DE3208198A1 - Process for bonding copper foil to laminate moulding material - Google Patents

Abstract

The present invention relates to a process for producing a bond between an unprocessed, chromate-treated surface of a copper foil and a surface of a laminate moulding material in the production of a copper-plated, laminated product. In the process according to the invention one of the unprocessed chromate-treated surfaces of the copper foil and the surface of the laminate moulding material are treated with a solution of a silicon compound represented by the general formula YRSiX3 (where Y represents a functional group reactive with high molecular weight compounds, R a hydrocarbon-containing linking group for producing a link between Y and silicon and X a hydrolytic group coupling with silicon), or an adhesive film mixed with a silicon compound represented by the general formula is formed on the surface treated with the silicon compound and the copper foil and the laminate moulding material are bonded together.

Description

Nippon Dehkai Co., Ltd,
2-1-1 Nishi Shinjuku
Shinjuku-ku

Tokyo Japan

5 ·. March 1982
Attorney file: 552.202

Process for connecting a copper foil to a laminate IORM material

Description:

A number of methods have been proposed for joining copper foils to laminate molding materials and practically used. In a common method of joining a copper foil to a laminate sheet material a surface of the copper foil is electrolytically roughened, and the roughened copper foil is' connected to the laminate molding material directly or through an adhesive layer to provide a Copper clad, laminated board or plate. When the so obtained, clad with copper, Laminated board is used as a printed circuit board by etching the board, it often occurs suggest that the etching stains the laminated board and the resulting printed circuit board has insufficient hydrochloric acid resistance.

One aspect of the present invention relates to a method for connecting a copper foil to a

ß £ D ORiGSMAL _

unprocessed, chromate-treated surface, such as it is produced industrially, with a surface of a Lam ± nat-3? standard material or of materials, wherein the unprocessed, chromed, treated surface the copper foil or the one surface of the lamina t - ^ ormma te rials or materials with a Solution of a silicon compound is treated, which is represented by the general formula YRSiX (where Y is a functional group reactive with high molecular weight compounds, R is a compound of Y and silicon are a hydrocarbon-containing linking group and X is a hydrolytic coupling group with silicon Group is), and 'those with the silicon dioxide compound acted surface with the surface of the larainate "molding material or .the chromate-treated surface of the copper foil is bonded, or alternatively a mixture of the silicon compound is placed on the chromate-treated surface of the copper foil which is represented by the above general formula, and an adhesive and the film are bonded to the laminate molding material to be a copper clad laminated one Product. Is such a copper clad, laminated product as a printed circuit is used, it eliminates the possibility of contamination on the resulting printed matter Circuit occurs, and the hydrochloric acid resistance of the printed circuit is improved.

The invention relates generally to a method of connecting a copper foil with a Larainat-mold material or materials, including the strength of the bond between the copper foil and de ^r; j laminar Formniaterial or the laminate-molding materials and to increase the chemical resistance significantly to

"^ ρ λ ry ORIGINAL

^ "* COPY

-G.

improve, particularly the hydrochloric acid resistance of copper clad laminated products which the connected copper foil and. Laminate molding material or materials.

In particular, the present invention relates to a method for joining a copper foil to a Laminate molding material or materials in which one on an unprocessed surface of a copper foil formed chromate layer or a surface of a laminate molding material treated with a 'solution which contains a silicon compound represented by the general formula YRSiX (where Y is a is a functional group reactive with high molecular weight compounds, R is a connection between Y and silicon Hydrocarbon-containing linking group; and X is a silicon-coupling hydrolytic group is), the t transformed surface with the surface of the, Laminate foramaterials or those treated with chromate On the surface of the copper foil, the above-mentioned silicon compound is alternatively mixed containing adhesive film is formed on the chromate-treated surface of the copper foil -and the adhesive film with the surface of the laminate molding material is connected.

