DE2427030C3 - Process for the pretreatment of a carrier surface to be electrolessly metallized and the use of the pretreated product - Google Patents

Description

The invention relates to a method for pretreating a carrier surface to be electrolessly metallized by applying a curable reaction product of a resin component (1) with a Compound containing epoxy groups and a hardener (2) suitable therefor, the carrier surface before the metallization is not to be made hydrophilic in a separate step. The invention (5 a use of the pretreated product.

During the past few years, a market for metallized polymerizate articles has emerged rapidly, what on the functional appearance of the parts coated with shiny metal coatings and those from the Replacement of metal by polymer molded parts results in economic advantages and weight savings is due. With such metal coatings, no pitting and no corrosion occur because a galvanic reaction does not occur between a polymeric carrier and a metal coating can.

Since polymeric materials typically do not conduct electrical current, it is common practice to pass through electroless deposition an electrically conductive layer or an electrically conductive coating, for example made of copper, so that metals, especially copper, nickel and chromium, in an additional Layer thickness can be applied galvanically on the electrolessly deposited copper layer. the

35 electroless metal deposition refers to the electrochemical application of a metal coating to an electrically conductive, non-conductive or semiconducting carrier in the absence of an external electrical power supply. Although there are already some methods of applying such a metal coating by the combined use of electroless and galvanic processes, processes have only recently been developed which result in even minimal adhesion of the electrically conductive coating to the polymer. This is due to the fact that the overall adhesion is determined by the bond strength between the polymer carrier and the electrolessly applied copper layer. Even with these improved processes, usable adhesion can only be achieved with a very small number of polymers, and only if all the production and coating stages of the polymer support are carried out with great care.

Polymers, which are used in particular in the industrial production of printed circuits in electroless metal deposition is carried out to a large extent, epoxy polymers are used in Hardening of non-hardened diglycidyl ethers from bisphenol Α resins, which in turn occurs through condensation obtained from bisphenol A with epichlorohydrin. These epoxy resins correspond the general structural formula

CTI ₂ -CH-CH ₁ -I

OH

OCH ₁ CH-CH, CH ₃

(D

where η indicates the number of recurring units. The various epoxy resins are characterized by their viscosity or their softening point, their epoxy equivalent weight and their hydroxyl number. The epoxy equivalent weight is defined as the amount of resin (g) that contains 1 gram equivalent of epoxy. The epoxy equivalent weight determines the number of recurring units in the epoxy resin chain. The hydroxyl number is defined as the number of hydroxyl group equivalents contained in 100 g of resin.

One of the valuable properties of these epoxy resins, i. H. the diglycidyl ether of bisphenol A and their Modifications, is the easy transition from a liquid or viscous state to a tough, hard, thermoset solids; d. H. the transformation of a linear structure into a three-dimensionally networked one Network. This hardening is achieved by adding a chemically active "hardener". Some hardeners promote the hardening through their catalytic effect, others take part directly in the hardening reaction part and are absorbed in the resin mass

The surface of a molded body made of hardened or crosslinked epoxy resin is hydrophobic and becomes therefore not wetted by liquid with high surface tension. As for electroless metallization As a rule, aqueous sensitizing and activating solutions containing metal ions are used, the resin surface is not wetted. As the sensitizing and activating solutions hit the surface do not wet, the catalytic components are not absorbed by the surface and as a result, metal ion deposition cannot occur.

So far, various methods have been available to create a polymer or plastic surface to make it hydrophilic. A common process used in the metallization of plastics is mechanical Roughening the surface. Originally this surface roughening was done by some kind of mechanical means Exposure such as scrubbing with a slurry of lubricating gel, Treatment in a wet cleaning drum, dry rolling or sandblasting causes after However, this known method is obtained for a copper pattern on a hardened polymer on the Bisphenol A diglycidyl ether base at 25 ° C only adhesion up to 0.54 kg / cm. This adhesion is insufficient for printed circuits with a slip pattern. It has been empirically found that a minimum peel strength of about 0.9 kg / cm at Peeling below 90 ° at a peeling speed of 5 cm / min at 25 ° C is required to

Vt-

prevent the formation of bubbles in a metal coating or detach it from a plastic surface with changes in temperature, and to enable various treatment steps to be carried out such as are conventionally used to produce the copper pattern. The adhesion request for printed circuits is therefore at least 0.9 kg / cm in peeling at 90 degrees at a Äbzugsgeschwindigkeit of 5 cm / min at 25 ⁰ C for 36 μΐη thick copper layer.

Besides, this mechanical roughening is costly in that many parts are surface-treated by hand must be subjected and it in the case of relatively small parts or parts with complicated outlines, it is very difficult to grind the surface evenly using the conventional method. However, this is extremely disadvantageous in the manufacture of printed circuit boards by means of imaging by exposure, for example according to the light-selective known from US Pat. No. 3,562,005 Metallization. When imaging by exposure, high resolution is required. This resolution is limited by the topography of the surface on which the image (pattern) was created. Unless a If mechanical roughening has occurred, for example by sandblasting, the resolution of the image suffers (Pattern) due to the mechanically roughened surface.

