JP2000001553A - Prepreg for printed wiring board, laminate and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a prepreg that has excellent ultraviolet shielding properties and does not deteriorate other properties required for a laminate for a printed wiring board such as water resistance, heat resistance, solvent resistance and electrically insulating properties by constituting a matrix resin of a resin containing a partially crystallized glass with a specified crystallinity. SOLUTION: A prepreg for a printed wiring board is obtained by impregnating a matrix resin that contains 60-200 pts.wt., based on 100 pts.wt. of a resin including a curing agent, of a partially crystallized glass with a crystallinity of 5-20 wt.% in a glass base material. In the production of the prepreg for a printed wiring board, 5-40 wt.% of one or more of a calcium carbonate, a dolomite, a talc and a calcium silicate are added to and mixed with E-glass and thereafter calcined at a temperature of 700-1,050 deg.C to obtain a partially crystallized glass with a crystallinity of 5-20 wt.%. The partially crystallized glass is kneaded with a resin to form a matrix resin. The matrix resin is impregnated in a glass base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg and a laminate for a printed wiring board having an excellent ultraviolet shielding property, and to an improvement of a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in a solder resist forming step in a manufacturing process of a printed wiring board, a photoresist method has been adopted, and simultaneous exposure on both sides has been performed. However, during double-sided simultaneous exposure, there often occurs a problem of show-through in which the resist on the opposite side is exposed by the irradiated ultraviolet rays. For this reason, the laminated plate is required to have an ultraviolet shielding property. Various proposals have been made for laminates having ultraviolet shielding properties. These are roughly classified according to their main additives, and laminated laminates using a resin to which an organic ultraviolet absorber is added as a matrix resin (Japanese Unexamined Patent Publication No. Hei 5-160532). A matrix resin made of a resin to which an inorganic ultraviolet absorber such as titanium oxide is added, or a laminated plate (described in JP-A-4-104920) added to a glass substrate, and an inorganic filler such as clay or calcium carbonate. (Japanese Patent Laid-Open No. Sho 54-3)
No. 2769) and a laminate (described in JP-A-9-19776) using a resin in which the above additives are used in combination as a matrix resin.

[0003]

However, although the laminated board according to the prior art described above has improved ultraviolet shielding properties, it has other properties required for printed wiring board laminates such as water resistance, heat resistance and solvent resistance. In some cases, the properties such as properties and electrical insulation properties may be reduced. For example, in some cases, heating may cause a decrease in heat resistance and a decrease in solvent resistance, and the organic ultraviolet absorbent may be degraded by light to cause variations in ultraviolet shielding properties. In such a case, a clear resolution may not be obtained when a high-sensitivity solder resist is used. In such a case, the impregnating property of the resin into the glass substrate is reduced, and the heat resistance and the electrical insulation may be deteriorated. However, this is merely a combination of the above-mentioned prior arts, and does not sufficiently solve the above-mentioned disadvantages.

The present invention provides a printed wiring board which is excellent in ultraviolet shielding properties and does not deteriorate other characteristics required for a printed wiring board laminate, such as water resistance, heat resistance, solvent resistance, and electrical insulation. It is an object of the present invention to obtain a prepreg for use, a laminate, and a method for producing these.

[0005]

According to the present invention, in order to achieve the above object, according to the first aspect of the present invention, the degree of crystallinity is 5 to 5.
The problem was solved by a laminate for printed wiring boards using a resin containing 20% by weight of partially crystallized glass as a matrix resin.
According to the second aspect of the present invention, the glass substrate is impregnated with a matrix resin containing 60 to 200 parts by weight of partially crystallized glass having a crystallinity of 5 to 20% by weight based on 100 parts by weight of the resin containing the hardener. The problem was solved by the prepreg for printed wiring boards. In the invention according to claim 3, after adding and mixing any one or more of calcium carbonate, dolomite, talc and calcium silicate to E glass in an amount of 5 to 40% by weight, the mixture is fired at 700 to 1050 ° C. To obtain a partially crystallized glass having a degree of crystallinity of 5 to 20% by weight, kneading the partially crystallized glass with a resin to form a matrix resin, and impregnating the glass substrate with the matrix resin to produce a prepreg for a printed wiring board. Solved by the method. According to a fourth aspect of the present invention, there is provided a method for manufacturing a laminate for a printed wiring board, wherein at least one prepreg obtained by the method for manufacturing a prepreg for a printed wiring board according to the third aspect is laminated and formed by a conventional method. Solved by the method.

