DE1569016B2 - MANUFACTURE OF PLASTIC-IMPREGNATED CELLULOSE MATERIAL - Google Patents

Description

OH

OH

OH

3 4

The for the plastics used according to the invention indirectly as crosslinking agents without further conversion

Resin binder used unsaturated polyester settlement can be used,

are known. As starting compounds according to the process

It is often desirable to use, for the meltable, water-soluble synthetic resin binders used according to the invention, flame-retardant polyesters which are saturated with unsaturation products of a phenol and an aldehyde. For this purpose, unsaturated polyesters, which are produced according to known methods, are known and can be used. The phenol-aldehyde, either a Diels-Alder adduct of a hexahalogen resin, can also be soluble in organic solvents, cyclopentadiene and an unsaturated polycarbonate such as acetone and they should not be converted into the acid compound or a Diels-Alder adduct of an io insoluble and cured resin (C-stage) hexahalocyclopentadiene and an unsaturated one. Contained when using phenol and polyhydric alcohol. The preferred formaldehyde has the phenol-aldehyde condensate unsaturated polyester, the reaction products are the following formula
of a Diels-Alder adduct from an unsaturated
Polycarboxylic acid with a hexahalogencyclopenta- 15
dien, another unsaturated carboxylic acid I
bond and a polyhydric alcohol. / '

Examples of Diels-Alder adducts of a hexa- HOCH ₂ - | -
halogencyclopentadiene and unsaturated polycarbonate

acid compounds that can be used, 20

are 1,4,5,6,7,7-hexachlorobicyclo- (2,2, l) -5-hepten- in the η a value of about 1 to 10 and often higher

2,3-dicarboxylic acid, or its anhydride or its has, provided the condensate is fusible and in acetone

Mono- or dimethyl ester or its chloride, 1,4,5, or other organic solvents is soluble.

6,7,7 - Hexachlor - 2 - methylbicyclo - (2,2,1) - 5 - hepten- The phenol-aldehyde condensate can for example

2,3-dicarboxylic anhydride, 1,4,5,6-tetrachloro-7,7-di- as contain more than 1 mole of aldehyde per mole of phenol, alo

fluorbicyclo- (2.2.1) -5-hepten-2,3-dicarboxylic acid, 1,4,5, be resol type.

6,7,7-Hexachlorbicyclo- (2.2, l) -5-hepten-2-acetic acid- For the production of novolaks with different-

3-carboxylic anhydride and the Diels-Alder adduct borrowed molecular weights can be the amount of the

of hexachlorocyclopentadiene with fumaryl chloride. the phenol to be condensed aldehyde varies

Examples of Diels-Alder adducts of a hexa- 3 ° are. The melting point of the finished condenser

halogencyclopentadiene and an unsaturated multi- sation product can be determined by the molecular weight

Valuable alcohols are 1,4,5,6,7,7-hexachloro-2,3-bis- of the novolaks. Preferably is

hydroxymethylbicyclo- (2,2,1) -5-heptene, 1,4,5,6,7,7- the molar ratio of aldehyde: phenol in the case of

Hexachlor - 2,3 - bis - hydroxymethylbicyclo - (2,2,1) - twist of a monofunctional (monovalent) or

2,5-heptadiene, 3- (1,4,5,6,7,7-hexachlorobicyclo- [2.2,1] - 35 difunctional (dihydric) phenol between 0.5

5-hepten-2-yl) -methoxy-1,2-propanediol, 1,4,5,6-tetra- and 1.0 mol per mol. When using a trifunk-

chloro-7,7-difluoro-2,3-bis-hydroxymethylbicyclo- (2,2,1) - ionic (trihydric) phenol may be the preferred

S-hepten ^ AS.o ^ -Hexabrom-iz ^ -bis-hydroxymethyl- upper limit of the amount of aldehyde about 0.85 mol

bicyclo- (2.2, l) -5-heptene, 3- (l, 4,5,6-tetrachloro-7,7-di- per mole of phenol amount to the formation of insoluble

fluorbicyclo-ß ^ lj-S-hepten-i-yrj-methoxy-l ^ -propane- 4 ° and infusible condensation products

diol. The making of these connections is in shun.

