DE2104948A1 - Laminate sheet consisting of fiberglass fabric or fiberglass mat and polymerized polyester - Google Patents

Description

DR. WALTER NIELSCH

Patent attorney

2 Hamburg 70 ■ P.O. Box 10914

Telephone: 6529707

Reichhold-Albert-Chemie Aktiengesellschaft Hamburg 70, Iversstrasse 57

Laminate sheet consisting of fiberglass fabric or fiberglass mat and polymerized polyester

The present innovation relates to an improved laminate web consisting of glass silk fabric or glass silk mat and polymerized polyester.

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.

Those cured with peroxides and common accelerators Polyester laminates usually have a residual monomer content immediately after curing, which is the same for many Intended uses.

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, a further aim of the present innovation is to contain such glass silk mats or glass silk fabrics To provide laminate sheets that are opposite to the same

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Chen polyester laminates produced according to previous processes, significantly improved mechanical properties and have only a relatively low content of residual monomers immediately after curing.

It is known that unsaturated polymerizable polyesters 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 and that this as a poto initiator Benzoin ethers of primary and / or secondary alcohols and / or Contains benzoinarylather.

The laminate sheet according to the innovation also contains disintegration products of the ÜV 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 Manufacture of laminate webs made of fiberglass fabric or fiberglass mat and light-polymerized polyester in the cured polyester layer, compared to conventionally cured polyester layers, from the unsaturated polyester and the same glass reinforcement the light-polymerized glass-reinforced polyester plastic much better mechanical properties

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has, in particular has improved bending, impact and tensile strengths. It is also found been that immediately after carrying out the polymerization in the usual way with peroxides as polymerization initiators and accelerators or after photopolymerization, the content of residual monomers that cannot yet be polymerized into the photopolymerized polyester plywood is essential 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 foodstuffs or pharmaceuticals «,

The new ones made of fiberglass or glass ™

Laminate sheet consisting of a silk-matt and polymerized unsaturated polyester resin can be produced in a very efficient way individually or by mass production processes thanks to the rapid light-curing of the pad tester. For example, after the preparatory work has been completed, the light-curable liquid unsaturated polyester resin is first placed on an auxiliary carrier with an anti-adhesive layer and distributed evenly. Subsequently, the glass fiber reinforcement (glass fiber fabric or mat) is placed and both covered with a plastic film, as far as in this case no polyester resin is used, which contains an addition of paraffin, wax or wax-like materials m. Subsequent squeezing with a roller system completely soaks and compresses the glass fiber reinforcement and presses the remaining air 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, the compaction being carried out in a separate device. The cover film and the auxiliary carrier cause the training

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a smooth surface and enable the an * - final curing of the unsaturated polyester resin takes place in the absence of atmospheric oxygen. By structuring the cover film accordingly the coating can also be provided with a corresponding pattern. To make special decorative effects to achieve ^ the fiberglass fabric can contain colored fiberglass threads.

The laminate sheet according to the invention is produced in that photopolymerizable unsaturated polyester resin Use finds which benzoin ether contains as UV sensitizers and optionally accelerators, and where the polymerisation of the unsaturated polyester resins with the glass fiber reinforcement to form the composite material Irradiation with short-wave light takes place. The radiation that is most effective in terms of the innovation has wavelengths between about 25OO S and about U500 S. In a surprising way it has it turns out that this special process also has the advantages already described in the Innovation result.

Both superactinic Fluorescent lamps as well as so-called high-pressure mercury lamps as well as sunlight, tungsten and xenon lamps are used. A two-stage hardening process is preferably used, according to which the unsaturated Polyester resin first by irradiation with superactinisers Light (approx. 6O to 280 sec.) Is pre-gelled; the final curing takes place through short-term irradiation under high-pressure mercury vapor lamps, with irradiation times of approximately 20 to 80 sec / mm laminate thickness required are.

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The laminate webs are in a special embodiment 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 cold-curable and warm-curable products are suitable for the paints that are used. 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 as well as 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

ρ
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 2 are preferred. The laminate web generally settles to about 55-60% by weight. made of polymerized polyester and 45- ^ 0 weight-? » Glass silk together, but other compositions are also possible for special purposes.