BEST MODE FOR CARRYING OUT THE INVENTION

The E glass used in the present invention is an alkali-free glass belonging to alumina borosilicate glass, and its main composition is, for example, SiO ₂ ; 52 to 56% by weight, Al ₂ O ₃ ;
-16% by weight, CaO; 16-25% by weight, MgO: 0
６6% by weight, B ₂ O ₃ ; 5-10% by weight, R ₂ O (R is Na and K); 0-3% by weight. As the form of E glass, glass bulk, glass powder, glass fiber and the like can be used without particular limitation. As the resin used in the present invention, a thermosetting resin such as a phenol resin, an epoxy resin, an unsaturated polyester resin, a polyimide resin, a polyphenylene oxide resin, a polyphenylene ether resin, and a fluororesin can be used. Is appropriately selected according to the characteristics required for the prepreg and the laminate.

In order to obtain the partially crystallized glass used in the present invention, first, one or more of calcium carbonate, dolomite, talc and calcium silicate (hereinafter, these are abbreviated as crystallization accelerators) are added to E glass. Is added, but E glass and a crystallization accelerator are previously added to an average particle diameter of 200.
It is desirable to pulverize to a size of μm or less. In order to promote crystallization, the amount of the crystallization accelerator added is 5 to E glass.
40% by weight. When the addition amount is less than 5% by weight, the number of crystal nuclei is small and crystallization does not proceed, and the addition amount is 40% by weight.
If it exceeds 3, unreacted portions where the added and mixed crystallization accelerator does not contribute to crystallization may remain, the adhesive strength between the partially crystallized glass and the resin is reduced, and the water resistance and heat resistance are deteriorated.

Next, in order to obtain a partially crystallized glass, E
After adding and mixing a crystallization accelerator to glass, 700 to 10
The firing is performed at 50 ° C, preferably 900 to 1000 ° C.
If the firing temperature is lower than 700 ° C., crystallization of E glass does not proceed, and if it exceeds 1050 ° C., the crystallized portion of E glass may be vitrified. The firing time for obtaining the partially crystallized glass is preferably 30 to 120 minutes. If the time is less than 30 minutes, an unreacted portion in which the crystallization accelerator added to the E glass does not contribute to crystallization may remain, and if the time exceeds 120 minutes, a loss occurs and the production efficiency is poor. The crystallinity of the E glass thus obtained is controlled by a combination of the amount of the crystallization accelerator added, the firing temperature and the firing time, to obtain a partially crystallized glass of 5 to 20% by weight. The higher the crystallinity, the higher the UV-shielding properties, but 5%
If it is less than 30, the obtained laminated board for a printed wiring board will not exhibit an ultraviolet shielding effect, and it may be difficult to produce partially crystallized glass having a crystallinity of more than 20%.

Further, the obtained partially crystallized glass is kneaded with a resin and uniformly dispersed to obtain a matrix resin. It is desirable that the partially crystallized glass is previously ground to an average particle size of 20 μm or less. Further, in order to strengthen the adhesive force between the partially crystallized glass and the resin, the partially crystallized glass is kneaded with the resin before kneading the partially crystallized glass with γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-
Aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane , Vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl (3-trimethoxysilyl) propylammonium chloride, γ-chloropropyl Known silane coupling agents such as methyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane It is preferable to perform a surface treatment with a brushing agent to obtain a glass filler. In the present invention, the type of the silane coupling agent is not particularly limited. When the partially crystallized glass is kneaded with the resin to form a matrix resin, the glass filler is preferably 60 to 200 parts by weight based on 100 parts by weight of the resin varnish containing a curing agent. 60
If the amount is less than 100 parts by weight, the effect of shielding ultraviolet rays is not obtained. If the amount is more than 200 parts by weight, the viscosity of the matrix resin increases, and the impregnation of the glass substrate with the resin decreases.

