DE7103911U - Laminate sheet made of glass silk fabric or glass silk matt and polymerized polyester - Google Patents

Description

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Please note: check the applicable box; heavily bordered »Release Fekier! German godparents

8000 Munich 2

ZanibfOdcenstraSett

Location:

Hamburg

Date. · I »February 1971

Properties:

Gbm

For the object described in the annex (tool or everyday object | or part thereof) fpe registration in the role for utility models is requested.

Applicant: (Vor-u.ZunoMe.b. Women atSStGeburftname; firrooe.firmonmtigeni Honebisreg.-Application.) seesKge denomination of the applicant) i »(PostleibaM, Ott, Slr., house no., if necessary au * tostfadi, at foreign locations avcb state oed district)

Representative:

(NaiM.AntdiriRnittPosHeirzaM, possibly audi ftjdi; Ainvallsgemeiiisdiaften in Specify top tuning with the full madit)

ZBStenungslbentungsligrigtor, Ceremony address

Marne. Address with postcode, possibly audi mtfadi)

Reichhold-Albert-Chemie share 2 Hamburg 70, Iversstrasse * |

free)

society

Dr. Walter Nielsch, patent attorney 2 Hamburg 7O ₉ P.O. Box 10914

Dr. Walter Nielsch, patent attorney 2 Hamburg 70, P.O. Box 10914

Registration is a | | The filing date for the elimination is the

*) Elimination from dt ~ -
Building sample registration Act.Z_

. claimed

The denomination is:

(short and exact tedinis the two sides of the

Subject matter to which the invention is based

relates, Obcniinstimn and with the title of

Description;

no fhantos o

The A «$ londsprlorit8t of the pre-registration is used (Order - registration log, country, file number, Kasldie »tick 1)

Approval priority

ibenfotgei 1st show day, cimtl. »Iduiung and place of the exhibition with

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

1626/70, February 5, 1970, Switzerland 57/71, January 5, 1971, Switzerland

wmmm,

-DM '

The fee for the utility model registration in the amount of 30 DM Q is paid. Q is paid. It is requested for the duration of - monot (s) (max. 6 months from the registration of the OBJ registration and announcement

suspend.

Attachments: (The documents marked with a cross are attached) 1. Another piece of this application 2 A description

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4th A Sate file drawings with sheet

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GtMLAntr.

w.ee

71033Ü22.4.? R

Gea. V. 33/63

J Met. 2250 Obm

Patent attorney

2 Staburg 70 · P.O. Box 10 S14

: 6529707

Beichhold-Albert-Chemie Aktiengesellschaft Hamburg 70, Iversstrasse 57

The end -. : Fiberglass fabric or fiberglass mat and polymerized polyester existing Laiainatbahn

Inventor: Dr. Burkhard Behrens and

Dip! · Chemist Hermann Delius

The present hiring concerns an improved from Laminate sheet consisting of glass silk fabric or glass silk mat and polymerized polyester.

Made of fiberglass fabric or fiberglass mat and polymerized Laminate webs made of polyester are known per se. However, these are not yet photopolymerized with Polyester and fiberglass fabrics or fiberglass mats have been produced.

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

The task of the present innovation is to create a fabric made of glass silk fabric 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

eoicne glass silk mats or glass silk fabrics To provide land tracks that are opposite to the same Polyester laminates produced according to previous processes, significantly improved mechanical properties own and immediately after hardening only one proportionately have a low content of residual monomers.

As is well known, “unsaturated polymerizable polyesters are grounded for coating purposes on a wide variety of substrates cured by photopolymerization to form dense lacquer coatings, but the lacquer coating layers obtained so far contain no fiberglass fabric or fiberglass mats 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 the photopolymerized Polyester resin contains a total combination as a photoinitiator before curing, consisting of:

(a) 0.1 to 4 wt. 36 benzoin ethers primary and / or secondary alcohols and / or benzoinary ethers and

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

(to *) 0.1 to 20 wt. organic ester of phosphorous Acid ma, t of the general formula

0 -R ₁

₂ (I) 0

where IL _t R ₂ and R. are identical or different

"" 7

and aliphatic can represent cycloaliphatic, aromatic, araliphatic or heterocyclic radicals - however, one of the radicals R ₁ , R ₂ or R ₅ must always be an aromatic radical - and (b ⁿ ) 0.05 to 2 % by weight of organic derivatives of phosphine with the general formula

