DE2104972A1 - Laminate sheet made of glass silk fabric or glass silk matt and polymerized polyester - Google Patents

Description

DR.WALTER NIELSCH _{File 225O pat}

Patent attorney

2 Hamburg 70 · Pc? 'Füch 10914
Telephone: 652 9707

Reichhold-Albert-Chemie Aktiengesellschaft Hamburg 70, Iversstrasse 57

The end . Laminate sheet consisting of glass silk fabric or glass silk mat and polymerized polyester

Inventor: Dr. Burkhard Behrens and

Graduate chemist Hermann Delius

The present innovation relates to an improved one made of fiberglass fabric or fiberglass mat and polymerized Polyester existing laminate sheet.

Laminate webs consisting of fiberglass fabric or fiberglass mat and polymerized polyester are known per se. However, these are not yet available with photopolymerized polyester and glass silk fabric or glass silk mats has been manufactured.

The cured with peroxides and usual accelerators « ι

th polyester laminates usually have a residual monomer content immediately after curing, which is the case with many Intended use interferes with »

The task of the present innovation is to create a fabric made of fiberglass or to provide the existing laminate sheet made of fiberglass mat and polymerized polyester is improved in different directions at the same time; which has, for example, improved transparency.

In addition, another aim of the present innovation is

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to provide such laminate webs containing glass silk mats or glass silk fabric which are opposite to the same Polyester laminates produced according to previous processes, significantly improved mechanical properties and have only a relatively low content of residual monomers immediately after curing.

As is well known, unsaturated polyesters capable of polymerisation are used for coating purposes on a wide variety of substrates cured by photopolymerization to form dense lacquer coatings, but the lacquer coating layers obtained in this way do not contain any glass silk fabric or glass silk mat reinforcement inserts.

The object of the innovation is one made of glass silk products or glass silk mats and polymerized unsaturated Laminate sheet consisting of polyester resin, characterized in that it consists of a glass silk or Glass silk mat reinforced photopolymerized polyester plastic consists and that the photopolymerized polyester resin before curing as a potoinitiator Complete combination contains, consisting of:

(a) O ₁ I to k wt -.% benzoin ethers of primary and / or secondary alcohols and / or Benzoinaryläthern and

(b) a sub-combination of at least two different compounds of trivalent phosphorus, consisting of:

(b ¹ ) 0 _t Ibis 20 wt. organic ester of phosphorous acid with the general formula

0 R ₁

O- R ₂ (I)

0 ——— R_ j

where R ₁ , R ₂ and R-. be the same or different

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can and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals - however, one of the radicals R ₁ , R «or R must always be an aromatic radical - and (b") 0.05 to 2% by weight of organic derivatives Phosphines with the general formula

(ID

where R ₁ , R «and R- can be the same or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals, but one of the radicals R ₁ , R« or R must always be an aromatic radical - and the stated percentages by weight relate to the total weight of unsaturated polyester resin and polymerizable monomers.

The laminate sheet according to the innovation also contains decomposition products of the UV sensitizers in the polyester plastic in particular caused by UV irradiation. The decomposition products are partly in the polymeric polyester plastic chemically incorporated.

Surprisingly, it has now been found that in the production of fiberglass fabric or fiberglass mat and light-polymerized polyester laminate webs in the cured polyester layer, in comparison to conventionally cured polyester layers, made of the unsaturated polyester and the same glass reinforcement the light-polymerized, glass-reinforced polyester plastic has significantly better mechanical properties, in particular improved bending, impact and Has tensile strengths. It is also found

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that immediately after the polymerization has been carried out in the usual manner with peroxides al3 polymerization initiators and accelerators or, after the photopolymerization, the content of residual monomers not yet polymerized essential in photopolymerized polyester plastic is lower and this has better mechanical properties immediately after light curing. aside from that the reduced content of residual monomers is important, as long as the laminate webs produced according to the invention with Come into contact with food or pharmaceuticals.

The new ones made from glass silk products or glass silk mats and polymerized unsaturated polyester resin made larainat web can through the quick Light curing of the polyester produced in a very efficient way individually or by a mass production process will. E.g. an auxiliary carrier with an anti-adhesive layer is applied after the preparatory work has been completed First the light-curable liquid unsaturated polyester resin is added and distributed evenly. Afterward the fiberglass reinforcement (fiberglass fabric or mat) is placed and both covered with a plastic film, as long as no polyester resin is used which contains β, γ-allyl groups. With a subsequent Squeezing with a roller system, the fiberglass reinforcement is completely soaked, compacted and the rest Existing air is pressed out of the laminate together with the excess unsaturated polyester resin. the Execution can also optionally be carried out with pre-soaked reinforcing material in an analogous manner, whereby the compaction is carried out in a separate device. The cover film and the auxiliary carrier cause the formation of a smooth surface and allow the subsequent curing of the unsaturated polyester resin takes place in the absence of atmospheric oxygen.

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By appropriately structuring the cover film, the coating can also have a corresponding pattern be equipped. In order to achieve special decorative effects, the glass silk fabric can contain colored glass silk threads contain.

According to the innovation laminate web is prepared by photopolymerizable unsaturated polyester resin is used which contains UV sensitizers and, optionally, accelerators, and the polymerization of the unsaturated polyester resins with glass fiber reinforcement is carried out for composite material by irradiation of d light of short wavelength. The radiation that is most effective in the sense of the innovation has wavelengths between about 2500 8 and about 4500 8. It has surprisingly been found that this special process also results in the advantages already described for the innovation.