A number of methods have been proposed for making copper clad laminated products and practically used, which are used for the manufacture of printed circuit boards. One common of these conventional methods is to "increase the strength of the connection between a copper sheet and a laminate form material or -materials a new surface of a copper fleece electrolytically roughened, which by the electrclytic or rolling process was obtained unu with

BATH

to be joined to the laminate molding material, a Series of dendrite protrusions are formed on the surface of the roughened copper foil, and then is the 'roughened surface of the copper foil with bonded to the surface of the laminate molding material. Especially when fiberglass-based epoxy resin is used as a Laminate molding material is used, the copper foil after the electrolytic treatment and the Formation of the knot-shaped gate projections on the laminate Fprmamaterial arranged, the roughened. Surface is down, .and they are heated under pressure, to make a copper clad, laminated product. If paper-based phenolic resin is used as a laminate molding material, the roughened surface of the copper foil is applied beforehand a phenolic resin adhesive layer is applied, the resin adhesive layer can dry outdoors, .the copper foil is placed on the laminate molding material, with the adhesive layer facing down, and they are heated under pressure to make one with copper to produce clad, laminated product. In the known methods described above, the Strength of the connection between the copper foil and the laminate molding material through the degree of roughness determined on the surface of the copper foil, which is generated by electrolytic roughening. Both However, the known methods described above have disadvantages: When to increase the strength of the connection between the copper foil and the laninate molding material the copper foil is highly roughened and / or has a large number of dendrite protrusions the copper foil is formed and if so then by connecting one of these. Copper foil with the lamina t-shaped material, clad with copper,

BAD LOCAL COPY

/ to-

laminated product is etched to create a printed circuit, then occurs when the printed Circuit has the serious disadvantage that part of the roughened copper foil on the complete, printed circuit remains, which is easy. results in the occurrence of a laminate stain that is common referred to as a "stain" or "dirt". To remedy this disadvantage, the roughened The surface of the copper foil is laboriously "electrolytically coated with zinc". It turned out- represents that the roughening treatment described above but not entirely to increase the chemical resistance, especially the hydrochloric acid resistance of the copper clad laminated product.

The present invention is based on the object; to provide a connection method by which the problem of the occurrence of pollution is eliminated and the laborious additional step required in the known connection methods becomes superfluous and in which, in addition, the chemical resistance of the remitting, copper-plated, chemical product is increased.

In the known method for joining a copper foil to a laminate molding material only the physical means used in the form of dendrite protrusions that are on the surface the copper foil can be formed. The invention is based on the idea that the strength of the connection and chemical resistance can be increased to whom. a chemical that acts as a chemical bridge

BAD OR! GJMAL

between the copper foil and the laminate molding material arranged'wird to the copper foil and the laminate molding material to connect with each other. There have been a number of vigorous chemical studies performed that as such, chemical Bridge can be used. A series of experiments confirmed that sufficient or strong Connection between a copper foil and a laminate molding material can be achieved by the chromate-treated surface of the copper foil or a surface of the laminate molding material with a solution of a silicon compound which is known and has the general formula YRSiX ^ (where Y is a functional group reactive with high molecular weight compounds, R is a compound of Y with silicon hydrocarbon-containing linking group and X one with silicon coupling group hydrolytic group), and the surface of the copper foil treated in this way with the surface of the Laminate molding material is connected and vice versa or a layer of an adhesive to which the silicon compound has been added v. rde, on the treated Surface of the copper foil is formed, whereupon then the surface provided with adhesive the copper foil with the surface of the laminate foramaterial is connected. The present invention is based on the results of the experiments.

