JPS5911244A - Laminated board containing glass textile - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate formed by laminating and molding a plurality of glass fabrics using a thermosetting resin as a binder, and more specifically,
The present invention relates to a laminate using glass fabric as a reinforcing base material, which has excellent dimensional stability, mechanical strength, electrical properties, heat resistance, and chemical resistance, as well as particularly cold punching workability.

Conventionally, glass fabric has been mainly used as a reinforcing base material for electrical insulating boards or copper-clad laminates for printed circuits used in electronic devices, telecommunications equipment, etc. that require extremely high quality. This is because laminates based on glass fabric are extremely excellent in properties such as dimensional stability, mechanical strength, electrical properties, heat resistance, and chemical resistance, which are most required in this field. However, laminates made of glass fabric as a base material have the disadvantage that cold punching is difficult and machinability such as drilling is extremely poor.

On the other hand, laminates using glass fabric, glass paper, glass strand mat, glass fiber, etc. as the base material are also widely known. These substrates have a weak reinforcing effect in the plane direction compared to glass fabric substrates, so although they have excellent machinability of laminates, especially cold punching, on the other hand, they are given top priority. Properties such as dimensional stability, mechanical strength, electrical properties, and chemical resistance are considerably inferior to those of glass fabric substrates. Furthermore, laminates using glass nonwoven fabrics containing inorganic fillers, glass paper, etc. as base materials have been proposed for the purpose of improving mechanical strength and other properties. Although this laminate is said to have excellent cold punching properties, and slight improvements in mechanical strength and electrical properties are observed, properties such as dimensional stability and heat resistance are still unsatisfactory.

In addition, glass fabric is used as the base material for both surface layers of the laminate.
A so-called composite type laminate using glass nonwoven fabric containing an inorganic filler, glass paper, etc. as the base material of the intermediate layer has been devised. Although these laminates have excellent cold punching properties and have considerable performance in terms of mechanical strength, electrical properties, heat resistance, etc., they do not have any other properties other than cold punching properties. The current situation is that it is nowhere near as good as a laminate made of glass fabric as a base material. In particular, these laminates have poor dimensional stability not only in the plane direction but also in the z-axis direction, resulting in fatal defects such as warpage and twisting, and breakage of through-hole plating. Furthermore, it is difficult to say that heat resistance, chemical resistance, etc. are also satisfactory.

The present inventors have developed properties such as dimensional stability, mechanical strength, electrical properties, heat resistance, and chemical resistance that are almost comparable to conventional laminates using only glass fabric as a base material. As a result of intensive research to develop a glass fabric-reinforced laminate with excellent cold punching properties, we succeeded in achieving the above-mentioned properties by suppressing the strength of the threads that make up the base glass fabric. I have found that my purpose can be achieved. This glass fabric reinforced laminate is a laminate formed by laminating and molding a plurality of glass fabrics using a thermosetting resin as a binder, and the tensile strength of the glass threads constituting the glass fabric is 10.1ilf/ for both the warp and weft. less than lax and the sum of both is 15
．． The applicant filed a patent application on the same date as the present patent application.

The laminate according to the above-mentioned patent application has excellent cold punching workability and maintains satisfactory levels of dimensional stability, heat resistance, and other properties. However, in terms of mechanical strength, especially bending strength, ordinary G-10 and FR-
4 (both are US HEMA standards), it is slightly inferior. An object of the present invention is to provide a glass fabric-containing laminate that is comparable in mechanical strength including bending strength to ordinary G-10 and FR-4 and has excellent cold punching properties. It is in.

The glass fabric-containing laminate according to the present invention is a laminate formed by laminating and molding a plurality of glass fabrics using a thermosetting resin as a binder. At least one piece of glass fabric with a tensile strength of 10 gf/l・X or more; B. The tensile strength of the glass threads constituting the glass fabric is less than 109 f/lax for both warp and weft, and the sum of both is 1
It is characterized by being made of at least one layer of glass fabric having a particle diameter of less than 59'/lax.