U.S. Patent 3,007,958. You can also use phenol-aldehyde condensation

According to the invention, other halogen products using at least 1 mol

containing polyester are used, as they are z. B. produce phenol per mole of aldehyde. The usable

derived from tetrachlorophthalic anhydride. The phenols and aldehydes specific to the 45 are above

Production of the aforementioned halogen-containing boards described and also those described above

Alder adducts and polyesters required poly-alkaline catalysts can be used. It is

carboxylic acid compounds and polyhydric alcohols, however, more common for this condensation an acidic

can be made from the aforementioned compounds catalyst, such as sulfuric acid, hydrochloric acid or oxalic

be asked. ⁵ ° acid to use.

The Diels-Alder adduct of a Hexahalogencyclo- For the preparation of the invention used

Pentadiene can also be present in the crosslinking agent. Resin binder emulsions are preferred

Examples of such crosslinking agents are diallyl diluents for the phenol-aldehyde condensate

1,4,5,6,7,7-hexachlorobicyclo- (2,2,1) -5-heptene-2,3-di-water. However, you can also use other diluents

use carboxylate, diallyl, 4,5,6,7,7-hexachloro-2-methylbi- 55, which use the phenol-aldehyde condensate

cyclo- (2.2, l) -5-hepten-2,3-dicarboxylate, diallyl-1,2,4,5, dissolve sate, e.g. B. Mixtures of water with alcohols,

6,7,7-heptachlorobicyclo- (2,2,1) -5-hepten-2,3-dicarboxy- such as isopropanol, butanol and amyl alcohol, or

lat and triallyl-l, 4,5,6,7,7-hexachlorbicyclo- (2.2, l) - mixtures of water with acetone or others

5-hepten-2-acetate-2,3-dicarboxylate. These compounds include ketones and the like. The proportion of the polyester

gene can by reacting hexachlorocyclo- ^6o to phenol-aldehyde condensate in the invention

pentadiene with the corresponding unsaturated di- according to used synthetic resin binder emulsions

carboxylic acid and esterification of the resulting dielectric depends on the type of product desired.

Aider adduct with an unsaturated alcohol, such as However, the proportion is generally

Allyl alcohol. You can also use in the range of about 1 part by weight of polyester each

use other crosslinking agents with advantage, e.g. B. ⁶ 5 parts by weight of phenol-aldehyde condensate to about

the reaction products of hexachlorocyclopenta- 20 parts by weight of polyester per part by weight of phenol-

diene or with isoprene or butadiene, which is an A idehyde condensate. The preferred range is

Maintain reactive double bond, the un, _N between 5 and 15 parts by weight of polyester per gen

5 6

weight phenol-aldehyde condensate. The amount of pressures in the order of magnitude of 3.5 to 176 kg / cm ² ratio of phenol-aldehyde condensate to be used to produce the desired layer thinner in the emulsion is generally molding material. The pressing temperatures are in the range of 0.2 to 1 part by weight per part by weight generally in the range of 140 to 170 ⁰ C.

Diluent, preferably in the range of 0.3 5 Other known methods of making up to 0.8 parts per part by weight of diluent. Laminates can also be used with the invention die Emulsion is prepared by mixing the cellulosic material treated in accordance with the application liquid unsaturated polyester, the unsaturated.

The following examples illustrate the invention.

