JP3358306B2 - Laminated board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg used as a material for printed circuit boards and the like, and a laminate.

[0002]

2. Description of the Related Art A plain woven glass cloth is used as a base material, and this glass cloth is impregnated and dried with a varnish containing a curable resin such as an epoxy resin, an imide resin, a phenol resin, a polyphenylene oxide resin (PPO resin), and a fluorine resin. The prepreg in which the semi-cured curable resin is held by the glass cloth is useful as a material for a laminated board to be processed into a printed circuit board. These printed circuit boards used for high-speed information processing and high-speed communication devices in recent years are required to have low dielectric constant and low dielectric loss tangent electrical characteristics. Such electrical characteristics depend on the amount of semi-cured curable resin held by the glass cloth.
That is, when the amount of the curable resin held by the glass cloth is large, the dielectric constant and the dielectric loss tangent of the laminate decrease,
It is suitable for high-speed processing and high-speed communication equipment. Therefore,
For a laminate having low dielectric constant and low dielectric loss tangent electrical characteristics, a prepreg having a large amount of curable resin held by a glass cloth is required.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a prepreg having a large amount of curable resin held by a glass cloth and a laminate having a low dielectric constant and a low dielectric loss tangent. The purpose is to:

[0004]

Means for Solving the Problems Claims1Pertain toLaminated board
Brushes the monofilaments that make up the yarn
Glass cloth with a thickness change rate of 10% or more after the treatment
And semi-cured curable resin held by this glass cloth
The prepreg made of oil and fat is used as the pressure object, and this pressure object is heated.
PressedThe curable resin contains inorganic filler dispersed
Is an epoxy resin having a heat resistance of 265
Pass the temperature of ℃Characterized by the claims2In charge of
ToLaminated boardCut the monofilament making up the yarn
The rate of change in thickness after applying a brushing treatment is 10% or more.
Lath cloth and this semi-cured glass cloth
Of prepreg composed of curable resinNo curable resin
Epoxy resin with machine filler dispersed.
Preg'sAbove and below, the monofilaments that make up the yarn
Continuous glass cloth and held by this glass cloth
Also, prepreg composed of semi-cured curable resin
Pressurized object is heated and pressurized.The heat resistance of this one
Pass the 265 ° C standardIt is characterized by the following.

[0005]

The prepreg has a thickness change rate of 10% after a raising treatment for cutting the monofilament constituting the yarn.
% Of the glass cloth and the semi-cured curable resin held by the glass cloth, and the raising of the glass cloth increases the retention of the semi-cured curable resin.
This prepreg provides a laminate having a low dielectric constant, a low dielectric loss tangent, and a high frequency suitability.

[0006] The prepreg is formed by dispersing an inorganic filler in the curable resin, and can prevent a decrease in heat resistance due to an increase in the amount of the curable resin held by the raised glass cloth.

[0007] laminate according to claim 1, the thickness change ratio after subjected to napping treatment to cleave monofilaments constituting the yarns are held in this glass cloth with 10% or more of glass cloth, curing the semi-cured A prepreg made of a conductive resin is used as a pressure-receiving body, and the pressure-receiving body is a laminated plate which is hot-pressed.

[0008] The laminate according to the second aspect is a glass cloth having a thickness change rate of 10% or more after being subjected to a raising treatment for cutting a monofilament constituting a yarn, and a semi-cured cured material held by the glass cloth. Above and below a prepreg composed of a conductive resin, monofilaments constituting the yarn were held by a continuous glass cloth and this glass cloth,
A prepreg made of a semi-cured curable resin is overlaid to form a pressurized body, and the pressurized body is heated and pressed, and the monofilaments constituting the yarn are held by a continuous glass cloth and the glass cloth. By using the prepreg composed of the above-mentioned curable resin arranged vertically, it is possible to avoid a decrease in surface smoothness due to the raised prepreg.

The details will be described below. In the prepreg of the present invention, a glass cloth is used as a base material for holding a semi-cured curable resin that gives a resin solid content constituting a laminate. As the curable resin, an epoxy resin, an imide resin, a phenol resin, a PPO resin, a fluorine resin, or the like is used. Epoxy resin is most suitable for versatility, and fluorine resin and PPO resin are suitable for improving high-frequency characteristics requiring low dielectric constant and low dielectric loss tangent.

