DE2749625B2 - Binder for road marking paints - Google Patents

Description

The present invention relates to binders for road marking paints.

A number of property requirements that are difficult to meet are made of such binders: At processing from the melt, they should be at temperatures of around 180 to 220 ° C for several Hours yellowing as little as possible, even when exposed to atmospheric oxygen, in order to keep the daytime and Not to impair night visibility of the markings made from them; their melt should im Temperature range from about 130 to 200 ° have the lowest possible viscosity so that the Let the marking compounds produced therefrom process at the lowest possible temperature and on the Road surface have the highest possible adhesive strength. This is particularly true when the Masses are to be processed by spraying. The markings must also be weatherproof, as well as being resistant to water and salt water. They dinghies also have a high pigment binding capacity have, so that the highest possible proportions of inexpensive fillers can be used. The adhesion To glass beads and hard fillers must be high so that night visibility, abrasion resistance and the grip of the markings is retained for as long as possible. Also must the binding agent of the marking paint or compound has high cohesion and sufficient elasticity mediate so that the markings are abrasion-resistant and do not become brittle even in cold weather and Form cracks. On the other hand, the markings should not soften so much in warm weather that they become plastic and pollute.

In DE-OS 24 07 159 binders with high heat yellowing and weathering resistance are indeed used described the problem of producing binders that have the contradicting properties of a low Melt viscosity, high cohesion as well as sufficient compressive strength and contamination resistance in itself unite, but so far could not be solved satisfactorily.

These products are not sufficiently block-proof and ίο therefore require a relatively expensive one Packaging. Their production and processing is complex, because both their binder and the Glue and block finished masses before processing.

It was therefore the object of the present invention to produce a binder which, in part, contains these contradicting properties combined in an optimal way

The present invention relates to binders for road marking paints, which consist of 60 to 90% by weight of at least one pigment and / or inorganic Filler and 10 to 40 wt .-% binder, which are characterized in that the Binder a copolymer is made from:

a) 55 to 95% by weight of a vinyl aromatic,

b) 2 to 20% by weight of at least one copolymerizable «, ^ - olefinically unsaturated carboxylic acid or a half-ester -olefinically unsaturated

in dicarboxylic acids with 1 to 18 carbon atoms

containing monoalkanols and

c) 0 to 30% by weight of at least one ester of acrylic acid and / or methacrylic acid with 1 to 12 Monoalkanols containing carbon atoms,

where the sum de 'under a) to c) mentioned percentages is equal to 100.

Those binders which have a KSN softening point of over 80 ° C. are preferred.

ad A preferred embodiment of the binders according to the invention also consists in adding plasticizers to the binder in amounts of 15 to 80, preferably 25 to 60,% by weight, based on the copolymer.

4 '> The road marking paints according to the invention show particularly good abrasion resistance, adhesive strength on concrete and asphalt and heat yellowing resistance very high softening points before processing with plasticizers, which means that the

Vi products to at least? 50 ° C are block-resistant and below The addition of a plasticizer can be easily processed.

In addition, the binders according to the invention dL-ch have particularly high impact strength and

Vi compressive strength (penetration hardness). This gives the Road marking paints high resistance to loads. Another benefit of the Processing of these road marking paints from the melt is due to their low melt viscosity

with the addition of a plasticizer, which leads to lower processing temperatures and thus to energy cost savings leads. Furthermore, the road marking paints according to the invention have only a slight odor nuisance when processing from the melt

hi and lower manufacturing costs than those in the DE-OS 24 07 159 products described.

One of the structural components of the copolymer to be used as a binder according to the invention is

to do the following:

a) Styrene and vinyl toluene are suitable as vinyl aromatics, in particular styrene, which is present in the copolymer in an amount of 55 to 95, preferably 70 to 90, % By weight are polymerized.

b) As component b) there are ^ -olefinically unsaturated Carboxylic acids such as mono- and dicarboxylic acids having 3 to 5 carbon atoms, e.g. B. Acrylic acid, methacrylic acid, crotonic acid, maleic

! · Acid, fumaric acid and itaconic acid, as well as dicar-

bonsäuremonoester in question, like the half esters of maleic acid and fumaric acid with 1 to 18

Monoalkanols containing carbon atoms

such as B. maleic or fumaric acid monomethyl,

ethyl, propyl, η-butyl, iso-butyl, hexyl, octyl,

% n-decyl, iso-decyl, lauryl, stearyl and ethylhexyl

ester. Maleic acid-n-bu-

jj tyl, iso-butyl and iso-decyl half esters. Likewise

- · Mixtures of the unseeded mentioned are suitable

saturated carboxylic acids and dicarboxylic acid monoesters.