Phenol-aldehyde condensate in the diluent. 10

The emulsification is often carried out in the presence of Example 1

Emulsifier carried out, but is such a means

unnecessary. Suitable emulsifiers are: A synthetic resin binder emulsion is

bonds with strongly polar groups made on the outside:

phatic or aromatic residues. Typical 15-10 parts of dicumyl peroxide are used with 1000 parts Examples of such compounds are alkylaryl poly- an unsaturated polyester resin mixed with a ether alcohols, polyoxyethylene sorbitan monolaurate and a polymerizable mixture of styrene and the

Sodium lauryl sulfonate. Settlement product of polycarboxylic acids and a

The carrier material to be impregnated is based on cellulose polyhydric alcohol, and with a base is treated with the synthetic resin propeller mixer according to the invention at 700 to 800 rpm for 10 minutes binder emulsion. This can be stirred up. Thereafter, 100 parts of water different manner will be made: for example, can be the soluble phenol-formaldehyde condensate with 50 TEI ■ ^ support material for a suitable time to sink a in a container len acetone and 100 parts of water with the aid of which contains the emulsion, or the propeller mixer can be mixed for 5 minutes. The carrier material is then continuously fed through this container with the aid of a propeller roller. Mix the emulsion with a mixer. An emulsion is obtained, and paper made from 0.36 mm thick cotton lint can also be sprayed onto the carrier material

or a web of the carrier material can be cut through cellulose in 28 x 28 cm sheets with a roller, which is moistened with the emulsion and weighs 15 g. The arches are in. The working temperature can be immersed in the binder emulsion for 5 minutes for 5 minutes, preferably between room temperature and about 30 ° C material is treated with the emulsion, it is allowed to dry. Each sheet of paper weighs approximately 37 g. Five excess expire or squeezes it off and dried paper sheet are in a platen press überdann the carrier material at a temperature up to 35 and superimposed at about 21 kg / cm ² 12 minutes, 150 ° C at 132 ⁰ C pressed. The laminate obtained

If the binder emulsion is tested on the cellulose, and it has the material specified in Table I, it probably supports the properties,
Diluents present in the emulsion have a ratio of> ie 1 2

Penetration and swelling of the cellulose fibers. The 40th

This increases the surface area of the cellulose fibers. In this example, the results of the

which explains a more thorough and uniform averting of the phenol-aldehyde condensate and the storage of the synthetic polyester, which is insoluble in the diluent, on cellulose material in the two-stage resin, ie the polyester, on the surface of the drive. Sheet of the fibers used in Example 1 is made. The enlargement of the openings of the paper are immersed in a bath for 5 minutes, which allows the entry of the phenol-aldehyde - the phenol-formaldehyde condensate used in Example 1, which remains within the fibers, itself contains condensate. Afterwards, the sheets are removed when the diluent is removed during drying and the bath, hardening is evaporated by squeezing rollers. The binding agents can be added and additives added for 5 minutes at 120 ° C in an oven, which dries in the thinner. The sheets obtained will then be soluble in a medium. As soon as the cellulose material is sunk with a bath, which is saturated with the emulsion used in Example 1 and then dried and contains polyester. The sheets are cured from the bath, the fibers are removed from their origin, passed through rollers and returned to the borrowed state for 5 minutes, but the phenol remains dried at 120 ° C. Five aldehyde condensates treated in this way and the polyester in the cellulose sheet are dispersed on top of one another in a multi-stage press. During curing, the individual synthetic resins are laid and crosslinked at about 21 kg / cm ^{2 for} 12 minutes at 132 ° C. and a compression is carried out. The laminate obtained is tested for stiffening of the product obtained. and has the properties given in Table I.

The properties of the invention with the synthetic resin binder are shown in the table below

treated cellulose materials are suitable before the laminates produced in Examples 1 and 2 in addition to the production of laminates. Such as well as that of a commercial laminate with Laminates can be easily made using ordinary phenolic resin as a binder, one can see several layers of treated cellulose- It can be seen that the properties of the

lanes together with layers of other fabrics, binder emulsion according to the invention produced how to clarify plastic films, e.g. B. made of polymethacrylic 65 laminates are much better than those of the acid methyl ester and a less expensive base, commercial laminate made from ordinary z. B. made of wood, stacked and built up phenolic resin, and they are usually the same or better than in a mold, e.g. B. there is a multi-stage press in which the properties of the two-stage process

produced laminate. Of particular importance is the fact that the electrical properties the laminates produced with the binder according to the invention are better than those of the laminate produced by the two-stage process.

Table I.