The invention will now be explained further: Y in the general formula described above contains functional groups which couple with high molecular weight compounds by reaction with the same, e.g. vinyl, - amino, diamino, chlorine, epoxy, mercapto and kethaaryloxy and R contains groups, Cie create a bridge between Y and silicon. e.g. -CH ^ '^ io · -H ₂ -

-CH ₂ -, -CH ₂ OCH ₂ - and -CH ₂ -NH-CH ₂ -. Furthermore, X contains groups which couple with silicon (Si), for example halogen. Methoxy and methoxyethoxy. High molecular compounds that can couple with Y groups in the above general formula include a variety of high molecular compounds such as phenol, epoxy, acrylic, melamine, polyimido and polyester, which are included in laminate molding materials used in the present invention ,, or high molecular weight rubber system compounds, eg butyl rubber, nitryl rubber and polyisoprene rubber. The series of silicon compounds shown in the above general formula YRSiX-, which are used for the connection between that with chromate. treated ι surface of the copper foil and the laminate molding materials

used which high molecular weight compounds

! exhibit. It was investigated for the invention how

Such silicon compounds can help increase the strength of the connection, and the result of the The examinations listed are explained below:

(1) From Maeda's dissertation published in "The Journal of the Metal Finishing Society of Japan" 31 (S), 402, published in 1980, it can be taken into account that the copper foil useful in the present invention is that treated with chromate Surface is a copper foil, on which there is a chromate film, the outer layer of which Contains hydrate chromium oxide (such a copper foil is later referred to as "M-OH").

(2) As the silicon compound in the above general formula YRSiX, in the form of an aqueous. Solution is used, can be taken into account according to the invention be that the duron X in general Formula expressed hydrolytic group below

■ u * j ORiGMAL

- Yes -

• / II-

the action of water produces silanol: YRSiX ₅ + 3H ₂ O - ■ *> YRSi (OH) ₃ + 3HX

(3) If the copper foil with the above described, surface treated with chromate and that according to the invention Laminate molding material, which is a high molecular compound with resin or rubber (which later collectively referred to as P) are molded under the action of heat and pressure, create the Y group in the silicon compounds in the above general formula and those in the laminate molding material or glue containing high molecular compound between them a chemical bond. It should also be taken into account that the silanol in the reaction formula shown in (2) with M-OH contributes (1.) reacts to produce a strong bond as by the reaction formula described below is shown:

P + YRSi (OH), + M-OH → P-YR-Si-O-M

It can thus be considered that the silicon compound used in the invention between .the surface of the copper foil treated with Chroroat and the surface of the larcinate molding material is to provide a strong chemical bond between them, creating the silicon connection to the adhesion between the adjacent surfaces the copper foil and the lair: inat forium material in a; - complete, copper-clad Lamir.at product contributes.

© OPY

/ Ik

A number of typical examples of silicon compounds that are used in the present invention will now be shown Invention are useful.

(1) Y-Ohlorpropyl-Trimethoxysilan (boiling point 196 ⁰ G)

GlGH ₂ · CH ₂ · GH ₂ · Si (OGH ₃ ) ₃

(2) ß> - (3, A -Ep oxy cyclohexyl) Ethyl-Tri.me thoxy-

silane. (Boiling point 310 ⁰ C)

OCHp-CHpSi (OCH,),

(3) vinyl tris ( β- methoxyethoxy) silane

(Boiling point 285 ° C)

CH ₂ = CHSi

(4) γ-methacryloxypropyl-trimethoxysilane

(Boiling, ankt 255 ° G)

CK-

if

(5) r'-G-lycidoxypropyl-trimethoxysilane

(Boiling point 29O ⁰ G)