(II)

'3 *

where R ₁ , R ₂ and R, can be identical or different and represent aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic radicals, but one of the radicals R ₁ , R ₂ 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 contains polyester plastic also decay products of the UV sensitizers, the 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 the Production of laminate webs made of ... glass silk fabric or glass silk 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 has significantly better mechanical properties, in particular improved bending, impact and Has 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 the photopolymerization., the content of residual monomers that have not yet been polymerized into the photopolymerized polyester plastic 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 far as the laminate webs produced according to the new with Come into contact with food or pharmaceuticals.

The new ones made from glass silk products or glass silk mats and polymerize »unsaturated polyester resin existing laminate web can through the rapid Light curing of the polyester produced in a very efficient way individually or by a mass production process are »E.g. will be placed on an auxiliary carrier with an anti-adhesive layer after completing the preparatory work First the light-curable liquid unsaturated polyester resin is added and distributed evenly. Follow-up the fiberglass reinforcement (fiberglass fabric or -mat) 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 an orphan 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 made with pre-soaked reinforcement material be carried out in an analogous manner, the compression being carried out in a separate device will. The cover film and the auxiliary carrier cause the formation of a smooth surface and enable that the subsequent curing of the unsaturated polyester resin takes place in the absence of atmospheric oxygen.

710331122.4.71

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.

The laminate sheet according to the invention is produced in that photopolymerizable unsaturated polyester resin Use finds what UV sensitizers and if necessary Contains accelerator, and wherein the polymerization of unsaturated polyester resins with the fiberglass reinforcement to the composite material is carried out by irradiation with short-wave light. The most effective in terms of innovation Radiation has wavelengths between about 2500 S and about 4500 8. It has surprisingly been found that This special process also results in the advantages already described for the innovation.

As light sources for UV irradiation, both super actinic fluorescent lamps as well as so-called high-pressure mercury vapor lamps as well as sunlight, tungsten and xenon lamps are used. It is preferred to use a two-stage hard longitudinal process, after which the unsaturated Polyester resin is first pregelatinized by irradiation with superactinic light (approx. 60 to 180 seconds); the final curing takes place by short-term irradiation under high pressure mercury vapor lamps, whereby Irradiation times of 20 to 40 sec / mm laminate thickness are required are.

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

O-C-o *

0 y

ο «

Cold-curing and warm-curing products can be used for the paints used. The following are listed in detail:

Unsaturated drying and air drying with addition of paraffira Polyester resins, alkyd resins and alkyd resin-melamine resin combinations, plasticized, acid-curable urea resins and one- or two-component polyurethanes.

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

As a reinforcement material for the production of the Laminate sheet glass silk mats or glass silk fabric with

soluble and insoluble binders weighing,. 2

about 120-900 g / m are used, but are also other grammages can be used.

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

2 roving fabrics with a weight per surface of 120-900 g / m can also be used. However, coarse roving fabrics with a weight per area of 400-600 g / m 2 are preferred. The laminate web is generally composed of about 55-60% by weight of polymerizing »polyester and ^ 5- ^ 0% 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

~ 7 "

Time possible. ! A benzoin ether content of about 2 weight percent, based on the mixture, is necessary to achieve sufficient reactivity. These mixtures but show an intense yellow coloration after exposure to high pressure mercury vapor lamps, which themselves does not fully recede 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 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 6 alkyl radical is used as a potoin initiator. 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 task of the present innovation is in the production of the glass silk fabric ".. glass silk mat and polymerized polyester laminate web are significant improvements over the prior art to achieve the technology, namely

1) au improve the dark storage stability of the ready-molding, impregnating and coating compositions at room temperature and at elevated temperatures up to about 6O ⁰ C very much t.

j 2) Me to increase the polymerization rate very significantly when carrying out the process, so that the loading

^Cüo § _t :, / ν- I

«Θ etaeo

Radiation time can be shortened accordingly.

3) The discoloration of the hardened polyester preparation by reducing the concentration of the sensitizers used reduce au for a relatively short irradiation time.