Both superactinic fluorescent lamps and so-called high-pressure mercury vapor lamps as well as sunlight, tungsten and xenon lamps can be used as light sources for UV irradiation. A two-stage curing process is preferably used, according to which the unsaturated polyester resin is first pregelatinized by irradiation with super-peractinic light (approx. 60 to 180 seconds); f the final curing takes place by short-term irradiation under high-pressure mercury vapor lamps, irradiation times of 20 to ¹ JO sec / mm laminate thickness are required.

In a particular embodiment, the laminate webs are coated with unpigmented or pigmented lacquers on one or both sides. It is noteworthy that the painting can be carried out after removing the cover film without intermediate treatment. As a binder

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for the paints that are used, cold and thermosetting products in question. In detail are listed :

Unsaturated polyester resins, alkyd resins and alkyd resin-melamine resin combinations that dry and air dry with the addition of paraffins, plasticized, acid-curable urea resins and one- or two-component polyurethanes.

Combinations of aliphatic or cycloaliphatic polyisocyanates are used to produce the lacquer coatings and hydroxyl-containing alkyd resins of non-drying fatty acids and copolymers based on acrylic or methacrylic compounds are preferred.

Glass silk mats or glass silk fabric can be used as reinforcement material for the production of the laminate web soluble and insoluble binders weighing

ο
about 120-900 g / m 2 are used, but other basis weights can also be used.

When using fiberglass fabrics, those with linen and twill weaves as well as sham leno fabrics can be used can be used.

Roving fabric with a weight per surface of 120-900 g / m can also be used, but coarse roving

fabrics with a weight per area of 400-600 g / m are preferred. The laminate web is generally composed of about 55-60% by weight of polymerized polyester and 45-40% by weight Glass silk together, but other compositions are also possible for special purposes.

When using benzoin ethers as sensitizers, the photopolymerization of mixtures is more unsaturated Polyester with unsaturated copolymerizable compounds at room temperature in a relatively short time

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Time possible. A benzoin ether content of about 2 percent by weight, based on the mixture, is necessary to achieve sufficient reactivity. These mixtures but show after irradiation under high pressure mercury vapor lamps an intense yellow color that does not go away completely even after several days.

In the Italian patent 839 021, unsaturated polyester preparations curable by irradiation are already specified for the production of lacquer coatings, which contain an unsaturated polyester with a hydroxyl number of 55 to 75, a polymerizable monomer, a stabilizer combination of 200 to 800 parts per million% of an alkyl phosphite or aryl phosphite and Contain 10 to 50 parts per million of a copper salt of organic acids; For this purpose, 0.1 to 5% benzoin or in the α-position by a C ₁ to Cg alkyl substituted benzoin used as photoinitiator. The curing takes place by irradiation with light with a wavelength of 2500 to 4000 S. These polyester preparations show improved dark storage stability, but they do not have a shortened curing time compared to comparable polyester preparations with different stabilization.

A special object of the present innovation is to Ä the webebzw in the production of Glasseideng ^e. Glass silk mat and polynerized polyester existing laminate web to achieve significant improvements over the prior art, namely

1) The dark storage stability of the ready-to-use molding, impregnating and coating compounds at room temperature and at Increased temperatures up to about 60 ° C to improve significantly.

2) To increase the rate of polymerization quite significantly when carrying out the process, so that the loading

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Radiation time can be shortened accordingly.

3) The discoloration of the cured polyester preparation due to lowering of the sensitizer concentration used with a relatively short irradiation time.

H) To produce the laminate with improved transparency and with improved adhesive strength between fiberglass and polyester plastic.

5) The composite plastic made of fiberglass fabric or fiberglass mat and light-cured polyester to give improved mechanical properties *

6) To produce fine composite cow material which immediately after its light cure has a reduced residual monomer content compared to a composite plastic hardened with peroxides and accelerators made of the same unsaturated polyester.

7) When using air-drying unsaturated polyester resins to achieve a tack-free surface through light curing.

These tasks are surprisingly solved by that benzoin ethers are used in certain combinations with compounds of trivalent phosphorus.

A special embodiment of the innovation is thereby characterized in that the photopolymerizable impregnating composition consists of mixtures of unsaturated stabilized in the usual way Polyester resins and polymerizable, monomeric compounds and photoinitiators is prepared, if necessary Contains additional polymerization initiators and / or metal accelerators, as a potoinitiator the already mentioned overall combination is included.

in a special embodiment of the innovation the component (a) from one or more benzoinaryl

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ether the general formula

O ο Ar

where Ar is an aromatic radical.

When using the overall combination, consisting of (a) and (b) ((b ¹ ) and (b ¹¹ )), a synergistic effect occurs surprisingly, the extremely short polymerization. ^ times with UV irradiation conditional. '

The extraordinarily high reactivity of the preparations used allows it to be compared with the known preparations with comparable curing times, to reduce the content of benzoin ethers considerably or, alternatively, at comparable contents of benzoin ethers to shorten the hardening times considerably.

The high reactivity of the preparations used allows rapid hardening even when exposed to ultraviolet and visible radiation of comparatively low-energy fluorescent lamps with an emission of about 3000 to 5800 8 * this is particularly advantageous.

The usual condensation products (cf. Johan Bjorksten, "Polyesters and their Applications ", Reinhold Publishing Corporation, New York, 1956, pages 21 to 155) understood, those from α, β-unsaturated dicarboxylic acids and / or their Anhydrides can be obtained by polycondensation with polyhydric alcohols used in a molar excess. The following can be used as α, β-unsaturated dicarboxylic acids, for example:

Maleic acid, maleic anhydride, pumar, itacon, citracon, Mesaconic and aconitic acid and halogenated acids,

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such as chloromaleic acid.