~ Component b) is in the copolymer in one

Amount from 2 to 20, preferably 5 to 15,% by weight polymerized

c) Suitable esters of acrylic or methacrylic acid are those containing 1 to 12 carbon atoms, such as monoalkanols. B. methyl, ethyl, propyl, η-butyl, isobutyl, hexyl, 2-ethylhexyl, octyl and lauryl esters of acrylic or methacrylic acid, preferably η-butyl and isobutyl acrylate monomers of component c) are in an amount of 0 to 30, preferably 0 to 25 wt .-% in the binder ¹ , einpoi; -merized.
Examples of preferred binders suitable

. Copolymers are mixed polymers from 70 to

: 90% by weight styrene, 5 to 15% by weight maleic acid-n-

; butyl or iso-butyl half ester and 0 to 25% by weight

: n- or iso-butyl acrylate.

: The inventively usable as a binder

Ren copolymers can according to different

'■. Polymerization processes, for example by

Bulk polymerization can be produced with evaporative cooling or by bead polymerization. the Softening points (according to KSN) of the binders to be used according to the invention are in generally above 80 ° C, preferably between 90 and 150, in particular between 100 and 120 ° C.

To reduce the melt viscosity at processing temperature and to set the desired properties of the markings, such as. B. cohesion, impact strength, compressive strength and softening temperature, 15 to 80, preferably 25 to 60 wt .-% of one or more compatible plasticizers are added to the polymer binder according to the invention. Plasticizers with very good gelatinizing properties for the polymer resin and low volatility at processing ^{temperature and a solidification temperature as far as possible below 0 °} C. are particularly suitable for this. Examples of such plasticizers are phthalic acid esters with a molecular weight above 400 such as e.g. B. the o-phthalic acid esters of n- and iso-nonyl, decyl and undecyl alcohol and their mixtures. Less well gelatinizing, limited and incompatible plasticizers can be used in part. B. vegetable or animal fats and oils, high molecular weight adipic or sebacic acid esters or mineral UIe.

The materials commonly used for street marking are suitable as pigments and fillers Fe such as anatase, rutile, crystallite, quartz, calcite, Dolomite, muscovite mica, barite, kieselguhr, glass beads, talc, pumice powder and mixtures of these Substances of different grain size ranges.

Pigments and fillers are generally used in

ίο Quantities from 60 to 90, parts by weight with 10 to 40 Parts by weight of binder (= copolymer) combined The road marking paints can also Auxiliaries, such as. B. anti-settling agents, adhesives, Dispersants and solvents are added.

The production of the marking compounds from the components listed is carried out in a known manner using conventional mixing units, such as. B. by mixing and melting. To the melting process To facilitate and accelerate the process, the solid components in the preheated plasticizer can be used be stirred in. The production of the ready-to-use melt from the liquid and the solid Components can be made directly at the place where the marking compound is processed.

The melt is processed in a known manner, for. B. by spraying or, with higher viscosity Melting, e.g. B. by pulling on with the pulling shoe or pressing out of a slot nozzle.

There is another possibility of processing

jo therein, the composition according to the invention with use of volatile solvents, such as. B. aromatic hydrocarbons, esters, ketones, alcohols or their mixtures to be processed in a known manner as marking paint. So made

j-) Colors stand out against those known with Inks produced by binding agents are characterized in particular by the fact that they have a lower solvent content and therefore greater environmental friendliness, better mechanical properties and therefore longer durability speed and better resistance to pollution.

The parts and percentages given in the following examples are parts by weight and percentages by weight, respectively.

Example I.

Manufacture of a binder
for road marking paints

-> i> A mixture of 70 parts styrene, 20 parts i-butyl acrylate, 10 parts of maleic acid mono-n-butyl ester and 2 parts of tert-dodecyl mercaptan are placed in a feed vessel. A second feed vessel contains 2.25 Partly tert-butyl perbenzoate. 10% each of inlets 1 and 2

Vi are placed in the reaction vessel and stirred heated to 130 ° C. The remainder of feeds I and 2 are added dropwise over the course of 2 hours and the Reaction temperature by means of negative pressure so that it does not exceed I4O "C

Wed I hour under reduced pressure (400 to 500 mbar) post-polymerized. The residual monomers still present are then distilled off at 10 Torr / 145 ° C.

The characteristics of the copolymer are listed in Table 1. As a comparative product A, this will be

π- · in Example 5 of DE-OS 24 07 159 described Binder used. Comparative product A consists of 50 parts of n-butyl acrylate, 45 parts of styrene and 5 parts Share acrylic acid.

Example 2

A mixture of 70 parts of styrene, 20 parts of i-butyl acrylate, 10 parts of maleic acid monoisodecyl ester and 2 parts of tert-dodecyl mercaptan are added to a feed vessel. Contains a second feed vessel 2.25 parts of tert-butyl perbenzoate are polymerized and worked up as described in Example 1. For characteristics of the binder, see table 1.

Example 3

In a feed vessel, 80 parts of styrene and 10 parts i-butyl acrylate, 10 parts of maleic acid mono-n-butyl ester

and 2 parts of tert-dodecyl mercaptan mixed 2.25 parts tert-Butyl perbenzoate as initiator are located in a second feed tank. The reaction will be like Described under Example 1, performed characteristics see Table 1.