In recent years, chemically working roughening or etching processes have been used for various plastics has been developed using strongly acidic solutions. In U.S. Patent 3,437,507 chromic acid treatment of plastics such as B. acrylonitrile-butadiene-styrene copolymers (ABS resins) and amine-cured bisphenol A diglycidyl ether epoxy resins specified to ensure adhesion to improve an electrolessly deposited metal layer on its surface. Here too, as above stated, a minimum adhesion of 0.9 kg / cm for printed circuits can be achieved. One with Chromic acid treated hardened bisphenol A diglycidyl ether epoxy polymer gives values of about 0.54 kg / cm for the adhesion of the applied metal patterns.

Another method commonly used for plastics such as ABS resins involves treating the Plastic with an organic solvent; see US Patent 34 25 946. Which solvents are effective, however, depends on the plastic used and is therefore empirical in nature. One Pretreatment with an organic solvent alone is to increase the adhesion of the metal pattern on cured epoxy resins of the type under consideration

ίο ineffective. A hardened one treated in this way Bisphenol A diglycidyl ether epoxy polymer has an adhesion of about 0.54 kg / cm, while, as stated above, that for printed circuits The minimum value aimed for at 25 ° C is 0.9 kg / cm.

The electroless plating of an untreated epoxy resin, i. H. a freshly cured epoxy resin without pretreating its surface with solvents, etchants, abrasives and the like To make the surface hydrophilic was therefore not previously possible

20 possible.

Proceeding from this, the object on which the invention is based is to provide a method for pretreatment to indicate an electrolessly metallized carrier surface without making the Good adhesion of the surface in a separate process step before the actual metallization Metal layer on the pretreated surface, in particular a peel strength of at least 0.9 kg / cm at 25 ° C.

The inventive solution to this problem is a method with those specified in claim 1 Features. Advantageous further developments of this method emerge from patent claims 2 to 7. Finally, another aspect of the invention relates to the use of the pretreated products for the production of metallized carriers, especially for printed circuits.

The invention thus relates to a method for the pretreatment of an electroless to be metallized Carrier surface, in which a reaction product of resin component (1) and carrier (2) is applied; the following materials are used for this, the parts by weight information always being 100 Parts by weight of resin component refer to:

Resin component (1) from (a), (b) and (c):
(a) 25 to 95 parts by weight of diglycidyl ether based on linoleic acid, namely (a] l an adduct of 2 moles of bisphenol A diglycidyl ether and 1 mole of linoleic acid with the structural formula:

H ₂ C CH-CH ₂ -O -

CH ₃ N- O C. "H ₂ - OH
] C ^ CH CH ₃

C ^- H, O-

OO OH

11 Il \

^X —C CO-CH ₂ -CH-CH ₂ -O

(CH ₂ ) ₇ (CH ₂ ),

CH ₂ - CH = CH- (CH ₂ ); - CH ₃

(CH ₂ ) ₅

CH ₃
with an epoxy equivalent weight of 650 to 750; or

/
OCH ₂ -CH

CH ₂

(a ₂ ) a linoleimeric diglycidyl ether with the structural formula:

ίο

H ₂ C

OO

CH-CH ₂ -OC CO-CH ₂ -CH CH ₂

(CH ₂ ), (CH ₂ ),

< ^^ -CH ₂ -CH = CH- (CH ₂ J ₄ -CH ₃

CH ₃

having an epoxy equivalent weight of 400 to 420; or (a ₃ ) mixtures of components (aj and (a ₂ )).

(b) 0 to 50 parts by weight of reaction product from 40% by weight of acrylonitrile-butadiene copolymer of the structural formula:

HOOC-CH ₂ CH ₅ C-

CN

; CH, CH = CHCH,) s — CH ₂ CH •

CH ₁

-C-CH ₂ CH ₂ COOH (4)

CN

with 2.37% terminal carboxyl groups, 18 to 19% bound acrylonitrile and an average number Molecular weight of 3200, with about 60 wt .-% bisphenol A diglycidyl ether with an epoxy equivalent weight from 180 to 195 or bisphenol F dialycidyl ether with an epoxy equivalent weight from 152 to 167;

(C) as the remainder of the resin component (1) a bisphenol A diglycidyl ether, a bisphenol F diglycidyl ether or a mixture of these;

Hardener (2) from (d), (e), (0 or (g):

(d) a combination of 16 to 60 parts by weight of acid anhydride with 0 to 30 parts by weight of dimer acid, trimer acid or mixtures of trimer acid and dimer acid, namely dimer acid of the structural formula:

O O

Il Il

HO-C-R "-C-OH

where R "stands for the divalent organic groups:

(d,) - CH ₂ (CH ₂ J ₅ CH ₂ -

(d ₂ ) -CH ₂ - (CH ₂ J ₆ (CH ₂ J ₆ -CH ₂ -

CH ₂ CH = CH (CH ₂ J ₄ -CH ₃ (CH ₂ J ₅ CH ₃

(d ₃ ) - CH ₂ CH ₂ -C

CN

(CH ₂ Ch = CHCH ₂ ) S-CH ₂ -CH

CN

-C-CH ₂ CH ₂ -CN

CH ₃ CH ₃

-CH ₂ CH ₂ C - fCH, CH = CHCH ₂ ) 5 _{- CH 2} CH fCH — CH ^ C — CH ₂ -CH ₂ -

CN | _ CN ₁₀ [ COOH JCN

Trimeric acid is a product of the stoichiometric composition C ₅₄ H ₉₆ O ₆ obtained by trimming linoleic acid; wherein at least one dimer acid with the organic radicals {ά $) or ^ d ₄ ) is present in the hardener, provided that the proportion of component (b) is less than 5 parts by weight;

12th

(e) a polyamine in a molar ratio equimolar to the resin component (1),

(F) a mixture of the polyamine in equimolar molar ratio to the resin component and at least 5 parts by weight of acid anhydride; or

(g) a mixture of components (d), (e) and (0-

The resin component contains (per 100 parts by weight of the resin component) χ parts by weight of component ai with the structural formula (2),
with π = Oor I ₁

where with η = 0 an epoxy equivalent of 400 to 420 and with η = 1 an epoxy equivalent weight of 650 to 750 is obtained.

Furthermore, the resin component (1) contains y parts by weight the component b; namely the reaction product of about 40% by weight of a static acrylonitrile-butadiene copolymer of structural formula (4), which has 237% carboxyl groups, an average number Molecular weight of 3200, 18 to 19 wt .-% bound acrylonitrile and a viscosity at 27 ° C of 110 Pa-s, with about 60% by weight of bisphenol A diglycidyl ether from the bisphenol A group an epoxy equivalent weight of 180 to 195 or bisphenol F diglycidyl ether with an epoxy equivalent weight represents from 152 to 167

Finally, the resin component contains ζ parts by weight of a suitable diglycidyl ether from the group of a bisphenol A diglycidyl ether (brominated or non-brominated), a bisphenol F diglycidyl ether or a mixture thereof; where: if for χ + y + ζ - 100, z is less than 100.

A preferred resin component contains about 25 to 95 parts by weight of the linoleic acid diglycidyl ether (x = 25 to 95), about 5 to about 50 parts by weight of component b (y = 5 to 50) and, as remainder c, a suitable diglycidyl ether (z = 0 to 70).

The invention is explained in more detail below with reference to a figure; the figure shows a Cross-sectional view of a laminated body consisting of one coated with a cured epoxy resin Carrier that has been electrolessly metallized.

The invention is described below primarily with reference to an adhesive copper coating, using a bath for electroless plating onto a cured epoxy polymer has been applied with improved adhesion properties.

Component b consists of 40% by weight of the stated acrylonitrile-butadiene copolymer of structural formula (4) and 60% by weight of bisphenol A diglycidyl ether of structural formula (1), the number π of recurring units being an epoxy equivalent weight guaranteed from 180 to 195, or from bisphenol F diglycidyl ether with the structural formula

30th

H, C CH-CH,

CH ₂

-O

O-CH ₂ CH-CH ₂

OH

-0OH ₁ CH-CH ₁ -H

the number of repeating units π reacted in a polymer for 30 minutes at 149 ° C, the

Epoxy equivalent weight of 152 to 167 guaranteed elastomer-modified epoxy resin mixture b formed

stead 45, which presumably has the following structural formula

The diglycidyl ether of bisphenol A or bisphenol has: F is usually mixed with the acrylonitrile-butadiene mixture

O R

> - OCH ₂ CH-CH ₂ -OC-CH ₂ Ch ₂ C-

fCH, CH = CHCH ^ k-CH, -CH

C — CH ₂ CH ₂ —C — OCH ₂ CH — ΦΉ, —ι

• where RffirH or € H ₃ stands

If bisphenol A diglycidyl ether is used as the reactant, the resulting reaction product has an eporyda equivalent weight of 335 to 355, a viscosity of 20 stokes and an acid number less than 0.2 (number of per gram of Reaction resin mixture neutralized mg KOH). If bisphenol F diglycidyl ether is used as a reactant is, the resulting reaction product has an epoxy equivalent weight of 285 to 305, a Viscosity of 15 stokes and an acid number less than 0.2.

The proportion of the elastomer-modified reaction product b ranges from about 0 to 50 parts by weight, preferably from about 5 to 50 parts by weight.

CH ₁ -CH-CH -, - O

Br

or epoxy resins of the structural formula containing both bisphenol A and tetrabromobisphenol A

The remaining part (c) of the resin component (1) consists of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or a mixture of the two, wherein the proportion of component (c) from the amounts of the other epoxy group-containing materials of Resin components (1) depends. The bisphenol A diglycidyl ethers preferably have an epoxy equivalent weight from 170 to about 4000. To make the hardened reaction product fire resistant or flame retardant To make, bromine-containing bisphenol A diglycidyl ethers can also be used, such as 33'Ä5'-tetrabromo-4,4'-isopropylidenediphenol or tetrabromobisphenol A diglycidyl ether of the structural formula

-O- CH ₂ -CH CH ₂

O — CH, - CH- CH, -!