GH ₀ CHOH ₀ OGH ₀ CH ₀ CH ₉ Si (OGH,),, c. ■ c c. cc yy

(b) / -Arainopropyl-triethoxysilane (boiling point 21

IiH ₂ CiI ₂ Jn. JH ₂ ^ K OJH ₂ Ch ₃ ) ₅

ÜAD ORiGSWAL

- .y6 -

(7) N- / i- (aminoethyl) - V-aminopropyl-trimethoxy-

silane (boiling point 259 ° C

NHgCHgCHgNHCHgCHgCHgSi

The present invention is not limited to the use of these silicon compounds. Any of the above silicon compounds can be effectively used to treat the copper foil useful in making a copper clad laminated product regardless of the thickness of the foil. For example, the silicon compound can be used effectively for copper foils with a thickness in the range of 5-35 µm. An unprocessed surface of a copper product that is industrially produced is slightly roughened, treated with chromate and then treated in a solution of one of the abovementioned silicon v -; - r: -ir.jui: gen. The copper foil treated in this way is connected to the Laoinate standard material. The concentration of the solution of the silicon compound which is to be used for treating the copper foil is preferably in the range between 0.001-5%. This is because the treating effect of the silicon compound solution is insufficient when the solution is diluted to a concentration below 0.001 f>. Although the silicon compound solution can be used in a concentration above 5 ° , it is not advisable for economic reasons to use the silicon compound solution in such a high concentration.

BATH ORIGINAL

_ τ ν _

If not the surface of the copper foil is treated with a solution of a silicon compound, but instead, a surface of the laminate molding material is treated with such a solution, According to the invention, the thus treated surface of the laminate molding material is treated with that treated with chromate Surface of the copper foil connected, which is not treated with the solution of the silicon compound has been to achieve the same effect as can be obtained when the surface of the copper foil is treated with the solution of the silicon compound. In such a case, the surface of the Laminate molding material with the silicon compound in a Men-θ between 0.001 to 5 wt. ^ Based on the weight of the laminate molding material, soaked. Furthermore, it is also intended according to the invention, that the chromate-treated surface of the copper foil has an adhesive film on top, which with a silicon compound in an amount between 0.001 to 5 wt. ^ i, based on the weight of the Solids content in the adhesive is mixed, and the adhesive film is bonded to the laminate molding material.

When the chromate-treated surface of a copper foil and a surface of a Laainat molding material are bonded to each other by the method of the present invention, the surface of the copper foil exhibits excellent adhesive strength with respect to the surface of the laminate molding material to be bonded to the surface of the copper foil even if the chromate-treated surface of copper is used, which is ι oce; rough as a result of the in.:uc t.rie Ilen hrzei.-gun ^ rough; π ° ι üocur:;. : has been slightly roughened to a degree to the

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Not to contaminate the surface. By using the copper foil treated in this way, a copper clad laminated product for use as a printed circuit board with an excellent Hydrochloric acid resistance can be easily produced. When a laminate molding material with a glass fiber, which has been impregnated with halogenated epoxy resin by using an aromatic amine hardener, and a copper foil according to the method according to the invention be joined together to form a heat-resistant, copper-clad, laminated In producing the product, the resulting laminated product was found to be deficient have been remedied, e.g. the insufficient hydrochloric acid resistance, which in the case of the with copper clad, laminated products occur.

The invention will now be based on a few examples which the method according to the invention was carried out successfully, described in detail. In everyone: of the three examples, the thickness of the copper foil used was 35 p.

Example 1

A copper foil that is 35 mm thick is electrodeposited in a conventional acid bath to produce a copper electroplating coating on the surface of a titanium cathode. The copper foil is then separated from the surface of the cathode and then washed out with water. The copper is adjusted to a pH of 35 5 g / l solution: immersed in! ^ C ^ O ^ · 2I ^ 0 and obtained for one minute at 20 C with a KatrioenstroffiGichxe of 1 A / a :: · , u ·: to treat the roughened surface of the copper foil ,

and then taken out of the bathroom. Then the copper is washed out with water and dried, to obtain a test piece for a copper foil having a chromate layer on its roughened surface is deposited.

There were two identical copper foil test pieces underneath produced under the same conditions using the same procedure described above ' became.