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When using benzoin ethers as sensitizers, the photopolymerization of mixtures is more unsaturated Polyester with unsaturated copolymerizable Connections at room temperature possible in a relatively short time. A benzoin ether content of about 0.1 to 5% by weight, preferably about 0.4 to 2.5% by weight, based on the mixture, necessary to achieve sufficient reactivity.

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 10 contain up to 50 parts per million of a copper salt of organic acids; for this purpose, 0.1 to 5% benzoin or a benzoin substituted in the α-position by a C ₁ to C 4 -alkyl radical is used as a potoin initiator. The curing takes place by irradiation with light of wavelength 2500 to 4000 S. These polyester preparations show improved dark storage stability.

A special task of the present innovation is in the production of the glass silk fabric or glass silk mat and polymerized polyester laminate web are significant improvements over the prior art to achieve the technology, namely

1) The laminate with improved transparency and with improved adhesive strength between fiberglass and polyester plastic to manufacture.

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

3) Making a composite plastic that directly

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after its Lichtau'shärtung a reduced residual monomer content compared to a composite plastic hardened with peroxides and accelerators made of the same unsaturated polyester.

These objects are achieved in a surprising manner in that benzoin ethers are used as potentosensitizers will.

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 additional polymerization initiators and / or metal accelerators and / or paraffin or wax or Contains waxy substances, one or more benzoin ethers being included as a potoinitiator.

In a special embodiment of the innovation the benzoin ether from one or more benzoin ethers of the general formula:

<Q__ ₀

Ii i

O O Ar

where Ar is an aromatic radical.

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 with added molar excess

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term alcohols can be obtained by polycondensation. As _a , ß-unsaturated dicarboxylic acids, for example, can be used:

Maleic acid, maleic anhydride, pumar, itacon, citracon, Mesaconic and aconitic acids and halogenated acids such as chloromaleic acid.

Some of the _α ^ -unsaturated dicarboxylic acids can be replaced 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 and linseed oil. and soybean oil fatty acid or its anhydrides.

Preferred polyhydric alcohols are dihydric alcohols, 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, then β, γ-unsaturated 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, be used, preferably with the addition of paraffin, wax or wax-like substances to the exclude inhibiting effect with regard to oxygen. For example: the monoallyl and mono-

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methallyl ethers of ethylene glycol, 1,2-propanediol, 1,3-butanediol and -I ₉ ^, of glycerol, trimethylolpropane and -ethane and of pentaerythritol, as well as diallyl ether and the corresponding methallylethers of glycerol and trimethylolethane, propane and pentaerythritol. Particularly useful here are those β, γ-unsaturated ether alcohols which contain at least two 3, γ-unsaturated ether groups, such as trimethylolpropane diallyl ether, trimethylol ethane diallyl ether and pentaerythritol triallyl ether.

As mischpolymerisationsfähige vinyl compounds, individually or in a mixture in amounts of from 20 to 45 wt -.% _T are based on the mixture of unsaturated polyester resin and anpolymerisierbaren monomers include, (see A.

for example: Bulletin IP 8, July 1961. Amoco Chemicals Corporation, entitled "The Effect of Resin Ingredients on the Properties of Isophthalic Unsaturated Polyesters ", pages 5 to 19)" are suitable, for example: Styrene, vinyl toluene, p-tert.-butylstyrene, divinylbenzene, Vinyl acetate, vinyl propionate, acrylic acid ester, methacrylic acid ester, 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. J The molding, impregnating and coating masses are by adding customary inhibitors, for example p-benzoquinone, 2,5-di-tert-butylbenzoquinone, Hydroquinone, tert-butyl catechol, Toluy! Hydroquinone, also copper compounds, such as copper naphthenate, stabilized in the known amounts, as for example in the book Kirk-Othmer Encyclopedia of Chemical Technology, Interscience Publishers, New York, 1969, second edition, volume 20, p 822 to 825, and may contain other additives customary in polyester chemistry.