Some of the α, β-unsaturated dicarboxylic acids can in a manner known per se by saturated dicarboxylic acids, for example o-, iso- and terephthalic acid, tetra- and hexahydrophthalic acid, tetrachlorophthalic acid, hexachlorendomethylene tetrahydrophthalic acid, Endomethylenetetrahydrophthalic acid, adipic and sebacic acid and dimerized Linseed oil and soybean oil fatty acids or their anhydrides are exchanged.

The polyhydric alcohols are preferably dibasic Alcohols in imprint, for example ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, Dipropylene glycol and its higher homologues, neopentyl glycol, 2,2,4-trimethylpentanediol-1,3> Pentyl glycol, alkoxylated bisphenols, hydrogenated bisphenol, dimethylolcyclohexane. However, trihydric and polyhydric alcohols such as glycerol, trimethylolethane, trimethylolpropane can also be used and pentaerythritol can also be used proportionally. The unsaturated polyester resins built up from these raw materials are known to have the disadvantage of forming a sticky surface on curing in the presence of atmospheric oxygen. If the air-drying properties of the polyester resin are important, β, γ-unsaturated nuts are used Ether alcohols in exchange for the polyvalent alcohols, as for example in the German Auslegeschrift 1,024,654 and U.S. Patent 2,852,487, can also be used. Examples include: the monoallyl and monomethallyl ethers of ethylene glycol, 1,2-propanediol, 1,3-butanediol and -1,4, des Glycerol, trimethylolpropane and -ethane and of pentaerythritol as well as diallyl ether and the corresponding methallyl ethers of glycerine and trimethylol ethane, propane and pentaerythritol. Those are particularly useful here β, γ-unsaturated ether alcohols containing at least two β, γ-unsaturated ether groups contain, such as

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propane diallyl ether, trimethylol ethane diallyl ether and pentaerythritol triallyl ether.

As copolymerizable vinyl compounds which are contained individually or in a mixture in amounts of 20 to 45% by weight, based on the mixture of unsaturated polyester resin and polymerizable monomers (cf. for example: Bulletin IP 8, July 1961, Amoco Chemicals Corporation, with the title "The Effect of Resin Ingredients on the Properties of Isophthalic Unsaturated Polyesters", pages 5 to 19), are, for example, suitable: styrene, vinyl toluene, p-tert-butylstyrene, divinylbenzene, vinyl acetate, vinyl propionate, acrylic acid esters, methacrylic A

acid esters, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylene glycol dimethacrylate and its higher homologues, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate. As allyl compounds The following can be used, for example: diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate. The molding, impregnating and coating compositions are made by adding conventional inhibitors, for example p-benzoquinone, 2,5-di-tert-butylbenzoquinone, Hydroquinone, tert-butyl catechol, Toluy! Hydroquinone, also copper compounds, such as copper naphthenate, in the known Quantities stabilized, as for example in the book Kirk-Othmer Encyclopedia of Chemical Technology, Interscience Publi- |

shers, New York, 1969, second edition, volume 20, p 822 to 825, and may contain other additives customary in polyester chemistry.

Examples of the sensitizers to be used are (a) in the overall combination (a) and (b) (Cb ') and (b ")) the benzoin ethers of the following alcohols: methanol, ethanol, propanol-1, propanol-2, butanol-2, pentanol-2, cyclohexanol, n-butanol, isobutanol, 2-methyl-1-pentanol, 2-methylpentanol-3, primary and secondary octanol, 2-ethylhexanol, n-

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Nonanol, n-dodecanol, 6-dodecanol, lauryl, myristyl, stearyl alcohol, 2-chloro-1-propanol, 3-bromo-1-propanol, 2,2-dichloro-1-propanol, 1-chloro-2- propanol, abiethyl alcohol and tetrahydroabiethyl alcohol. Of the ethereally bound monoalcohols, the compounds which have primary alcoholic hydroxyl groups are preferred. However, the monoalcohols with secondary and tertiary alcoholic hydroxyl groups are also useful. In addition to the saturated alcohols, the unsaturated alcohols are also suitable. The following may be mentioned by way of example: β, γ-unsaturated alcohols such as allyl alcohol, methallyl alcohol, ethallyl alcohol, chlorallyl alcohol, crotyl alcohol, phenylallyl alcohol, methyl vinyl carbinol, and also unsaturated fatty alcohols obtained by selective hydrogenation of unsaturated fatty acids. Examples of the benzoin ethers (a) to be used in the overall combination (a) and (b) ((b ^f ) and (b ¹¹ )) are the lensoin ethers of phenol, 2-cresol, 3-cresol, ^ -cresola 3 »^ -Dimethylphenols, 2,6-diethylphenols, 4-tert-butylphenols, 2-methoxyphenols, 4-methoxyphenols, 2-chlorophenols, iJ-chlorophenols, 2,6-dichlorophenols, 2,4,6-trichlorophenols, naphthols- (l ), Naphthols (2) and 2,2-bis (M-hydroxyphenyl) propane (bisphenol A). The preparations used according to the invention contain the benzoin ethers (a) mentioned individually or mixed with one another in amounts of 0.1 to about ¹ I weight percent, preferably 0.1 to about 1.5 weight percent, in combination with compounds of the trivalent Phosphorus (b) ((b ¹ ) and (b ")). Suitable esters of phosphorous acid (b ¹ ) which contain at least one aromatic radical are, for example, triphenyl phosphite, tri-p-toluyl phosphite, trisnonyl phenyl phosphite, didecyl phenyl phosphite .

