DE7103921U - Laminate sheet made of glass silk fabric or glass silk matt and polymerized polyester - Google Patents

Description

DR. WALTER N ElSCH

File 2251

g 70 - P.O. Box 10914
Furaft β 62 β / O /

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 one made of fiberglass fabric or fiberglass mat and polymerized tem 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 polyester laminates cured with peroxides and customary accelerators usually show directly after the Curing has a residual monomer content that interferes with many uses.

The task of the present innovation is to make one 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, 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

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

As is known, unsaturated polymerizable polyesters are used cured for varnish purposes on a wide variety of substrates by photopolymerization su dense varnish overlays, but contain the varnish top layers obtained so far no fiberglass fabric or fiberglass mat reinforcement inserts.

The object of the innovation is one made of glass silk products or glass fiber wadding and polymerized unsaturated polyester resin existing laminate web, thereby characterized in that these are made of a glass silk or glass silk mat reinforced photopolymerized polyester plastic exists and that this as a photoinitiator benzoin ether of primary and / or secondary alcohols and / or Contains benzoinarylather.

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. Some of the decomposition products are chemically built into the polymeric polyester plastic.

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 has significantly better mechanical properties

has, in particular improved bending, impact and Has tensile strengths. Aufierdea is determined been that immediately after carrying out the polymerization in the usual way with peroxides as polymerization initiators and accelerators or after photopolymerization, the amount of residual goods that cannot yet be polymerized The photopolymerized polyester plastic is much lower and this immediately after the light has turned on has better mechanical properties. AuAerdea is the reduced content of Hestaoneren important, as far as the newly established Lawdnatbahnen bit Food or arsenic in contact

The innovations from glass silk products or "Glasseideneatten and polyaerizedB unsaturated polyester resin existing Lavdnat web can through the quick-acting Light curing of the polyester in a very efficient way or by a Hassenfertigungsverfahrc be asked. S.B. comes on a subcarrier kit one anti-adhesive layer after completing the preparatory work first the light-curable liquid unsaturated Polyester resin given and evenly distributed. Connection * The fiberglass reinforcement (fiberglass or - cotton wool) and both cover a plastic film, as long as no polyester resin is used, which is a mixture of paraffin, wax or wax-like material Contains substances. By then squeezing it off In the neck system, the glass silk reinforcement is complete Sn ^ ^ g soaked, compressed and the air still present The excess unsaturated polyester resin is squeezed out of the laminate. The execution can & »Λ optionally with pre-impregnated reinforcement material in in an analogous manner, the compaction being carried out in a separate device. The cover film and the auxiliary body carry out the training

BwKoi witter “Is OTT-Senaibilille Accelerator removed, and feel the relssaristics of the action

trehlung "i * hMiwiiiiy Lieht epfol ^ t. The in meaning

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Eieb »deft see through this special one

«You see the advantages of the

as Uxhtqeallen for the PV irradiation Mkmwn both su-Lettchtatofflenpen ela you soeeaunnte Ojaeek- «Ie

A leeJBleilgBti rartunce ^ erehreu »n« eh «eleheai of the satisfied Poleeterher swerst dvreh> * ⁱ " nit perectiniseheai light (approx. 60 to 280 sec.) Treels wtrftj the final stop time, with short-term exposure to the alarm Irradiation lines of 20 to 80 sec. Asi. Min. Strength 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 binding agent for the paints that are used, cold-curing and pre-curing products come into question. The following are listed in detail:

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

Combinations of aliphatic or cycloaliphatic !! Polyisocyanates and non-drying alkyd resins containing hydroxyl groups 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 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, but coarse roving fabrics with a weight per area of Ί00-600 g / m 2 are preferred. The laminate web is generally composed of about 55-60 weight percent of polymerized polyester and 115- ^ 0 weight percent. Glass silk together, but other compositions are also possible for special purposes.

7 1 * \ r \ r \ r * J.
iÖobiZ 1 29.4. 71

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

In the Italian patent 839 021, unsaturated polyester preparations curable by radiation 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 Hillion of a copper salt of organic acids; For this purpose, 0.1 to 5% benzoin or substituted in the o-Stelluiig by a C ₁ to Cg alkyl benzoin be used as photoinitiator. The curing takes place by irradiation with light of the wavelength 2500 to 4000 2. 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 sit better Establish adhesive strength between fiberglass and polyester plastic.