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Examples of the sensitizers to be used are 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-nonanol, n-dodecanol, 6-dodecanol _s lauryl, myristyl, stearyl alcohol, 2-chloro-1-propanol, 3-bromine 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 unsaturated fatty alcohols obtained by selective hydrogenation of unsaturated fatty acids. Examples of benzoin ethers that can be used are the benzoin ethers of phenol, 2-cresol, 3-cresol, 4-cresol, 3,4-dimethylphenol, 2,6-diethylphenol, 4-tert.-butylphenol, 2-methoxyphenol, 4-methoxyphenol, 2 -Chlorophenols, 4-chlorophenols, 2,6-diehlophenols, 2,4,6-trichlorophenols, naphthols (1), naphthols (2) and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A ). The preparations used according to the invention contain the benzoin ethers individually or mixed with one another in amounts of about 0.1 to about 5 percent by weight, preferably about 0.4 to 2.5 percent by weight.

Optionally, conventional polymerization catalysts can also be used (cf. for example Johan Bjorksten, "Polyesters and their Applications", Reinhold

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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.

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

The addition of peroxides can in some cases comparable g

cause better adhesion of the cured polyester to the fiberglass reinforcement. Furthermore, the use of peroxides, namely methyl ethyl ketone peroxide, is particularly recommended if it is desired to reduce slight discolouration of the hardening products, which can occur during exposure to light, but also under certain circumstances during storage. It is also possible to use small amounts of customary accelerators, for example cobalt octoate, cobalt naphthenate, zirconium naphthenate, dimethylaniline, acetoacetic acid ester. 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 to 826. In connection with the use of ketone peroxides you can for accelerated hardening of 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 is the storage stability of the masses

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however reduced.

The addition of UV absorbers as light stabilizers of the cured preparations, such as derivatives of Oxybenzophenohs, the salicylic acid ester, o-oxyphenyl-benzotriazole, in the usual amounts between 0.01 to 0.4 wt .- /?,. conditionally none noteworthy or still portable Retardation of the photopolymerization, although the absorption of the UV absorber is in the range of the photopolymerization required long-wave UV radiation.

For the production of fiber-reinforced, especially glass fiber-reinforced, Plastic parts using the preparations mentioned are, of course, only such processes suitable that allow irradiation after shaping or the lamination process. As examples are called: the laying on of hands, the lining of containers and pipes as well as the double-sided coating of chipboard and blockboard or plywood with glass fiber reinforced Laminates for the production of so-called container panels. As reinforcement materials are suitable all common fiberglass products such as mats, rovings and fabric qualities. After completing the lamination process, which is not tied to a limited processing time or "pot life" as is usually the case, the laminate can through low-energy UV radiation over a longer period of time or with the help of high-pressure mercury vapor lamps be cured in the short term. Due to their very short curing time, the used masses for a rational processing method tailored to the assembly line method.

example 1

By condensing 750 g of 1,2-propanediol and 587 g of maleic anhydride and 578 g of tetrachlorophthalic anhydride is a self-extinguishing un-

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saturated polyester resin and stabilized with 136 mg hydroquinone and 68 mg p.tert.-buty! catechol. The mixture of 65 parts by weight of this polyester resin with 25 percent by "parts by 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 ethyl ether. With this preparation, two glass fiber mats with a conventional synthetic resin binder based on polyester and a weight per unit area 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. After impregnation of the mat with the above-named M overall formulation, the laminate having a transparent film provided with a release agent on the surface, covered and 250 lake is irradiated under the high pressure mercury vapor lamps. The UV light curing channel is equipped with a high pressure burner and two HTQ 7 high pressure mercury vapor lamps (length 755 mm, diameter 12 mm, distance 15 cm from one another) from Philips. After cooling to room temperature, the film can be peeled off and the laminate can be separated from the aluminum plate. In this way, a flame-retardant and self-extinguishing glass fiber reinforced plate with good transparency is obtained. j

Further evidence of the technical progress achieved

Test series A

A laminate was produced from the coating compound C with a proportion of ¹ JO% by weight glass silk fabric and was light-polymerized. The flexural strength, tensile strength and impact strength of the light-polymerized laminate obtained were determined. The following measurement

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get values:

Flexural Strength Tensile Strength
Impact strength

DIN 53 452
DIN 5.3 ** 55
DIN 53 453

3200 Kp / cm ² 1850 Kp / cm ² 87 Kpcm / cm *

Test series B

In a further comparison, coating composition C was used in an analogous manner to produce a laminate _{, but without the addition of benzoin ethyl ether 9.} The curing of the coating compound C was done by adding 2 parts by weight of methyl ethyl ketone peroxide ($ 50) and 0.8 parts by weight of cobalt accelerator (IS?). After cold curing, the laminate obtained was tested in the same way and the following measured values were obtained:

Flexural Strength Tensile Strength

Impact strength

DIN 53 452
DIN 53 455
DIN 53 453

2525 Kp / cnr 1290 Kp / cm ² 110 Kpcm / cm '

In addition, all test panels on 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 in this laminate is likely in the usual way higher than for unsaturated polyester cured by UV radiation.