As organic derivatives of phosphines (b "), the at least contain an aromatic radical, for example: Tripheny! phosphine, tri-p-toluyl-phosphine, di-

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phenyl-methyl-phosphine, diphenyl-ethyl-phosphine, diphenylpropyl-phosphine, dimethyl-phenyl-phosphine, diethyl-phenyl-phosphine, dipropyl-phenyl-phosphine, divinyl-phenyl-phosphine, divinyl-p-methoxyphenyl-phosphine, divinyl-p- bromophenyl-phosphine, divinyl-p-toluyl-phosphine, diallyl-phenyl-phosphine, diallyl-p-methoxyphenyl-phosphine, diallyl-p-bromophenyl-phosphine, diallyl-p-toluyl-phosphine. The esters of phosphorous acid (b ¹ ) are in amounts of 0.1 to 20 wt .- / S, based on the total weight of unsaturated polyester resin and polymerizable monomers, preferably 0.1 to 2 wt .- #, in a mixture with the mentioned benzoin ethers (a) and phosphines (b ") contain.

The stated phosphines (b ") are in amounts of 0.05 to 2 wt. SS, based on the total weight of unsaturated polyester resin and polymerizable monomers, in a mixture with the stated benzoin ethers (a) and esters of phosphorous acid (b ¹ ) The most preferred total combinations consist of: benzoin ethers of primary alcohols (a), esters of phosphorous acid (b ¹ ) which contain only aromatic radicals, such as triphenyl and / or tri-p-toluyl phosphite and organic derivatives of phosphine ( b ") which contain only aromatic radicals, such as triphenyl- and / or tri-p-toluyl-phosphine.

Optionally, conventional polymerization catalysts can also be used (See, for example, Johan Bjorksten, "Polyesters and their Applications", Reinhold Publishing Corporation, New York, 1956, pages 48 to 51) in amounts of 0.1 to about 2 wt .- ^, based on the total weight of unsaturated polyester resin and polymerizable monomers, be advantageous because the latter can be stimulated to the polymerization catalysis by the UV radiation itself as well as by the heat occurring during the UV radiation.

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Suitable preferred polymerization catalysts are, for example, tert-butyl perbenzoate, dicumyl peroxide, benzoyl peroxide, Lauryl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, Cyclohexanone peroxide, azobisisobutyronitrile.

The addition of peroxides can in some cases improve the adhesion of the cured polyester to the Effect glass fiber reinforcement. Furthermore, the use of peroxides, namely methyl ethyl ketone peroxide, is predominant then to recommend, if it is desired, slight discolouration of the hardening products, as in the case of Irradiation, but possibly also during storage, which can occur through exposure to light, to reduce. The use of small amounts of conventional accelerators, for example cobalt octoate, cobalt naphthenate, zirconium naphthenate, Dirnethylaniline, acetoacetic acid ester also possible. The use of accelerators in the copolymerization of unsaturated polyester resins with polymerizable monomers is for example in the book Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience Publishing, New York, 1969, second edition, Volume 20, pages 825-826. In connection with the use of ketone peroxides, metal compounds, such as cobalt, zirconium and vanadium naphthenate, or metal chelates such as cobalt and zirconium naphthenate, can be added. With the simultaneous presence of peroxides and metal accelerators, the storage stability of the masses is however reduced.

The addition of UV absorbers as light stabilizers of the hardened preparations such as derivatives of Oxybenzophenons, the salicylates, the o-oxyphenyl-benzotriazole, in the usual amounts between 0.01 and 0 ₃ parts by weight k-X, caused no appreciable or even wearable Retardation of photopolymerization, although the

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sorption of the UV absorber is in the range of the long-wave UV radiation required for photopolymerization.

These impregnating compositions used have an excellent dark storage stability compared to the known compositions and are therefore eminently suitable as stable one-component systems. The best results are obtained when the phosphite content is approximately three times the phosphine content.

To test the dark storage stability of the preparations to be used, 61 parts by weight of an unsaturated polyester resin stabilized in the customary manner with 0.015% by weight of hydroquinone and composed of 1 mole of maleic anhydride, 1 mole of phthalic anhydride and 2.18 moles of 1,2-propanediol with 39 Parts by weight of styrene are mixed and various total combinations of (a) benzoin ethyl ether, (b ·) triphenyl phosphite and (b ^Mt ) triphenyl phosphine * dissolved in styrene are added according to the following table.

Table 1 Dark storage stability

Benzoin ethyl Triphenylphos Triphenylphosphere Dark- ether in weight phit in weight phin in weight Bearing Share, related Share, related Share, related mobility gen to 110 gen to 110 gen to 110 (60 ⁰ C) Parts by weight Parts by weight Parts by weight in days mixture mixture mixture 0.25 0.2 0.1 Zk 0.5 0.2 o, i 24 0.5 0.1 » 0.1 24 0.5 0.6 0.2 22nd

The impregnating compounds used are for the production of fiber-reinforced Plastic parts ideally suited.