In the present invention, "the tensile strength of the glass threads constituting the glass fabric" refers to the tensile strength of the glass threads constituting the glass fabric immediately before lamination molding using a thermosetting resin as a binder. In other words, in general, glass fabrics are made by interweaving warp and weft yarns, but glass fabrics have a binder (sizing agent) attached to them that is used as a binding agent during spinning of raw yarns and warping of warp yarns. After weaving, the size is usually removed by heat cleaning or washing. Furthermore, the desized glass fabric is usually coated with a coupling agent to strengthen the bond with the thermosetting resin (for example, a coupling agent such as a silane compound is used to strengthen the bond with the epoxy resin). After surface treatment, it is laminated and molded. In the present invention, the tensile strength of the glass threads refers to the tensile strength of the glass threads constituting the glass fabric immediately before being laminated and formed after such standard pretreatment. Point.

In general, the tensile strength of glass threads that make up ordinary glass fabrics for both warp and weft after desizing treatment is
~149 f/lex, and furthermore, after surface treatment with a coupling agent, that is, immediately before use for lamination molding, it is approximately 16 to 20 jif/lax.

At least one of the glass fabrics that is the base material of the laminate of the present invention is such that the tensile strength of the glass threads constituting it is the same as the warp and weft immediately before being used for lamination molding using a thermosetting resin as a binder. ] Og'/lax, and the sum of both is less than 15 gf/lex, which is quite low compared to conventional glass fabric substrates. Thus, even though the tensile strength of at least one layer of yarns in the glass fabric substrate of the present invention is considerably lower than that of the yarns of conventional glass fabric substrates, the glass fabric substrate laminate of the present invention It has properties such as dimensional stability, mechanical strength, electrical properties, heat resistance, and chemical resistance that are comparable to those of conventional glass fabric base laminates; It is surprising that the material exhibits far superior cold punching workability in comparison.

Thermosetting resins used as binders in the present invention include epoxy resins, polyimide resins, phenolic resins, polyester resins, silicone resins, polyurethane resins, and polyvinyl butyral, which are conventionally used in the production of laminates based on glass fabrics. Although resins and the like can be used, the material is not limited to these materials.

Additionally, inorganic fillers and other commonly used additives can be blended with the thermosetting resin.

The threads used in the glass fabric used as the base material in the present invention are not limited in terms of single thread diameter, number of converged threads, etc., as long as they are long glass fibers. Furthermore, there are no particular restrictions on the composition of the glass, but E glass with a low alkali content and D glass with a low dielectric constant are generally advantageously used as glasses for electrical insulating boards or printed circuit boards.

Glass fabrics are usually made of warp and weft interweaved, and weave structures include plain weave, twill weave, satin weave, etc., but the structure of the glass fabric used in the present invention is not particularly limited.

Glass fabrics have a binder (sizing agent) mainly composed of starch, I-lipinyl alcohol, etc. used as a binding agent during yarn spinning and warping, but usually after weaving, heat cleaning and washing are carried out. De-glue using the method.

Furthermore, after de-sizing, the surface is treated with a coupling agent such as a silane compound to form a base material for a laminate. The coupling agent exerts a crosslinking effect between the glass and the resin binder,
Increase the bond between the two. A suitable coupling agent is selected to match the resin binder used.

For example, compatible coupling agents for epoxy resin binders can be selected from among silane compounds.

As mentioned above, the glass threads in at least one layer of the base material layers constituting the glass fabric base material laminate of the present invention are characterized by extremely low tensile strength, and the tensile strength is JIS-
This is significantly lower than the tensile strength of glass thread specified in R.3413-3.2(3).

Generally, the tensile strength of glass thread varies depending on the amount of glue attached, the amount of coupling agent attached, and the temperature and time of heat cleaning, but it is possible to obtain a low-strength glass fabric as used in the present invention. This requires special strength reduction treatment. Other methods of reducing strength include heat cleaning at a high temperature of 400°C or higher for a relatively long period of time, or immersion in an acid or alkali solution, but the former method requires a long period of time in a special furnace. The latter method is not very advantageous from an industrial perspective because of its processing, and the latter method has the problem of adversely affecting the electrical properties of the glass fabric base laminate finally obtained. A particularly preferred strength-lowering treatment method is to apply a dilute solution of a specific silane compound such as tetraalkoxysilane, trialkoxysilane, or soalkoxysilane to the glass fabric, and then remove the glass fabric with a trace amount of the silane compound attached. This is a heating method. By such a method, it is possible to reduce the strength very effectively and industrially.