The glass cloth used in the present invention is a glass cloth obtained by cutting a monofilament constituting a yarn and raising the end of the monofilament.
It is limited to a glass cloth having a thickness change rate of 10% or more after a monofilament constituting a yarn is cut and subjected to a raising treatment. For this glass cloth, for example, a plain weave in which warp yarns and weft yarns alternately float and sink can be used, but the present invention is not limited to the plain weave.
Each of the warp yarn and the weft yarn is constituted by a single yarn or a twin yarn obtained by bundling a large number of glass monofilaments, and a part of the monofilament is cut, and the end of the yarn constitutes a glass cloth which is fluffed and raised. The brushed glass cloth of this type has a continuous monofilament constituting the yarn, for example, a thickness of 10 μm to several hundred μm.
The monofilament is cut by spraying a high-pressure water stream onto the glass cloth original cloth, and the tip thereof is obtained by fuzzing on the glass cloth original cloth. Alternatively, it can also be obtained by spraying high-pressure air onto the glass cloth original cloth instead of the high-pressure water flow. Alternatively, it can be obtained by rubbing or rubbing the original cloth of glass cloth. Furthermore, a glass cloth made by weaving a yarn with a monofilament raised may be used, and there is no restriction on the method of construction as long as a part of the monofilament is cut and its tip is a fluffed and raised glass cloth. However, as the number of cut monofilaments increases and the level of nap increases, the retention of the curable resin increases, and as a result, the laminate has a reduced dielectric constant and dielectric loss tangent, but the mechanical strength of the glass cloth is reduced. The diameter of the monofilament is preferably 5 μm or more in consideration of the tension applied when dipping in a varnish of a curable resin via a roll.

Further, when the holding ratio of the curable resin of the glass cloth increases, the ratio of the cured product of the curable resin constituting the laminated plate increases, so that the heat resistance of the laminated plate tends to decrease. In order to avoid a decrease in the heat resistance of the laminate, a prepreg in which an inorganic filler is dispersed in a semi-cured curable resin held by a glass cloth is effective. As the inorganic filler, for example, aluminum hydroxide, silica, talc,
E glass powder, titanium oxide, magnesium hydroxide and the like are useful. The mixing ratio of the curable resin and the inorganic filler is not particularly limited, and has an appropriate range depending on the type of the inorganic filler used. Generally, if the inorganic filler is excessively mixed, the amount of the curable resin contributing to the adhesion decreases,
If the amount is too small, the heat resistance will not be improved. Further, the smaller the particle size of the inorganic filler, the higher the heat resistance, but the more difficult it is to mix uniformly with the curable resin.

[0012] In addition, the prepreg using the glass cloth thus brushed has a laminar tip at the cut monofilament, compared with the prepreg using the glass cloth in which the monofilament constituting the yarn is continuous. When processed into a board, the smoothness of the surface of the laminate is reduced, and as a result, the smoothness of the circuit pattern on the surface of the laminate is lost. In order to obtain a laminate having a low dielectric constant and a low dielectric loss tangent, and having a high smoothness, for example, a monofilament constituting a yarn is cut and subjected to a raising treatment to have a thickness change rate of 10% or more. Above and below a prepreg composed of a glass cloth and a semi-cured curable resin held by the glass cloth, a glass cloth having a continuous monofilament constituting the yarn and a semi-cured curable resin held by the glass cloth By pressing a prepreg consisting of
Alternatively, the problem can be considerably solved by adopting a prepreg using a glass cloth having a high yarn driving density among brushed glass cloths.

By using the glass cloth raised as described above, the thickness of the obtained prepreg is large, so that a laminated plate having the same thickness can be obtained with a smaller number of sheets compared with the conventional prepreg. In addition, it is possible to obtain effects such as a reduction in the number of man-hours during manufacturing.

Examples and comparative examples will be described below.

[0015]

EXAMPLES ( Reference Example 1) A MIL spec. # 7628 (single-thread plain woven glass cloth in which 9 μm monofilaments are bundled 42 × 32 in length and width) is used as a base cloth, and a high-pressure water stream is sprayed on the base cloth to obtain a monofilament. Was cut and subjected to a raising treatment to obtain a glass cloth having a thickness change rate of 30% after the raising treatment. This glass cloth was impregnated with the following epoxy resin varnish containing dicyandiamide as a curing agent and then dried to obtain a prepreg in which the epoxy resin was semi-cured. The amount of the epoxy resin retained on the glass cloth constituting the prepreg was 55% by weight (hereinafter abbreviated as%). This prepreg is 4
Copper foil (Furukawa Circuit Foil, 1
8 μm) and heat and pressure (conditions: 30 kg / cm ² −
170 ° C. for 60 minutes) to obtain a 1.6 mm double-sided copper-clad laminate.