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For the production of fiber-reinforced, especially glass fiber-reinforced, Plastic parts using the preparations according to the invention are, of course, only such Process suitable that allow irradiation after shaping or the lamination process. As examples are to be mentioned: the hand lay-up process, the lining of containers and pipes as well as the bilateral Coating of chipboard and blockboard or plywood with glass fiber reinforced laminates for the production of so-called container plates. All common fiberglass products are suitable as reinforcement materials, such as mats, rovings and fabric qualities. After completing the lamination process, which is not the usual is tied to a limited processing time or "pot life", the laminate can be replaced by energy poor UV radiation over a longer period of time or short-term with the help of high-pressure mercury lamps to be cured.

Because of their very short hardening time, the used masses for a rational processing method tailored to the assembly line method.

Mixture A;

100 parts by weight of a polymerizable mixture consisting of 67 parts by weight of polyester resin (produced from 1 mole of maleic anhydride, 1 mole of phthalic anhydride and 2.18 moles of 1,2-propanediol) and 33 parts by weight Styrene, stabilized with 0.015 weight percent hydroquinone, a viscosity of approx. 1500 cP at 20 ° C and an acid number of 28, are diluted with a further 10 parts by weight of styrene and with 0.5 parts by weight of a 10% by weight solution of paraffin (melting point 52 ° -53 ° C.) in toluene.

Mixture B:

100 parts by weight of a polymerizable mixture, be

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standing on 67 parts by weight of polyester resin (prepared from 2 moles of maleic anhydride, 1 mole of phthalic anhydride and 3.08 moles of 1,2-propanediol) and 33 parts by weight styrene, with 0.014 wt -% stabilized hydroquinone, a viscosity of approx. . 1100 cP at 20 ⁰ C and an acid number of 30 are diluted with xreiteren 10 parts by weight styrene, and 0.5 parts by weight of a 10 wt, -ftigen solution of paraffin (mp 52 -. 53 ° C) added in toluene.

Comparative studies 1 - 31;

Mixture A contains various benzoin ethers and esters of phosphorous acid or various benzoin ethers and triphenylphosphine in the concentrations given in Table 2 are added. The ones won in this way Solutions are poured onto a glass plate in an approx. 1 mm thick layer and exposed to radiation from a UV lamp (EL-VAK, LUMINOTEST, Elektro-Vakuum-GmbH, Berlin) at a distance of 17 cm. The gel times are in the table 2 specified. In comparison, the gel times of the phosphite- and phosphine-free mixtures are also specified.

Table 2

Verse,- Benzoin ether Phosphate Triphenyl Gelation No. additional in weight rate in weight phosphine time in Share, related Share, related sentence in lake gen to 110 gen to 110 Parts by weight, Parts by weight Parts by weight based on Mixture A Mixture A 110 parts by weight le mixture A 1 0.5 benzoin 55 methyl- ether 2 0.5 " 0.6 triph _ 45 ny lphos- phit 3 0.5 " 0.8 " - 45

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Table 2

Verse, - I.
No. Benzoin ether
additive in weight
Share, related
gen to 110
Parts by weight
Mixture A Phosphite i
rate in weight
Share, related
gen to 110
Parts by weight
Mixture A Triphenyl
phosphine
sentence in
Parts by weight,
based on
110 parts by weight
le mixture A 3elier
time in
lake 4th 0.5 benzoin
methyl-
ether 1.0 triple
nylphos-
phit - 40 5 1.0 " - - 35 6th 1.0 " 0.6 " - 32 7th 1.0 " 0.8 " - 30th 8th 1.0 " 1.0 " - 30th 9 0.5 benzoin
ethyl-
ether 55 10 0.5 " 0.6 " - 45 11 0.5 " 0.8 " - 43 12th 0.5 " 1.0 " - 45 13th 0.5 " 5.0 » - 37 IiJ 0.5 " 10.0 " - 29 15th 0.5 " 20.0 " - 32 16 0.5 benzoin
ethyl-
ether 0.6 trisnonyl
phenyl
phosphite ' 50 17th 0.5 benzoin
methyl -
ether 0.2 18th 18th 0.5 " - 0.6 15th 19th 0.5 " - 1.0 15th 20th 1.0 » - 0.2 12th 21st 1.0 " - 0.6 10 22nd 1.0 " - 1.0 8th 23 0.25 benzoin
ethyl-
ether 0.2 40 24 0.25 " - 0.6 25th

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Table 2 Phosphite
rate in weight
Share, related
gen to 110
Ge Vi. Parts
Mixture A 2 104972 Triphenyl
phosphine
sentence in
Parts by weight,
based on
110 parts by weight
le mixture A Be lie r
time in
lake Comparative examinations 32 - 34: - trisnonyl
phenyl
phosphite 1.0 20th Benzoin ether
addition in weight
Share, related
gen to 110
Parts by weight
Mixture A - 0.2 30th Verse,-
No. 0.25 benzoin
ethyl-
ether - 0.6 20th 25th 0.5 " - 1.0 15th 26th 0.5 " - 0.2 18th 27 0.5 " - 0.6 12th 28 1.0 ⁿ - 1.0 9 29 1.0 " 30th 1.0 " 31

The mixture B are benzoin ethyl ether and triphenyl phosphite or benzoin ethyl ether and triphenyl phosphine in the concentrations given in Table 3 are added. Under the same conditions as in the comparative tests 1-31, the gel times given in Table 3 are achieved.

