DE1569166A1 - Binders or adhesives - Google Patents

Description

EDWARD LORENZ. BERNHARD SEIDLER · MARGRIT SEIDLER

Bavarian Supreme Court · Higher Regional Court Munich · Regional Courts Munich I and Il

8 Munich 22, WidenmayerstraBe 23 Telephone [0811] 297194/297834 Postal check: Munich 170280 Bank account: Bayerische Hypotheken- und

Exchange bank Munich Re 8787 Your sign Our mark ή 3 Q 9 La / st

Ta ₈ November 26, 1968

rionaanto Company, St. Louis 66, Mis3ouri / USA

Binders or adhesives

The invention relates to an improved, heat and moisture resistant and water-thinnable resin systems, in particular an improved ilarzsysteni, which is a mixture of Phenol formaldehyde, dicyandiamide formaldehyde and / or urea formaldehyde or mixed resins thereof and an aminotrialkoxysÜan contains.

Phenoplasts and aminoplasts are widely used as binders for various purposes. These become in use Resins generally in liquid form on the substances to be bound, for example glass springs, applied and then increased Exposed to temperatures to turn the resin system into an infusible State is transferred. The use of a phenol-formaldehyde resin alone has the disadvantage that this resin has a relatively low heat resistance. For elimination this disadvantage, various measures have been applied, which consist in that the resin system determined

909841/1626

BATHROOM ΟΒΓ

Additives were incorporated, uebeispielswelje nitrogenous Links. These additives u ^ aingen ai.Jt.-r others Problems, for example, are encountered by the frienol-formaldehyde-dicyandiarnide-formaldehyde resin systems a higher heat resistance and a higher ignition resistance, but is under the Influence of moisture greatly diminishes your jindelcraft, vras the quality of the material can be Surprisingly, it has now been discovered that the introduction of small .ionrjoii of a certain additive in the Iiarzsysteme their lacerbesty, indolence and oil resistance 3 very strong increased v / ground, v; i> .IironJ them all other desired Llr.enschaften, for example the dilutability with water, heat resistance, FlaTinandämpfunr; and maintain ignition resistance.

The invention is therefore primarily aimed at creating a new, improved, water-thinnable, v / arm-hardenable, liquid Resin system. This and other purposes of the invention are achieved by a resin composition composed of a mixture of (1) Condensation products of phenol and formaldehyde, (2) condensation products of formaldehyde and xthercyandiamide, urea, a mixture of dicyandiamide and urea or mixed resins thereof and a certain aminotrialkoxysilane.

It is already known to use phenoplasts and aminoplasts as binders for fiber materials or adhesives for coatings and the like. For example, US Pat. No. 3 0O4 9 * 11 describes mixed resins made from phenol-dicyandiamide-formaldehyde condensates; in the Australian patent 236 461 amino or phenoplasts are proposed as binders, to which aminopropyltriethoxysilane is added in amounts of 0.02 to 2 % to improve the resistance to swelling.

909841/1626 _8AD

According to the invention binders for fiber materials or adhesives for coatings and the like. Proposed that from mixed resins or resin mixtures that occur during condensation are formed by phenol, dicyandiamide, urea and formaldehyde, and aminaalkyltrialkoxysllane and are characterized by this are that a water-soluble carboxylic acid salt of the aminoalkyltrlalkoxysilane of the formula

in which

R is an alkyl radical with 2 to 9 carbon atoms, R 'is hydrogen or an alkyl radical with up to 2 carbon atoms and A mean a carboxylic acid residue,

in an amount of up to 2 percent by weight of aminoalkyltrialkoxysilane, based on the weight of the Farz solids, used will.

The aminoalkyltrialkoxysilanes, their salts according to the invention are added to the mixed resins or resin mixtures include, for. B. N-lithyl-j'-aminopropyltriäthoxysilan, ir-aminopropyltrimethoxysilane, / ^ - aminopropyltributoxysilane, ^ r-aminopropyltricyclohexyloxysilane, tf ^ -aminobutyltriethoxysilane and 5-aminohexyltriethoxysilane. The preferred aminotrialkoxysilane is / "- aminopropyltriethoxysilane.

The organic acid components used are acids which are water-soluble when bonded to the aminoalkyltrialkoxysilanes Salts result, for example acetic acid, benzoic acid, citric acid, citraconic acid, formic acid, oxyesslgsäure, isophthalic acid, Maleic acid, phthalic acid and succinic acid. Acetic acid is preferably used as the carboxylic acid.

