JPH0289635A - Treating method of glass base material for laminated board - Google Patents

Abstract

PURPOSE:To obtain a glass base material for a laminated board with excellent moistening property and infiltrating property of cyanic acid ester resin by infiltrating, and then drying, solution containing many-valued phenol or the like, in a glass substrate treated in its surface with an epoxy silane coupling agent. CONSTITUTION:Solution containing many-valued phenol or the like is infiltrated, and then dried, in a glass substrate treated in its surface with an epoxy silane coupling agent, and the epoxy silane coupling agent and many-valued phenol or the like are reacted to each other. In this case, the solution of many-valued phenol is mixed with reactive catalyst such as first class, second class or third class amines, or imidazole composite. The cyanic acid ester resin is infiltrated in the glass base material treated in its surface in this manner in order to form prepregs, and the prepregs are superimposed in a plurality of sheets, and molded in heat and compression so as to form a laminated board. At this time, the moistening property and infiltrating property of cyanic acid ester resin relative to the glass base material become excellent, and the moisture resistance and chemical resistance of the laminated board can be improved.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for treating a glass substrate for a laminate used in the manufacture of printed wiring boards.

[Conventional technology]

When manufacturing a laminate, prepreg is prepared by impregnating a glass base material such as glass cloth or glass nonwoven fabric (glass vapor) with thermosetting mui fat and drying, and this prepreg is laminated and molded. The first thing is that the second thing is being said. Then, the surface of the glass base H is treated with a silane coupling agent in order to improve the wettability and impregnation of the resin to the glass base material, and to improve the heat resistance, moisture resistance, and chemical resistance of the laminate after molding. things are being done. There are various types of silane coupling agents depending on the resin to which they are applied, and they can be broadly classified into vinylsilane, ami/silane, imigzolinsilane, chlorosilane, epoxysilane, styrene silane, acrylic silane, cationic silane, phenylsilane, and methacrylic silane. There are silanes, etc. For epoxy resins, ami/silane, epoxy silane, and Kanaoni γ Kunran are mainly used; for polyester resins, vinyl silane, methacryl silane, etc. are used; O (vinyl silane for fat,
Methacrylsilane and the like are mainly used. On the other hand, in recent years, frequencies used in fields such as electronic industry, communications, and computers have shifted to high frequency regions such as MHz and GHz. The resin that makes up the laminated board, which is the substrate for printed wiring boards used in such high frequency ranges, has a lower dielectric constant in order to shorten signal propagation delay, and also in order to reduce power loss. It is desired that the dielectric loss tangent be smaller, and cyanate ester resins have been attracting attention and being used as resins that satisfy such electrical characteristics.

[Problem to be solved by the invention]

However, cyanate ester-based fats have poor wettability and impregnation properties for glass substrates, and silane coupling agents such as silane and epoxy silane are mainly used for surface treatment of glass substrates. However, it is still not possible to improve these problems, and the current situation is that the moisture resistance and chemical resistance of the laminate cannot be satisfied.The present invention has been made in view of the above points, It is an object of the present invention to provide a method for treating a glass substrate for a laminate that has excellent wettability and impregnation property with cyanate ester resin. A method characterized by impregnating a glass substrate surface-treated with a coupling agent with a solution containing polyhydric 7-ethers, drying it, and reacting the epoxysilane coupling agent with the polyhydric phenols. The present invention will be described in detail below.The glass base material made of glass fiber or lath nonwoven fabric (FF lath vapor) is treated in advance with an epoxy silane coupling agent. As the coupling agent, those commonly used for surface treatment of glass substrates can be used.For example, γ
-glycidoxypropyltrimethoxysilane and β-(3
, 4-evoxinechlorohexyl)-ethyltriethoxysilane, and the like. The process of attaching the epoxy silane coupling agent to the surface of the glass substrate can be carried out by impregnating the glass substrate with a solution containing the epoxy silane coupling agent and drying it. The amount of epoxy silane coupling agent attached to the glass substrate is 0.3 to 2.0% by weight based on the glass base material.
