DE2136633A1 - STORAGE-STABLE MOLDING AND COATING DIMENSIONS - Google Patents

Description

Storage-stable molding and topping compounds

The invention relates to curable, storage-stable molding and coating compositions, consisting of mixtures of conventional V / ice containing stabilized α, ß-unsaturated dicarboxylic acid residues Polyesters, polymerizable vinylraononates, α-hydroxy ketones and / or benzoin ethers of primary alcohols, which are characterized by the presence of dibasic and / or more than dibasic phosphorus-containing acids as additional stabilizers.

Mixtures of polyesters containing α, β-unsaturated dicarboxylic acid residues, polymerizable vinyl monomers, α-hydroxyketones and / or benzoin ethers of primary alcohols are known. You can use aliphatic a-hydroxyketones according to DAS 1 150 805 with and without the addition of peroxide thermally, or in combination with soluble compounds of vanadium, phosphorus acids and peroxides according to Patent application P ■ (Le A 15 864) at room temperature, or when using aromatically substituted α-hydroxy ketones, such as benzoin or benzoin ethers of primary alcohols cured by exposure to UV light to form molding and coating compounds.

The mixtures mentioned generally have the disadvantage themselves not being sufficiently stable in the dark (MS 1 694 149). Due to the presence of the additional stabilizers according to the invention

Le A13 865

- 1 - * 2098δ6 / 12δ6

Surprisingly, their camp status in the Darkness increased so much that 'it now meets the requirements suffice the technology and on rationally working .Form- and Coating systems can be processed safely without the risk of premature, uncontrolled polymerisation consists. The additional stabilizers Meten also The advantage of being metal-free compounds is that neither the unhardened nor the hardened mixtures are discolored adversely affect or delay the polymerization. Furthermore, oils offer mixtures according to the invention the processing has the advantage that a-hydroxy ketones and / or Benzoin ethers of primary alcohols no longer have to be stored separately from the polyester solutions, as was previously the case, which represents another significant technical advance.

The invention thus provides curable, storage-stable molding and coating compositions, consisting of mixtures of conventionally stabilized polyesters containing α, β-imsaturated dlearboxylic acid radicals, polymerizable vinyl monomers, α-hydroxyketones and / or benzoin ethers of primary alcohols, which are characterized by the presence of two- and / or more than two-based phosphoruslialtigen acids as additional stabilizers in an amount corresponding to 0.0005 1 wt. -fo, preferably 0.001-0.01 wt .- ^, phosphorus per 100 g mixture, furthermore the use of the Mixtures described for the production of hardened Pormlbodies or coatings.

It is true that there are already esters of phosphoric acids in polyester coating compounds used in combination with metal accelerators and peroxides to improve the color of the hardening products. Better, however, are the special phosphorus-containing ones according to the invention Acids as additional stabilizers for the mixtures mentioned new.

Le A 13 865 - 2 - · - ** D ORfGlNAL

209386/1266

Polyesters containing α, β-unsaturated dearhonic acid residues . For the purposes of the invention, as usual, those formed by polycondensing α, β-unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, kesaconic acid, itaconic acid, citraconic acid and / or dimeric methacrylic acid, or their esters or anhydrides or their mixtures with optionally unsaturated polyhydric alcohols such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, _butene-t (2) diol-1, 4, 1,6-hexanediol, diethylene glycol, Polyalkylenglyko] ethers, bis-.beta.-hydroxyalkyl ethers of aromatic dihydroxy compounds, for example 2 , 2-bis- (4-ß-hydroxy-alkoxyphenyl) -alkanes and -cycloalkanes, xylylene glycols, 1,3-diniethylolcyclobutane, quinite and 2,2-bis- (hydroxycyclohexyl) -alkanes and -cycloalkanes, optionally with the addition of other dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, endome thy lentetrahydrophthalic acid, hexs-chloi ^ endomethylenetetrahydrophthalic acid, succinic acid , Glutaric acid, adipic acid and pimelic acid or monocarboxylic acids such as acrylic acid and methacrylic acid, or other monohydric or higher alcohols such as glycerol, trimethylolethane, pentaerythritol, allyl alcohol and partial ethers of monohydric and polyhydric alcohols (cf. eg the book by I. Jörksten et al. "Polyesters and their Application" Reinhold Publishing Corporation, New York, 1956) »optionally in combination with terbindungen that have the allyl ether configuration and can be built into the polyester or added to the solutions, such as β, jf'-unsaturated alkyl ethers, such as allyl, methallyl, Athallyl-, chloroallyl and Crotyläther of the aforementioned polyalcohols, further comprising ß, unsaturated alcohols yf etherified methylol _s derived from urea or melamine, such as Methylolglyoxalureine or Mothylol-Me amine!; by Um ™