909841/1626

BATH ORIGINAL

156i166

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The method according to J3A patent specification 3 004 9 ^ 1 can be used for the production of mixed resins from phenolic and aminoplasts. The starting resin is preferably produced by converting phenol and an excess of formaldehyde in the presence of an alkaline catalyst until the free formaldehyde content is reduced to a predetermined level determined by the hydroxylamine hydrochloride test. Jas formaldehyde can be in a 'close of 1.5 - 5.0 moles per phenol, preferably from 1.5 - 3.5 to ¹ IOI per mole of phenol verviendet earth v /. A reaction product of phenol and formaldehyde containing formaldehyde is cooled to about 30 - 50 ° C. The dicyandiamide or the urea or the mixture of dicyandiamide and urea is then added in such an amount that formaldehyde is added per 0.5-2.0 viird.. ^: ; anac2i v / iri Can Carboribäure-Galz äes A; ainotrialkoxyailano in the ge ^ dnschtii ..enge augesetat. ^ If a mixture of Üicyandiair.id and urea is used, this mixture of 10 - 90 percent by weight jicyanuiamide and decently appropriate 90 - 10 percent by weight, oxygen, vorzu, j3 \; 3i3ü also at least 65 percent by weight of cyanogen dia: niJ, -lest iiarnstoff ^ est

All mixtures can also be prepared by converting the dicyandiamide or urea or the genus of dicyandiamide and urea in the presence of a reaction product of phenol and formaldehyde obtained with an alkaline catalyst without the presence of an excess of free formaldehyde. This process can be carried out by first reacting phenol with formaldehyde in the opposite direction to an alkaline catalyst to give a water-dilutable phenol-formaldehyde condensation product which does not contain free formaldehyde. Then, the carboxylic acid salt of Aminotrialkoxysilans is added in the desired klenge.

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BAD ORlGlNAt

Another method for producing the resin niches is that the condensation products contained in the resin composition individually generated v / earth. That way need separately prepared, water-dilutable resins then only to be mixed with one another, whereupon the carboxylic acid salt of aminotrialkoxysilane is added.

In the manufacture of the Karz-Camische the chemical nature of the mixture of condensation products can be varied. During the reaction of the condensation products do react the phenol, the dicyandiamide and the urea preferably with the formaldehyde. However, it is to be assumed that during the condensation reaction also: form iisehkondensate. These reaction products but are only available in small "! narrow".

According to the invention, the amount of the water-soluble carboxylic acid salt to be added is up to 2 percent by weight of aminoalkyltrialkoxysilane, based on the weight of the resin pesticides. The use of the carboxylic acid salt has the advantage over the use of the free amine that the dilutability of the resin systems containing large amounts of the free aminosilane is not reduced or eliminated. Salt formation with the carboxylic acids increases the solubility of the respective aminosilanes in the resin systems, since the aminosilane is in the form of a soluble product, so that the high dilutability of the resins with water is maintained, but the moisture resistance of the cured resin is not impaired. This is based on Example II, in which the resin containing the acetic acid silane salt can be diluted with 9 volumes of water without turbidity occurring, whereas such turbidity occurs when using the free aminosilane after the addition of only 2 volumes of water was observed. If the resin was originally unlimited, i. h, 2 ¹ I or more volumes of water was thinned, it remains indefinitely dilutable even if the water-soluble salt of organosaure Amintrialkoxysilans is used. If with BADOwOiNAL 90984t / 1626

Use of the essip; acidic silane salt a slight TrüLun; -; occurs, this cloudiness can be eliminated by adding r.ssi; aüure to the kars. In the Rannen Ilrfindun- ulrä preferably uses the acetic acid sais of Anintrialkoxysilans to each nögliche fiera'osetsun ^ YordPjnnbariceit of the resin with water or jeds nörjlicne irüoun = - eu avoid the I'arses.

The invention is now based on a ¹ ; practical example explained.

Example I.