It is generally about % by weight. Merely surface-treating the glass substrate with an epoxy silane coupling agent in this way does not provide sufficient wettability or impregnability with the cyanate ester resin. Therefore, the present invention is characterized in that it is further treated with a polyvalent 7-ether. As polyhydric phenols, those represented by the following formula (1) or formula (IT) can be used. (In formula (1) (II), n is an integer of 2 to 6. l is 1 to 5
an integer of R1 is a substituent containing no active hydrogen. L is 1 or 2° x is an integer from 2 to 4. , R2 is a C9-03 hydrocarbon or one containing a heteroatom such as -0- or 0. ) Examples of such polyhydric phenols include, but are not limited to, the following. (OH) Mouth CH. C10゜C11,3 (Otl)m These polyhydric phenols are used in a solution state such as an aqueous solution, and this solution further contains a reaction catalyst for reacting the epoxysilane coupling agent and the polyhydric phenols. Mix it up. The catalyst for this reaction is - grade,
It is possible to use secondary or tertiary amines, imiguzol compounds, and the like. For example, -grade amines include ethylamine, secondary amines include noethylamine and bennorthmethylamine, tertiary amines include triethylamine, and imiguzole compounds include 2-methyl imiguzole (2MZ) and 2-ethyl-4-methyl. imiguzol (2
E4MZ> etc. - on board. This reaction catalyst has a ratio of 0.1 to 5.
It is preferable to add and use it in the range of 0% by weight. The solution containing the polyhydric phenols and the reaction catalyst thus prepared is impregnated into a glass substrate whose surface has been treated with the above-mentioned epoxysilane coupling agent, and the polyhydric phenols are applied to the surface of the glass substrate. Make it adhere. Then, this is dried by heating at a temperature of about 100 to 160° C., and the epoxy silane coupling agent is reacted with the polyhydric 7-ether. This reaction causes the guccinol group of the epoxysilane coupling agent to have a polyvalent 717
The phenolic hydroxyl group is thus introduced as a functional group into the epoxysilane coupling agent. As the cyanate ester resin to be impregnated into the glass substrate surface-treated as described above, Japanese Patent Publication No. 41-1928
The cyanate group <-0-C provided in the publication No.
It is possible to use those obtained from aromatic cyanate esters having bis7E7
It is also possible to use cyanic acid nistermo 7mer or a prepolymer obtained by reacting -L A with cyanogen halide. Also, patent application publication 1986-50043
It is also possible to use cyanate esters (polyaromatic cyanates) provided in Publication No. 4. Preferred cyanate esters are the following formula % formula % (D) t (D) t (D) t (D) t (D) t
...Formula (III) (wherein ^r is aromatic. B is C6-
C20 aliphatic group or C7-2o polycyclic aliphatic group. D
are each independently a substituent containing no active hydrogen. q, r, and s are each independently an integer of o, 1°2, or 3, provided that Q+
The sum of r+S is greater than or equal to 2. (Each is independently an integer from 0 to 4. This gives aromatic polytrianone (aromatic cyanate ester O (fat)) with excellent stability. In the aromatic cyanate ester of formula (1), the aromatic group Ar is a It means the group of
For example, benzene, naphthalene, 7-enanthracene, anthracene, or a biaromatic group, two or more aromatic groups bridged by an alkylene moiety. Preferred are benzene, naphthalene, biphenyl, binaphthyl, and nophenylalkylene groups, with benzene group being particularly preferred. As the aliphatic group B of Co-2o, -(CH2)+bi can be used (n=0 to 20). Also C7
The polycyclic aliphatic group B of ~2o means an aliphatic group containing two or more rings, and the polycyclic aliphatic group includes one or more double bonds or triple bonds. It may be Suitable polycyclic aliphatic groups include the following. (In the formula, Y is -CH2--3--3=-3-,
D' is a C1-5 alkyl group. ) especially (a)
(b) (c) (d) (e) (f) (g) or (1) is preferred, more preferably (a) (b) (c) (d
)(t'), and (, ) are particularly preferred. D in formula (I [I) means all substituents that can be substituted on the organic hydrocarbon group, and activated water CH. Another preferred embodiment of the cyanate ester of formula (III) is represented by the dog formula. Therefore, a cyanate ester resin (aromatic polytrianone,
Polyaromatic cyanate resin) has a low dielectric constant (C2,7
8), low dielectric loss tangent (tan δ around 0,003), and high heat resistance (77' lath transition temperature Tg 250 or higher, oven heat resistance approximately 300°C), making it an excellent resin for the insulating substrate of printed wiring boards. It has the following characteristics. In addition, in order to improve the impact resistance of this cyanate ester resin, polyhydric alcohols and cyanate groups and
Substituents containing ethyl water atoms are excluded. Active hydrogen atom means a hydrogen atom bonded to an oxygen, sulfur, or nitrogen atom. Each in formula (III) is defined independently, for example, alkyl, alkenyl,
Alkynyl, aryl, alkaryl, alfurkyl,
Halo, flukoxy, nitro, carboxylate, sulfone, sulfide, carbonate, etc., preferably C
3~. Most preferred are alkyl of C8, alkenyl of C8, nitro, halo, alkyl of C+~, alkynyl of C1~, bromo, and chloro. In addition, in formula (III) is an integer from O to 4,
Among these, an integer of 0, 1 or 2 is preferred, more preferably 0 or 1, and 'R is preferably 0. Each t in formula (III) is defined independently. , q, r%S is 0.