Composition of epoxy resin varnish (parts are parts by weight) Epoxy resin (Epicoat (trademark) 1001 manufactured by Shell Chemical Co., Ltd.) 100 parts Dicyandiamide 4 parts Benzylmethylformamide 0.2 parts Methylcellosolve 100 parts ( Reference Example 2) ) A MIL spec. # 7628 was used as a base cloth, and the monofilament was cut by mechanically squeezing the base cloth to obtain a glass cloth whose tip was brushed on the base cloth. The thickness change rate of this glass cloth after the raising treatment was 20%. This glass cloth was impregnated with the epoxy resin varnish of Reference Example 1 and then dried to obtain a prepreg in which the epoxy resin was semi-cured. The amount of epoxy resin retained on the glass cloth constituting the prepreg was 55%. Four prepregs were stacked, the same copper foil as that of Reference Example 1 was placed on both sides thereof, and heated and pressed (conditions: 30 kg / cm ² -170 ° C.-60 minutes) to obtain a 1.6 mm-thick laminated plate. Obtained.

[0017] (Reference Example 3) the MIL spec ♯7628 the original cloth, a reference to the original cloth Example 1
The monofilament was cut by injecting a high-pressure water stream of a lower pressure than that, and a glass cloth whose tip was raised on the original cloth was obtained.
The thickness change rate of this glass cloth after the raising treatment was 12%. This glass cloth was impregnated with the epoxy resin varnish of Reference Example 1 and then dried to obtain a prepreg in which the epoxy resin was semi-cured. The amount of epoxy resin retained on the glass cloth constituting the prepreg was 55%. The prepregs piled four and placed prepreg obtained in Reference Example 1 on both sides, and the same copper foil as in Reference Example 1, heat and pressure (conditions: 30kg / cm ² -170 ℃ -60 min) to A double-sided copper-clad laminate having a thickness of 1.6 mm was obtained.

( Reference Example 4) Three prepregs obtained in Reference Example 1 were stacked, and MI was
One piece of prepreg (the amount of epoxy resin held by the glass cloth is 43%) manufactured by impregnating the epoxy resin varnish of Reference Example 1 with a glass cloth of L spec. And the same copper foil as in Reference Example 1 was placed, and heated and pressed (conditions: 30 kg / cm ² -170 ° C.)
-60 minutes) to obtain a laminate having a thickness of 1.6 mm.

Reference Example 5 Four prepregs obtained in Reference Example 1 were stacked, and MI was
L-spec # 2116 (plain woven glass cloth in which 60 × 58 7 μm monofilaments are bundled lengthwise and widthwise) is used as a base material, and the base material is impregnated with the epoxy resin varnish of Reference Example 1 and dried to manufacture. The same prepreg (the amount of epoxy resin held on the glass cloth constituting the prepreg is 40%) and the same copper foil as in Reference Example 1 were placed, and heated and pressed (condition: 30 kg / cm ² -170). ℃-
60 minutes) to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm.

Example 6 The brushed glass cloth of Reference Example 1 was used as a prepreg base material. The epoxy resin varnish of Reference Example 1 and the epoxy resin and aluminum hydroxide were added to this glass cloth in a weight ratio of 5%.
An epoxy resin varnish blended at a ratio of 0:50 was impregnated and then dried to obtain a prepreg in which the epoxy resin was semi-cured. The amount of the epoxy resin retained on the glass cloth constituting the prepreg was 60%. Four prepregs were stacked, and the copper foil of Reference Example 1 was placed on both sides thereof, and heated and pressed (conditions: 30 kg / cm ² -170 ° C.-60 minutes) to form a 1.6 mm-thick double-sided copper-clad laminate. I got a board.

( Reference Example 7) A yarn of G75 · 1/0 used for a glass cloth of MIL spec. # 7628 is used as a raw yarn, and the raw yarn is temporarily strongly twisted to eliminate post-twist. Then, the monofilament was cut to obtain a yarn whose tip was raised. 44 / 25mm length, 30 yarns / 25m width
m into a brushed glass cloth. This glass cloth was impregnated with the epoxy resin varnish of Reference Example 1 and then dried to obtain a prepreg in which the epoxy resin was semi-cured.
The amount of epoxy resin retained on the glass cloth constituting the prepreg was 55%. This prepreg is 4
Copper foil (Furukawa Circuit Foil, 1
8 μm) and heat and pressure (conditions: 30 kg / cm ² −
(170 ° C. for 60 minutes) to obtain a 1.6 mm-thick double-sided copper-clad laminate.