ASTM test standard condition
the sample

example 1

Example 2

Commercial laminate

Flexural Strength, kg / cm ²

Barcol hardness

Water absorption,%

Layer thickness, mm

Dielectric constant, 10 ⁶ Hz

Loss factor, tg <5, 10 ⁶ Hz

Insulation resistance, megohm.
Paper content,%

D-790 D-570 D-150

D-150 D-150 D-257 A
A.
D-24/23

D-24/23
D-24/23
C-96-35-90

1266
50 to 55
0.68
1.6
4.03
0.029
240,000
47

1266
50 to 55 0.50
1.6
4.60
0.040
100,000 40

844

35 to 45

0.75

1.6

4.80

0.035

20,000

40

Example 3

20th

One or more sheets of paper, which were produced according to Example 1, are placed on top of one another on plywood in a multi-stage press. The structure is pressed at about 21 kg / cm ² for about 10 minutes at 280 ° C. The laminate obtained with plywood as a base has an extremely smooth, glossy surface through which the grain of the wood shines through and which looks very pretty. The treated paper layer is an excellent protective coating which gives the laminate greater moisture resistance and dirt resistance.

Example 4

According to Example 1, a synthetic resin binder emulsion is prepared as follows: For 5 minutes 1000 parts of an unsaturated polyester resin, which is a polymerizable mixture of Styrene and the reaction product of polycarbonate

35

40 acids, including 1,4,5,6,7,7-hexachlorobicyclo- (2,2,1) -5-hepten-2,3-dicarboxylic acid and aliphatic glycols, mixed with 20 parts of dicumyl peroxide. 100 parts of a water-soluble phenol-formaldehyde condensate are then mixed with 50 parts of water and 100 parts of methanol for 5 minutes. The two solutions are then mixed with one another for 10 minutes, an emulsion being formed.

This synthetic resin binder emulsion is used for treating paper and making a Laminate according to Example 1 used. The properties of the laminate obtained are in Table II given.

Comparative experiment

Example 4 is repeated, but no phenol-formaldehyde condensate solution is used. That So paper is only treated with the polyester. A laminate made from the treated paper has the properties given in Table II.

Table II

ASTM test standard

Comparative experiment

Example 4

Paper content,%

Resin content, ° / o

Water absorption, ° / o

Dielectric constant, 10 ⁶ Hz

Loss factor, tg <5, 10 * Hz

Insulation resistance, megohm

It can be seen that the properties of the binder emulsion according to the invention of Example 4 Laminate produced are much better in every respect than the properties of the according to Example 5 produced laminate in which only the polyester was used as a binder.

The cellulose carrier materials treated with the binder emulsions according to the invention can contain various proportions of polyester to phenol-aldehyde condensate, depending on the desired properties of the end products. The D-150
D-150
D-150
D-257

45.0
55.0

3.120

5.010

0.068

2.8 ■ 10 '

45.0 55.0

0.620

4.150

0.035

2.4 · 10 ⁹

However, the quantitative ratio is generally between about 1 and 20 parts of polyester per part of phenol-aldehyde condensate and preferably between about 5 and 15 parts of polyester per part of phenol-aldehyde condensate. In the same way, the total synthetic resin content of the cellulose material can also be varied within wide limits vary. Generally it is in the range of about 0.5 to 1.5 parts synthetic resin per part cellulose and preferably between 0.8 and 1.2 parts synthetic resin per part cellulose.

209 531/501

Claims (5)