An integer of 1.2 or 3, optimally 1. q,
Although r and s are defined independently, their total is set to be 2 or more. One of the preferred embodiments of the cyanate ester of formula (I[I) is represented by the following formula. An aromatic cyanate ester 7er7-el having an acid group can also be blended. Furthermore, a flame retardant can be added to improve flame retardancy. As the flame retardant, those containing Br, such as 7-E/xy-terminated tetrabromobisphenol carbonate oligomer, can be used. The flame retardant effect due to the combination of flame retardants is determined according to the amount of Br, and the
- In order to obtain flame retardancy at the standard 94V-0 level,
It is desirable to adjust the amount of flame retardant so that the content of B is 10 to 15% by weight based on the total amount of cyanate ester and flame retardant.If the amount of flame retardant is too large, the heat resistance will deteriorate. The upper limit should be set at 15% by weight, as there is a risk of problems with the properties.As a reaction catalyst for polymerizing cyanate ester to form a trianone ring, imidazoles, tertiary Fully metal salts and Lewis bases such as amines, organic cobalt mM such as cobalt naphthenate and cobalt octylate can be used, and organic cobalt salts are particularly preferred.The amount of the reaction catalyst is not particularly limited, but for example, When organic cobalt salts are used as reaction catalysts, the weight ratio of cobalt ions to the weight of cyanate ester is blended in the range of about 10 to 700 ppm, depending on the desired deltime of the varnish (described later). A varnish is prepared by dissolving an acid ester, a flame retardant, a reaction catalyst, etc. in an organic solvent.The organic solvent may be aromatic as long as it dissolves the cyanate ester or flame retardant and does not adversely affect the reaction. Hydrocarbons, alcohols, and ketones are not particularly limited. For example, toluene, acetone, methyl ethyl ketone, trimethylformamide, methyl cellosolve, etc. can be used alone or in combination of two or more. The concentration of the varnish is such that the solid content is 50 to 50. Generally, the content is adjusted to 70% by weight. Therefore, a glass substrate whose surface has been treated with an epoxy silane coupling agent and a polyvalent 7-ether is impregnated with the above varnish. The prepreg can be heated to 71 AvI by heating and drying.The amount of varnish impregnated into the glass substrate is preferably set so that the solid content ratio to the glass substrate is 45% by weight or more.Resin content The level of dielectric constant is affected by the content of 45% by weight when the material is made of D glass cloth
With the above impregnation, a dielectric constant of 3.5 or less can be achieved. The heating and drying conditions when preparing prepreg are influenced by the amount of reaction catalyst blended, etc., but for example, if the heating temperature is 160°C, the desired prepreg can be obtained by setting the heating time to about 3 to 10 minutes. - It is possible to obtain stroke del time. The stroke del time of prepreg varies depending on molding conditions, etc., but 1
Generally, the film is formed at 70°C for about 2 to 10 minutes. The cyanate ester in the prepreg is then polymerized and hardened by layering multiple sheets of prepreg prepared in this way, then layering gold pA foil such as copper foil on both or one side of the top and bottom, and molding this under heat and pressure. It is possible to create a double-sided metal foil-clad or single-sided metal foil-clad laminate in which metal foil is laminated and bonded to both sides or one side of an insulating and edged substrate. An inner-layer printed wiring board can be created by etching the metal foil of the laminate thus produced to form a circuit, and by stacking a plurality of inner-layer printed wiring boards via a plurality of the prepregs mentioned above, By layering metal foil on the outer layer and molding it under heat and pressure, 1. Multilayer printed wiring boards can be created. The molding conditions are heating temperature of 170°C to 230°C, maximum pressure of 30 to 40 kHz/cm2, and time of 90°C.
