DE2260132A1 - USE OF UNSATURATED POLYESTER MATERIALS FOR THE PRODUCTION OF COATINGS - Google Patents

Description

Use of unsaturated polyester compounds for the production of transfers

The invention relates to the use of unsaturated polyester compositions, consisting of

1. an unsaturated polyester

2. one with 1. co-polymerized » available vinyl monomers

3. an activator system _s . 4. Usual auxiliaries and additives

for the production of coatings, which by curing with. Infrared rays having a wavelength of 1 to 5 W can be obtained.

It is known that unsaturated polyester resins can be used as molding and coating compounds after addition of suitable initiators and accelerators for hardening at room temperature, for coating wood, glass, as well as stone slabs can be used. The polyester compounds can also be used as fillers after adding fillers will. A significant reduction in the curing times until the coated surfaces can be stacked and sanded possible through the use of UV rays and the addition of suitable UV sensitizers. By means of UV rays in particular Clear lacquers or glaze colored lacquers can be hardened.

The unsaturated polyester resins hardened with UV rays show however, the disadvantage that light-colored pigmented paints can yellow, for which the presence of the UV sensitizer is responsible is made. Another disadvantage is that

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Solid filler compounds, especially those with a thicker layer than 100 μ, cure incompletely, so that defects can occur during use such as crack formation or peeling phenomena occur.

It is known that these disadvantages can be overcome by curing by infrared rays can be avoided (DT-OS 2 029 657) »This The type of hardening is particularly suitable for clear lacquers, pigmented lacquers and highly filled fillers. The drying times but are longer than with UV curing.

These longer exposure times cause undesirable effects Measure a heating of the substrate, which often leads to the formation of stress cracks. It was found that using conventional Polyester the irradiation times cannot be shortened. The lacquer films then do not harden at all or only incompletely the end. As a result, the films swell or even dissolve when treated with xylene,

The object of the invention was to make it more suitable by using polyesters Composition Manufacture coatings with good properties obtained by curing by infrared rays can be, and wherein the disadvantages of the prior art listed above are avoided.

This object was achieved in that the acid component of the unsaturated polyester

A. to 20 to 85 mole percent from fumaric acid or Maleic acid

B. 80 to 15 mole percent from an aliphatic, cycloaliphatic or aromatic dicarboxylic acid, with at least 15 mole percent of the total acid component must be tetrahydrophthalic acids and / or their anhydrides "

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In addition to ± the Säurekömponente necessary fumaric n _s maleic acid and tetrahydrophthalic acid and / or anhydrides thereof are used as aliphatic ^ dicarboxylic acids' succinic acid ₉ adipic acid, as the cycloaliphatic dicarboxylic acids Hexahydrophthaisäure and the aromatic acids, phthalic acid or anhydride, isophthalic acid, trimellitic acid, Hexachlorοendomethylentetrahydr © phthalic, tetrabromo - or tetrachlorophthalic acid in question »

According to the invention, pumaric or maleic acid and tetrahydrofluoric acid in the specified amounts are necessary in each pail. A preferred proportion of fumaric or maleic acid is from 10 to 85 mol percent. A preferred lower limit for tetrahydrophthalic acid is 30 mole percent. Particularly suitable polyesters are those which contain exclusively fumaric or maleic acid on the one hand and tetrahydrophthalic acid on the other in the acid component. The acids specified below can partly replace the acids that are absolutely necessary according to the invention in order to make the production of the polyester more economical. .

The fumaric or maleic acid used causes good crosslinking ' tongue, which increases with increasing quantity; on the other hand, the Tetrahydrophthalic acid achieves a good surface hardness that also increases with increasing quantities. -

For the unsaturated polyesters according to the invention, ethylene glycol (1. Z), propanediol (1. 3), butanediol (1.4) or hexanediol (1.6) are usually used as unbranched, ether group-free diols for the diol component; Propanediol (1.2), butanediol (1.2) or butanediol (1.3) »furthermore neopentyl glycol as branched-chain ethereal

group-free diols; as ether group-containing straight-diols primarily diethylene also Triäthylen- or Tetraäthylenglykolj as branched ether groups containing ¹ especially dipropylene glycol or TripropyTLenglykol used are, furthermore ,.

