laminate resin compsn. based on a PPE resin and an epoxy reisn, to prepare a laminate improved in UV-intercepting capability by using the compsn., and to provide a process for producing a printed circuit board whereby the UV-intercepting capabilty of an insulating layer is enhanced and a solder resist can be formed efficiently without causing defects. SOLUTION: This compsn. contains a polyphenylene ether resin, a difunctional epoxy resin, an amine-base curative, and a cure catalyst and further contains at least one compd. selected from among a benzophenone compd., a salicylate compd., and a cyanoacrylate compd. Insulating layers of a printed circuit board having circuits on both sides are formed from laminates prepd. from the compsn. A solder resist is applied to the front and back sides of the printed circuit board, and both the sides are exposed to UV simultaneously.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a laminate and a laminate using the same, and more particularly to a method for producing a printed wiring board using the resin composition for a laminate.

[0002]

2. Description of the Related Art In recent years, electronic devices including semiconductor components such as ICs and LSIs have been highly integrated, and electronic devices have been reduced in size and multifunctional. As a result, printed wiring boards on which such electronic components have been mounted have become increasingly expensive. There is a tendency to increase the density and increase the number of layers. Conventionally, various resin-based resin laminates have been used as an insulating substrate that constitutes an insulating layer of such a printed wiring board. Among them, polyphenylene ether (hereinafter, referred to as a resin laminate having excellent electrical characteristics) has been used. , Abbreviated as PPE)
There is known a resin composition using a resin composition of a compound of a kind and an epoxy resin as a resin material.

[0003]

On the other hand, in a printed wiring board having a high-density circuit pattern, since a dense circuit pattern is apt to cause a defect such as a solder short when mounting an electronic component or the like, To prevent this, a protection mask made of a solder resist is formed on the surface of the substrate on which the circuit is formed. The formation of the protective mask using this solder resist is performed by coating the surface of the circuit-formed substrate with solder resist,
UV from above so that only the necessary parts of the mask remain
Usually, the exposure is performed by removing unnecessary portions of the resist. In general, performing the step of applying the solder resist leads to an increase in the manufacturing cost of the printed wiring board. Therefore, it is desired to increase the efficiency of the process and suppress the increase in the cost. For example, in the case of a printed wiring board having a circuit pattern on both the front and back surfaces of the substrate, it is possible to improve production efficiency by applying a solder resist to both the front and back surfaces of the substrate and simultaneously performing UV exposure from both sides, but at this time, from one side Due to the fact that the irradiated UV penetrates the substrate and reaches the opposite surface, a problem arises in that a portion of the resist applied thereto that is not required to be exposed is exposed by the transmitted UV. Met. Therefore, the substrate constituting the insulating layer of the printed wiring board is required to have a property of not transmitting UV light (UV blocking property).

The present invention has been made in view of the above circumstances, and a first object of the present invention is to improve the UV blocking property of a laminate resin composition comprising a PPE compound and an epoxy resin. It is a second object of the present invention to provide a laminate having improved UV blocking properties by using the laminate resin composition. It is a third object of the present invention to provide a method of manufacturing a printed wiring board that can efficiently form a solder resist on both front and back surfaces without any problems by improving the UV blocking property of an insulating layer.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have studied the addition of a substance that imparts UV blocking properties to a resin composition of a compounding system of a PPE and an epoxy resin. By the way, a technique of adding an inorganic filler to impart UV impermeability to a resin composition is conventionally known, but in this case, it adversely affects the handling and moldability of a resin varnish when producing a laminate. In some cases, this may adversely affect the electrical properties of the insulating layer of the laminate, the drilling property, and the like. On the other hand, the present inventors blended at least one of a benzophenone-based compound, a salicylate-based compound, and a cyanoacrylate-based compound to form a PPE.
It has been found that UV impermeability can be imparted to the resin composition of the compound type of epoxy resin and epoxy resin without giving the above-mentioned adverse effects, and the present invention has been accomplished.

That is, the present invention comprises PPEs, bifunctional epoxy resin, amine curing agent, and curing catalyst,
Further, there is provided a resin composition for a laminate comprising at least one of a benzophenone-based compound, a salicylate-based compound and a cyanoacrylate-based compound. The resin composition for a laminate according to the present invention is provided with good UV blocking properties due to the UV absorption effect of any one of the benzophenone-based compounds, salicylate-based compounds, and cyanoacrylate-based compounds. And, at this time, since the benzophenone-based compound, salicylate-based compound, and cyanoacrylate-based compound are all organic components, there is little fear of adversely affecting the properties of the resin composition as in the case of using an inorganic filler. It becomes.

