DE1940220A1 - Resins suitable for preparing layered or - Google Patents

Abstract

Resin comprising the condensation product of 1-2.5 moles of formaldehyde and 1 mole of a mixture of phenol and an aralkyl phenol in which the molecular proportions 1 pt. of phenol to 0.05 - 0.4 pt. of aralkylphenol (I) can be impregnated onto leaves or plates to afford stratified materials. (I) is pref. the reaction product of phenol and styrene.

Description

PATENT LAWYERS T940220

dr. W. Schalk dipl.-ing. P. "Wirth · dipl.-i ng. C, Dannenbexv.

DR-V-SCHMIED-FCOWARZIK-DR-R-WEIMHqLD: Λ

6 FRANKFURT AM MAIN OR. ESCHENHEIMER- STR. S9

■■ -2LB 2394 /

3P GHEMIGlIS "(ü.Xi-) Limited: _; . ..., Britannic House ■ _" ■ / -. · ^: - '; .- """'. .. Moor La2ie, _: . '-' ■ :.. Λ ^ London EG 2-, England '.: _ ■ _

Resins for electrically usable Schiclitstoffe and processes for the production of these.

The present invention relates to a method for the production of resins for electrically usable Laminates,

Heretofore, cresol-based resins have been used because of their low cost and superior electrical properties, Widely used as compared to phenolic-based resins Binder resin used for electrically usable laminates. Because of the increasing shortage of cresol natural sources and their increasing cost compared to phenol, are also cresol-based resins expensive. Phenol is cheap and readily available., however, phenol-formaldehyde resins, odez · resins, aos, Phenol mixed with cresols or xylenols and - .. Formaldehyde to laminates with poor electrical Properties and lower water resistance

009840/2082

- ■ ..... '■ ^: ■■■■■ ·, ■ - 2 - "■ ■ - ■■: ■..; ■

with laminates made with unmodified cresol
or xylenol resins.

The object of the present invention is. hence the. Sces. ■ £?:. a resin for electrically usable laminates,
which is characterized in that it is a condensation product of 1 to 2.5 molecular parts of formaldehyde and 1 molecular part of a mixture of phenol and a
Aralkylphenol product, the molecular
Quantities of phenol to aralkylphenol product in one
ratio of about 1 (phenol) to about 0.05 to 0.4
(Aralkylphenol product).

The term `` aralkylphenol product ¹¹ is used here as a reaction product. Understood by phenol with an aromatic tinyl compound, above the named product in ■. ^;
Ortho and / or para position to the phenolic ilydro ^ l 'group with formaldehyde has reactive sites.
Suitable aromatic ^ vinylidene compounds are z.3.
Styrene, egg, methylstyrene, ortho-, meta- and para- methyl styrene, ortho-, meta- and para-ethylstyrene and ring-substituted mono- and dihalostyrenes. The preferred aromatic
Vinylidene compound is styrene.

Suitable aralkylphenol products and processes for
these are described in the literature (e.g. in
"Experimental Plastics and Synthetic Resins"'by GP-.
D ¹ AIeIiO, John Wiley Press 1964, p. 30). The aralkylphenol product can be prepared by adding an aromatic vinylidene compound to phenol at a molecular ratio of 1 part of phenol to about 1 to 2 parts
table vinylidene compound in the presence of acid Friedel Crafts catalysts in a known manner,
will.

QQ98A0 / 2082

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In general, the aromatic vinylidene compound is used. ^. . ·. " _: Slowly to your phenol, which contains the acid or Irriedel-Graf-ua-KJatalysator _f such as concentrated sulfuric acid, joluenesulioiic acid, boron fluoride or stannous chloride, /" at an temperature of about 50 to 150 G added. The aralkylphenol product can be used in crude formol: ne further treatment for the production of the Karse according to the invention or it can be distilled off, and the aralkylphenol from any polymeric material present or from aralkylphenol compounds which are in the ortho or para position, are not reactive to formaldehyde. It is preferred that the aralkyl phenolic oil product be free of phenolic compounds which are non-reactive in the ortho or para position to formaldehyde.

Ss is a surprising advantage of the invention Resins that they are good electro-usable laminates even if these are made from crude, i.e. unrefined, axalkylphenol products.

The condensation reaction of formaldehyde with the mixture of phenol and the aralkylphenol product should be at least can sometimes be carried out under alkaline conditions. Preferred is ammonia or an ataine, e.g. 'Iriätaylaciin, used.

The reaction is preferably carried out at a temperature of about 50 to 120 ⁰ G.

The formaldehyde can be used in any form as a Paraverbindurig or similar formaldehyde polymers or as aqueous Solution, e.g. formalin, can be used.

0098AO / 2062

Preferred amounts of aralkylphenol product to phenol in the phenolic mixture are from about 0.05 to 0.25 molecular parts of aralkylphenol product to 1 part phenol, and the preferred range of total phenolic Compounds to formaldehyde is 1 molecular part of the total phenolic compounds to "1.0 to 1.5 molecular parts formaldehyde.

If necessary, the resin can be modified by adding additives, such as fillers, plasticizers, stabilizers and flame retardants.