Table 3

Verse.
No. Benzoin ethyl
ather in weight
Share, related
gen to 110
Parts by weight
Mixture B Triphenyl
phosphite in
Parts by weight,
based on
110 parts by weight
le mixture B Triphenyl
phosphine in
Parts by weight
based on
110 parts by weight
le mixture B Gelation
time in
lake 32
33
34 0.5
0.5
0.5 0.6 0.2 45
30th
14th

1 & 9833/1967

.. As shown in Table 2, experiment No. 2 to 4, 6 to 8, 10 to 16 and Table 3, Experiment No. 33, stating causes a charge of 0.6 to 20 wt -.% Phosphates, .bezogen to 110 wt . Parts of mixture A or 110 parts by weight of mixture B, already a reduction in the gel time on UV irradiation. An addition of triphenylphosphine, according to Table 2, Experiment No. 17 to 31, or Table 3, Experiment No. 34, causes a considerable reduction in the gel time j on UV irradiation, but the dark storage stability is also worsened. However, as can be seen from Table i + ^, according to the invention, by using the total combination, both the gelation time is surprisingly shortened and the dark storage stability is surprisingly improved at the same time.

The components of the overall combination, namely benzoin ether (a), phosphite compound (b ¹ ) and phc- · r-jiin compound (b ") can be added in any order. In the preferred order, the phosphite compound (b ') is added first, then the Phosphine compound (b ") with the benzoin ether compound (a) added last. It is only essential that the stated constituents (a), (b ·) and (b ") must be contained in the polyester preparation as a combination prior to UV irradiation.

Examples 1-11

The specified mixture A is various benzoin ethers (a), triphenyl phosphite (b ') and triphenyl phosphine (b ") in the concentrations given in Table 4. Under the same lighting conditions as given in the comparative tests 1-31, the gel times given in Table 4 are achieved.

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Table 4

Ex.
No. Sensitizer
add in weight
Share, related
to 110 wt.
Parts mixture
A. Triphenyl
phosphite
sentence in
Parts by weight,
based on
Mixture A Triphenyl
phosphine
sentence in
Parts by weight,
based on
Mixture A Gelation
time in
lake 1 0.25 benzoin
methyl-
ether 0.2 0.1 45 CVl 0.25 " 0.2 0.2 30th 3 0.5 0.2 0.1 30th 4th 0.5 " 0.4 0.2 10 5 0.25 benzoin
ethyl-
ether 0.2 0.1 30th 6th 0.25 " 0.4 0.2 25th 7th 0.5 " 0.2 0.1 16 8th 0.5 0.4 0.1 15th 9 0.5 0.4 0.2 10 10 0.5 0.6 0.2 9 11 1.0 " 0.4 0.4 5

Example 12-13

Benzoin ethyl ether (a), triphenylphosphite (b ^f ) and triphenylphosphine (b ") are added to the indicated mixture B in the concentrations indicated in table 5. Under the same exposure conditions as indicated in the comparative tests 1-31, the in table 5 specified gel times reached.

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Table 5

Ex. Benzoin Triphenyl Triphenyl Gelation No. ethyl- phosphite phosphine time in ether in rate in weight rate in weight lake Part by weight Share, related Share, related len, related gen to 110 gen to 110 gen to 110 Parts by weight Parts by weight Parts by weight Mixture 3 Mixture B Mixture B 12th 0.5 0.2 0.1 17th 13th 0.5 0.6 0.2 12th

The described synergistic effect, which occurs when the total combination (a) and (b) ((b ¹ ) and (b ″)) is used, emerges from the gel times listed in Table 4 and Table 5.

This is particularly surprising in that the esters of phosphorous acid are used in conventional hardening of unsaturated polyester resins and polymerizable monomeric compounds with peroxides, even in small amounts Quantities are known as potent inhibitors.

Example 14-20

The specified mixture A contains 0.5 part by weight of benzoin ethyl ether (a), 0.6 part by weight of triphenylphosphite (b ^f ) and 0.2 part by weight of triphenylphosphine (b ") and, in addition, various conventional polymerization initiators or accelerators mixed in in the concentrations indicated in Table 6. Under the same exposure conditions as indicated in the comparative tests 1-31, the gel times indicated in Table 6 are achieved.

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•. mmm

Table 6

Ex. Additives in parts by weight, based on Gel time No. 110 parts by weight of mixture A in see Ik 2 methyl ethyl ketone peroxide (50% by weight) 35 15th 1 benzoyl peroxide paste (50% by weight JSig) 18th 16 1 cobalt octoate (6% by weight JSig Co content) 23 17th 1 zirconium octoate (6 wt .- / Sig Zr content) 39 18th 2 azobisisobutyronitrile 16 19th 1 acetoacetic ester 16 * 20 2 dimethylaniline (10% by weight solution) 31

Example 21

HO parts by weight of the above mixture A, but without the addition of paraffin, 1 _S 5 parts by weight Benzoinäthylather (a), 0.6 parts by weight of triphenyl phosphite (b ^f) and 0.2 wt, parts by triphenylphosphine (b "). With this preparation, two glass fiber mats with the usual soluble synthetic resin binder based on polyester and a weight per unit area of 450 g / m 2 are laminated onto a sheet of plywood using the hand lay-up method , which contains a release agent on the surface, covered and irradiated 150 seconds under high pressure mercury lamps in a UV light curing channel. The UV light curing channel is equipped with a high pressure burner and two HTQ 7 high pressure mercury lamps (length each 755 rom, diameter 12 mm, distance 15 cm from each other) from Philips. The cooling is carried out by air, the irradiation distance is 20 cm. After cooling to room temperature, the film can be peeled off. In this way, a firmly adhering glass fiber reinforced coating of the plywood panel is obtained.