Therefore, a laminate prepared using the above resin composition for a laminate has good UV blocking properties, and the laminate is used as an insulating layer to form a printed wiring having a circuit pattern on the front and back surfaces. The board can be efficiently and satisfactorily formed on the front and back surfaces by manufacturing the board by the manufacturing method described below. That is, after forming a circuit pattern on both sides of a double-sided copper-clad laminate having the above-mentioned laminate as an insulating layer, coating both sides of the resulting double-sided circuit board with a solder resist, and simultaneously performing UV exposure from both sides. Then, a protection mask made of a solder resist is formed on both the front and back surfaces of the printed wiring board. In a printed wiring board manufactured in this way, since a protective mask using a solder resist can be simultaneously formed on both front and back surfaces, production efficiency is improved. Does not transmit the UV light, so that the problem that the resist at the portion that does not need to be exposed is exposed by the transmitted UV light is also prevented.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

First, each essential component of the resin composition for a laminate according to the present invention will be described. The PPE used in the resin composition for a laminate is not limited to a specific compound as long as it has a so-called polyphenylene ether chain in the skeleton, and the type and arrangement of the substituents bonded to the phenylene group And modified products obtained by modifying a terminal hydroxyl group with an epoxy group, an amino group, or the like. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is an example of a commercially available product.

As the bifunctional epoxy resin used in the resin composition for a laminate of the present invention, various ones can be selected within the scope of the technical idea of the present invention. In the examples, a bisphenol A type epoxy resin is used.
Epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, and the like.

The amine-based curing agent used in the resin composition for a laminated board of the present invention is preferably a bifunctional or more amine-based compound, and is known as a curing agent for epoxy resins such as diaminodimethylmethane. Can be used. Incidentally, in Examples described later, an amine compound represented by the following (Formula 6) is used.

[0012]

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As the curing catalyst used in the resin composition for a laminate of the present invention, those known as curing catalysts for accelerating the reaction between an epoxy resin and an amine-based curing agent can be used. Salts, imidazoles, tertiary amines and the like can be mentioned.

In the resin composition for a laminate according to the present invention,
It contains at least one selected from a benzophenone-based compound, a salicylate-based compound, and a cyanoacrylate-based compound. These are used as UV absorbers to impart UV blocking properties to a cured product of the resin composition for a laminate.

The benzophenone-based compound includes, for example, compounds having the structural formulas represented by the following chemical formulas (7) and (8). The materials are not particularly limited as long as they do not significantly deteriorate the performance such as moldability and moldability.

[0016]

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[0017]

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The salicylate compound includes
For example, compounds of the structural formula shown in the following (Chemical formula 9) may be mentioned, and particularly those compounds which impart UV blocking properties to the resin composition and which do not significantly deteriorate the properties such as electrical properties and moldability of the resin composition. It is not limited to those examples.

[0019]

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Examples of the cyanoacrylate compound include compounds having the structural formulas shown in the following chemical formulas (Chemical Formula 10) and (Chemical Formula 11). The materials are not particularly limited as long as they do not significantly degrade the performance such as electrical characteristics and moldability.

[0021]

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[0022]

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In blending the above components,
Usually, it is performed by dissolving in an appropriate solvent to form a resin varnish. The solvent is not particularly limited as long as it can dissolve the above-mentioned components.
It is preferable to select one that can dissolve PEs favorably. Examples thereof include chlorinated organic solvents such as trichlene, methylene chloride, and chloroform; and aromatic hydrocarbon solvents such as toluene, benzene, and xylene.

In the present invention, a method for obtaining a laminate using the above-mentioned resin composition for a laminate is usually performed by using the resin composition for a laminate as a resin varnish as described above, and using the same as a base such as glass cloth. A method is used in which a material is impregnated and dried to produce a prepreg, a plurality of the prepregs are laminated, and heated and pressed by pressing or the like. The laminate thus obtained can be made into a copper-clad laminate by laminating copper foil together at the time of molding, and a circuit is formed by forming a resist pattern on the copper foil and etching it. It can be formed into a printed wiring board.

In the present invention, a good solder resist protective mask can be formed on both front and back surfaces of a printed wiring board having a circuit pattern on both front and back surfaces by the following method using the resin composition for a laminate. . That is, a double-sided copper-clad laminate is prepared using the resin composition for a laminate by the method described above, and a circuit is formed on both sides of the double-sided copper-clad laminate. After coating with a solder resist, both sides are simultaneously exposed to UV light to form a desired solder resist protection mask on each of the front and back surfaces. At this time, since the protective mask of the solder resist can be simultaneously formed on both the front and back surfaces, the production efficiency is improved. Further, the insulating layer of the printed wiring board is formed by the action of the above-mentioned tetrafunctional epoxy compound blended as a component of the resin composition.
Since it has V opacity, UV light emitted from one side does not transmit to the other side, so that a problem that a portion not requiring exposure is exposed by the transmitted UV light is also prevented.

[0026]

EXAMPLES As shown below, while the resin compositions for laminates of the present invention were specifically prepared as Examples 1 to 5,
A resin composition for comparison with these was prepared as Comparative Example 1, and a laminate for evaluation was prepared using the resin composition.
The effect of the present invention was confirmed by evaluating the V light blocking performance (UV transmittance).