2) The composite plastic made of glass silk fabric or glass silk mat and photo-cured polyester to give mechanical properties.

3) Making a composite plastic that directly

7103321: 9 /,. 71

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.

These tasks are surprisingly solved by that benzoin ethers are used as photosensitizers.

A special embodiment of the innovation is characterized by the fact that the photopolymerizable impregnating compound from mixtures of unsaturated polyester resins stabilized in the usual way and polymerizable, moomer compounds and photoinitiators is produced, which may contain additional polymerization initiators and / or metal accelerator and / or paraffin or wax or Contains waxy substances, one or more benzoin ethers being included as a photoinitiator.

In a special embodiment, the fire exists the benzoin ether from one or more Beczoinary ether the general formula:

I.
0 0 ar

where Ar is an aromatic radical.

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, 8-unsaturated dicarboxylic acids and / or their Anhydrides with added molar excess

7103321 -3.4.71

term alcohols obtained by polycondensation

As «, ^ - unsaturated dicarboxylic acids, Uf 1n |> 1r are avalanche

useful:

_y ntd Aconi'tsSmpe sonxe ^ **

like for example

Some of the “, B-saturated dicarboxylic acids can be replaced by saturated ones, for example o-, iso- and terephthalic acid _}

MIpin- and awuMrinulre mrie di ~ rised linseed oil and soy oil can be removed. their anhydride

Alcohols in question, for example ethylene glycol, diol-1,2, butanediol-1,3, butanedxol-1, *, diethylene glycol, dipropylene glycol and their colors howologs, glycol, 2.2% - triethylpentanediol-1,3, alkylated Bij ^ rl ^ iwolff, hydrogenated bisphenol, diaethylol-eyclohezane. However, trivalent and non-valent alcohols, such as glycerine, triethylolethane, tribethylolpropane and pentaerythritol, can also be used proportionally. The aas these Robstoffen built unsaturated polyester resins known lent have the stream part of the formation of a sticky surface on curing in waiting of Loftsanerstoff · *** f ΎηΨ ^ ** * + ****> equity transactions of the polyester is placed worth unsaturated Itheralkohole in exchange for the valuable alcohols, as for example in the German text 1 O2% 65% and OSA-Patent 2 written, can be used, preferably water additive of paraffin, Maehs or other chemical substances, esc the inhibiting effect besgl «Oxygen as

7iü3S2'.2ii.7i

Methyl ether of ethylene glycol, 1,2-propanediol, 1,3-butanediol and -1,4, of glycerol, trimethyiolpropane and -ethane and pentaerythritol and diallyl ether and the corresponding methallyl ethers of glycerol and trimethylolethane, propane and pentaerythritol. Particularly useful are those β, γ-unsaturated ether alcohols which at least contain two β, γ-unsaturated ether groups, such as trimethylolpropane diallyl ether, trimethylol ethane diallyl ether and pentaerythritol triallyl ether.

As copolymerizable vinyl compounds, the individually or as a mixture in amounts of 20 to 45% by weight, based on on the mixture of unsaturated polyester resin and polymerizable monomers are included (cf. 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 for example suitable: 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. The molding, impregnating and topping compositions are made by adding conventional inhibitors, for example p-benzoquinone, 2,5-di-tert-butylbenzoahinone, 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.