In an Iieaktionsr, ef ^i; In order to have a cooler, a helper and an ahler for the return flow under Vaiuiuibedln ^ unKen, 100 i'ello pnenol, 3 "" »3 Telia 37-: jroaenti ^ gas formalin and 3.7 Parts iiatrlumhyäroxyd, ur.i a j.:-:.'ert of 3.5 - 9> 0 to set, "iei a xenperatur of et: ia 7" J ° C the genic will react ^ aIa33an. The Haal-iticm; #irti continued until the content of the free formaldehyde in the reaction mixture sinks to a predetermined value of about 12.0 percent by weight of the reaction mixture. This is verified by the rlydroxylaminhydrochlorld test; festj -., jstell. The proäuüt; fird lanri is cooled to 40-5O ⁰ C and the o-.-./ert by I'u ^ at ^: from i-oic acid to 7j5 - j '0 einjesfcellt' In Jiije..i uuatanü is a reaction mixture with ./asser pre-thin'oar, since 9 or aaeiir Yoluuien ".. 'aaser with 1 volume ded ^ eaktions ^ eiaijchej oei a" Jeidoeratur of 2 "! - 2ό C can be mixed without eel daa? 3 .. iiscä trCto oaev l ^ // ird. Jann . ^ o '> - «lan 4J Jcilj -ic ^ a: .- La..ld Ilii ^ ua; u. heated da3 Geniacii to JO- 70 ° ΰ. .'enii ^ ion das -Mcyandi »!» dissolves or etv / a at the time in üe-.i daa iea ^ tlciu? ^ · .iac:. a temperature of 60-70 C reached, wlrö alt »JouÄtlcv. * iurah a cooling to etv / a ¹ IO ° 0. To the hua * .tLunai £ e; -ilach is then / • -aminopropyl-tril'thoxyollane in οίη.τ lm ^ from a _s 0l weight percent of the resin solids au-o ^ at-t,.; Crauf das Reikttonu mixture cools down to room temperature ϊ / ird.? A-: Tfodukt nlrd .nt;

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BAD ORiGINAt

9 solid barrels to a solid content of approx. 5 Gesent. diluted without it becoming cloudy.

The diluted and diluted in this way of learning becomes rait (a) designated.

3ei3i> iel II

• reil A

Example I is repeated except that the j ^ -Aminopropyltriätiioxysilan not jedocn in a len; -e O ₉ OOl, but from 0.1 weight percent Au teaetat viird. The dilution of the resin by 2 volumes leads to a slight turbidity, probably as a result of the silane contained in the silane. To avoid a slight turbidity, therefore, the amino propyl triet the essiecsaux-s Caiz of / -Aminopropyltriätäoxysilans to. ^ eiiandelt. these Evreciie it is a lu-prosenfcigen ".rässeri ^ s hs si3s £ urelösung 10 percent by weight Si lan 2u" this solution viird dejü IAR in. '! close of 0.1 Gev: iciitsprosent silane su ^ esetst. The reaction is terminated by cooling to "immerte-iperatui", et: - / a 29-25 ° G. The product is then diluted with 9 volumes of water, so that it becomes turbid.

The diluted resin produced in this way is described with (b). designated.

Part of the undiluted product obtained under Part A, is left to stand for 2 ^ 1 hours at Zimraerteiapatur. Then ifipd. it was diluted with 9 volumes of water, with no turbidity is observed.

BATH ORIGINAL

909841/1626

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This thinned liars is denoted by (, c). . Part C.

Another part of the undiluted product that is referred to in Part Λ is obtained for three years at a temperature of O - 10 ° G held. At the end of this timeframe there was no clouding observed. The product is then diluted with 9 volumes of Yasser » without an advance occurring. So Ks shows "there?> the product containing the acetic acid salt of silane is one has excellent lacquer resistance and that the lacquer does not affect its dilutability.

This thinned glass is denoted by (d).

The addition of the water-soluble carboxylic acid salts of the aminoalkyltrialkoxysilanes added to the resins according to the invention also results in a great increase in the bond strength of the fiber materials, as can be seen from Table I. To examine this strength property, test specimens are produced by connecting two glass fibers with a length of about 50 mm and a diameter of 0.23 mm with a drop of resin at right angles. The test specimens prepared in this manner are about 90 minutes, dried at 90 ° C then for about 15 minutes and dried in a forced air oven at about 177 ⁰ C. The bond strength is determined by placing a load on the test specimen and determining the time after which the fibers tear apart. During exposure, live steam from IQO ⁰ C is directed onto the bonded interface between the two fibers. The relative humidity at the bound interface is 100 %. To carry out the test, one glass fiber of the test object is clamped in a clamping device and then the other glass fiber of the test object is loaded. The load on the test

linge is in dynes / cm and the time to tear apart is in

9 0 9 8 4 17 1 6 2 6 bad original

.. 'i ä-i- v

measured uinutane »The results given in Table I. are the Durclisclinit't '"of three' examinees for" 'each Ilär'z.