It is common to set the film for about 0 to 120 minutes. When 77 turquoise is carried out at a temperature of about 220 to 230°C after molding, a molding temperature of about 170 to 180'C is sufficient. Further, V-rill processing is performed to form through holes, and the outermost layer of metal foil is etched to form a circuit, and through-hole plating is applied to finish it as a multilayer printed wiring board. [Actually, Example 1] The present invention will be explained in detail below with reference to Examples. 1m Using bisphenol A shown in the following formula as a polyhydric phenol, H3C11° was dissolved in methanol to prepare a concentration of 1% by weight, and 2-ethyl-4-methylimigusol was added as a reaction catalyst. 2% by weight (0.02% by weight based on the entire solution) of 2% by weight based on the polyhydric 7-ether (0.02% by weight based on the entire solution) was added to prepare a treatment solution yj4. and 21 treated with an epoxysilane coupling agent.
16 Type E Lath cloth base material (216L manufactured by Asahi Schubel Co., Ltd.)
/ . Here, from the change in weight of the glass substrate before and after treatment with the treatment solution, the amount of polyvalent 7-ethers attached was 0.8% by weight relative to the glass substrate. On the other hand, 80 parts by weight of a cyanate ester represented by the following formula (XU-71787, manufactured by Dow Chemical Company) was used as a flame retardant, and 7E/Xy Terminated Tetrabromobis7E7-R8 Carbonated was used as a flame retardant. Added 20 parts by weight of oligomer (Great Lake IBC-58; n is a mixture of 10-20), further added 450 ppm of cobalt octylate as a catalyst, and mixed these with methyl ethyl ketone (MEK) and dimethyl formamide (DMF).
A varnish with a solids content of 70% by weight was prepared by dissolving it in a 1:1 mixed solvent of Y4. This varnish was impregnated into the above-mentioned surface-treated glass substrate so that the solid content was 4 a wt %, and heated at 160°C.
A prepreg was prepared by heating and drying for 5 minutes. Next, four sheets of this prepreg were stacked together, and double-sided roughened copper foil with a thickness of 70μ was stacked on both the top and bottom sides, and the molding temperature was 170'C.
, laminated molding was carried out under conditions of molding pressure of 40 kg/c for 2.90 minutes, and after molding, it was heated in an electric oven for 220 min.