The test pieces are immersed in three different ethyl alcohol solutions of γ-glycidoxypropyl-trimethoxysilane (which is a silicon compound useful in the present invention) which are diluted with water and adjusted to pH 4.5 to 5.0 with acetic acid and has a concentration of 0.01 fo, 0.1 $> and 3.0 ^, respectively. The residence time in each solution is 1 minute at normal temperature. After removal from the respective solutions, the test pieces at room temperature are dried and ANCC: .liegend arranged i a dryer with a Temperatur.von 110 to 120 ⁰ C and there for 3 minutes forcibly dried. The dried test pieces are removed from the dryer. Each of the test pieces is then placed on an epoxy verse izien with glass fibers. ^j ι, with oils lit Chrc- ^ atbeh ^ ae ^ ". f- surface of the test piece ^ i-Lec nee :, ut: ie;. points, ui.-j them wc2;: e :. at a« - .-:!. Li'ujä von- 1Cl *., · /, Jt: · at Vc- -'J 30 Lii.ut .'- i. Liii ..- 'ai>:' -. Y..p ::: l, u:. \ ei :, rr.iz Koipi "-: · pl ^ ttie: tes, ia:,; ii; je: Lee Tests tiijr. ;: ^ eri.sjf.:., wi.-l2: .e ..- üie IU :. f. \. iic: .e :. <- \. ^ζ ~ Χ- · -Ό x <- '' · ■■ - UUi ¹ Wt ^1. , j; . Ϊ + '- ue. ";

Ί tv I ^

BATH

Copper foil control piece, which is not connected to the silicon compound was treated as described above, connected to an epoxy resin sheet, which is identical to that which is used in the manufacture of the above-described inventive, with copper plated, laminated test pieces was used. The conditions here are the same as described above in order to obtain a copper-clad, laminated control piece, which is the same Has dimensions like the test pieces according to the invention. Those according to the invention clad with copper Test pieces and the control pieces are tested in terms of their peel strength, deterioration rate investigated against cyanide pickling and the rate of deterioration compared to hydrochloric acid pickling, using test procedures (A) through (C) described below.

(A) Peel Strength Test Method -

The test for examining the peel strength or the adhesion is carried out in accordance with JI3 C6431 "Copper-Glad Laminated Sheet for Use as Printed Circuit Test Procedure ".

(B) Rate of deterioration by gyanide stain

The copper-plated, laminated test piece is kept immersed in a 1G aqueous solution of potassium cyanide at 70 ° C. for 30 minutes and then removed from the solution. The test piece is examined for the peel strength, which indicates the deterioration rate of the test piece by J ■ i r.zei r t.

BATH ORIGINAL

- rs -

(C) Test method for examining the rate of deterioration caused by hydrochloric acid pickling

The copper-clad laminated test piece becomes. Immersed in a mixture solution consisting of a hydrochloric acid reagent for 1 hour at normal temperature and water in equal amounts. Then the test piece is removed from the solution. That so "treated Test piece is examined for peel strength, which is the rate of deterioration by hydrochloric acid stain against a control piece that has not been treated with the silicon compound is.

The results of the investigations are shown in Table -1 below.

Table 1
Test item

0.01 O ,1 ~ Z , 0 O , 70 Peel strength
ο
(kg / cm) 1.67 1 , 75 " 1 , 77 9 , 2 Obscuration
rate through oyanide
Stain (^) 4.5 3 , 5 4th , 0 9 , 5 Spanking
rate by hydrochloric acid
Stain (? '>) 1.5 1 , C 1 , 3

The following results from Table 1 above: If the: ui and Jr.roxa ι ber.andei ten Ub * rl'iäouen oer copper foil have been treated in solutions with a silicon compound, they prove. with copper

BATH

plated, laminated test pieces with such copper foils versus the control pieces, their Copper foil not treated with silicon dioxide was subject, in terms of peel strength and chemical resistance, in particular the resistance to hydrochloric acid, as significantly improved. When the concentration of the Silicon compound is above 3.0 ^, which is not shown in Table 1, then tend various properties of copper clad laminated products for acceptance. When the concentration of silicon compounds is below $ 0.001, on the other hand, the test results show that the silicon compound in such a low concentration does not exhibit the desired effect.