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, L & uryl-, hyristyl-, Stearyl alcohol, 2-chloro-1-propanol, 3-broia-1-propanol, 2,2-dichloro-1-propanol, 1-chloro-2-propanol, abiethyl alcohol and tetrahydroabiethyl alcohol. Of the ether-like monoalcohols, those compounds which have primary alcoholic hydroxyl groups are preferred. However, the ronic alcohols are bait secondary and tertiary alcoholic hydroxyl groups are also useful. In addition to the saturated alcohols, there are the unsaturated alcohols also suitable. Examples include: β, γ-unsaturated alcohols, such as allyl alcohol, hethallyl alcohol, Ethallyl alcohol, chloralyl alcohol, crotyl alcohol, Phenylallyl alcohol, methyl vinyl carbinol, as well as unsaturated fatty alcohols obtained by selective hydrogenation; from unsaturated fatty acids. Examples of benzoin ethers that can be used are the benzoin ethers of phenol, 2-cresol, 3-cresol, 4-kreeol, 3,4-Diraethy! Phenols, 2,6-diethylphenols, 4-tert.-butylphenols, 2-methoxyphenols, 1-llethoxyphenols, 2-chlorophenols, 4-chlorophenols, 2,6-dichlorophenols, 2, ^, 6-trichlorophenols, Naphthols (1), naphthols (2) and 2,2-bis (4-hydroxyphenyl) propane 3 (Bisphenol A). The preparations used in accordance with the renewal 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 up to 2.5% by weight,

If necessary, conventional polymerization catalysts can be used (See, for example, Johan Bjorksten, "Polyesters and their Applications" *, Beinhold

Publishing Corporation, New York, 1956, pages 48 to 51) in amounts of 0.1 to about 2 percent by weight, 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 heat and polymerization catalysis that occurs during UV radiation can be stimulated.

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

The addition of peroxides can in some cases be improved Bring the hardened polyester to the glass fiber reinforcement. Further is the use of rite of peroxides, namely ethyl ethyl ketone peroxide, to be recommended primarily when it is desired, minor ones Discolouration of the hardening products, as seen during irradiation, under utastases but also during storage Exposure to light may decrease. A hit use of small amounts of customary accelerators, for example cobalt octoate, cobalt naphthenate, xircon naphthenate, Dimethylaniline, acetoacetic acid ester, is also possible. The use of accelerators in the copolymerization of unsaturated polyester hareses with polymerizable nonoaers is, for example, in the book Kirk-Othaer, Encyclopedia of Chemical Technology, Interscirmce Publishing, New York, 1969 "second edition, Volume 20, pages 825 to 826. In connection with the use of ketone peroxides, metal compounds, such as carbon, 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 shelf life of haters

sation bendtigteti

tmt flterstelluae of faerie reinforcements

ilufnellim « are according to nor sol

ι fttsres fls ^^ fipsfc »d £» £ ays— »BwfcwiiA ¹

asked. des Τι — 1 nierproMB permitii. as examples the BanAaufleeeverfaliren, those dressed up;

ι Mlteni and pipes as well as the two-sided coated vns

and table tops or plywood slt eXsstaserver-

tainer plates. suitable as Teretftrtnaagsaaterialien see all "borrowed fiberglass novelties," de Hatten,

ien · Matii Dnrchfilhrunc des I> aninierpn> ~ aeaaes »which is not usually to a frenste

»ItvafBaeit or" pot life * is bound,

whose energlearae UV radiation over an »Iftnearen leitraasi or old help from Qneeksilbe

»Since you see them

Fct races for a rational on the flow ban method sugescfanittene processinguoesnethode ·

example 1 By condensation of 750 g of 1,2-propanediol, 5β7 β

insSwreanhydrid and 578 ς

becomes in the well-known manner a self-respecting unsightly

saturated polyester resin and stabilized with 136 Hg hydroquinone and 68 mg p.tert.-buty! catechol. The mixture of 65 parts by weight of this polyester resin Bit 25 parts by weight 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 admixed 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 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 under the high-pressure mercury lamps for 250 seconds. The W light curing channel is equipped with a high pressure burner and two HTQ 7 mercury vapor high pressure lamps. (Length in each case 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 glass fiber-reinforced plate which is difficult to flan and which is self-extinguishing and of good transparency is obtained.