Example 4

70 parts of styrene, 25 parts of n-butyl acrylate, 5 parts Acrylic acid and 2 parts of tert-dodecyl mercaptan are mixed ίο and placed in a feed vessel. In a second The feed vessel is filled with 2 ^ 5 parts of tert-butyl perbenzoate. The polymerization is carried out in the same way Example 1 described. Characteristic data see table 1.

Table 1

Characteristic data of the binders from Examples 1 to 5 and Comparative Product A.

example 1 Example 2 Example 3 Example 4 Example 5 Comparison
product A Weight loss
after 5 h at
2OO ^C C in% 2.9 . ", 9 2.6 1.4 3.3 4.8 Melt viscosity at
180 ° C (Pas) 15.5 6.5 18.9 9.5 7.9 0.8 Softening point after
KSN ( ⁰ Q 106 101 113 109 86 62 Blocking resistance
at 23 ° C
at 50 C very good
very good very good
very good very good
very good very good
very good see well
Well insufficient
insufficient K value (1% in
Ethyl acetate) 20.1 19.3 18.5 20.7 22.7 19.0 Example 5

90 parts of styrene, 10 parts of maleic acid mono-n-butyl ester and 03 parts of tert-dodecyl mercaptan are based on 20 parts of a commercially available plasticizer of ophthalic acid esters with C9 to Cu alcohols

mixed and made with 1.5 parts of tert-butyl perbenzoate polymerized and processed in a second feed tank as in Example 1, characteristic data see Table 1.

Example 6

To 100 parts of the copolymer from Example 1 forms. The melt is then drawn up 28 parts of the plasticizer from Examples 5 and 2 are applied to concrete or asphalt with a 3 mm drawing gap

Parts of coconut fat are added. The mixture is ^{heated to IfK) 0} C until a uniform melt is obtained

applied. The characteristics of the modified binder are summarized in Table 2

Table 2

Characteristic data of the modified binder from Examples 6 and 7

Example 6 Example 7 Comparative product Λ Plasticizer additive 30% 48% _ on polymer bandage (= 28 parts soft middle doer based Phthalic acid ester + 2 parts coconut fat) Melt viscosity 0.65 1.0 0.8 at 180 ⁰ C (Pas) Shore hardness A 59 65 39 at 23 C after 15 " load Impact resistance at 23 C 22-23 42-46 7-11 (Fall height of a Round bolt of 109 g in cm)

Example 7

100 parts of the copolymer from Example 5 are mixed with 23 parts of the plasticizer mentioned in Example 5 at 160 ^° C. to form a uniform melt. The characteristics of the cooled melt are summarized in Table 2.

Example 8

Production of a solvent-free,
sprayable hot melt marking compound

30.0 parts of the binder from Example 5 are used in Temperatures between 160 and 200 ° C melted and with

5 parts anatase
11 parts of fine Kristobalit flour (0.001 to

0.02 mm grain diameter)
20 parts of crystallite grain 0.02 to 0.2 mm
19 parts of Kristobalite mixture 0.00 to 1.0 mm
15 parts of reflective glass beads 0.2 to 0.4 mm

evenly mixed by vigorous stirring at this temperature.

The pigmented mass produced in this way stands out in comparison to a marking produced analogously

compound from comparative product A due to its lower melt viscosity. You can therefore even at lower temperatures by the known methods such. B. process spraying or drawing up (see Table 3). The coated at a draw shoe from the melt on concrete at 170 ⁰ C melt is adherent after cooling, tough, impact-resistant and pressure-resistant than that of Comparative Product A.

Table 3

Characteristics of the hot melt marking compound

Example 8

COMPARATIVE PRODUCT Λ

Viscosity (Pas) at

130 (70 200

150 t 20 60

180 C ⁷ 18

200 C 4 8

220 C 2 3

Minimum temperature for

processing in

Spray experience 180 C 200 C

Drawing process 130 (150 C

Claims (3)

Patent claims: 1. Binder for road marking paint !!, which consists of 60 to 90% by weight of at least one pigment and / or inorganic filler and 10 to 40% by weight of binder, characterized in that that the binder is made of a copolymer a) 55 to 95% by weight of a vinyl aromatic, b) 2 to 20% by weight of at least one copolymerizable, "^ -Olefinically unsaturated carboxylic acid or a half ester" ^ -olefinic unsaturated dicarboxylic acids with 1 to 18 carbon atoms containing monoalkanols and c) 0 to 30 wt .-% of at least one ester of acrylic acid and / or methacrylic acid with 1 to Monoalkanols containing 12 carbon atoms, where the sum of the percentages mentioned under a) to c) is equal to 100. In that the copolymer comprises 2 binder according to claim 1, characterized by a softening point of about 80 ⁰ C KSN 3. Binder according to claim 1 or 2, characterized in that the copolymer plasticizer is added.