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This coating has excellent transparency, so that the natural wood structure of the plywood surface comes into its own. Surprisingly, it was found that such a The coating produced has significantly better mechanical properties, in particular improved bending, Has impact and tensile strengths than a comparable produced coating, but using a conventional hardening process using has been cured by peroxides as polymerization initiators and accelerators. In addition, it was found that immediately after the photopolymerization was carried out, the content of not yet polymerized monomers in the photopolymerized polyester plastic is significantly lower than directly after the polymerization has been carried out in the usual manner with peroxides as the polymerization initiator λ and accelerators.

Example 22-29

The procedure is as in Example 10, but with the addition of 5 parts by weight of v / more polymerizable Vinyl compounds, as shown in Table 7, and 1.5 parts by weight of benzoin isopropyl ether instead of benzoin ethyl ether (parts by weight based on 110 parts by weight of mixture A).

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Table 7

Ex. copolymerizable vinyl ver Gel time No. ties in see 22nd Methyl methacrylate 20th 23 Isobutyl methacrylate 17th 24 Butyl methacrylate 17th 25th Butanediol 1,4-dimethacrylate 23 26th Triethylene glycol dimethacrylate 17th 27 Vinyl toluene 18th 28 Chlorostyrene 16 29 p-tert-butyl styrene 18th

A proportionate use of methyl methacrylate, corresponding to Example 22, increases the refractive index of the cured coating and thus adapted to the refractive index of fiberglass reinforcements, see above that transparent glass fiber reinforced coatings are obtained.

By using butanediol-ljlJ-dimethacrylate or triethylene glycol dimethacrylate according to Examples 25 and 26, .wird increases the crosslinking density, so that cured polyester with improved solvent resistance can be obtained. The use of p-tert-butylstyrene accordingly Example 29 causes a reduced polymerization shrinkage and thus improved strengths of the cured Polyester.

Example 30

By condensing 750 g of 1,2-propanediol and 587 g of maleic anhydride and 578 g of tetrachlorophthalic anhydride vrird in a known manner a self-extinguishing unsaturated Made of polyester resin and stabilized with 136 mg hydroquinone and 68 mg p.tert - buty!

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sated. The mixture of 65 parts by weight of this polyester resin with 25 parts by weight of styrene and 10 parts by weight Trichloräthylphosphat has a viscosity of 1400 cps at 20 ⁰ C and an acid number of 28th 100 parts by weight of this mixture are mixed in with 1.5 parts by weight of benzoin propyl ether (a), 0.6 part by weight of triphenyl phosphite (b ¹ ) and 0.2 part by weight of triphenyl phosphine (b "). With this preparation two glass fiber mats with a conventional polyester-based synthetic resin binder and a surface weight of 450 g / m 2 are laminated one after the other onto a polished aluminum sheet, the surface of which is provided with a release agent. which is provided with a release agent on the surface, covered and irradiated for 150 seconds under the high-pressure mercury vapor lamps described in Example 21. After cooling to room temperature, the film can be peeled off and the laminate separated from the aluminum plate Plate obtained with good transparency.

Further evidence of the technical progress achieved

Test series A

% Glass fiber fabric prepared a light cured laminate and - from the coating composition C was treated with a content of 40 wt.. The flexural strength, tensile strength and impact strength of the light-polymerized laminate obtained were determined. The following values were obtained:

Flexural strength DIN 53 452 3150 Kp / cm ² Tensile strength DIN 53 455 2920 Kp / cm ² Impact strength DIN 53 453 95 Kpcm / cm ²

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Test series B

Another light-polymerized comparative laminate was produced in an analogous manner, but in the coating compound C triphenyl phosphite and triphenyl phosphine have been omitted. The following measured values were obtained:

Flexural strength DIN 53 452 3200 Kp / cmf Tensile strength DIN 53 455 1850 Kp / cnT

Impact strength DIN 53 453 87 Kpcm / cm ²

Test series C

In a third comparison, coating compound C was used in an analogous manner to produce a laminate, but without the addition of benzoin ethyl ether, triphenyl phosphite and triphenyl phosphine. The curing of the coating compound C was done by adding 2 parts by weight of methyl ethyl ketone peroxide (505C) and 0.8 parts by weight of cobalt accelerator (1%). After cold curing, the laminate obtained was tested in the same way and the following measured values were obtained: Flexural strength DIN 53 452 2525 Kp / cm ² Tensile strength DIN 53 455 1290 Kp / cm ² Impact strength DIN 53 453 110 Kpcm / cm ²

In addition, all test panels from the laminate were made to be comparable To obtain values, annealed for 2 hours at 60 ° C, whereby they were homogenized. All measured values are mean values from measurements on 10 test pieces each.

These measured values show that the usual classic cold curing with peroxide and accelerators has low flexural strength and provides low tensile strength and relatively high impact strength. The high value for the impact strength is probably due to the fact that the residual monomer content likely in this laminate in the usual way

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borrowed higher than when cured by UV radiation unsaturated polyester.

It can be clearly seen that the light curing, wherein a benzoin ether alone (according to test series B) as photoinitiator was used, compared to the laminate obtained by cold curing (according to test series C) provides improved values in flexural strength and impact strength, while the tensile strength somewhat is reduced.

In addition, these studies show that the light-polymerized Laminates in which the total combination of benzoin ethyl ether and triphenyl phosphite is used as a photo-initiator and triphenylphosphine (according to test series A) was used, very good flexural strengths and the highest tensile strength was achieved. Also is the impact resistance compared to that light-polymerized polyester, which only contains benzoin ethyl ether alone as a photoinitiator, is significantly improved.

The comparative tests also show that through the present invention in the photopolymerized laminate achieves unexpected improvements in several directions will.