Compartment of an embodiment of the present invention in the process for the production of electrically usable laminates, foils or layers with the inventive Impregnated or coated, the foils or resins. Layers pre-hardened and then by heat and Print deformed into laminates *

For the satisfactory impregnation or coating of the Layers or foils, which can consist e.g. of Kraft paper, asbestos paper, cotton or glass fabric or wood the resin as a solution in an organic solvent, e.g. in methanol, ethanol, toluene or methyl ethyl ketone, be used. "A particularly preferred solvent is denatured industrial alcohol, us. it's a beneficial one Feature of the present invention that the Resins generally in aqueous, denatured industrial alcohol are soluble.

The impregnated or coated layers or films, v / ground to a temperature of about 70 to 170 ⁰ C, preferably about 90 to 13O ⁰ C, heated before they joined together and pressed under heating to a laminate.

00 9840/2062 '

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This in itself. known pre-hardening is used? to the; Removal of the solvent and allows the hardening of the resin to proceed so far that during the following: heating. and compression stage, optimal pleating properties are obtained. Optimal flow properties are achieved when the resin is sufficiently flowable under the heat and pressure conditions to produce good adhesion between the layers or foils of the laminate, but has little or no tendency to emerge laterally from the laminate. -. """"'"-"' - "-_- - -.

The laminates made from the resins of the invention can be in any desired form; e.g. as flat; ^; Foils or round or rectangular, wound tubes. The laminates can "be used in Hieder- or high frequencies and for use be plated in · Fernühertragungs- and similar electronic equipment, for example with copper.-'.-..

The laminates can also be used for purposes where electrical properties are not important, however, are those made from the resins of the invention Laminates for electrical applications: "Sector "particularly suitable.

The following examples serve to explain the present invention. Example 1 "tracks manufacture of a resin according to the invention and Example 2 Wschrerbt the production of an electrically usable laminate from the Harz.

Example 1 . ■

1880 g of phenol and 8 g of concentrated sulfuric acid were combined with a stirrer, reflux condenser and thermometer -given piston. The msclrun'g was .on 130 to

009 84 0/2062

14O ⁰ O heated and 2080 g of styrene containing 15 ropes;. Per Mill p-tert-butylcatechol contained, was slowly and continuously added within 90 minutes, v / ooei. the reaction was maintained at 130 to 14O ⁰ C. After further heating in this temperature for a further 30 minutes the mixture to 60 ⁰ G was cooled and there were added 7 tnl · ammonia (d. = 0.910) to give a crude styrenated / phenol product.

Distillation of a sample of this product under reduced pressure (20 mm Hg) indicated that this approximately 10 # unreacted phenol, 80 # monostyrene, is a boiling point phenol. point from 190 to 210 ⁰ C and about 10 ■ $ di- and tri-styrene "sated phenol and polymer material. '■' · ■ ', -"'

In a flask, which was equipped with a stirrer, reflux condenser and! Thermometer, were 1116 g of phenol, the red not .distilled styrenated phenol product (594 g), 1785 g of Pormalin (etv / a 37 & ev ^. ^) And 90 g of ammonia ( "d = 0.910) ,, the mixture was heated for one hour ^N back flowing, was applied followed by a vaccum (20 mm Hg) until the resin clear and reaches a temperature of 75 ⁰ C / was. the resin obtained showed, after being diluted with 1500 g of a "denatured alcohol (76% by weight ) , a clear, pale orange solution with a viscosity of 28 cps.

Example 2 - · ■ - ^: -

The solution from Example 1 was used for impregnation electrical usable kraft paper is used, with a nominal / ' Dry resin content of 50 wt. 50 was obtained. laugh the ■ 60 minutes pre-curing of the impregnated paper at 100 ° C Was the necessary for the production of a 1.6 mm laminate Number of layers 45 minutes at 145 C and 70 kg / cm, pressed. The Polie, coldly removed from the press, had

χ given.

0098A0 / 2062

a dielectric ^{strength of 74 KV} "and the via adsorption of a 38.1 mm laminate square" was 21.1 mg. 24 hours. The laminate conformed to the following British Standard regulations:

Grade 1 B.S. 1137 (194-9). ' P.3 B.S. 2572 (1955)

which proves that he has good electrical properties and a possesses good water resistance.

0098AO / 2062

Claims (6)

Claims 1. Resin for electrically usable laminate, characterized in that it has a condensation product of about 1 "to 2.5 molecular parts of formaldehyde and 1 molecular Part of a mixture of phenol and an aralkylphenol product comprises, v / 6at the molecular Quantities of phenol-to-aralkylphenol product in one Ratio of about 1 (phenol) to about 0.05 to 0.4 (Aralkylphenol product). 2. Resin according to claim 1, characterized in that the Aralkylphenol product is the reaction product between phenol and styrene. 3. Resin according to claim 1 and 2, characterized in that the aralkylphenol product by the reaction of an aromatic vinylidene compound with a phenol in the presence of a catalyst in a molecular ratio of 1 (phenol) to about 1 to 2 (a'romatische Vinylidene compound). 4. Resin according to Claim 1 to 3, characterized in that -da3 it by condensation of the crude aralkylphenol product made with phenol and formaldehyde / st. ■ 5 .. Resin according to claim 1 to 4, characterized in that the molecular ratio of alkylphenol product to phenol -about 0.05 to 0.25 to 1. 6. Resin according to claim 1 to 5, characterized in that the molecular ratio of the total phenol product to formaldehyde is in the range from 1 to about 1.0 to 1.5, 0 0984 0/20 62