Example 2

An unworked surface of a 35 Mtn thick copper foil is obtained in the same way as was described in connection with Example 1. This surface is at a temperature of 2C ^U C

2 and a cathode current density of 4 A / dm in a bath for the production of a copper electroplating coating, roughened, soft 100 g / l CuSO, 5H ₂ and 50 g / l HgSO. to such an extent that the surface is not stained. The roughened surface of the copper foil is then treated with chromate under the same conditions as in Example 1. The chromate-treated surface of the copper foil is then treated with the same silicon compound as in example 1 and under the same conditions as in example 1. After the copper foil has been treated with the silicon compound, it is placed on an epoxy resin mixed with glass fibers, whereby the

ORIGINAL, COPY

. «22 ·

The surface treated with the silicon compound faces downward, and they are bonded together at 155 ° C under a pressure of 100 kg / cm to obtain a copper-clad laminated test piece having dimensions of 250 × 250 × 2 .mm. Two similar plucked foil test pieces are produced under the same conditions and with the same method as were used to produce the first-mentioned copper foil test piece of Example 2, only the concentration of the solution of the silicon compound being different . I ¹ Ur purposes of comparison control pieces with the same dimensions as the first-mentioned copper clad laminated test piece of Example 2 was produced, wherein there are the same conditions as were described in connection with the first-mentioned, the copper-plated laminated test piece, with the exception that the copper foil is not treated with the silicon compound. The pieces are then examined for the same league sheepxes as in BeisDiel 1. The results of the investigations are shown below.

Table 2

Test item fj »» »^« »^ X control

O , 01 ü , ι 3 , 0 I, 4-0 Peel strength
f * / \ O , 07 2 , 15 2 , 1G Deterioration
rate by Cysnid-
Stain (£) 2 VJl 0 , 5 1 , 5 5, ώ, Vers 3hlechtei \;:; rP-
rate through 6a 1 z-
acid stain (■ / j 1 , 2 1 , '■ 0

The following results from Table 2: When the copper foil is treated with the silicon compound the copper clad, laminated tea pieces of the invention are opposite to the test pieces, the copper foil of which has not been treated with the silicon compound, with regard to the pull-off strength • and the chemical resistance is improved, in particular, the resistance to hydrochloric acid. Thus, the surface of the copper foil must be roughened not 'done to the extent that the surface of the copper foil is soiled, as is usually necessary is.

Example 3

Copper clad, laminated test pieces are prepared using essentially the same procedure as in Example 1 except that an ethyl alcohol solution of g. -Aminopropyl-triethoxysilane is used as a silicon compound; unprocessed, offset with glass epoxy resin is used as a laminate Formnaterial with the silicon compound in the proportions of 0.01 ^c / t, 0.1 ^c ji and 3.0 ° / o impregnated, based on the; respective weight of the epoxy resin mixed with the glass fibers, - and then the volatile constituents of the laminate porcelain materials are evaporated and dried to remove these constituents. The 35 .mu.m thick copper foils, which have been treated with chromate as described in Example 1, are arranged on the thus treated glass fiber parts, with the surfaces of the copper foils treated with chromate facing downwards. They are heated under pressure, and the same bed-in fi <iii ^r e: -. vie beici Example 1 prevail, u: .. - :: i ι copper-clad, laminated test pieces to be obtained which have the same dimensions as the test pieces

BATH ORIGINAL

-SLk-

Examples 1 and 2 include. Purely for comparison purposes become copper clad, laminated control pieces which have the same dimensions as the test pieces of the invention and below essentially the same conditions as in Examples 1 and 2 have been treated with the Except that the laminate molding material does not have the silicon compound has been treated. The test pieces according to the invention and the control pieces are examined for their properties, and the results of the examinations are indigenous Table 3 shown.