ji &äi; js ^ i »-!" -.- · U ^ - '■

20988G / 1266

Acrolein is the addition of polyhydric alcohols belong to.

Customary stabilizers can be used before or after the esterification such as hydroquinone, toluhydroquinone, benzoquinone, 2,5-di-tert.-butylbenzoquinone, Chloranil, tert-butylbren ^ eatechin and the like to the esterification approach; in usual IJengen sugesets will.

Polymerizable vinyl monomers are styrene, the core of which is substituted Styrenes, divinylbenzene, acrylic, methacrylic acid or their esters or amides, esters of vinyl or AUyI alcohol and vinyl ketones.

α-Hydroxyketones for the purposes of the invention are aliphatic-cycloaliphatic-aromatic, mixed aromatic- (cyclo) -aliphatic-substituted a-hydroxyketones, such as acetol, dihydroxyacetone, Acetoin, a-hydroxycyclohexanone, a-hydroxycyclopentanone, Benzoin, substituted benzoins. Some a-hydroxy compounds exist as crystalline dimers that however, they disintegrate again into the monomers on melting and are advantageously incorporated into the mixtures in this form can be.

Suitable benzoin ethers of primary alcohols are, for example, benzoin methyl, ethyl, n-propyl, n-butyl ether or their derivatives substituted in the nucleus, such as 4,4'-dimethyl, A , 4 ^f -dihlor-, 4,4 * -dimethoxy benzoin ethyl ether.

The molding and coating compositions according to the invention contain the called a-IIydroxyJcetone and / or Benzoinäl.her primary Alcohols expediently in amounts of about 0.001-10, preferably from about 0.005 to 3.0 wt .- '/ ί, based on misschung.

O »! GINAL 209886/12 66

Suitable additional stabilizers are: di- and / or more than dibasic phosphorus-containing acids such as phosphoric acid, pyrophosphoric acid, Polyphosphoric acid, phosphorous acid, as well as the possible two- and / or more than two-base acids Esters of the acids mentioned, such as monomethyl-, -ethyl-, -propyl-, -cyclohexyl-, -phenyl-phosphoric acid esters, the corresponding Mono- and / or diesters of pyrophosphoric acid, and the corresponding ones of polyphosphoric acid, partial dibasic and / or more than dibasic acidic salts) of the acids mentioned and / or their esters, such as the acidic ammonium salt of a partial pyro- or polyphosphorus acid ester.

The molding and coating compositions according to the invention contain mentioned additional stabilizers in amounts corresponding to 0.0005-1 % By weight, preferably 0.001-0.01% by weight, phosphorus per 100 g Mixture, with amounts around 0.002 wt. ~ $ Phosphorus especially are preferred, since with this amount there is usually an optimum in storage stability.

The additional stabilizers are advantageously the polyester solutions added. However, you can also at the beginning of the esterification of the polyester or during its production are added to the melt, but usually lose activity in this procedure, v / as due to a correspondingly higher dosage can be compensated for again.