j. au υ χχ "Since 'until the' '■■' »- • The last tin ■ Ause tear into each other '""'" 2
dyn / ciiv 'min. 40 50. '" ₍ ,' . > 100 50 > 100 50 > 100 50 ^;

(he "

oei same load vergant so then a \;. 'e sent lent longer time to tearing of the fibers, the binder Ünn earbonsaures a salt of Aininoalkyltrialkoxysilans was zubegeben ,, _t. . . _; ,. .

If under the. Fulfillment of the xlarz as a means of _: 3in-. ei en of fibrous materials, for example glass fibers, are used for thermal ... insulating products. it is, according to its, in the presence of a hardening agent, converted into an infusible state, inflammable. and heat-resistant and flame-retardant .. Furthermore, the hardened resin retains its increased ... Bipd, ekraft even when there is moisture; is exposed., .. The binding strength of the resin has a high level of moisture, which is primarily due to the addition of d.es. Silane. to the ,. Har a composition is due. ... ...,. ^ _r .. ". . _; . ..

The resin according to the invention can be applied in both concentrated or diluted form. In cases, the ability to bind is not vindicated. The .erfindungsgemälte H ^ ^ rzzu ainmenset ^ wetting is ausgezeiAhnet verdünnba _f ^ -and can be used as with water without. ^

BATH

Cloudiness or lilchiijv / earth can be diluted indefinitely on v / earth. In the examples, the Karzprouen ;; ere only rg 3 volumes of 1 / ater diluted, they I: but 3nnen uit 2-Ί oderraeär volume "barrels diluted viorclen, o» ine tvni o-ier r.iilcliig..au -uerdeii.. Ir.i, general - ^ iIt a -lar ^ than lalt "., 'Ater unbe ^ renat? Er _{; :} dunn'oar, v / enn it with 2'4 Yoluii ^ n ^r . "aGuc-r raünnt \ -ercien ia without it being cloudy or r.iilciiif; - ;; ir-'i _a In one« -: Veraueii - .- to a volume of resin 5- Complete " ^T a: jner sujeset ^ t, o ^: ine..i * a5. a ^ rübunc; or .iilchi: k3it occurred.

The erfindunfjagen ^ SEN "ass --- '" niien to a rinrlon iineral-. Of glass fibers or from?''Ollfasern b ^ i dev manufacture of _iiärmeiso-. _ lating products used i-rerden. The -arfinduni ^ sgetaäSen ilarze are also ala "-. Indoalttel for glass fibers ^ lineralvils and cellulose products oei eggs Zorstsllun ^ of separators for batteries, electrical ei.era Isoiitinnaterlal, filters and clien it.

BAD ORfGlNAL 9098411/1626 ί

Claims (3)

- i- F at e η t a a ..s- -gr r S.gj «,; Inde3lttel fir Jaserasaterlallen oJer ^ Il ^ bs-tofile fur uber- zü ^ ß raid der;: l. -, consisting of '-üseliharsen or liar ζ mixtures, the fei der -londaiisatloix of? Jieüol _s dicyandiamide, urea and FonaalJeliy-c. .-eüilden - "'earth, -and AMiiioalkyltriallcoxysilan, äadurcii. - ^ ekeiüKieiclinet, "daS'ein vcsösrlöslicliec Garb ons S oals des Ai; iiiiaalliylt.rialkoxysilano aer Fomel in welcaer .1 one Älky-lreot uit 2 to 9 U-Arο'nen, .H ¹ 'Jaasstoff or an alkyl rt with up to 2 carbon atoms and A eiiiea Carl / Oiioi-urereot mean, in a =: en-; e of up to zn 2 percentages of aminoalkyl triall; oxyslla: i ₉ besoden on the dish of the resin solids _s verifendet i « 2. 3indenlttel or adhesives according to claim 1, characterized in that: Seleimet that the acetic acid HaIz is used. 3. -iindeeittel or -Siebstoffe according to claims 1 to 2, -dadürea gekennseic: met that. Aainopropyltriethoxy & ilane used vrirfi. -..- '. ■ SAD ORfGaNAL 90984W16T26