. , Table 3 test item f ???!? ^ ™ ?? l !! l control

0 , 01 0.1 3 , 0 0.81 Peel strength
(kg / cm ² ) 1 , 60 1.75 1 , 70 6.4 Obscuration
rate by cyanide
Stain (^) 4 , 3 4.2 3 , 7 10.5 Deterioration
advise by salt
acid stain (-; l) 1 ,8th 1.5 0 , ö;

From table 3 it follows: If that with the silicon compound soaked laminate i'orarcaterial and the sit Chrcnat treated copper foils bonded together are the peel strength and the chemical resistance, especially the resistance to Hydrochloric acid, the resulting copper-clad laminated products, significantly improves regeneration n jer Xontroilötücke.

BATH

32ÜB133

Example 4

The unprocessed surfaces of 35 / im thick copper foil are lightly roughened in the same way as was described in Example 2 '. The roughened surfaces of the copper foils are then treated with chromate, and adhesives with a solids content of 18 $ phenolic resin are applied, which ν -methacryloxypropyl-trimethoxysilane in proportions of 0.01 wt. $, 0.1 wt. Fi or 3 , 0 wt. based on the solids content in each adhesive. The volatile constituents contained in the adhesive are then removed to form a 30 µm thick layer of adhesive on each of the treated surfaces of the copper foils. Each of the copper foils thus treated is placed on a phenolic resin layer on a paper base or a substrate such as the laminate molding material with the surface provided with the adhesive facing downward, and they are bonded together in the manner described in Example 1 to obtain a copper-clad laminated test piece of dimensions 250 250 χ 2 xnui . For comparison purposes, control pieces with the same dimensions as the test pieces are made under the same conditions as described in Example 3, with the exception that the roughened surface of the Xontroll copper foil is not treated with an adhesive containing a silicon compound. The test pieces and the control pieces are examined for their properties by the same method as described in Example 1. The results of the investigations are given below.

- ir! -

Test item

Table 4

Amount of silicon compound added based on the weight of the contaminant content in the adhesive
(Wt. ^)

control

0.01 0.1 3.0 1, 65 Peel strength
(kg / cm ² ) 2.13 2.27 2.18 ⁸ ' 3; Deterioration
rate by cyanide
Stain {$>) 4.1 3.8 2.4 9, 8th Deterioration
advise by salt
acid stain ($>) 1.3 0.8 1.2

From table 4 "results: Even if the copper foil, in which the adhesive film on the treated with chromate Surface has been applied with your Laminate molding material is bonded to one with ..To obtain copper clad laminated product, is the copper clad laminated product versus the copper clad laminated product Improved product, the copper foil of which has not been treated with the silicon compound, in terms of on chemical resistance and also on peel strength.

BATH

Claims (14)