It can be clearly seen that the light curing, wherein a benzoin ether alone (according to test series A) as photo initiation

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tiat'or was used, compared to the laminate obtained by cold curing (according to test series B) provides improved values in flexural strength, tensile strength and impact strength.

The comparative tests also show that the present invention in the light-polymerized laminate unexpected improvements can be achieved in various directions.

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

Coating Compound C W.

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 0.014% by weight . Ji-hydroquinone, a viscosity of 1100 cps at 20 ⁰ C and an acid number of 30 are diluted for preparing an impregnating with a further 5 parts by weight of styrene. To produce a photopolymerizable mixture, 100 parts by weight of the above mixture are admixed with 1.5 parts by weight of benzoin ethyl ether.

Fig. 1 shows a made of glass silk products or glass silk W matt and polymerized unsaturated polyester resin consisting of laminate web, the laminate web made of consists of the photopolymerized polyester plastic, in which there is also a glass silk fabric, a glass silk mat or another fiberglass product is used as a reinforcing material and the photopolymerized Polyester plastic contains the marked components. '

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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 sheet according to Fig. 1 or 2, but with an additional coating 1 »

The invention also relates to the use of molding and coating compositions from mixtures stabilized in the usual way unsaturated polyester and polymerizable, monpmerer Compounds containing benzoin ethers and, if appropriate, additionally a peroxide catalyst and / or a metal accelerator or / and contain paraffin or wax or waxy substances as an impregnating compound for glass silk mats or Glass silk fabric for the production of reinforced plastic molded parts by means of UV radiation.

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Claims (9)

Claims 1) Made of glass silk products or glass silk mats and polymerized unsaturated polyester resin existing laminate web, characterized in that it consists of a There is glass silk or glass silk mat reinforced photopolymerized polyester plastic and that this contains benzoin ethers of primary and / or secondary alcohols and / or benzoin ether as a potentiator. 2) laminate sheet according to claim 1, characterized in that this decay products in the polyester plastic Contains UV sensitizers. 3) laminate sheet according to claim 1 or 2, characterized in that in the laminate sheet glass silk mats or glass silk fabric with soluble or insoluble binders with a weight of about 120-900 g / m are included. 4) laminate web according to claim 1 or 2, characterized in that in the laminate web roving fabric with a weight from 120-900 g / m are included. 5) laminate web according to one or more of claims 1 to 4, characterized in that the laminate web from about 55 - 60 wt. polymerized polyester and 45-40 d Wt -.% Glass fiber is. 6) laminate web according to one or more of claims 1 to 5, characterized in that this additionally Polymerization initiators and / and metal accelerators and / and paraffin or wax or waxy Contains substances in the polyester plastic. 7) laminate web according to one or more of claims 1 209834/1127 to 6, characterized in that the polyester plastic is a cured, air-drying polyester resin is what residues of 3, γ-unsaturated ether alcohols contains built-in. 8) The laminate sheet according to one or more of claims 1 to 7 »characterized in that individually or in a polyester resin benzoin ethers mixed together in amounts of from 0.1 to about 5 wt -.% Are included. 9) laminate web according to one or more of claims 1 to 8, characterized in that it has a coating having. £} XBx £ xfxnäKKgxfeKfcxx ££ iExaHKl! IxQtxs Use of form and Coating compositions made from mixtures of unsaturated polyesters stabilized in the usual way and polymerizable, monomeric ones Compounds containing benzoin ethers and, if appropriate, additionally a peroxide catalyst and / or a metal accelerator or / and contain paraffin or wax or waxy substances as an impregnating compound for glass silk mats or Glass silk fabric for the production of reinforced plastic molded parts by means of UV radiation. 209834/1127