DE2749625C3 - Binder for road marking paints - Google Patents

Description

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 monoalkanols containing 1 to 15 carbon atoms and

c) 0 to 30 wt .-% of at least one ester of acrylic acid and / or methacrylic acid with 1 to 12 carbon atoms containing monoalkanols,

where the sum of the percentages mentioned under a) to c) is equal to 100

2. Binder according to claim 1, characterized in that that the copolymer has a KSN softening point of over 80.degree

3. Binder according to claim 1 or 2, characterized in that the copolymer plasticizer is added

In DE-OS 24 07159 binders are used high resistance to heating and aging described the "problem of making binders that the contradicting properties of a low

Melt viscosity, high cohesion and sufficient Compressive strength and pollution resistance in itself

unite, but so far has not been able to achieve a satisfactory result be solved.

These products are not sufficiently resistant to blocking and

ίο therefore need a relatively expensive one Packaging. Their production and processing is complex, because both their binder and the Glue and block finished masses before processing.

The object of the present invention was therefore to produce a binding agent which in part contradicting property characteristics in optimal

Wise united in itself The present invention relates to binding

Agent for road marking paints, consisting 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:

25th

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

b) 2 to 20% by weight of at least one copolymerizable a ^ -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 wt .-% of at least one ester of Acrylic acid and / or methacrylic acid with 1 to 12 carbon atoms containing monoalkanols,

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 4ii Temperatures of around 180 to 220 * C for several hours even when exposed to atmospheric oxygen Yellowing as little as possible in order to ensure the day and night visibility of the markings made from them not to affect; their melt should be in the temperature range from about 130 to 200 * a Have the lowest possible viscosity so that the marking compounds produced therefrom are as low as possible Let it work at a low temperature and achieve the highest possible adhesive strength on the road surface exhibit. This is particularly true when the masses are to be processed by spraying. The markings must also be weatherproof and resistant to waiter and salt water. They should also have a high pigment binding capacity r. have, so that the highest possible proportions are inexpensive ger fillers can be used. The adhesion to glass beads and hard fillers must be high, thus the night visibility, the abrasion resistance and the grip of the markings over a possible ω Long service life is preserved In addition, the binding agent of the marking paint or matting must be a convey high carbon and sufficient elasticity, so that the markings are abrasion-resistant and even in cold weather do not become brittle and form a ride. On the other hand, the Markleningen are great do not soften so much in warm weather that they become oleastic and pollute.

where the sum of the percentages mentioned under a) to c) is equal to 100

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

A preferred embodiment of the binder according to the invention is also that the Binder plasticizer in amounts of 15 to 80, preferably 25 to 60 wt .-%, based on the Copolymer, is added.

The traffic paints of the invention have in addition a particularly good abrasion resistance, adhesion to concrete and asphalt and heat yellowing resistance very high softening points prior to processing with plasticizers, are resistant to blocking by which the products up to at least 50 ⁰ C and are easily processed with addition of a plasticizer könnet).

In addition, the inventive Binder is characterized by its particularly high impact resistance and compressive strength (penetration hardness). This gives the Road marking paints high resistance to loads. Another benefit of the Processing of these street markings from the Melt Ut their low melt viscosity after adding a plasticizer, resulting in lower Processing temperatures and thus for energy * itenerspamfi drive further expand the inventive · dimensions of road marking colors only low Oe * odorization when processing in the melt and lower hernia tkoites than those in the Dg-OS 24 07159 described products.

One of the structural components of the copolymers to be used according to the invention is old binders

to do the following;

a) vinylaromatics is styrene and Vinylto-Iiiol are suitable, in particular styrene, in the Copolymerjsat in an amount of 55 to 95, preferably 70 to 90, GeWr- ¹ Hi are empolymerisiert,

b) As component b) there are ^ -olefinically unsaturated Carboxylic acids such as mono- and dicarboxylic acids having 3 to 5 carbon atoms, e.g. Acrylic acid, methacrylic acid, crotonic acid, maleic acid, Fumaric acid and itaconic acid, and dicarboxylic acid monoesters in question how 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 esters. Maleic acid n-bu-yl, isobutyl and isodecyl ester are particularly preferred. Likewise Mixtures of the unsaturated carboxylic acids and dicarboxylic acid monoesters mentioned are suitable.

Component b) is in the copolymer in an amount of 2 to 20, preferably 5 to 15 wt .-% polymerized

c) Possible esters of acrylic or methacrylic acid are those with monoalkanols containing t to 12 carbon atoms, such as methyl, ethyl, propyl, η-butyl, iso-butyl, hexyl, 2-ethylhexyl, Octyl and lauryl esters of acrylic or methacrylic acid, preferably η-butyl and iso-butyl acrylic monomers of component c) are polymerized in the binder in an amount of 0 to 30% by weight, preferably 0 to 25% by weight .
Examples of copolymers preferably suitable as binders are copolymers of 70 to 90% by weight styrene, 5 to 15% by weight maleic acid n-butyl or isobutyl half-ester and 0 to 25% by weight n- or isobutyl acrylate

The copolymers which can be used according to the invention as binders can be prepared according to various Polymerization processes, for example by bulk polymerization with evaporative cooling or can be produced by bead polymerisation. The softening points (according to KSN) according to the invention The binders to be used are generally 80.degree. C., preferably between 90 and 150, especially between 100 and 120 ° C.