Expectations : 1. A method for producing a bond between an unprocessed, chromate-treated surface of a copper foil and a surface of a laminate molding material in the production of a with. Copper clad, laminated product, characterized in that that one of the unprocessed, treated with chromate Surfaces of the copper foil and the surface of the larainate form material with a solution of Silicon compound, which is represented by the general formula YRSiX, (where Y is a functional group reactive with high molecular weight compounds, R is a linking group with hydrocarbon to create a connection between Y and silicon and X one with silicon coupling hydrolytic group)> or that one having a represented by the general formula BATH COPY Silicon compound mixed adhesive film on the surface "treated" with the silicon compound is formed, and that the copper foil and the laminate ·. Molding material are connected to each other. 2. The method according to claim 1, characterized in that the unprocessed, chromate-treated surface of the copper foil is used as the surface to be treated with the silicon compound. 3. The method according to claim 1, characterized in that one of the surfaces of the laminate molding material is used as the surface to be treated with the silicon compound. 4. The method as claimed in claim 2, characterized in that the unprocessed, chromate-treated surface of the copper foil is treated with 0.001 to 5% by weight of a solution with a silicon compound, based on the weight of the laminate material. 5. The method according to claim 3> characterized in that the surface of the laminate molding material with 0.001 to 5 wt. $ A solution with a silicon compound, based on the weight of the laminate molding material is treated. 6. The method according to claim 1, characterized in that the reactive with the high molecular weight compounds functional group was selected from the class which contains vinyl, amino, diamino, chlorine, epoxy, mercapto and methacryloxy that the hydrocarbon to produce a connection between Y and silicon-containing linking group was selected from the class which -OHp -OH ₂ -'J ^ -1 -CH ₂ -, -CH ₂ OJH ₂ - and -CH ₂ -IiK-CH ₂ -, unc -sr- .3- that the silicon coupling hydrolytic group selected from halogen, methoxy and methoxyathoxy containing Class was selected and coupled with silicon. 7. The method according to claim 1, characterized in that the high molecular weight compounds contains phenol, acrylic, melamine, polyimido and polyester, which . is contained in the laminate IORM material. 8. The method according to claim 1, characterized in that the high molecular weight compounds contain butyl rubber, nitryl rubber and polyisoprene rubber. 9. The method according to claim 1, characterized in that the silicon compound represented by the general formula YRSiX was selected from the class, which ^ -Chlorpropyl-trimethoxysilane, ■ ß> - (3,4 - epoxycyclohexyl) ethyl-trimethoxysilane, Vinyitris (/ 5-methoxyethoxy) silane, y-methacryloxypropyl-trimethoxysilane, glycidoxypropyl £ Triroethoxysilan, y-aminopropyl-triethoxysilane and N-β- (Arainoäthyl ) -i ^ -aminopropyl-trimethoxysilane contains. 10. The method according to claim 1, characterized in that the laminate Forramateriai one with epoxy resin ■ Includes impregnated fiberglass fabric base. 11. The method according to claim 2, dadu rc h geke nnzeich that a phenolic acid adhesive is applied to the Ghromat-treated surface of the copper foil, which is mixed with the silicon compound, and that the laminate molding material comprises a paper base impregnated with phenolic resin . PAD COPY 12. Method of making a connection between: an untreated, chromate-treated one Surface of a copper foil and a surface of a laminate molding material in manufacture a copper clad, laminated product for use as a printed circuit board, : characterized in that the unprocessed, ■ '■; Chromate treated surface of the copper foil ; with a solution one by the general formula YRSiX ^ illustrated silicon compound treated J becomes (where Y is one with high molecular weight compounds Γ reactive functional group, R is a hydrocarbon linking group containing a compound between Y and silicon and X is a hydrolytic group coupling with silicon), and that a connection between the I surface treated with the silicon compound the copper foil and the one surface of the • laminate molding material is made. 13. Method for establishing a connection · between - ■. one unprocessed, treated with chromate \ Surface of a copper foil and a surface ; . of a laminate molding material during manufacture «. a copper-clad, laminated product ΐ ducts for use as a printed circuit, I characterized in that the unprocessed, I chromate treated surface of the copper foil I an adhesive film is applied that the adhesive contains a silicon compound, which is represented by - the general formula YRSiX (where Y is a functional group reactive with high molecular weight compounds, R is a linking group containing hydrocarbons to establish a connection between Y and silicon, and A is an ax silicon-coupling hydrolytic group BATH ORIGINAL Group), and that the adhesive film applied to the surface of the copper foil and the a surface of the laminate molding material with each other get connected. 14. A method for producing a connection between an unprocessed, chromate-treated surface of a copper foil and a surface of a larainate molding material in the production of a • copper-clad laminated product for use as a printed circuit, ' characterized in that one surface of the laminate Molding material is treated with a solution of a silicon compound, which is represented by the general formula YRSiX, (where Y is a functional group reactive with high molecular weight compounds, R is a linking group containing hydrocarbons to establish a connection between Y and silicon, and X is a silicon-coupling hydrolytic group), and that the silicon-treated surface of the laminate molding material and the unprocessed, chromate-treated surface of the copper foil are connected to one another.