Finally, the partially crystallized glass is dispersed and a resin varnish is impregnated into a glass substrate and dried to obtain a prepreg for a printed wiring board. Further, at least one of the obtained prepregs is laminated and molded by a conventional method such as pressure molding to obtain a desired laminate for a printed wiring board. Here, there is no limitation on the number of prepregs to be used. As a glass substrate, a woven fabric containing at least glass fiber,
One or more of nonwoven fabric and paper are used.

[0011]

EXAMPLES Glass composition SiO ₂ : 55% by weight, Al ₂ O ₃ : 14% by weight, Ca
O; 22% by weight, B ₂ O ₃ ; 7% by weight, Na ₂ O and K
₂ O: E glass bulk having a composition of 0.5% by weight as a main component was used. A glass woven fabric having a thickness of 0.18 mm and a unit weight of 209 g / m ² is used as a glass substrate, and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane hydrochloride is used as a silane coupling agent. (Toray Dow Corning Silicon SZ603
It was prepared by dipping in 2). Preparation of Resin Varnish 100 parts by weight of a brominated epoxy resin (Araldite N80 manufactured by Asahi Ciba), 12 parts by weight of a phenol novolak type epoxy resin (Epicoat 154 manufactured by Yuka Shell Epoxy), and 2-ethyl-4-methylimidazole were used. 0.2 parts by weight and 20 parts by weight of 2-methoxyethanol were prepared to obtain an epoxy resin varnish.

Example 1 E glass bulk was prepared with an average particle size of 2
After pulverizing to a size of not more than 00 μm, 15% by weight of calcium carbonate was added to E glass and mixed. This was baked at 950 ° C. for 60 minutes to partially crystallize E glass. After cooling, the partially crystallized E glass was pulverized to an average particle size of 20 μm, and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane hydrochloride (Toray Dow) was used as a silane coupling agent. Corning Silicon SZ6
032) to obtain a glass filler. After 120 parts by weight of the obtained glass filler is kneaded with the epoxy resin varnish described above to obtain an epoxy resin composition, the epoxy resin composition is added to a glass woven fabric so that the resin composition becomes 43% by weight. To obtain a prepreg. The obtained eight prepregs were sandwiched between copper foils having a thickness of 18 μm and press-molded at 170 ° C. for 90 minutes under a condition of 3 MPa to prepare a copper-clad laminate having a thickness of 1.6 mm. The copper foil of the produced copper-clad laminate was removed by etching to obtain Example 1. Example 2 Example 2 was carried out in the same manner as in Example 1 except that 20% by weight of calcium carbonate was added to and mixed with E glass.
It was created. Example 3 Example 3 was performed in the same manner as in Example 1, except that 30% by weight of calcium carbonate was added to and mixed with E glass.
It was created. Example 4 The bulk of E glass was pulverized to an average particle size of 200 μm or less, and then dolomite was added to E glass at 30% by weight and mixed. Hereinafter, Example 4 was created in the same manner as in Example 1.

Comparative Example 1 A prepreg was obtained by impregnating and drying a resin varnish described above in a glass woven fabric so that the resin composition was 43% by weight. Thereafter, press molding was performed under the same conditions as in Example 1 to prepare a 1.6 mm-thick copper-clad laminate, and the copper foil of the copper-clad laminate was removed by etching to obtain Comparative Example 1. [Comparative Example 2] E glass bulk was pulverized to an average particle diameter of 200 µm or less, and calcium carbonate was added to and mixed with 20% by weight of E glass, and the mixture was pulverized to an average particle diameter of 20 µm or less. A surface treatment was carried out with a silane coupling agent, and a mixture of E-glass and calcium carbonate subjected to the surface treatment was used as a glass filler, and Comparative Example 2 was prepared in the same manner as in Example 1 below.