77 turquoise under the conditions of 12 hours at °C, thickness 01
．． A double-sided copper-clad laminate for an inner layer printed wiring board of 4 aam was obtained. By etching the copper foil of the double-sided copper-clad laminate obtained in this way to form a circuit, an inner layer printed wiring board was created. Layering 18μ thick copper foil on top and bottom of the prepreg with three sheets of prepreg interposed therebetween, laminated and molded under the same conditions as above, and further turquoiseed at 230°C for 2 hours. A multilayer laminate with a thickness of 2.4 +aa+ was prepared by the following method. Then, this multilayer laminate is drilled to form through holes, and the copper foil on the outer layer of the multilayer laminate is etched to form a circuit, and the through holes are also repaired. A multilayer printed wiring board was obtained. "Shakukuwan" - Biphenol shown in the following formula was used as a polyhydric 7-ether, and this was dissolved in MEK to a concentration of 1.5% by weight, and benzyldimethylamine was added as a reaction catalyst to a polyhydric phenol. 3% by weight (0.045% based on the entire solution)
% by weight) to prepare a treatment solution. Using this solution as a treatment solution, a glass substrate surface-treated with an epoxysilane coupling agent was treated in the same manner as in Example 1. The amount of polyhydric phenols adhered to the glass substrate at this time was 1.1% by weight. Then, in the same manner as in the example, a double-sided copper-clad laminate with a thickness of 0.4 am and a multi-no-print wiring board with an 8-layer circuit configuration and a thickness of 2.41 mm were obtained. In addition, (60 parts by weight of a cyanate ester shown in the following formula, 20 parts by weight of an aromatic cyanate ester/phenol shown by the following formula, and 20 parts by weight of the flame retardant used in Example 1) A varnish with a solid content of 70% by weight was prepared by adding 100 ppm of cobalt heptenoate as a catalyst and dissolving these in a 1:1 mixed solvent of MEK and DMF. A double-sided copper-clad laminate with a thickness of 0.41 mm and a multilayer printed wiring board with a circuit configuration of 8 chips and a thickness of 2.4111 m were obtained in the same manner as in Example 1, except that a 4111 m thick multilayer printed wiring board was obtained. A material surface-treated with the same epoxy silane coupling agent as in Example 1 was used, and this glass substrate was not treated with polyvalent 7-7-ols.
The rest was carried out in the same manner as in Example 1 to obtain a double-sided copper-clad laminate having a thickness of 0.4 ff1m and a multilayer printed wiring board having a circuit configuration of 8 chips and having a thickness of 2.41. Examples 1 to 3 and Comparative Example 0 obtained as above
, the moisture resistance, chemical resistance, and copper foil adhesion of a 4 mm thick laminate were measured, and the results were shown to adults. For adults, "water absorption rate" and "copper foil peeling strength" are JI
Measurements were conducted based on SC6481. Also"
"Alkali resistance" is a laminate plate with etched copper foil.
It was cut into cmX 3 caa pieces, immersed in a 10% NaOH aqueous solution at 80°C, taken out at predetermined intervals, washed thoroughly with water, and then observed the surface with a microscope. Evaluation was made based on the time when no change in appearance was observed. . In addition, the inner wall roughness of the through-hole surface and the reliability of the through-hole were measured for the 2.41-thick multilayer printed wiring boards of Examples 1 to 3 and Comparative Example. In each Example and Comparative Example, through-hole drilling was performed using a drill bit with a diameter of 0 and 9 maa, and a diameter of 400 mm.
00 rpm, - feed rate per revolution 50μ
/rev conditions, through-hole plating is performed using a combination of electroless plating and electrolytic plating, and "through-hole inner wall roughness" is measured by observing the cross section of the through-hole with a microscope. Hole reliability was evaluated by observing the cross section of the through hole with a microscope and measuring the depth of penetration of the plating solution. Show the results to an adult. As seen in the results in the table, examples 1 to 3 in which the glass substrate surface-treated with an epoxy silane coupling agent was further treated with a polyvalent filler. Compared to the comparative example in which the glass substrate was not treated with polyhydric phenols, the moisture resistance and chemical resistance were improved as seen in the items of ``water absorption rate'' and ``alkali resistance.'' It is confirmed that the wettability and impregnation of cyanate ester-based (fat) on the glass substrate are improved. , a glass substrate surface-treated with an epoxy silane coupling agent was impregnated with a solution containing polyhydric phenols, and as it dried, the epoxy silane coupling agent and polyhydric phenols were allowed to react. The polyhydric 7-ethyl group reacts with the glycityl group of the coupling agent, and a 7-ethyl hydroxyl group can be introduced into the epoxysilane coupling agent. The wettability and impregnability of the cyanate ester resin can be improved, and the moisture resistance and chemical resistance of the laminate can be improved.

Claims (2)

[Claims] (1) Impregnating a glass substrate surface-treated with an epoxy silane coupling agent with a solution containing polyhydric phenols,
A method for treating a glass substrate for a laminate, which comprises drying and reacting an epoxy silane coupling agent with a polyvalent phenyl. (2) A method for treating a glass substrate for a laminate, characterized in that the solution containing polyhydric phenols according to claim 1 contains a reaction catalyst.