^L O

-C - <^ VO-CH ₂ -CH-CH,

CH ₁

where χ stands for bromine or hydrogen, depending on the manufacturing process. Exemplary bromine-containing components are:

an epoxy resin with an epoxy equivalent weight of 325 to 375, a softening point of 45 up to 55 ° C and a bromine content of 44 to 48% by weight;

45

50

an epoxy resin with an epoxy equivalent weight of 350 to 450 and a bromine content of 50 Wt%.

Typical examples of epoxy resins containing both bisphenol A and tetrabromobisphenol A, are:

an epoxy resin with an epoxy equivalent weight of 450 to 500 and a bromine content of 19 % By weight; and

an epoxy resin having an epoxy equivalent weight of 455 to 500 and a bromine content of 19 to 23 Wt%.

60

Typical bisphenol F diglycidyl ethers have an epoxy equivalent weight of 156 to 180.

The resin component (1) is combined with a hardener (2) and results in the hardenable reaction product Suitable hardeners (2) are

(d) certain acid anhydrides with optionally selected carboxylic acids,

(e) polyamines,

. (f) a mixture of the acid anhydride and the

Polyamine, and
(g) a mixture of components (d), (e) and (f).

Typical examples of suitable anhydrides are marketed under the name "chlorendic anhydride" known _l> 4,5,6,7-hexachloro- ₁ 7 (2,2, l) -5-heptene-23-dicarboxylic acid, also the maleic anhydride adduct of methyl cyclopentadiene with the structural formula

(a light yellow, semi-viscous liquid with a viscosity at 25 ° C of 138.4 mPa-s (commercially available available under the name »Nadic Methyl Anhydride«)), also phthalic anhydride, citraconic anhydride, Glutaric anhydride, maleic anhydride, and mixtures thereof; other suitable anhydrides are set forth in US Pat. No. 3,329,652.

The total amount of non-combined acid anhydride ranges from about 16 to about 60 parts by weight, with an anhydride: epoxy molar ratio of 0.6: 0.9 results in optimal adhesion of the cured reaction product

Furthermore, the acid anhydride can be combined with 0 to 30 parts by weight of carboxylic acid. Suitable Are carboxylic acids

Linoleic acid of the structural formula
OO

Linoltrimeric acid of stoichiometric composition C54H96O6 with an acid number of 145 up to 185 and an average molecular weight of 810,

Azelaic acid of the structural formula

O O

Il Il

HOC— (CH,) ₇ —C -

(16)

(HO-C

C-OH)

(15)

(CH ₂ ), (CH ₂ ),

4 V-CH, -CH =

(CH ₂ J ₅ CH ₃
-that obtained in the trimerization of linoleic acid

CH ₃

statistical acrylonitrile Butadienmischpolymerisate carboxyl-terminated, such as a copolymer of the structural formula (4) with 2.37% of carboxyl groups, 18 to 19% bound acrylonitrile medium number moderate molecular weight of about 3200 and a viscosity of 1 i0 Pa.s at 27 ⁰ C; or

a copolymer of the structural formula
CH,

HOOC-CH ₂ CH ₂ C-CN

JCH ₂ CH = CHCH ₂ ) T-CH ₂ CHl - / - CHCH ₂ ]

CN

COOH

C-CH ₂ CH ₂ COOH (17)
CN

with 2.93% carboxyl groups, 18 to 19% bound acrylonitrile, an average number Molecular weight of about 3400 and a viscosity of 125Pas at 27 ° C.

Preferably in an acid anhydride / carboxylic acid hardener mixture the carboxylic acid content is 0 to about 20 parts by weight combined with about 20 to 60 parts Parts by weight of acid anhydride.

Typical examples of suitable polyamines include dicyandiamine, methaphenyldiamine, hexamethylenediamine, Triethylenetetraamine, polyoxypropylenedinine of the structural formula

H ₂ NCH-J ₁ CH ₂ -OCH ₂ CH-

TT NH ₂

(18)

with η about 2, and

Polyoxypropylenetriamine of structural formula

CH ₂ -

H ₃ C-CH ₂ C-CH ₂ - [(

CH ₁
OCH, CH-

-NH ₂

CH,

-NH,

CH, -

CH

OCH ₂ CH

-NH ₂

(19)

with χ + y + ζ = 5.3.

The polyamine hardener is usually combined so that equimolar proportions of amine hydrogen and Epoxy present. Furthermore, a mixture of the polyamine and a suitable acid anhydride, such as Glutaric anhydride, maleic anhydride, citraconic anhydride and the like can be used as long as the Acid anhydride portion of the mixture makes up about 10 parts by weight

Furthermore, the selected hardener can also be combined with other hardeners or accelerators, such as Benzyldimethylamine. Furthermore, common fillers such as aluminum oxide, Silicon dioxide, titanium dioxide and flame-retardant additives such as antimony trioxide in the resulting resin / hardener mixture can be added.

The mixture of epoxy resin and hardener, the partial curing will be heated for 5 to 60 minutes at 50 to 100 ⁰ C then until homogenized, complete liquefaction and introduction. Alternatively, the mixture can also be used without a pre-hardening heat treatment. Finally, the mixture can also be dissolved in a suitable solvent, such as. B.

Acetone.