The claimed storage-stable Form.- and coating compositions can with or without the addition of peroxide, thermally, or in combination with soluble compounds containing vanadium, containing phosphorus Acids and peroxides according to patent application P (Le A 13 864) at skin temperature, or when used aromatic-ßubstituted α-hydroxy ketones, such as benzoin or benzoin ethers of primary alcohols by irradiation

Le A 13 065 - 5 -

• with UV light without any disadvantageous discolouration on the additional stabilizer would be due to be hardened.

You can of course also use pigments, dyes, fillers, glass or textile fibers, thixotropic agents, UV absorbers, waxes, paraffin, smoothing and leveling agents and the like can be added.

Examples

"In the following examples, an unsaturated polyester is used, the composition of which is given in parts by weight. It is prepared in a known manner by melt condensation and dissolved in styrene 65%. Toluhydroquinone is added before it is dissolved.

Maleic anhydride 588 g phthalic anhydride 592

Propylene glycol-1,2'798 Toluhydroquinone 0.36

Key figures of the styrene solution:) Fixed salary $ 65

Viscosity (2O ⁰ G) ¹ ^ 1800 cP acid number 21

1 )
'Measured in the falling ball viscometer according to the coupler

In all the following examples dio Polyesfcerloöiing with the tabulated weight is. ~> Ό, based on PoIyeaterlüüung, äbhern ΒαηκοΙη-to λ -Ilydroxikotonen priiaaror or alcohols, and in each case a voruohi vduiu

Le A 13 865 - 6 -

^ u- 20Üf) aS / 123S SADORtGiNAL

Amounts of additional stabilizer solution added. The additive stabilizer solutions contain the listed 'zv; egg ~ and / or more alc' dibasic acids of phosphorus in butyl acetate dissolved in an amount corresponding to 7 wt .- ^ phosphorus . ,

Polyphosphoric acid in butyl acetate, 7 wt .- ^ phosphorous Acid "7" phosphorus phosphoric acid "7"

Pyrophosphoric acid "7"

Dibutylpyrophos

phosphoric acid ester "7"

Unused comparison solutions:

Pi diisooctyl phosphate G: dibutyl phosphite II: tris-chloroethyl phosphite

Additive- A. stabili " B. sator C. solution I) E.

7th dd 7th ti 7th Il

Determination of the dark cell stability

In each case 35 g of the mixture is filled into a 50 ml powder bottle with a screw cap without a seal, the bottle is screwed on and ^{stored at 60 0} O in the dark. At certain time intervals, tilt it slightly to determine whether the sample has gelled. The stated values are mean values of at least 3 samples.

The quantities given in the tables are percentages by weight lied to the PoÜyersterlöoung. In the following Table 1 lists various additional stabilizer solutions the same phosphorus content (7% by weight) compared with one another.

Lo A 13 HG ^r j - 7 -

209886/1266. “Ouch

CD
HH

CD O CD
KN O CD
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_r y φ ^ i r! uo cvi -H: * cd 4 ⁵ ο RH CQ ^ TJ

20G086 / 12GG

In Table I, Examples 1 bio 5 clearly show the effect of the additional stabilizers according to the invention in comparison, to the examples 1a bits 4a.

The amounts of the additional stabilizer solutions A and B are varied in Tables TI and III below. The stabilizing one The effect emerges here particularly clearly in the optimal examples 9 and 16, in which the dark storage stability at 6U ° o is increased from 2 hours to 6 days.

Table e II

Example no. Compare 6 7 8 9 10 11

Benzoin 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0

Additive-

stable-

sator

LöBg. A without 0.010 0.025 0.05 0.1 0.5 1.0 2 * 0

Dark storage 2

stable - hours 5h 3 days 5 days 6 days 5 days 3 days 2 days, contributed

Ie A 13 865 - 9 -

209888 / 12Sun

Table III

Example no. - 13 H 15 16 17 18 same

Benzoin 1.0 1.01.0.1.0 1.0 1.0 1.0 1.0

Additional satoi ^{11 "without} ° ^'010 °' ⁰¹³ ° ^'025 °' ⁰³ ° ^'25 °' ^{5 2 '5} soln. B

Dark storage

^{2 hours 4 hours 1 day 4 days} * ^{6 days} - ^{4 days} *

Table IV shows the stabilizing effect of an additive stabilizer solution A for different a-hydroxyketones - or Benzoin ethers were compared to mixtures containing alcohols. Examples 23, 24 and 25 contain additional toluhydrοquinone.