With respect to each of the above Examples and Comparative Examples, the crystallinity, ultraviolet shielding property and water resistance of the partially crystallized glass were measured by the following methods. Measurement of crystallinity; measured by X-ray diffraction method. Measurement of ultraviolet shielding properties; spectrophotometer (Hitachi Ltd. 22
(0-A type) was used to measure the transmittance at wavelengths of 350 nm and 420 nm, which was used as a measure of ultraviolet shielding properties. Measurement of water resistance; First, the insulation resistance under normal conditions was measured,
Each example was placed in a pressure cooker and subjected to a moisture absorption treatment under the conditions of 121 ° C. and 2 atm. The insulation conformed to the measurement method of JIS C6481. Table 1 shows the measurement results of each example.

[0015]

[Table 1]

As is clear from the above Examples and Comparative Examples, the Example of the present invention has a significantly smaller ultraviolet transmittance than Comparative Example 1 containing no partially crystallized glass, and has an insulation resistance, ie, water resistance. The decline is almost the same. On the other hand, as compared with Comparative Example 2 in which an epoxy resin containing a mixture of E glass and calcium carbonate is used as the matrix resin, the ultraviolet transmittance is almost the same, but the insulation resistance, that is, the decrease in water resistance is small. This is because the crystalline components of partially crystallized glass are wollastonite, anorthite, etc., and both wollastonite and anorthite have no problem in water resistance, heat resistance, solvent resistance, and electrical insulation. As the glass filler is used as a glass filler, a resin composition is obtained by kneading with a matrix resin, and the resin composition is used as a matrix resin to mold a laminate by a conventional method, so that the obtained laminate has an ultraviolet shielding property, and It is thought to be effective in maintaining water resistance, heat resistance, solvent resistance, and electrical insulation. Further, when firing E glass as an additional configuration, a transition metal such as cobalt or iron is added to the partially crystallized glass in an amount of 0.1 to 2.0.
The present invention also relates to a prepreg for a printed wiring board, a laminated board, and a method for producing these, which are obtained by adding an organic ultraviolet absorber and / or titanium oxide when kneading a partially crystallized glass with a resin, or by kneading the partially crystallized glass with a resin. Included in the scope.

[0017]

According to the present invention, since the matrix resin is a resin in which partially crystallized glass is used as a glass filler, the obtained prepregs and laminates have excellent ultraviolet shielding properties, and are resistant to water, heat, and solvents. An excellent prepreg for a printed wiring board, a laminated board, and a method for producing the same, which are not present in the prior art and have little decrease in electrical insulation.

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Claims (4)

[Claims] 1. A laminate for a printed wiring board, wherein a resin containing partially crystallized glass having a crystallinity of 5 to 20% by weight is used as a matrix resin. 2. A partially crystallized glass having a degree of crystallinity of 5 to 20% by weight based on 100 parts by weight of a resin containing a curing agent.
A prepreg for a printed wiring board, wherein a glass substrate is impregnated with a matrix resin containing 0 parts by weight. 3. E-glass is mixed with one or more of calcium carbonate, dolomite, talc and calcium silicate in an amount of 5 to 40% by weight, and then mixed.
A partially crystallized glass having a crystallinity of 5 to 20% by weight is obtained by firing at 0 ° C., and the partially crystallized glass is kneaded with a resin to form a matrix resin, and the matrix resin is impregnated into a glass substrate. A method for producing a prepreg for a printed wiring board. 4. A method for producing a laminate for a printed wiring board, wherein at least one prepreg obtained by the method for producing a prepreg for a printed wiring board according to claim 3 is laminated and molded by an ordinary method. Method.