As shown with the figure, a substrate can o ^ er Carrier 21 of any material coated on its surface 22 with the curable reaction product will. For the production of printed circuits, the substrate 21 can be made of a rigid (rigid) Material, for example made of glass, metal and the like. Or made of a flexible material, for example a Plastic such as polyester are made. The curable applied to a surface 22 of the substrate 21 The reaction product consists of the resin component (1), the hardener (2) and any solvents, Fillers or additives. The reaction product can in the usual way, for example by spraying, Dipping, spinning and the like. Are applied to the surface 22 and forms the coating or the Layer 23. Layer 23 can be any desired thickness; usually the layer thickness has a Value from 0.01 to 0.50 mm.

030 235/228

The coated substrate 21 is heated to complete cure, such as 5 to 60 minutes at 140 to 170 ⁰ C. Under full cure is to be understood that the originally existing epoxy groups have been consumed during the curing reaction, and the degree of the resulting cross-linking optimum provides physical properties for the desired use. With regard to the specified time and temperature ranges, the IR spectrum shows that the anhydride and epoxy groups have been consumed. In addition, the epoxy polymer is no longer flowable after it has been subjected to a heat and pressure cycle

After completion of this pretreatment process according to the invention is on a surface 24 of cured epoxy layer of the coating 23, a suitable material is applied, such as that when introduced into aqueous or non-aqueous baths for the electroless coating of the resulting components.

The particular advantage of the cured coating produced according to the invention is that the untreated epoxy resin, i.e. the cured epoxy resin obtained (which also includes an aged material and / or a material recovered from waste material) has not been pretreated (etched, solvated, sandblasted and the like. ) must be in order to make it hydrophilic, in order to subsequently deposit a well-adhering metal layer on it in an electroless manner. After sufficient thermal aging or post-drying, for example, adhesion of the electrolessly or galvanically applied metal coating with a peel strength of at least 0.9 kg / cm at 25 ° C. is obtained. For example, the thermal aging conditions between 10 can min at 12O ⁰ C and 1 h at 180 ° C provided.

If the material to be applied is an electrolessly deposited metal, a customary, electroless metallization process can be used for the deposition. For this purpose, the hardened, not further pretreated, "virgin" epoxy resin surface 24 does not have to be etched, roughened, solvated, swell etched and the like, in order to guarantee the acceptance of the sensitizing, activating and metallizing solutions common in electroless metallization. Typically, the cured epoxy resin surface 24 is thoroughly rinsed with water or some other suitable cleaning agent. A vigorous flushing is essential ^r to virtually all impurities to be removed, whereby a contamination of the sensitization, activation, o and plating solutions can be prevented. Contamination, in particular of the electroless metallization bath, is undesirable because its durability is impaired as a result.

Example I 1

To produce a liquid, hardenable reaction product, the following components are combined:

150 g (= 75 parts by weight per 100 parts by weight Resin component of the mixture) commercial epoxy resin, namely an adduct of 2 mol Bisphenol A diglycidyl ether (epoxy equivalent weight 180 to 195) and 1 mol of linoleic acid (component ai) with the structural formula (2);

50 g of component (b), namely the reaction product of 40% by weight of an acrylonitrile-butadiene copolymer of structural formula (4) with 60% by weight bisphenol A diglycidyl ether;

40 g of chlorendic acid anhydride; and
5 g of phthalic anhydride.

^{The mixture obtained was heated to 60 °} C. for 30 minutes for liquefaction. The liquid reaction product was applied to the surface 22 of the substrate 21 shown in the figure, made of commercially available epoxy glass laminate, a 0.01 to 0.50 mm thick, partially cured epoxy polymer layer 23 was formed. The coated substrate 21 was heated to complete curing of the Epoxypolymerisatschicht 23 for 30 min to 150 ⁰ C. Complete curing was indicated by the disappearance of the functional anhydride and epoxy absorptions in the IR spectrum

The substrate 21 coated with fully cured epoxy polymer was immersed in a conventional aqueous tin oxide hydrate solution (3.5% by weight aqueous solution of SnCb × 2 H2O and 1% by weight) for 1 min at 25 ° C. for sensitization without further pretreatment. % Aqueous solution of SnCU.5 H2O), immersed in a 0.05% strength by weight aqueous PdCb solution for activation, then rinsed with water for 2 minutes and then immersed in a commercially available bath for electroless copper plating. The electrolessly deposited copper layer 26 was then reinforced by electroplating up to a 0.038 mm thick copper layer and then dried ^{at 120 ° C. for 10 minutes.}

The measurement of the peel strength of the applied metal layer at a peel of less than 90 ° at a speed of 5.1 cm / min at 25 ⁰ C gave a value of 2.56 kg / cm and at 90 ⁰ C a value of 0.2 kg / cm.

Example 2

The procedure of Example 1 was essentially repeated; differently, the curable reaction product was generated from the following components:

30 g (= 30 parts by weight per 100 parts by weight resin component) of component ai;

30 g of component b, namely the reaction product of 40% by weight of butadiene-acrylonitrile copolymer with 60% by weight bisphenol A diglycidyl ether;

40 g of brominated bisphenol A diglycidyl ether with an epoxy equivalent weight of 450 to 500 with 18 to 20 wt .-% bromine of the structural formula (13) given above;

as hardener 30 g of chlorendic acid anhydride and 16 g of adduct of methylcyclopentadiene and maleic anhydride of the structural formula (14) given above.