Example 8 A 75 g / m 2 glass nonwoven fabric was impregnated with the epoxy resin varnish of Example 6 and dried to obtain a prepreg in which the epoxy resin was semi-cured. The amount of epoxy resin retained in the glass nonwoven fabric constituting the prepreg was 60%.
The prepreg 2 ply double-sided arranged prepreg one and Reference Example 1 the same copper foil and Reference Example 1, placed, heat and pressure (conditions: 30kg / cm ² -170 ℃ -60 min) to A laminate having a thickness of 1.6 mm was obtained.

Reference Example 9 A peroxide of 2,5-dimethyl 2,5-dibutyl peroxy-hexyne-3 (Perhexin 25 manufactured by NOF Corporation) was used as a reaction initiator on the brushed glass cloth of Reference Example 1. A varnish of the following PP0 resin was impregnated and then dried to obtain a prepreg. The amount of the PPO resin retained on the glass cloth constituting the prepreg was 60%. Four prepregs were stacked, and the copper foil of Reference Example 1 was further disposed on both sides of the prepreg, and heated and pressed (conditions: 30 kg / cm ² -200).
C. for 90 minutes) to obtain a 1.6 mm double-sided copper-clad laminate.

PPO resin varnish (parts are parts by weight) PPO resin (Noryl PX9701 manufactured by GE Japan) 100 parts Styrene butadiene block polymer (Sorprene (trademark) T406 manufactured by Asahi Kasei Corporation) 5 parts Triallyl isocyanurate 35 parts Reaction Initiator 1 part ( Reference Example 10) A fluororesin (PTFE) was applied to the brushed glass cloth of Reference Example 1.
Aqueous dispersion, 30-J, manufactured by Mitsui / Dupont Fluorochemical Co.) aqueous solution, applied and impregnated at 400 ° C.
And baked into a prepreg. The amount of the fluorine resin retained on the glass cloth constituting the prepreg was 73%. Overlap four prepregs, and join both sides
Disposing copper foil considered Example 1, heat and pressure (conditions: 30kg / cm
² -380 ° C. -60 minutes) to obtain a laminate of the double-sided copper-clad plate thickness 1.6 mm.

( Reference Example 11) Two prepregs of Reference Example 1 having an epoxy resin content of 55% were stacked, copper foils were further disposed on both sides thereof, and heated and pressed (condition: 3).
0kg / cm ² -170 ° C for 60 minutes)
m was obtained. Both sides of the copper-clad laminate were subjected to a conventional etching treatment to form a circuit pattern, thereby obtaining an inner layer material of a multilayer printed circuit board. The both sides of the inner layer member overlapping amount of the epoxy resin 55% prepreg Reference Example 1, after a further overlapping a copper foil of Example 1, heat and pressure (conditions: 30kg / cm ² -170 ℃ -60 minutes) Thus, a printed circuit board having four layers was obtained. The copper foil of the printed circuit board was etched by a conventional method to obtain a four-layer printed circuit board. As a result of the test for heat resistance to moisture absorption, no visual abnormality was confirmed even after 6 hours.

[0026]

[Comparative Example] (Comparative Example 1) A glass cloth of MIL spec. # 7628 was used as a base material of a prepreg, and the base material was impregnated with the epoxy resin varnish of Reference Example 1 and then dried to obtain a prepreg in which the epoxy resin was semi-cured. Obtained. The amount of the epoxy resin retained on the glass cloth constituting the prepreg was 43%. Eight sheets of this prepreg are stacked, the copper foil of Reference Example 1 is placed on both sides thereof, and heated and pressed (conditions: 30 kg / cm ² -170 ° C.-6
0 minutes) to obtain a double-sided copper-clad laminate having a plate thickness of 1.6 mm.

(Comparative Example 2) A glass cloth of MIL specification # 7628 was used as a base material of a prepreg, and the base material was impregnated with a varnish of the PPO resin of Reference Example 9 and then dried to obtain a prepreg. The amount of the PPO resin retained on the glass cloth constituting the prepreg was 43%. Eight sheets of this prepreg are stacked, the copper foil of Reference Example 1 is arranged on both sides thereof, and heated and pressed (condition: 30 k
g / cm ² -200 ° C. for 90 minutes) to obtain a double-sided copper-clad laminate having a plate thickness of 1.6 mm.