Application of the specific silane compounds described above is preferably carried out prior to heat cleaning of the pot to remove the size agent.

This application can be accomplished by dipping the glass fabric in a dilute solution of the silane compound or by spraying the glass fabric with a dilute solution. The applied amount of the silane compound and the heat cleaning heating temperature as described above have a positive correlation with the amount of decrease in the tensile strength of the glass thread, and by changing the applied amount and the heat cleaning heating temperature, the tensile strength of the glass thread can be adjusted arbitrarily. can be controlled.

The lower limit of the tensile strength of the glass threads constituting the above-mentioned low-strength glass fabric depends on the dimensional stability of the resulting laminate,
Although not particularly limited as long as the mechanical strength and other properties and compatibility in the lamination molding process are satisfactory, it is desirable that the tensile strength of the warp is about 5 gf/lax or more.

The laminate according to the present invention is similar to the conventional one in that at least one of the above-mentioned low-strength glass fabrics and the glass threads constituting the glass fabric have a tensile strength of 10.9 f/'tex or more for both warp and weft. It is formed by laminating and molding at least one glass fabric (hereinafter referred to as "high-strength glass fabric"). The number of laminated glass fabrics constituting the base material of the laminate is not particularly limited and varies depending on the use of the laminate. Generally, a laminated structure in which at least three glass fabrics are laminated and a high-strength glass fabric is disposed on at least one surface layer side is preferred. In particular, a laminated structure in which one high-strength glass fabric is placed on each surface is best.

The laminate can be manufactured according to conventional methods.

That is, generally, glass fabric is impregnated with resin and semi-cured silipreg is layered on top of each other, and compression and heat molding is performed. Further, a casting method and a low pressure heating method are also possible.

For printed circuit boards, a metal film such as copper foil is attached to one or both sides of the laminate, but a method such as an additive method in which the circuit forming material is attached after molding is also possible.

The present invention will be specifically described below with reference to Examples and Comparative Examples. In the examples, "parts" mean parts by weight.

The following margins [Example 1] The warp and weft are made of ECG75 (67,5 tex), and the density is 44 warp/25i++m weft 32/2
I wove a glass fabric consisting of 5 pieces.

The tensile strength of this glass fabric is 110Krf/25m for the warp.
11. The weft was 80Kgf/25si+. This glass fabric was processed using the following two methods.

That is, (A) it was cleaned for 20 hours in a heating furnace at 400°C.

(B) The glass fabric obtained by the above method was immersed in an aqueous solution of tetraethoxysilane 5 CC/A, squeezed, dried, and heat-cleaned again in a heating furnace at 400° C. for 20 hours.

The glass fabrics obtained in (4) and (B) were then immersed in an aqueous solution of niboxysilane 5f/13 and dried. The tensile strength of the epoxy silane-treated fabric (4) is 50KLi7 for the warp.
/25q weft 40KIf/25mm, the leg is warp 16.9#/1e-x weft 18.5? f/tex
and that of (B) is warp 22.3Klf/25fl
, weft 15.1Kf7/25+u, tax 7.5 warp? f/lex weft7. Of? It was f/lex.

These glass fabrics were impregnated with an epoxy resin varnish having the following composition, and heated and dried at 160° C. to prepare Gripreg. Next, a total of 2 prepregs made of the fabric of (4) are placed on the top and bottom surfaces, and 6 prepregs made of the fabric of 03) are sandwiched in the middle, and then 35μ copper foil is layered on both surfaces and heated to 175℃. , compression molded at 40 min., 1.5
A copper-clad laminate having a thickness of ms+ was obtained.

Resin varnish composition AER-710 Asahi Kasei epoxy resin) 100 parts dicyanthamide 3 parts pencil dimethylamine 0.2 parts methylformamide 20 parts methyl ethyl ketone
The various properties of the laminate obtained in 100 copies are as shown in Table 1. It has very good properties such as hardness, gunching resistance, heat resistance, chemical resistance, coefficient of linear expansion in the thickness direction, etc., and bending strength. It is also on the same level as general glass fabric reinforced laminates.