The combined resin and hardener components were prior to the application of the reaction product on the substrate. 21 not heated. The substrate coated with the reaction product substrate was heated to complete curing for 30 minutes at 12O ⁰ C and further dried according to the metallization for 30 minutes at 170 ⁰ C. The peel strength of the metal layer

was at 0 ⁰ C from 0.46 to 0.66 kg / cm, at 25 ° C from 1.61 to 1.79 kg / cm and at 90 ⁰ CC 89 to 1.25 kg / cm.

Example 3

The procedure of Example 1 was essentially repeated; differently, the curable reaction product was generated from the following components:

40 g (= 40 parts by weight to 100 parts by weight of Resin component) component ai;

30 g of component b, namely the reaction product of 40% by weight of the acrylonitrile-butadiene copolymer with 60% by weight bisphenol F diglycidyl ether; and

30 g of brominated bisphenol A diglycidyl ether with the structural formula (13);

as hardener a mixture of:

20 grams of chlorendic acid anhydride;
10 g adduct of methylcyclopentadiene and maleic anhydride of structural formula (14);
10 grams of citraconic anhydride;

1 gbenzyldimethylamine; and

2 g of antimony trioxide.

The combined components were applied directly to the substrate 21 and at over the course of 1 hour Fully cured at 150 ° C. After post-drying, the metal layer had a peel strength of 1.43 kg / cm at 25 ° C.

Example 4

The driving according to Example 1 was essentially repeated; In contrast, the curable reaction product was produced from the following components:

30 g (= 28.8 parts by weight per 100 parts by weight of the resin component) of diglycidyl linoleic acid (Component 82) of structural formula (3);

34 g of component b, namely reaction product of 40% by weight of a butadiene-acrylonitrile copolymer with 60% by weight bisphenol A diglycidyl ether; and

40 g of brominated bisphenol A diglycidyl ether of structural formula (13);

as hardener a mixture of:

25 grams of CWorendic anhydride;

25 g adduct of methylcyclopentadiene and maleic anhydride of structural formula (14); and

1 g accelerator of the structural formula

Example 5

The procedure of Example 1 was essentially repeated; the curable reaction product was different generated from the following components:

g (= 17 parts by weight per 100 parts by weight of resin component) linoleic acid diglycidyl ether (component a ^);

1250 g component ai; and

g brominated bisphenol A diglycidyl ether of structural formula (13);

as hardener a mixture of:

⁵ 1000 g of chlorendic acid anhydride;

1000 g adduct of methylcyclopentadiene and maleic anhydride of structural formula (14); 400 g copolymer of structural formula (4); 200 g of a ground mixture of 70 parts by weight of antimony oxide and 30 parts by weight of a butadiene-acrylonitrile copolymer with 33% acrylonitrile, a spec. Weight of 0.98 and an average Mooney viscosity of 80; and
50 g benzyldimethylamine.

A 0.10 mm thick glass fabric was impregnated with the combined components and then irn Complete hardening of 6 min at 160 ° C and 15 min at 150 ° C. After a 30 min Drying at 170 ° C. was the peel strength Metal layer 1.25 to 1.61 kg / cm at 25 ° C.

Example 6

The procedure of Example 1 was essentially repeated; In contrast, the curable reaction product was produced from the following components:

g (= 50 parts by weight per 100 parts by weight resin component) component ai;

g brominated bisphenol A diglycidyl ether of structural formula (13);

as hardener a mixture of:

500 g adduct of methylcyclopentadiene and maleic anhydride of structural formula (14); 300 grams of chlorendic acid anhydride; 240 g copolymer of structural formula (4); 200 g linoltrimeric acid;
66 g paste of 60 parts by weight of antimony oxide and 40 parts by weight of bisphenol A diglycidyl ether; and

20 g benzyldimethylamine.

(CH ₂ I ₂ NCH:

CH ₂ N (CH,),

A 0.10 mm thick glass fabric was impregnated with the combined components and then im Completely cured in the course of 20 minutes at 150 ° C.

(20) After drying for 30 minutes at 170 ° C., the

Peel strength of the copper layer 2.86 to 3.58 kg / cm at 25 ° C.

Example 7

In a solution

The combined components were applied directly to the substrate 21 and over the course of 30 min fully cured at 150 ° C. After drying, the metal layer showed a peel strength of 1.43 kg / cm at 25 ° C.

g component ai;
6.2 grams of hexanediamine;
ml of xylene; and
ml of acetone

a 0.10 mm thick glass fabric was immersed, and

then h in the course of 1 fully cured at 14O ⁰ C, After metallization analogously to Example 1 was dried for 10 minutes at 120 ⁰ C. The peel strength of the copper layer is less than 90 ° at a speed of 5.1 cm / min was 1.43 kg / cm at 25 ⁰ C.