The coating compound used in the above test series C was made as follows:

Coating Compound C

100 parts by weight of a polymerizable mixture consisting of 67 parts by weight of polyester resin (prepared from 2 moles of maleic anhydride, 1 mole of phthalic anhydride and 3.08 moles of 1,2-propanediol) and 33 parts by weight of styrene, stabilized with 0, 01 ¹ I wt. 55 hydroquinone, a viscosity of 1100 cP at 20 ⁰ C and an acid number of

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30, are diluted with a further 5 Ge ^ r.-parts of styrene to produce an impregnation compound. To make a fo ~ 100 parts by weight of the mixture listed above, 1.5 parts by weight of benzoin ethyl ether, 0.6 part by weight of triphenyl phosphite and 0.2 part by weight of triphenyl phosphine are mixed in.

Fig. 1 shows one made of glass silk products or glass silk mats and polymerized unsaturated polyester resin is a laminate sheet consisting of consists of the photopolymerized polyester plastic, in which there is also a glass silk fabric, a glass silk mat or another glass silk product as reinforcement material is located and the. photopolymerized polyester plastic the marked components contains,

Fig. 2 illustrates a laminate web according to Fig. 1, but is the laminate sheet is formed in the form of a corrugated sheet.

FIGS. 3 and 4 show the embodiment of the Laminate web according to FIG. 1 or 2, but with an additional one Painting 1.

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Claims (1)

Claims polymerized unsaturated polyester resin Laminate web, characterized in that it is photopolymerized from a glass silk or glass silk mat reinforced There is polyester plastic and that the photopolymerized polyester resin before curing as a photoinitiator contains a total combination, consisting of: (a) 0.1 to 4% by weight of primary and / or benzoin ethers secondary alcohols and / or benzoinary ethers and (b) a sub-combination of at least two different ones Compounds of trivalent phosphorus, consisting of: (b ¹ ) 0.1 to 20 wt. organic esters of phosphorous acid with the general formula (D where R ^, R ₂ and R ~ can be the same or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals * ■> however, one of the radicals R ₁ , R ₂ or R must always be an aromatic radical - and ( b ⁿ ) 0.05 to 2% by weight of organic phosphine derivatives with the general formula (ID where R ₁ , R and R, can be the same or different and aliphatic, cycloaliphatic, aromatic 109833/1967 represent tables, araliphatic ^ or heterocyclic radicals, but one of the radicals R ₁ , R ₂ or R must always be an aromatic radical - and the percentages by weight refer to the total weight of unsaturated polyester resin and polymerizable monomers. 2) laminate web according to claim 1, characterized in that that these decomposition products of the photoinitiator in the polyester plastic contains. 3) laminate web according to claim 1 or 2, characterized in that that these additional polymerization initiators and / or JJ Contains metal accelerator and / or paraffin or wax or waxy substances in the polyester plastic. k) laminate web according to one or more of claims 1 to 3, characterized in that the polyester plastic is a cured air-drying polyester resin, which Contains residues of β, γ-unsaturated ether alcohols incorporated. 5) laminate web according to one or more of claims 1 to 4, characterized in that in the polyester plastic benzoin ethers (a) individually or mixed with one another in amounts of 0.1 to about 1.5 wt .- * in combination with compounds of trivalent phosphorus (b) ((b ^f ) and (b ">) are included. 6) laminate web according to one or more of claims 1 to 5, characterized in that the polyester plastic as esters of phosphorous acid (b ¹ ), which contain at least one aromatic radical, triphenyl phosphite, trip-toluyl phosphite, trxsnonylphenyl phosphite, didecylphenyl phosphite are contained individually or in a mixture. 109833/1967 7) laminate web according to one or more of claims 1 to 6, characterized in that in the polyester plastic as organic derivatives of phosphines (b "), the at least contain an aromatic residue, triphenylphosphine, tri-p-toluyl-phosphine, diphenyl-methyl-phosphine, Diphenyl-ethyl-phosphine, diphenyl-propyl-phosphine, dimethyl-phenyl-phosphine, Diethyl-phenyl-phosphine, dipropyl-phenyl-phosphine, Divinyl-phenyl-phosphine, divinylp-methoxy-phenyl-phosphine, Divinyl-p-bromophenyl-phosphine, Divinyl-p-toluyl-phosphine, diallyl-phenyl-phosphine, diallyl-p-methoxyphenyl-phosphine, Diallyl-p-bromophenylphosphine, diallyl-p-toluyl-phosphine individually or as a mixture are included. 8) laminate web according to one or more of claims 1 to 7, characterized in that the esters of phosphorous acid (b ¹ ) are contained in amounts of 0.1 to 2.0 percent by weight, based on the total weight of unsaturated polyester resin and polymerizable monomers. 9) laminate web according to one or more of claims 1 to 8, characterized in that the total combination of benzoin ethers of primary alcohols (a), esters of phosphorous acid (b ¹ ) containing only aromatic residues and organic derivatives of phosphine (b ") containing only aromatic residues in the polyester plastic as photoinitiator included, is included. 10) laminate sheet according to one or more of claims 1 to 8, characterized in that glass silk mats in the laminate sheet or glass silk fabric or roving fabric are included as reinforcement material. 11) laminate web according to one or more of claims 1 to 10, characterized in that it consists of about 55 to 109833/1967 60 wt. polymerized polyester and about 45 to 40 % By weight of fiberglass. 12) laminate web according to one or more of claims 1 to Hf characterized in that this is a paint job having. 109833/1967 Lee side