[Example 2] The same glass fabric as in Example 1 was further processed in two different ways.

That is, (C) the sticking paste was partially burned by exposing it to a high-temperature furnace at 625'C for 6 seconds, and then heat-cleaning it in a heating furnace at 400°C for 20 hours. / in an aqueous epoxy silane solution and dried.

A glass fabric was prepared by exposing it to a high-temperature oven at @625° C. for 6 seconds to partially burn off the adhering sizing agent, which was then immersed in an aqueous solution of 1 oy/A of tetraethoxysilane, squeezed, and dried. Next, this was heat cleaned in a heating furnace at 400° C. for 20 hours, and then immersed in a 5ff/A aqueous epoxy silane solution and dried.

The tensile strength of the glass fabric obtained by method (C) is
8, 9f/25m1. Weft 38Kyf/2511'l
Yes, the tax is warp 16.1? f/tex,
Weft 17.6? The tensile strength of the glass fabric obtained by method (b) is 29.5Kyf/25 in warp.
m, weft 9,714f/25i+m, warp 9.71 per tex? f/tex weft 5.0? f/tex
Met.

Next, one Gripreg made from the woven fabric (C) was placed on each of the upper and lower surfaces, and 6 pieces of Silipreg made from the woven fabric (B) were sandwiched in the middle to form a copper-clad laminate in the same manner as in Example 1. I got it.

[Example 3] Warp and weft are ECG37-1/1l (135tex)
A glass fabric with a density of 25 fibers/25111 fibers in both warp and weft was woven. The tensile strength of this glass fabric is 125 hf/25 mm for the warp and 110 hf/25 mm for the weft.
25m1! Met.

When this was processed in the same manner as in Example 2), the tensile strength was 30.5Kff/25in for warp and 17.5Kff for 1 weft.
8Kyf/25111! So, the warp is 9.
0? f/tex.

The weft was 5.34'f/lax.

Next, one Gripreg made of the glass fabric obtained in Example 2 (Q) was stacked on each of the upper and lower surfaces, and four Gripregs made of the glass fabric obtained in this example were sandwiched in the middle. A copper-clad (17) laminate was obtained in the same manner as in 1.

[Comparative Example 1] Warp and weft are ECG75110 (67,5tex)
A glass fabric with a density of 44 warps/251 III and 32 wefts/25 m was woven. The tensile strength of this glass fabric is 110 f / 25 III
E. The latitude was 80 kgf/25 ho. Next, this fabric was cleaned in a heating furnace at 400° C. for 20 hours to burn off the adhering sizing agent. Next, this glass fabric was treated with tetraethoxysilane 5α! It was immersed in an aqueous solution of Squeeze the liquid,
After drying, this glass fabric was heat-cleaned again in a heating furnace at 400°C for 20 hours, and then epoxysilane 5? was added as a coupling agent. /! It was immersed in an aqueous solution of and dried. The tensile strength of the glass fabric treated in this way is warp 22.3Kyf725 silk, weft 15.1Kff/25m
With g+, warp 7.5 per tex? f/tex weft 7.0? It was f/Leg.

This glass fabric was impregnated with the epoxy resin varnish of Example 1 and dried by heating at 160°C to prepare a prepreg. A copper foil of (18) 35 μm was layered on the surface of 8 of these Presolegs, and compression molded at 175° C. and 40 KfΔ to obtain a copper-clad laminate with a thickness of 1.611 m.

[Comparative Example 2] In Comparative Example I, 2
The glass fabric heat-cleaned for 0 hours was immediately immersed in an aqueous solution of epoxy silane 5 V7 and dried to obtain a surface-treated glass fabric. The tensile strength of this glass fabric is warp 50Kyf/25m5+, weft 40Kgf72
5xx, terx warp 16.9if/la
x, weft 18.5Pf/tex. Next, a copper-clad laminate was obtained in the same manner as in Example 1.