4) The laminate with improved transparency and with improved Establish adhesive strength between fiberglass and polyester plastic »

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

6) Do not manufacture composite plastic that is directly a reduced residual monomer content after it has been light-cured 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 objects are achieved in a surprising manner that benzoin ethers in certain combinations with Compounds of trivalent phosphorus are used.

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 produced, which may contain additional polymerization initiators and / or contains metal accelerators, the aforementioned total combination being included as the potentiometer.

In a special embodiment of the innovation, component (a) consists of one or more Eenzoinaryl-

- 9 ethers of the general formula:

O O Ar

where Ar is an aromatic radical.

When using the total combination, consisting of Ca) and (b) ((b *) and (b ")), surprisingly occurs a synergistic one Effect that causes extremely short polymerisation times in the case of UV irradiation. The extraordinarily high reactivity of the preparations used allows it to be compared with the known preparations with comparable curing times, the content to significantly reduce the amount of benzoin ethers or, alternatively, to shorten the hardening times considerably with comparable contents of benzoin ethers.

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.

Among unsaturated polyester resins are the usual ones Condensation products (see 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. As α, B-unsaturated dicarboxylic acids are, for example useful:

Maleic acid, maleic anhydride, fumaric, itaconic, citrai ", Mesaconic and aconitic acid as well as halogenated acids,

O r ₀ ο

*> 0 C C

»Co r

such as chloromaleic acid. Some of the α »ß-unsaturated dicarboxylic acids can in known tit by saturated dicarboxylic acids, for example o-, iso- and terephthalic acid, tetra- and hexahydrophthalic acid, tetrachlorophthalic acid, hexachloroendomethylene-tet rahydrophthalic acid, endomethylenetefcpahydrophthalic acid, Adipic and sebacic acid as well as dimer ized linseed oil and soybean oil fatty acids or their anhydrides, be replaced·

The polyhydric alcohols are preferably dibasic Alcohols in question, for example ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, Dipropylene glycol and its higher homologue, neopentyl glycol, 2.2, lt-trimethylpentanediol-l, 3 »pentylglycol, alkoxylated Bisphenols, hydrogenated bisphenol, dimethylolcyelohexane. However, trivalent and polyvalent 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 on air drying properties of the polyester resin is important, β, γ-unsaturated Ether alcohols in exchange for the polyvalent alcohols, as for example in the German Auslegeschrift 1 02 * 1 654 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 -l, * t, des Glycerine, trimethylol propane and ethane and pentaerythritol as well as diallyl ether and the corresponding methallyl ethers of glycerol and trimethylolethane, propane and pentaerythritol. Particularly useful here are those O, Y-unsaturated ether alcohols which contain at least two contain ß, Y-unsaturated ether groups, such as trimethylol

a ce e

3 a

- 11 -

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

As raise-polymerizable vinyl compounds, which are contained individually or in a mixture in amounts of 20 to 5% 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 ^w The Effect of Resin Ingredients on the Properties of Isophthalic Unsaturated Polyesters ¹¹ , pages 5 to 19), are, for example, suitable: styrene, vinyl toluene, p-tert-butyl styrene, divinyl benzene, vinyl acetate, vinyl propionate, acrylic acid esters, 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. Examples of allyl compounds that can be used are: diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate. The molding, impregnating and coating compositions are, by adding conventional inhibitors, for example p-benzoquinone, 2,5-di-tert.-butylbenzoquinone, hydroquinone, tert.-butyl catechol, toluyl hydroquinone, and also copper compounds such as copper naphthenate, stabilized in the known amounts, as described, for example, in the book Kirk-Othmer Encyclopedia of Chemical Technology, Interscience Publishers, New York, 1969, second edition, Volume 20, pages 822 to 825, and can contain other additives customary in polyester chemistry .