1 2 basic acid with a polyhydric alcohol so- claims: as optionally contains a water-immiscible vinyl monomer. The pre-pressing takes place at 1. Process for producing impregnated elevated pressures and temperatures instead,
Woven or non-woven carrier material on 5 Such emulsions, however, do not result in a cellulose base by applying an emulsion particularly useful laminates for electrical a synthetic resin solution in an unsaturated purpose, since melamine resins are usually too strongly polar polyester resin on the carrier material and on. final drying, characterized by it was found that instead of the melamine one draws, that one uses an emulsion, io formaldehyde condensation products in such which in the unsaturated polyester resin is a 16-emulsion phenol-aldehyde condensate in one Can use 50% solution of a water-soluble phenol diluent, the pre-aldehyde condensate in an amount of 1 part of these resins with respect to the electrical weight part phenol-aldehyde condensate to 1 to with the advantages of the polyester with respect to 20 parts by weight of unsaturated polyester resin emulsify the water resistance and the mechanical inherent force contains. shafts can be combined. 2. The method according to claim 1, characterized in that this could not be foreseen, as phenolic substances draws that one as an unsaturated polyester as an inhibitor for the by peroxides or peracids Product used that a Diels-Alder adduct induced polymerization of unsaturated polyeines Contains hexahalocyclopentadiene, in which esters are known. Although they are in the French chem the halogen atoms fluorine, chlorine or patent 1,320,980 solutions of phenol-form bromine atoms are. aldehyde resins, melamine-formaldehyde resins or 3. The method according to claim 1 and 2, characterized in urea-formaldehyde resins together with water marked, that as unsaturated poly-soluble unsaturated polyesters as binders for ester is the reaction product of 1,4,5,6,7,7-hexa- 25 cellulose-based laminates known, with water chlorobicyclo- (2.2, l) -5-hepten-2,3-dicarboxylic acid used with soluble or insoluble, an aliphatic glycol suspended in the solution. Vinyl monomers can also be used. However 4. The method according to claim 1 to 3, characterized in that there is no free radical polymerization of the unmarked, that paper is used as the carrier material instead of saturated polyester when phenol-formaldehyde is used. There are 30 resins in the solution. 5. Use of the impregnated carrier Since thus phenol-aldehyde condensates the melamine material according to claim 1 to 4 for the production of aldehyde condensates neither with regard to the electrivon Laminate moldings. still see properties in terms of compatibility with radical polymerizing unsaturated 35 polyesters are equivalent, the success was not predictable by using the phenol-aldehyde condensates in the per se as a binder known emulsions for laminates can be achieved The invention relates to a method for Her- can. make of plastic-impregnated carrier material 40. According to the invention, better laminate form and its use for the production of laminated bodies with a low dielectric constant, molded bodies made of material with improved dielectric drawn insulation resistance and good stamping and mechanical properties. properties for the production of electrical construction It is well known that paper is impregnated with phenolic panels, e.g. B. for printed circuits, created, resin and used it for the production of layer 45 The invention is therefore a method of fabric moldings that have a good moisture resistance for the production of impregnated woven or fabric and good electrical properties z. B. non-woven cellulose-based carrier material by having an unsaturated polyester resin on the carrier with regard to the dielectric constant, the elec- applying an emulsion of a synthetic resin solution in Irish dissipation factor and the insulation resistance. Such laminates were used for the production and subsequent drying, whereby one position of electrical building boards for printed an emulsion used, which is used in the unsaturated circuits. The properties of the polyester resin has a 16 to 5O ° / _O term solution of a thus-treated carrier materials to cellulose water-soluble phenol-aldehyde condensate in a free base can also be improved if they amount of 1 part by weight of phenol-aldehyde condensate treated with a polyester. However, since a phenolic resin for 1 to 20 parts by weight of unsaturated polyester resin is generally water-soluble and contains polyester emulsified. are insoluble in water, it should be expected that they will be useful in the process of the invention Treatment of cellulosic material with both a cellulosic carrier material derive from Phenolic resin as well as a polyester from a bi-natural source, such as wood, cotton, etc., step process is required, which is therefore un- 60 and chemically treated substances, such as regenerated is economical. rated cellulose and rayon. Generally will From German patent specification 1 034 012, the cellulose material is in the form of self-supporting knows, such laminates using a film or webs, such as paper or in the form of Manufacture oil-in-water emulsion that is used in the dis- fabric or fleece. Paper is for that pergiert phase an aqueous solution of a water 65 inventive method the preferred cellulose soluble melamine-formaldehyde condensation pro-material. All types of paper come duktes and in the continuous phase a solution into consideration, which her- from a polymerizable polyester one more can be made.