(Comparative Example 3) Four prepregs of Comparative Example 1 using a glass cloth having a continuous monofilament as a base material were stacked, and further, the copper foil of Reference Example 1 was disposed on both sides thereof, and heated and pressed (condition: 30 kg). / Cm @ 2 -380 DEG C.-60 minutes) to obtain a double-sided copper-clad laminate having a plate thickness of 1.6 mm. Both sides of the copper-clad laminate were subjected to a conventional etching treatment to form a circuit pattern, thereby obtaining an inner layer material of a multilayer printed circuit board.
On each side of this inner layer material, two prepregs of Comparative Example 1 were stacked,
Further, after laminating the copper foil of Reference Example 1, heating and pressing (conditions:
30 kg / cm ² -170 ° C. for 60 minutes) to obtain a printed circuit board having four layers. The copper foil of the printed circuit board was etched by a conventional method to obtain a four-layer printed circuit board. As a result of the test for moisture absorption and heat resistance, after 6 hours, measling occurred partially.

Prepregs of Examples, Reference Examples and Comparative Examples,
The physical properties of the laminates are shown in (Table 1) and (Table 2).
The measurement of dielectric constant, dielectric loss tangent, surface roughness, and heat resistance was performed in the following manner. The dielectric constant, dielectric loss tangent, surface roughness, and heat resistance are based on JIS C-6481.

[0030]

[Table 1]

[0031]

[Table 2]

As shown in Table 1, Examples 6 and 8 and Examples 6 and 8 corresponding to Comparative Example 1 among Reference Examples 1 to 11 are referred to.
Remarks Example 1 to 7, when comparing the laminated board using a prepreg and the prepreg of Reference Examples 9 and 10 corresponding to Comparative Examples 1 and 2, prepreg using the brushed glass cloth, resin held in the glass cloth As a result, the dielectric constant or the dielectric loss tangent of the laminate using these prepregs is reduced, so that the suitability for high frequency is improved.

In addition, when the inorganic filler is dispersed in the curable resin, a decrease in heat resistance due to the use of a brushed glass cloth can be prevented.

Further, Reference Example 11 corresponding to Comparative Example 3
When comparing the prepreg with the multilayer laminate using this prepreg, the monofilament constituting the yarn is cut, and the tip of the monofilament is made of a glass cloth raised and raised by the glass cloth, and is composed of a semi-cured curable resin. A laminated plate obtained by using a prepreg as a pressure-receiving body and hot-pressing the pressure-receiving body can avoid a reduction in moisture absorption heat resistance due to a reduction in surface smoothness of the raised glass cloth.

[0035]

The prepreg and the laminate according to the present invention provide a laminate having a low dielectric constant, a low dielectric loss tangent and a high frequency characteristic.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI H05K 1/03 630 H05K 1/03 630F // B29K 105: 08 B29K 105: 08 C08L 63:00 C08L 63:00 (56) Reference Document JP-A-4-149246 (JP, A) JP-A-5-309789 (JP, A) JP-A-5-315716 (JP, A) JP-A-51-105477 (JP, A) 261438 (JP, A) JP-A-61-213142 (JP, A) JP-A-5-70675 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 5/04-5 / 08 C08J 5/24 B29B 11/16 B29B 15/08-15/14 B32B 5/28

Claims (2)

(57) [Claims] 1. A prepreg comprising a glass cloth having a thickness change rate of 10% or more after a raising treatment for cutting a monofilament constituting a yarn and a semi-cured curable resin held by the glass cloth. The pressurized body is heated and pressurized , and the curable resin is filled with inorganic material.
Epoxy resin composed of dispersed materials.
A laminate characterized in that the laminate has passed the level of 265 ° C. 2. A prepreg comprising a glass cloth having a thickness change rate of 10% or more after a raising treatment for cutting a monofilament constituting a yarn and a semi-cured curable resin held by the glass cloth. The curable resin is
Epoxy resin with inorganic filler dispersed.
On the upper and lower sides of the repreg, a prepreg made of a glass cloth in which the monofilaments constituting the yarn are continuous and a semi-cured curable resin held by the glass cloth is overlapped to form a pressure object, and the pressure object is heated and pressed . The heat resistance of this
A laminate characterized by passing a temperature of 265 ° C.