Examples of the sensitizers to be used (a) in the Gesaratkombination (a) and (b) (Cb ') and (b ")) 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-methylpemtanol-3, primary and secondary octanol, 2-ethylhexanol, n-

Nonanol, n-dodecanol, 6-dodecanol, lauryl, myristyl, steary alcohol, 2-chloro-1-propanol, 3-bromo-1-propanol, 2,2-dichloro-1-propanol, 1-chloro 2-propanol, abiethy! Alcohol and tetrahydroabiethy! 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. Examples include: Ρ, γ-unsaturated alcohols such as allyl alcohol, methallyl alcohol, ethyl alcohol, chlorallyl alcohol, crotyl alcohol, phenyl allyl alcohol, methyl vinyl carbinol, and unsaturated fatty alcohols obtained by selective hydrogenation of unsaturated fatty acids. Examples of the benzoin ether (a) to be used in the overall combination (a) and (b) <(b *) and (b ^w )) are the benzoin ethers of phenol, 2-cresol, 3-cresol, 4-cresol, 3 _> M-dimethylphenols, 2,6-diethylphenols, 4-tert-butylphenols, 2-methoxyphenols _, 4-methoxyphenols, 2-chlorophenols, 4-chlorophenols, 2,6-dichlorophenols, 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 (a) mentioned individually or mixed with one another in amounts of 0.1 to about k weight percent, preferably 0.1 to about 1.5 weight percent, in combination with compounds of trivalent phosphorus (b) C (b ^f ) and (b ¹ *)). Suitable esters of phosphorous acid (b ') ₉ which contain at least one aromatic radical are, for example, triphenyl phosphite, tri-p-toluyl phosphite, trisnonylphenyl phosphite, didecylphenyl phosphite.

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

- 13 -

pheayl-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, diviny1-p-toluyl-phosphine, dially1-phenyl-phosphine, dially1-p-methoxyphenyl-phosphine, dially1-p-bromophenyl-phosphine, dially1-p-toluyl-phosphine. The ester of phosphorous acid (B ·) are in amounts of from 0.1 to 20 parts by JC, based on the total weight of unsaturated polyester resin and anpolymerxsierbaren monomers, preferably ₃₁ I O to 2 parts by JS, in admixture with the aforementioned Benzoin ethers (a) and phosphines (b ") contain.

The stated phosphines (b ") are in amounts of 0.05 to 2 wt .- $, 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») The most preferred total combinations consist of: benzoin ethers of primary alcohols (a), esters of phosphorous acid (b ·) which contain only aromatic residues, such as triphenyl and / or tri-p-toluyl phosphite and organic derivatives of phosphine ( b ^w ) 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, pp. 48-5D in amounts of 0.1 to about 2 wt. 55, based on the total weight of unsaturated polyester resin and polymerizable Monomers, be advantageous because the latter through the UV radiation itself as well as through the UV radiation occurring heat can be excited for polymerization catalysis.

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.

In some cases, the addition of peroxides can improve the adhesion of the cured polyester to the glass fiber reinforcement. Furthermore, the additional use of peroxides _Λ is by name, primarily to be recommended methyl ethyl ketone peroxide, if desired, minor discoloration of the cured products, but such as may occur during storage, exposure to light during irradiation, may also decrease. 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 described, 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, metal compounds such as cobalt, zirconium and vanadium naphthenate, or metal chelates such as cobalt and zirconium naphthenate, can be added to accelerate hardening. However, if peroxides and metal accelerators are present at the same time, the storage stability of the compositions is reduced.

The addition of UV absorbers as light stabilizers of the cured preparations, such as derivatives of oxybenzophenone, the salicylic acid ester, o-oxyphenyl-benzotriazole, in the usual amounts between 0.01 and 0.% wt Retardation of photopolymerization, although the

sorption of the DV absorber in the area of the photopolymerization required long-wave UV radiation.

These impregnating compounds used have compared to the known masses have excellent dark storage stability and are therefore excellently suited as stable one-component systems. «The best results are obtained, if the phosphite content is about three times the pnosphine content.

To test the dark storage stability of the preparations to be used, 6 l parts by weight of an unsaturated polyester resin stabilized in the usual way with 0.015 wt Parts by weight of styrene mixed and, according to the following table, various total combinations of (a) benzoin ethyl ether, (b) triphenyl phosphite and (b ^wt ) triphenylphosphine dissolved in styrene are added.