Preparation of Base Resin First, the base resin compositions of Examples 1 to 5 and Comparative Example 1 were prepared. That is, bisphenol A
Type epoxy resin (Dow Chemical Co., Ltd., product name: D
450 g of ER542T30), 90 g of poly (2,6-dimethyl-1,4-phenylene ether) (manufactured by Nippon GE Plastics Co., Ltd.), and an amine-based curing agent (oilification) having the structural formula shown in the above Chemical Formula 4. 3 g of Shell Co., Ltd., product name: Etacure), and zinc octanoate as a curing catalyst was 14 g.
g and 1 g of 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) were respectively mixed in a toluene solvent, and this was used as a varnish of the base resin composition.

Example 1 1.2 g of 2,4-dihydroxybenzophenone (manufactured by Cipro Kasei Co., Ltd.) shown in the above (Chemical formula 7) was further added to the above-mentioned base resin composition. A varnish of the resin composition was used.

Example 2 1.2 g of 2,2-dihydroxy-4,4-dimethoxybenzophenone (manufactured by Chemipro Kasei Co., Ltd.) shown in the above (Chemical formula 8) was further added to the above-mentioned base resin composition.
This was used as a varnish of the resin composition of Example 2.

Example 3 1.2 g of 4-t-butylphenyl salicylate (manufactured by Cypro Kasei Co., Ltd.) shown in the above (Chemical Formula 9) was further added to the formulation of the base resin composition. Of the resin composition of Example 1.

Example 4 1.2 g of ethyl (β, β-diphenyl) cyanoacrylate (manufactured by Cypro Kasei Co., Ltd.) shown in the above (Chemical Formula 10) was further added to the above-mentioned base resin composition, and this was added. A varnish of the resin composition of Example 4 was used.

Example 5 1.2 g of 2-ethylhexyl (β, β-diphenyl) cyanoacrylate shown in the above (Chemical Formula 11) was further added to the formulation of the base resin composition, and this was added to the resin composition of Example 5. Varnish.

Comparative Example 1 The varnish of the above-mentioned base resin composition was directly used as the varnish of the resin composition of Comparative Example 1.

Evaluation of UV Light Blocking Performance (UV Transmittance) First, a sample substrate (laminate) for performance evaluation was prepared as follows. That is, for each of Examples 1 to 5 and Comparative Example 1, a varnish of the resin composition was impregnated in a glass cloth and dried to prepare a prepreg. Further, two prepregs were stacked and heated at 200 ° C. for 2 hours. Press molding was performed to obtain a sample substrate having a thickness of 0.2 mm. This sample substrate was irradiated with UV light from one side, and the transmittance of UV light transmitted through the other side was measured. The results are shown in Table 1.

[0035]

[Table 1]

As can be seen from the results in Table 1, the substrates of Examples 1 to 3 containing a benzophenone-based compound, a salicylate-based compound or a cyanoacrylate-based compound as a UV absorber, respectively, were not used in Comparative Examples 1 to 3. UV transmittance is reduced to about 1/3 to 1/5 as compared with the substrate, and the UV blocking performance is greatly improved.

[0037]

As described above, the resin composition for a laminate of the present invention can provide a laminate having good UV impermeability (UV blocking property). Therefore, when producing a printed wiring board having a circuit on both front and back surfaces, by forming the insulating layer using the resin composition for a laminate of the present invention, the front and back surfaces can be efficiently and favorably formed by the following method. It is possible to form a suitable solder resist. That is, a circuit is formed on both sides of a double-sided copper-clad laminate having the above-mentioned laminate as an insulating layer, and both sides of the resulting double-sided circuit board are coated with a solder resist, and then simultaneously subjected to UV exposure from both sides for printing. A protective mask made of solder resist is formed on both the front and back surfaces of the wiring board. In a printed wiring board manufactured in this way, since a protective mask using a solder resist can be simultaneously formed on both front and back surfaces, production efficiency is improved. Does not transmit the UV light, so that the problem that the resist at the portion that does not need to be exposed is exposed by the transmitted UV light is also prevented.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // H05K 1/03 610 H05K 1/03 610H (C08K 5/00 5:17 5:13) (C08K 5/00 5:17) 5: 134) (C08K 5/00 5:17 5: 315)

Claims (6)

[Claims] 1. A composition comprising a polyphenylene ether, a bifunctional epoxy resin, an amine-based curing agent, and a curing catalyst, and further comprising at least one selected from a benzophenone-based compound, a salicylate-based compound, and a cyanoacrylate-based compound. A resin composition for a laminated board characterized by the following. 2. The resin composition for a laminate according to claim 1, wherein the benzophenone-based compound is a compound represented by the following chemical formula (1) or (2). Embedded image Embedded image 3. The resin composition for a laminated board according to claim 1, wherein the salicylate compound is a compound having a structural formula represented by the following chemical formula (3). Embedded image 4. The resin composition for a laminate according to claim 1, wherein the cyanoacrylate compound is a compound having a structural formula represented by the following chemical formula (4) or (5). Stuff. Embedded image Embedded image 5. A laminate prepared using the resin composition for a laminate according to any one of claims 1 to 3. 6. A circuit is formed on both sides of a double-sided copper-clad laminate prepared using the resin composition for a laminate according to any one of claims 1 to 3, and both sides of a double-sided circuit board thus obtained are solder-resisted. A method for producing a printed wiring board, comprising: simultaneously performing UV exposure from both sides after coating.