Example 8

A commercially available epoxy resin-glass hardboard was made with a solution

550 g component
16.2 grams of diethylenetriamine;
150 ml of xylene; and
300 ml of toluene

coated to form a 0.013 mm thick layer and cured under ambient conditions for 1 day. After the metallization analogous to Example 1, ^{drying was carried out at 140 °} C. for 1 hour. The peel strength of the copper layer was 1.43 kg / cm.

Example 9

A commercially available epoxy resin-glass hardboard was made with a solution

150 grams of component ai;

3 g diethylenetriamine;

25 grams of polyoxypropylenediamine

(18) with π = 15.9;
50 ml of xylene;

75 ml isophorone; and
100 ml acetone

coated to form a 0.051 mm thick layer and cured at ambient conditions for 1 day. After the metallization analogous to Example 1, ^{drying was carried out at 140 °} C. for 1 hour. The peel strength of the copper layer was 2.15 kg / cm at 25 ⁰ C.

Example 10

Essentially the procedure of Example 9 was repeated; was deviating prior to metallization 30 minutes long dried at 14O ⁰ C at 140 ⁰ C and after metallization. 1 The peel strength of the copper layer was 1.43 kg / cm.

Example 11

A commercially available epoxy resin-glass hardboard was made with a solution

125 g component

12.2 grams of polyoxypropylenetriamine of structural formula

(19) with λ · + y + ζ = 5.3; and
125 g of toluene

coated and cured for 1 h at 120 ° C Metallization analogous to Example 1 was 10 minutes long

the structural formula

dried at 12O ⁰ C. The peel strength of the copper layer was 1.34 kg / cm at 25 ° C.

Example 12

An epoxy resin glass hardboard was mixed with a solution of:

75 g component

25 g of component b, namely the reaction product from

40 wt .-% butadiene-acrylonitrile copolymer with

60% by weight bisphenol A diglycidyl ether;
12 grams of polyoxypropylenetriamine of structural formula (19); and
25 g xylene

coated and ^{cured at 120 °} C. for 1 hour. After the metallization analogous to Example 1, ^{drying was carried out at 170 °} C. for 30 minutes. The peel strength of the copper layer was 1.07 kg / cm at 25 ⁰ C.

Example 13

An epoxy resin glass hardboard was mixed with a solution of:

24 g of component b, namely the reaction product of 60% by weight of bisphenol A diglycidyl ether with 40 wt .-% butadiene-acrylonitrile copolymer;

80 g of bisphenol A diglycidyl ether with an epoxy equivalent weight of 180 to 195; and
32 g polyoxypropylenetriamine of structural formula (19)

coated and ^{cured at 100 °} C. for 1 hour. After the metallization analogous to Example 1, ^{drying was carried out at 170 °} C. for 30 minutes. The peel strength of the copper layer was 1.57 to 1.88 kg / cm at 25 ° C .; at C 1.25 kg / cm and at 90 ° C 0.63 kg / cm.

Example 14

An epoxy resin glass hardboard was mixed with a solution of:

50 g of component b, namely the reaction product of 60% by weight of bisphenol A diglycidyl ether with 40 wt .-% butadiene-acrylonitrile copolymer;

50 g of tetrabromobisphenol A diglycidyl ether with an epoxy equivalent weight of 450 to 500 (Formula 13); and 13 g of polyoxypropylenetriamine of structural formula (19)

coated and cured for 30 minutes at 120 ⁰ C. The cured panel was plated and then 30 minutes at 17O ⁰ C dried, the peel strength of the metal layer was 1.73 kg / cm at 25 ° C.

For this] sheet of drawings

Claims (8)