Table 1 Dark storage stability

Benzoin ethyl
ether in weight "-
Share, related
gen to 110
Parts by weight
mixture Triphe nyIpho s-
phit in weight
Share, related
gen to 110
Parts by weight
mixture Triphenylphosphere
phin in weight
Share, related
gen to 110
Parts by weight
mixture Dark-
Sta
mobility
(60 ³ C)
in days 0.25
0.5
0.5
0.5 0.2
0.2
0.4
0.6 0.1
0.1
0.1
0.2 24
24
24
22nd

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

For the production of fiber-reinforced, in particular glass fiber-reinforced, plastic parts using the preparations according to the invention, only those processes are naturally suitable which allow irradiation after the shaping or the lamination process. Examples include: the hand lay-up process, 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. All customary glass fiber products such as mats, rovings and fabrics are suitable as reinforcement materials. After carrying out the lamination, the life is bonded ¹¹ is not as commonly pot to a limited working time or ", the laminate may be cured in the short term by low-energy UV radiation over a longer period or by using Quecksilberdamp'hochdrucklampen.

Due to their very short hardening time, the masses used are suitable for an efficient assembly line method tailored processing method.

Mixture A:

100 parts by weight of a polymerizable mixture consisting of 67 parts by weight of polyester resin (made from 1 mole of maleic anhydride, 1 mole of phthalic anhydride and 2.18 moles of 1,2-propanediol) and 33 parts by weight of styrene, with 0.015% by weight -jS hydroquinone stabilized, a viscosity of about 1500 cP at 20 ⁰ C and an acid number of 28, are diluted with a further 10 parts by weight of styrene and 0.5 parts by weight of a 10 wt. -% solution of paraffin (melting point 52 ° -53 ° C.) in toluene.

Mixture B:

100 parts by weight of a polymerizable mixture, be

C -

C C

- 17 -

made up of 67 parts by weight of polyester resin (made 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, with 0.014% by weight? Hydroquinone stabilized, a viscosity of about 1100 cP at 20 ⁰ C and an acid number of 30 are diluted with a further 10 parts by weight styrene, and 0.5 parts by weight of a 10 weight Jtigen solution of paraffin (m.p. 52-53 ° C.) in toluene.

Comparative examinations 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 into a 1 mm thick layer on a glass plate and exposed to radiation from a UV lamp (EL-VAK, LÜMINOTEST, Elektro-Vakuum-GmbH, Berlin) at a distance of 17 cm. The gel times are given in Table 2. Comparatively, those under are equal Conditions determined gel times of the phosphitutkI Phosphine-free mixtures also indicated.

Table 2 Verse·- Benzoin ether Phosphite Triphenyl Selier- No. additive 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 related to Mixture A Mixture A 110 parts by weight le mixture Ά 1 0.5 benzoin 55 raethyl ether 2 0.5 " 0.6 triple - 15th nylphos- phit 3 0.5 " 0.8 « - 15th

do β

gäbeile 2

Verso
Mp. Benzoin ether
addition in weight "-
Share, related
gen to 110
iew.-parts
mixture A Phosphite i
rate in weight
Share, related
gen to 110
Parts by weight
Mixture A rriphenyl-
phosphine
sentence in
ßew.-parts,
related to
.10 parts by weight
le mixture A elier
in
ec 4th 0.5 benzoin
mefchyl-
ether 1.0 triple
nylphos-
phit - 40 5 1.0 « - - 35 6th 1.0 · 0.6 ^m 32 7th 1.0 ■ 0.8 " - 30th 8th 1.0 · 1.0 ^m - 30th 9 0.5 benzoin
ethyl-
ether - - 55 10 0.5 0.6 " - 45 11th 0.5 ^w 0.8 " - 43 12th 0.5 ^w 1.0 ^M. - 45 13th 0.5 ^w 5.0 - 37 14th 0.5 10.0 » - 29 15th 0.5 ^w 20.0 » - 32 16 0.5 benzoin
ätJHyl-
ätlner 0.6 trisnonyl
phenyl
phosphite 50 i 17th 0.5 benzoin
uföbhyl-
ätner 0.2 18th 18th 0.5 ⁿ - 0.6 15th 19th 0.5 " - 1.0 15th 20th 1.0 » - 0.2 12th 21 1.0 " - 0.6 10 22nd 1.0 · - 1.0 8th 23 0.25 Ben2oin
Ethyl
ether 0.2 40 24 0.25 " - 0.6 25th