Lg A 13 865 - 10 -

209885/1265

I. I. m in I. cö OJ O O in Ln O - * OJ OJ «V O O O .. I. in . «! O O O : ί Jt in in rH -rH OJ CM O C; ti I. O in I I O c \ 3 O O -st " in I. «■. OJ CV O O V. C \ J LΓ ^ O CJ O vj O OJ I. O I " in co OJ · <■ [ O CM O •H O C) , C) Ln (J Ui, O OJ ■ i 'Ui cT CD to : < > OJ U rl OJ -P f, a n ■ η λ > ', i f. C \ J [1 'II CM crt CM τ—
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209806/1

In the following examples, Hürtunken aAireh are listed. They tend to cause additional fi-tabilizers to harden Do not affect mixtures.

Production of a leveling compound by mixing the following: Components

30.00 g polyester solution, containing 0.1 wt .- ^ additional stabilizers Sator solution A

6.00 grams of styrene
28.7Og talc

1.60 g titanium dioxide RKB (Bayer)
28.70 g of asbestine

4.80 g of lithopone

0.18 g of a-IIydroxyeyclohcxanone, melted 3.03 g of methyl ethyl octone peroxide 50 #ig.

The same cash register as above, but with a polyester solution that does not contain an additive stabilizer, serves as a forgetting example. For hardening, 3 g of a 0.5 % by weight of vanadium-containing solution of VpOf- in n-butyl acid phosphorate and toluene are worked into the putty and toluene, and the mass is about 1 mm thick on iron sheets.

ZuoatBstabilizer: with without? Tack-free after: 15 Uiη. 15 LIin. Can be sanded after: 30 l £ in. 30 L-: in.

Le A 13 »f ' ^r i - 12 -

• AD 209886 / 12GG

Example 27 ■ β

Also in the following hardening of paint films s i cn shows no impairment of the lliirtungsprozesseB by the addition of a stabilizer.

execution

8.3 g of polyester solution containing 0.1% by weight of additional stabilizer solution A, 1.7 g of styrene, 0.2 g of a paraffin solution containing 10% by weight in toluene (paraffin with a melting point of 51-53 ° C. ) 'and 0.2 g of benzoin ethyl ether mixed. The same mixture with a polyester solution without additional stabilizer serves as a comparison example. The solutions are drawn on glass plates with a film applicator as 250 p. strong 'films' drawn on and exposed to radiation from a fluorescent tube (Osrain L lamp for breaks, 40 watts, length 97 cm) at a distance of 10 cm.

Additional stabilizer with no swim-out time of the

Paraffins after: 2 min. 2 min.

Lead hardness

after 15 min. J> 6 H > 6 II

IV- /, Π · Ί

OHlGlHAL

Claims (3)

Claims 1. A curable molding and lagorafabile -Uborsugsma ^ ijen consisting of mixtures of stabilized in the usual manner, C ^, ß-unsaturated Dicarbonsäureres-te-containing polyesters, anpolymerisierbaren Vinylmoriomei'en, a-JIydroxykoionon and / o r Benzoinäthorn primary alcohol! e, characterized by the presence of two and / or more than two-base acids. I see phonophore-containing acids as additional stabilizers. 2. Mixtures according to claim 1, characterized by a content of 0.0005 to 1 wt .- ^, preferably from 0.001 "0.01 ^weight: i, of phosphorus per 100 g of mixture in the form of two- and / or Mohr dibasic phosphorus acids as additive stabilizers. 3. Use of the mixtures according to claims 1 and 2 for the division of hardened molded bodies or overhangs, wherein the curing is carried out with peroxides and / or with UV rays will.