Patent claims: 1. Process for the pretreatment of a carrier surface to be electrolessly metallized by application a curable reaction product of a resin component (1) having an epoxy group containing compound and a suitable hardener (2), wherein the carrier surface before the Metallization cannot be made hydrophilic in a separate step, characterized in that that the following materials are used as resin component (1) and hardener (2) The parts by weight data always relate to 100 parts by weight resin component: Resin component (1) from (a), (b) and (c):
(a) 25 to 95 parts by weight of diglycidyl ether based on linoleic acid, namely (a]) an adduct of 2 moles of bisphenol A diglycidyl ether and 1 mole of linoleic dimer acid with the structural formula: H ₁ C CH- CH, - O- 9H OO OH Il Il I - CC - 0 - CH ₂ - CH - CH, - (CH ₂ J ₇ (CH ₂ J ₇ / OCH ₇ -CH CH, with an epoxy equivalent weight of 650 to 750; or
(a ₂ ) a linoleic acid diglycidyl ether with the structural formula: O O / \ Il H ₂ C CH-CH ₂ -OC O O Il / \ CO-CH ₂ -CH-CH ₂ (CH ₂ J ₇ (CH ₂ J ₇ -CH ₂ -CH = CH- (CH ₂ J ₄ -CHj CH ₃ having an epoxy equivalent weight of 400 to 420;
or (a ₃ ) Mixtures of components Ui ₁ ) and (a ₂ ). (b) 0 to 50 parts by weight of conversion product from 40% by weight of acrylonitrile-Buladiene copolymer Structural formula: CH., CH ₃ HOOC CH ₂ - CH ₂ -C '4 (CH ₂ CH = CHCH ₂ J ₅ -CH ₂ ChT- C- CH ₂ -CH ₂ -COOH CN CN CN with 2.37% terminal carboxyl groups, IS up to 19% bound acrylonitrile and a middle one number molecular weight of 3200, with. iwa 60 wt .-% bisphenol A diglycidyl ether with a Epoxy equivalent weight from 180 to 195 or bisphenol F diglycidyl ether with an epoxy equivalent weight from 152 to 167; (C) as the remainder of the resin component (1) a bisphenol A diglycidyl ether, a bisphenol F diglycidyl ether or a mixture of these; Hardener (2) from ~ (d), (e), (f) or (g): (d) a combination of 16 to 60 parts by weight of acid anhydride with 0 to 30 parts by weight. Dimer acid, trimer acid or mixtures of trimer acid and dimer acid, namely dimer acid of the structural formula: O Il Il HO-C-R "-C-OH where R "stands for the divalent organic groups: (d.) -CH ₂ (CH ₂ J ₅ CH ₂ - (d ₂ ) -CH ₂ - (CH ₂ J ₆ (CH ₂ J ₆ -CH ₂ - CH ₂ CH = CH (CH ₂ J ₊ - -CHj CH ₃ (d ₃ ) -CH ₂ CH ₂ -C- CN or CH, (d ₄ ) -CH ₂ CH ₂ C-CN (CH ₂ J ₅ CH ₃ (CH ₂ CH = CHCH ₂ ) j -CH _{2 -CH} (CH ₂ CH = CHfH ₂ J ₅ -CH ₂ CHl -— f CH -C-CH ₁ -CH, - CN CH,
CH ₂ C-CH ₂ - CH ₂ - \ COOH CN CNj ₁₀ Trimeric acid is a product obtained by trimerizing linoleic acid and having the stoichiometric composition C ₅₄ H ₉₆ O ₆ ; where at least one dimer acid with the organic radicals (d ₃ ) or (d ₄ ) is present in the hardener, provided that the proportion of component (b) is less than 5 parts by weight: (e) a polyamine in a molar ratio equimolar to the resin component (1), (f) a mixture of the polyamine in an equimolar molar ratio to the resin component and at least 5 parts by weight of acid anhydride; or (g) a mixture of components (d), (e) and (f). 2. The method according to claim 1, characterized in that a hardener (2) with at least one Acid anhydride, the amount of which results in an acid anhydride: epoxy molar ratio of 0.6 to 0.9: 1, is used. 3. The method according to claim 1 or 2, characterized in that the resin component (1) 75 Parts by weight of component (ai) and 25 parts by weight of component (b) with bisphenol A diglycidyl ether contains and with a hardener (2) of 20 parts by weight of chlorendic acid anhydride and 2.5 parts by weight Phthalic anhydride is combined. 4. The method according to claim 1 or 2, characterized in that the resin component (1) 30 Parts by weight of component (ai), 30 parts by weight of component (b) with bisphenol A diglycidyl ether and 40 Parts by weight of brominated diglycidyl ether of bisphenol A with 18 to 20% by weight of bromine and one Contains epoxy equivalent weight of 450 to 500 and with a hardener i.t from 30 parts by weight Chlorodic anhydride and 16 parts by weight of methylcyclopentadiene-maleic anhydride adduct is combined. 5. The method according to claim 1 or 2, characterized in b5 characterized in that the resin component (1) 40 parts by weight of component (ai), 30 parts by weight of component (b) with bisphenol F diglycidyl ether and 30 parts by weight of brominated diglycidyl ether of bisphenol A with 18 to 20 wt .-% bromine and an epoxy equivalent weight of 450 to 500 contains and with a hardener (2) composed of 20 parts by weight of chlorenedic acid anhydride and 10 parts by weight of methylcyclopentadiene-maleic anhydride adduct and 10 parts by weight of citraconic anhydride is combined. 6. The method according to claim 1 or 2, characterized in that the resin component (1) 28.8 Parts by weight of component (a2), 32.7 parts by weight Component (b) with bisphenol A diglycidyl ether and 38.5 parts by weight of brominated diglycidyl ether Contains bisphenol A with 18 to 20% by weight of bromine and an epoxy equivalent weight of 450 to 500, and with a hardener (2) made of 24 parts by weight of chlorendic acid anhydride and 24 parts by weight of Me- ethyl cyclopentadiene maleic anhydride adduct
is combined. 7. The method according to claim 1 or 2, characterized in that the resin component (1) 50 Parts by weight of component (ai) and 50 parts by weight of brominated diglycidyl ether of bisphenol A with 18 to 20 wt .-% bromine and an epoxy equivalent weight of 450 to 500, and with a Hardener (2) from 15 parts by weight of chlorendic acid anhydride, 25 parts by weight of methylcyclopentadiene maleic ; l., fi ^^ acid anhydride adduct, 12 parts by weight of dimer acid (d3) and 10 parts by weight of trimer acid is combined.
8. Use of the pretreated products according to any one of claims 1 to 7 for production Metallized carriers, in particular for printed circuits.