Angela 0

Table 2

Verse.-
No. Benzoin ether
add in weight
Share, related
gen to 110
Parts by weight
Mixture A Phosphite
rate in weight
Share, related
gen to 110
Parts by weight
Mixture A Triphenyl
phosphine
sentence in
Parts by weight,
related to
110 parts by weight
le mixture A elier
since in
> ec 25th 0.25 benzoin
ethyl
ether - trisnonyl
phenyl
phosphite 1.0 20th 26th 0.5 ^B - 0.2 30th 27 0.5 " - 0.6 20th 28 0.5 " - 1.0 15th 29 1.0 ^w - 0.2 18th 30th 1.0 · - 0.6 12th 31 1.0 " - 1.0 9

Comparison tests 52 - 3 * t:

Mixture B contains benzoinä thy lather and triphenyl phosphite or benzoin ethyl ether and triphenylphosphine in the concentrations given in Table 3 are admixed. Under the same conditions as in the comparison tests 1-31, the gel times given in Table 3 are achieved.

Table 3

Verse· Benzoin ethyl Triphenyl Triphenyl Gelation No. ether in weight phosphite in phosphine in time in Share, related Parts by weight, Parts by weight lake gen to 110 related to related to Parts by weight 110 parts by weight 110 parts by weight Mixture B le mixture B le mixture B 32 0.5 - - 15th 33 0.5 0.6 - 30th 3 * 0.5 - 0.2 14th

: "cr ac

e co

COP C O CC

cc to

- 20 -

As from Table 2, Experiment No. 2 to M, 6 to 8, 10 to 16 and Table 5, Experiment No. 33, results in an addition of 0.6 to 20 wt. SS phosphates, based on 110 parts by weight 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 amount of UV radiation Reduction in gel time; however, the Bunkel storage stability is also worsened. However, as goes from Tabellet + U, according to the Invention by using the overall combination both the gel time and surprisingly shortened the dark storage stability also surprisingly improved at the same time.

The components of the total combination, namely benzoin ether (a), phosphite compound (b ¹ ) and phosphine ^{compound (b M} ) can be added in any order. In the preferred sequence, the phosphite compound (b *) is added first, then the phosphine ^{compound (b w} ) and finally the benzoin ether compound (a). It is only essential that the mentioned constituents (a), 0> ») and (b ^M ) must be contained in the polyester preparation as a combination before the UV irradiation.

Examples 1-11

Various benzoin ethers (a), triphenyl phosphite (b ^f ) and triphenyl ^{phosphine (b M} ) are mixed into the specified mixture A in the concentrations specified in Table M. The gel times given in Table k are achieved under the same exposure conditions as given in the comparative tests 1-31.

"OCC O

Table k

Ex.
No. Sensitizer
additive in weight
Share ,, related
to 110 wt.
Parts mixture
A. Triphenyl
phosphite
sentence in
Parts by weight,
related to
Mixture A Tripbenyl
phosphine
sentence in
Parts by weight,
related to
Mixture A Belier
time in
lake 1 0.25 benzoin
methyl-
apcher 0.2 0.1 45 2 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
äfchyl-
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 0.1 0.1 15th 9 0.5 0.1 0.2 10 10 0.5 0.6 0.2 9 11th 1.0 ⁿ 0.1 » 0.4 5

Example 12-13

Benzoin ethyl ether (a), tripfoenylphosphine (b ^f ) and triphenylphosphine (b ^w j) 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.

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, be zo 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 using the total combination (a) and (b) ((b ') and (b ⁿ )) emerges from the gel times listed in Table k and Table 5.

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

Example lfr - 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 ^M ) and, in addition, various conventional polymerization initiators or accelerators mixed in in the concentrations given 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.

Table 6

Ex. Additives in parts by weight, based on Gel time No. 110 parts by weight of mixture A in see 14th 2 methyl ethyl ketone peroxide (50% by weight) 35 15th 1 benzoyl peroxide paste (50 % by weight) 18th 16 1 cobalt octoate (6% by weight) 23 17th 1 zirconium octoate (6% by weight Zr content) 39 18th 2 azobisisobutyronitrile 16 19th 1 acetoacetic ester 16 20th 2 dimethylaniline (10% by weight solution) 31