Further evidence of the technical progress achieved Test series A

From the Bes sealing compound C was with a proportion of 40 Gew.-X glass silk fabric made a laminate and light polymerized. From the obtained light-polymerized Laminate, the flexural strength, tensile strength and impact strength were determined. The following measurement

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get values:

Flexural strength DIN 53 * 52 32OO Sp / cm ²

Tensile strength DIN 53 «55 I85O Kp / cm ²

Schlait DIM 53 * 53 87 Kpcn / e » ²

Test series B

In a further comparison, the coating compound C ₉ was used in an analogous manner for the production of a laminate, but without the addition of benzoin / ethyl ether. The coating compound C was cured by adding 2 parts by weight of ethyl ethyl ketone peroxide (50?) And 0.8 parts by weight of cobalt accelerator (If). After cold aging, the laminate obtained was tested in the same way and the following measured values were obtained: Flexural strength BW 53 * 52 2525 Kp / cm ² Tensile strength DIK 53 $ 55 1290 Kp / cm ²

Impact strength DIM 53 * 53 IiO Kpcm / cm ²

In addition, all test plates on the laminate, NNR comparable ¥ were erte obtain 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 Kesswert show that the usual classic cold hardening with peroxide and accelerators, provides low flexural strength and low tensile strength and relatively high impact strength. The high value for the impact strength is probably due to the fact that the Probably the usual titmouse content in this laminate is higher than with UV irradiation cured unsaturated polyester.

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

71C3921I9.4.7T

tiator uses «earth, compared to that used by laltaushSr · tong e Lamnat (genSe test series B) significantly improved values in the flexural strength, in the Provides tensile strength and impact resistance.

The comparisons also indicate that through the present invention is light polymerized undesired improvements in various directions sows

The wet C hurdle in the above test series is produced:

Bes ****** ^ fofcMnrsse C

100 wt .- 'ropes of a polyaerizable consisting of 67 parts by weight of polyester resin (made from 2 mols of seairid, 1 hol of PhthalsSureanhy drid and 3.0> 8 fetch prapandiol-1,2) and 33 parts by weight Styrene, stabilized ax 0.01 * weight-f ochincc,

Viscosity of HOO cP at 20 ° C tmd a SSuresahl τα » 30, will zuj? Making a Tr & sse Kit «fester 5 parts by weight of styrene diluted. For the production of a photo-polymerizable item Geraisches "ground 100 parts by weight of the mash 1.5 parts by weight

. 1 illustrates one of Lrlasseidenerzeugiiissen or glass silk "rich muH polymerized unsaturated polyester resin besteäenäe tr ^ wrf Tfrait ir ^ yttT represents wherein dxe Laninatbahn y * the roti ^ olynerisierten PolyestertranststofT consists, in the sicöi auctc elm Glasseidenw, a glass fiber mat or other Glasseidenerzeusnis as hardening material and the photopolymerized polyester pulp contains the marked components.

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Fig. 2 shows the forms.

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Claims (7)

Protection claims 1) from glass fiber products and fiber glass mats and polymerized unsaturated polyester resin existing laminate web, characterized in that <fl "ft? This""" a glass silk or glasseidemactenvetärkten fotopolynerisierten polyester plastic is and daft the-er of primary and / or alcohols and, as photoinitiator benzoin ethers / or benzoinary ether. 2) Lanriix *? Ahn according to claim 1, characterized in that that this in Poljesterkunststoff decay products of the Contains UV sensitizers. 3) Laninatbahn according to claim 1 or 2, characterized in that in the Lavinatbahn glass silk matting or glass silk fabric o with soluble or insoluble binders vdt a weight of about 12O-900 g / «E are included. 4) laninat web according to claim 1 or 2, characterized in that in the Larainat web roving fabric adt eiziec Qe- 2
weight of 12O-900 g / n are included. 5) Laainatbahn according to one or more of claims 1 to 4, characterized in that the Laainatbahn from about 55-60% by weight polymerized polyester and 45-40 Gev.-f glass silk consists. 6) Lasinat web according to one or more of claims 1 to 5, characterized in that they also have polymerization initiators and / or metal accelerators or / and contains paraffin or wax or waxy substances in the polyester plastic. 7) Laninatbahn according to one or more of claims 1 r » to 6, daAarch substance a sea-bound air is, «elebes best-won EIT. It ¹ to Ί. there Fabrics BenxoiflBt in a twin or one above the other
ie -van 0.1 to about 5 CJew.-J till 8, aeloennseiebnet that this one