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Suitable unsaturated, copolymerizable vinyl monomers are the customary ones, such as styrene, substituted styrenes, such as tert-butyl styrene or methyl styrene; also mixtures of the latter with styrene. Other ethylenically unsaturated monomers that can be used in combination with styrene in amounts of less than 50 percent by weight, based on the monomer _{mixture, are lower (C 1} -C.) - alkyl esters of acrylic acid or methacrylic acid and halogenated styrenes such as chlorostyrene, diclorostyrene, also diallyl phthalate.

The unsaturated polyesters are produced at temperatures from 150 to about 250 C by customary azeotropes or Melt condensation of the components. In general, the diols are used in about a 2 to 10% molar excess the dicarboxylic acids used. The molar ratio of diols and dicarboxylic acids however, it is not critical.

The acid numbers of the unsaturated polyesters are generally between 10 and 70, preferably 20 to 50, in particular around 25 to 40. Accordingly, the molecular weight is not critical for the invention is between 5500 and 800, preferably between 3000 and 1000, in particular between 2500 and 1500.

Catalysts which form free radicals can be used to harden the coatings such as diacyl peroxides, e.g. dibenzoyl peroxide, dilauryl peroxide, peresters such as tert-butyl perbenzoate, hydroperoxides such as cumyl or tert-butyl hydroperoxide, ketone peroxides such as methyl ethyl ketone or Cyclohexanone peroxides used in amounts of 0.1 to 3 percent by weight will. The peroxydicarbonates are particularly suitable, especially those with 3 to 6 carbon atoms in the alkyl radical, such as diisopropyl peroxydicarbonate, Di-tert-butyl peroxydicarbonate or dicyclohexyl peroxydicarbonate. Curing accelerators such as tertiary, aromatic amines or cobalt salts can also be added,

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The polyester compositions can also be conventional polymerization inhibitors, for example hydroquinone, tert-butylcatechol, benzoquinone, Di-tert-butylbenzoquinone and the like, generally about 0.001 to about 0.1 percent by weight, based on the total mixture, contain.

Other auxiliaries and additives can be fillers, pigments, Paraffin, thixotropic agents and / or light stabilizers.

The polyester compositions according to the invention are distinguished by a A number of good properties: In addition to good general properties, IR curing quickly becomes a fast Drying and. good curing of the coatings achieved. The drying time depends essentially on the amount of acids according to the invention used.

During curing, the drying time depends on the proportion of the acid according to the invention from the polyester: Using 0.5 percent by weight of peroxide, based on the polyester molding composition may at an acid content of 17 mole percent of tetrahydrophthalic drying times of about "h minutes, at a proportion of about 33 mole percent drying times of approx. 3 minutes can be achieved.

As the explanations show, the polyester compositions according to the invention can be processed quickly and easily with the aid of IR radiation will. The curing is very good, so that coatings produced according to the invention - even in toluene - have good solvent resistance are. In contrast, correspondingly hardened polyester coating compositions whose polyesters show only fumaric acid or tetrahydrophthalic acid contained as acid component, insufficient solvent resistance. .

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OZ 2678 December 6, 1972

Examples

A polyester resin was applied to glass plates (17 cm × 7 «5 cm) with a film applicator applied in a layer thickness of 100, ji, Predried for one hour at room temperature and on-. finally with an IR radiator type H 8 from Heraeus hardened. The distance between the radiator and the paint film was 4.5 cm.

The results obtained in the tables were achieved with the polyesters I to VIII listed below (Table 1). The numerical values indicate the pendulum hardness in see according to DIN 53 157. In experiment a, the sample was cured with 0.5 percent by weight isopropyl peroxide carbonate, in experiment b with 0.5 percent by weight isopropyl peroxide carbonate and 1 percent by weight of a cobalt octoate solution whose cobalt content is 1 ⁰ Jo.