Example 21

110 parts by weight of the specified mixture A, but without the addition of paraffin, 1.5 parts by weight of benzoin ethyl ether (a), 0.6 parts by weight of triphenyl phosphite (b ¹ ) and 0.2 part by weight of triphenyl phosphine (b ^w ) see it. With this preparation, two glass fiber mats with the usual soluble synthetic resin binder based on polyester and a surface weight of 450 g / m 2 are laminated one after the other onto a plywood board using the hand lay-up method. After the mats have been soaked with the above-mentioned preparation, the laminate is covered with a transparent film which contains a release agent on the surface and irradiated for 150 seconds under high pressure mercury lamps in an OT light curing channel. The UV light curing channel is equipped with a high pressure burner and two HTQ 7 mercury vapor high pressure lamps (length 755 tubes each »diameter 12 mm, distance 15 cm from one another) from Philips. The cooling is done 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.

ep

This coating has excellent transparency, so that the natural wood structure of the plywood surface comes into its own. Surprisingly, it has been found that such a produced coating significantly better mechanical properties, in particular improved bending, Has impact and tensile strengths, as a comparable produced coating, however, using using a conventional curing process has been cured by peroxides as polymerization initiators and accelerators. In addition, it was found that the content immediately after the photopolymerization was carried out 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 polymerization initiators and accelerators.

Example 22-29

The procedure is as in Example 10, but below Addition of 5 parts by weight of further copolymerizable vinyl compounds, as indicated in Table 7, and 1.5 parts by weight of benzoin isopropyl ether an- ■ place the benzoin ethyl ether (parts by weight based on 110 parts by weight of mixture A).

Table 7

Ex. copolymerizable vinyl ver Gel time No. ties in see 22nd Methyl methacrylate 20th 23 Isobutyl methacrylate 17th Zk Butyl methacrylate 17th 25th Butanediol-1, ^ - dimethacrylate 23 26th Triäthy lengly koldime thacrylate 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.

With the use of butane-1,1-dimethacrylate or triethylene glycol dimethacrylate according to Examples 25 and 26, the crosslink density is increased, so that cured polyesters with improved resistance to solvents 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

Condensation of 750 1,2-propanediol, 587 g of maleic anhydride and 578 g Tetraehlorphthalsäureanhydrid \ d.vd g produced a self-extinguishing unsaturated polyester resin in a known manner and with 136 rag of hydroquinone and 68 mg p.tert.-butyl-catechol stabilized

J-- ^ ^fc 2Jg

sated. The mixture of 65 parts by weight of this polyester resin with 25 parts by weight of styrene and 10 parts by weight of trichloroethyl phosphate has a viscosity of 1400 cP at 20 ° C and an acid number of 28.

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 ») and 0.2 part by weight of triphenylphosphine (b ¹¹ ). With this preparation, two glass fiber mats with the usual synthetic resin binder are applied one after the other

2 polyester base and a weight per unit area of 450 g / m 2, laminated onto a polished aluminum sheet, the surface of which is provided with a release agent. After the mats have been soaked with the above-mentioned preparation, the laminate is covered with a transparent film with a release agent on the surface 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 can be separated from the aluminum plate. In this way, a flame-retardant and self-extinguishing glass fiber-reinforced panel with good transparency is obtained.

Further evidence of the technical progress achieved

Test series A

The coating compound C became with a proportion of i | 0 Gew.-J {glass silk fabric made a laminate and lictot polymerized. From the obtained light-polymerized Laminate, the flexural strength, tensile strength and impact strength were determined. The following values were obtained obtain:

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

Test series B

In an analogous way, another licbt-polynized Comparative laminate produced, but in the Bescbicntungsmasse C tripbenyl phosphite and triphenyl phosphine was omitted. The following measured values were obtained:

Flexural strength DIN 53 452 3200 Kp / eraf
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. Coating compound C was cured by adding 2 parts by weight of methyl ethyl ketone peroxide (505?) And 0.8 parts by weight of cobalt accelerator <!?>. 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 HO Kpcm / cm ²

In addition, all test plates from the laminate were to obtain comparable Wej'te, annealed for 2 hours at 6O ⁰ 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 fourth for impact resistance is probably due to the fact that the residual monomer content likely in this laminate in the usual way

0 C

- 28 ~

borrowed higher than when cured by UV radiation unsaturated polyester.