[Comparative Example 3] Wet paper was made with a basis weight of 70y-7m2 and a single fiber diameter of 9μ, but it was lath base-t! - was impregnated with the resin varnish of Example 1 and dried to create a Silipreg. Ten sheets of this presoreg were layered with 35 μm copper foil on the surface, and compression molded at 175° C. and 40 to tm” to obtain a 1.6 μ thick copper-clad laminate.

[Comparative Example 4] Eight sheets of Silipreg from Comparative Example 3 were stacked as an intermediate layer, two sheets of Silipreg from Comparative Example 2 were stacked on the upper and lower surface layers, and a 35μ copper foil was stacked on the surface, and compression molded at 175°C and 40 h/m''. Then, 1.6
A copper-clad laminate having a thickness of u was obtained.

The properties of the glass fabrics and the resulting laminates used in each of the Examples and Comparative Examples are shown in Table 1 below.

Below are the margins Example 1 Example 2 Surface layer/inner layer Surface layer Inner layer Surface layer
Inner layer glass fabric style 7628
7628 7628 7628 (Asahi Shi, Knibel) Thread user 餞 g to Tsumuyo 3 children ``Susou 3 children's arms 1st division cgs
-h3廿：T・・餞 %″7.% 6″I
, 5 7: Lg copy: De (f/10100O Gajyu 4 quantity 210 210
210 210 tensile strength g
Kiki:,' 2:,550
4840
38 to He5 Maro) - Punishing strength He8: Enemy 7.0 "x9: A
s.

7 (yf/1ax) Board thickness wm) 1.6
1.6 Resin content (wt%)
41 42 Punching property (room temperature, A8TMD-617) Excellent
Excellent shear strength (rostral shear strength:
9.6 9.3AS
TMD732-78) Bending strength 1 Yo 33
3238 4
2G Wisdom L4-) “”” I 1740
17001860
1920 (Wl) (!fffF!/65+D-V100) 6.2
xlO124, 8x1012 Todoroki 01”aeFm”/”A
/dsg) 2.6 x 10-52.4 x
10'''' Chemical resistance (5(i, -vglJF > No abnormality No abnormality Example 3
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Surface layer Inner layer
Surface layer Inner layer 7628 372
6 7628 7628 Glass paper 7628 Glass paper MS-' =7s4 7 6'1 210 270 210 21G
-210-5 1゛.

1.6 1.6
1.6 1.6 1
．． 648 41 39
65 62 Yu Yu
Bad Good Good 9.0
8.8 13.5
9.0 9.6 Same left Same left Same left Blister Blister occurrence Occurrence 9, lX10" 5jX10 5.2X1
0123.9X10' 4. lX10112 8.2x10-52x10-52.2X10-51.2
xlO-'10-'No abnormality
No abnormality Blistering Slightly frequent blistering Occurrence procedure amendment glossy) Y/2/1980 Director of the Japan Patent Office Kazuo Wakasugi 1, Indication of the incident 1983 Patent Application No. 120354 2, Name of the invention Glass woven laminate 3 , Relationship with the person making the amendment Patent applicant name Asahi Schniebel Co., Ltd. 4o agent (3 others) 5. Full text of the specification to be amended 6. Contents of the amendment I will amend the attached document. (There are no changes to the contents.) 7. List of attached documents

Claims (1)

[Claims] 1. A laminate formed by laminating and molding a plurality of glass fabrics using a thermosetting resin as a binder, A. The tensile strength of the glass threads constituting the glass fabrics is 1091 for both warp and weft.
At least one glass fabric having a tensile strength of /lax or more, B. A glass whose tensile strength of the glass threads constituting the glass fabric is less than 01'/lax and the sum of both is less than 1511f/lax. At least 1 fabric
A laminated board containing glass fabric that is characterized by being stacked one on top of the other. 26 A laminate made by stacking at least three glass fabrics, in which a glass fabric having a tensile strength of glass threads of 101'/l@x or more for both the warp and weft is arranged on at least one surface layer side. A laminate according to claim 1. 3. The tensile strength of the glass thread is 109 for both warp and weft.
3. The laminate according to claim 2, wherein glass fabrics having a thickness of 1/lax or more are arranged on both surface layers. 4. The glass fabric-containing laminate according to any one of claims 1 to 3, wherein a metal film is formed on at least one surface.