Tables 3 "to 5 show the extent to which the polyesters I to VIII produce solvent-resistant coatings. The values under a and b have the meaning already given above. The value ν means that the sample is measured directly after curing, while the value η, the pendulum hardness indicates after the cured sample immersed for 15 minutes in a xylene bath (Table 3 and k) followed by an hour had been dried at room temperature. k the polyester samples of tables and 5 of the experimental set were cured b accordingly.

Table 1 FS PS 4L . . Γ THPS PD Min] 1.0 - Exposure time [ 2.1 Styrene # polyester 2.0 0.9 PPE 0.1 3.06 33 I (comparison) 2.0 0.5 1.0 0.5 3.06 35 Il (comparison) 2.0 - - 1.0 3.03 35 III 1.0 - - 1.0 2.1 35 IV 1.0 - - 1.85 2.95 33 V 1.0 - - 3.0 k.ok 33 VI - - - 1.0 1.03 35 VII - 4 / U94i 33 VIII (comp.) - i 9 Ö 2

OZ 2678 December 6, 1972

* FS = s fumaric acid, PS. = Phthalic acid, PSA = phthalic anhydride, THPS = tetrahydrophthalic acid, PD = propanediol- (1.2)

Table 2 cd, 0. B.
3 B.
V. gszeit [kin] Iin7 "
ν ⁵ η a
b 156
196 196 180
202 202 - a
b 120
201 201 146
244 244 - ■ a
b IO6
212 212 113
246 246 201 a
b 51
191 191 62
217 217 216 a
b 137
183 183 152
212 212- 208 a
b 64
215 215 89
225 225 214 a
b 83
169 169 9h
193 193 - 192 10
124 124 27 174. - V polyester 191 2
η lungs time (l
4th
ν η I. 142 - blast
4th 203 II .164 - 177
203 222 III 157 17th 132
222 230 167 IV 173 21st 104
23Ο 208 197 V- 200 149 56
208 201 197 VI 165 183 144
201 218 219 VII 106 100 75
218 183 186 VIII - 91
183 141 Table 3 16
141 estrah
³ η - - 26th 167 16O 212 I69 - polyester I. II III IV V VI VII VIII

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Table 4 a
b - 1
ν η ν Exposure time ν 3
η ν ( ¹ min 5.
ν η a
b 172 130
191 2
η 156
196 ■ - 177
203 4th
η 180
202 polyester a
b 95
142 120
201 - 132
222 - 146
244 I. a
b 107 25
143 15 128
173 - - 137
183 30th
16Ο 144
201 152 45
212 208 II 60 106 30th
149 124 - 141 4ο
197 174 V - - VIII

Table 5

polyester Besti
2
ν η 'ahlungsze
3
ν η it / minJ
ν η 5
ν η solvent VII 161 96
161 150
161 164 173 164
173 169
173 175 183 183
183 178
183 176 192 191
192 191
192 190 Xylene
Xylene: test
petrol (1: 1)
White spirit
Xylene
Xylene Test
petrol (1: 1)
White spirit VIII 98 -
98 103
98 100 114
114 118
114 115 133
133 123
133 120 163 -
163 126
163 124

A dash in the tables means that the surface is sticky and therefore no pendulum hardness can be measured.

409824/0944

Claims (2)

- 9 - 0.Z8 2678 December 6, 1972 Patent claim Use of unsaturated polyester compounds, ordering from 1. an unsaturated polyester 2. one with 1. copolymerizable Vinyl monomers 3 · an activator system H. usual auxiliaries and additives for the production of coatings which are obtained by curing with infrared rays with a wavelength of 1 to 5 P- , characterized in that the acid component of the unsaturated polyester A. to 20 to 85 mole percent from fumaric acid or Maleic acid B. 80 to 15 mole percent from an aliphatic, cyclοaliphatic or aromatic Dicarboxylic acid, with at least 15 mole percent of the total acid component being tetrahydrophthalic acid and / or their anhydrides have to. {?. mJM 409824/0944