It can be clearly seen that the light curing, with a benzoin ether alone (according to test series B) as the photoinitiator was used, compared to the laminate obtained by cold curing (according to test series C) provides improved flexural strength and impact strength values, 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 the photo initiator and tripheny! phosphine (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 containing only benzoin ethyl ether contains as photoinitiator alone, significantly improved.

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

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

Coating Compound C
j 100 parts by weight of a polymerizable mixture, consisting of 67 parts by weight of polyester resin (made from 2 grains of maleic anhydride, 1 column of phthalic anhydride and 3.08 grains of 1,2-propanediol) and 33 parts by weight of styrene, stabilized with Ο , ΟΙή Gew.-Ä hydroquinone, a viscosity of 1100 cP at 20 ⁰ C and an acid number of

c c

- 29 -

30, are used to produce an impregnation compound with further 5 parts by weight of styrene diluted. To make a photopolymerizable Mixture 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 trphenyl 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 fiberglass product used as a reinforcement material and the photopolymerized polyester plastic contains the marked components contains.

FIG. 2 shows a laminate web according to FIG. 1, but the laminate web is designed in the form of a corrugated web.

3 and k show the embodiment of the laminate web according to FIGS. 1 and 2, but with an additional coating 1.

Claims (12)

A laminate web consisting of polymerized unsaturated polyester resin, characterized in that it consists of a glass silk or glass silk mats reinforced photopoly- «Nerized polyester plastic and that the photopolymerized Polyester resin contains a total combination as a photoinitiator before curing, consisting of: (a) 0.1 to k % by weight of benzoin ethers of primary and / or secondary alcohols and / or benzoin ethers and (b) a sub-combination of at least two different compounds of trivalent phosphorus ,, consisting of: (b ¹ ) 0.1 to 20% by weight of organic esters of phosphorous acid with the general formula (D R ₃ , 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 ^ff ) 0.05 to 2% by weight of organic phosphine derivatives with the general formula (ID where R ₁ , R ₂ and R, can be the same or different and are aliphatic, cycloaliphatic, aromatic . C * * OQ CC Ό .. oecc C '. SC C O Γ O 0 0 »~ cc coc - 31 - 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 this contains decomposition products of the photoinitiator in the polyester plastic. 3) laminate web according to claim 1 or 2, characterized in that that these additionally polymerization initiators and / or metal accelerators and / or paraffin or wax or contains waxy substances in the polyester plastic. 4) laminate web according to one or more of claims 1 to 3 »characterized in that the polyester plastic is .a hardened air-drying polyester resin., Which Residues of β, γ-unsaturated ether alcohols incorporated contains. 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 *) and (b ⁿ )) are included. 6} Laminate sheet according to one or more of claims 1 to 5 »characterized in that in the polyester plastic as esters of phosphorous acid <b ^f ), which contain at least one aromatic radical, triphenyl phosphite, triptoluyl phosphite, trisnonylphenyl phosphite, didecylphenyl phosphite individually or im Mixture are included. 7) laminate sheet according to one or more of claims 1 to (S, characterized in that the polyester plastic as organic derivatives of phosphines (b ^w ) which contain at least one aromatic radical, triphenylphosphine, tri-p-toluy1-phosphine, diphenyl-methy1 -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-brompheny1-phosphine, Mvinyl-p-toluy 1-phosphine, diallyl-phenyl-phosphine, dially1-p-methoxypheny1-phosphine, di ally1-p-brompheny1-phosphine, diallyl-p-toluyl-phosphine individually or in 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 ·) in amounts of 0.1 to 2.0 wt «- £, based on the total weight of unsaturated polyester resin and graft polymerizable Monomers, are included. 9) laminate web according to one or more of claims 1 to 8, characterized in that the total combination of ßenzoinäthern primary alcohols (a), esters of phosphorous acid (b ^T ), which contain only aromatic residues and organic derivatives of phosphines (b ⁿ ), which contain 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 boving fabric as Reinforcement material are included. 11) laminate web according to one or more of claims 1 to 10, characterized in that this is approximately from 55 to ö ο ο ο β ο ο 60 wt. Ji polymerize polyester and about k5 to ¹ M) wt. Consists of fiberglass. 12) laminate rail according to one or more of claims 1 to ill * characterized ₉ that it has a coating ·