To reduce the melt viscosity at processing temperature and to set the desired Usage properties of the markings, such as cohesion, impact resistance, compressive strength and Softening temperature, the polymer binder according to the invention are expediently 15 to « 80, preferably 25 to 60,% by weight of one or more Contractual plasticizer added Plasticizer with very good gelatinization properties for the polymer satharz and low volatility at processing temperature and a solidification temperature as possible well below 0 * C are particularly suitable for this. Examples of such plasticizers are phthalic acid esters with a Molecular weight above 400 such as B. the o-phthalic acid esters of n · and iso-nonyl, decyl and undecyl alcohol as well as their mixtures. Less gelatinizing 6; limited contractual and incompatible plasticizers can be partially used: Such plasticizers are z. B, vegetable or animal fats and oils, high molecular weight adipic acid or sebacic acid esters or mineral oils.

For pigments and fillers, the for Road markings commonly used fabric

Fe such as, for example, anatase, rutile, crystallite, quartz, calcite,

Dolomite, muscovite mica, barite, kieselguhr, Glass beads, talc, pumice powder and mixtures thereof Substances of different grain size ranges. Pigments and fillers are generally used in

in amounts of 60 to 90, parts by weight with to up to 40 Parts by weight of binder (»copolymer) combined. The road marking paints can as well 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 Way z. B. by spraying or, with higher viscosity Melting, e.g. B. by pulling up 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 mixtures thereof in a known manner as Process marking paint. So made

In comparison to the colors produced with known binders, η colors are particularly distinguished by this from the fact that they are better in spite of a lower solvent content and therefore greater environmental friendliness mechanical properties and therefore longer durability and better resistance to contamination.

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

■ Ti

example 1

Manufacture of a binder
for road marking paints

A mixture of 70 parts of styrene, 20 parts of 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 Parts of tert-butyl perbenzoate 10% each of feeds 1 and 2 are placed in the reaction vessel and heated to 130 ° C. while stirring. The mixture is left for 2 hours Add the remainder of feeds 1 and 2 dropwise and adjust the reaction temperature by means of reduced pressure so that it 140 ° C is not exceeded Post-polymerization for 1 hour under reduced pressure (400 to 500 mbar), the residual monomers still present It is then distilled off at 10 Torr / 145 ° C.

The characteristics of the copolymer are listed in Table 1. Comparative product A is the in Example 5 of DE-OS 24 07159 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 j-butyl acrylate, 10 parts of majeic acid monoisodecyl ester and 2 parts of tert-dodecyl mercaptan are added to a feed vessel. Contains a second feed vessel 2 £ 5 parts tert-butyl perbenzoate polymerization and Work-up takes place as described in Example 1, Characteristic data 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

10

and 2 parts of tert-dodecyl mercaptan mixed, 2.25 parts tert-Butyl perbenzoate as initiator are in a second feed tank. The reaction is as Described under Example 1, carried out 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 and placed in a feed vessel. In a second 2 ^ 5 parts of tert-butyl perbenzoate are precipitated in the feed vessel The polymerization is carried out as described in Example 1. 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 p Comparison product A Weight loss 2.9 3.9 2.6 1.4 3.3 4.8 after 5 h at 200 ⁰ C in% Melt viscosity at 15.5 64 18.9 94 7.9 0.8 180 ⁰ C (Pas) Softening point after 106 101 113 109 86 62 KSN ( ⁰ Q Blocking resistance at 23 ° C very good very good very good very good see well insufficient at 50 ⁰ C very good very good very good very good Well insufficient K value (1% in 20.1 19.3 18.5 20.7 22.7 19.0 Ethyl acetate)

Example 5

90 parts of styrene, 10 parts of maleic acid mono-n-butyl mixed and 1.5 parts of tert-butyl perbenzoate

Ester and 0.5 part of tert-dodecyl mercaptan are added to a second feed tank as in Example 1

20 parts of a commercially available plasticizer based on polymerized and processed characteristics see Table 1.

of o-phthalic acid esters with Cr to Cn alcohols

Example 6

To 100 parts of the copolymer from Example 1, the melt is then formed by drawing 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 applied for as long as 45 The characteristics of the modified binder 160 ° C heated until a uniform melt means are summarized in Table 2

Table 2 Characteristic data of the modified binder from Examples 6 and 7

Example 6 Example 7 Comparative product A Plasticizer additive 30% 48% on polymer binding (= 28 parts soft mittil doer based Phthalic acid ester + 2 parts coconut fat) Melt viscosity 0.65 1.0 0.8 at 180 ° 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 that mentioned in Example 5 Plasticizer at 160 ° C to form a uniform Melt mixed. The characteristics of the cooled melt are summarized in Table 2.

Example 8

Making a solvent-free.
sprinkled / salable healing oil / milk

30.0 parts of the binder .ms Example 5 are used in Temperatures between IbO and 200 (melted and with

5 parts anatase
11 parts Kristobalit-I'emstmehl (0.001 to

0.02 mm grain knife)
20 parts Kristobalit-KornO.O.> Up to 0.2 mm
19 parts Kristobalii mix 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 compared to a similarly produced marking compound from comparative product A by lower Melt viscosity. It can therefore be seen at lower temperatures by the known methods such as B. process spraying or drawing up (see., Table 3). The ones with a pulling shoe from the melt hot melt mass drawn onto concrete at 170 ° C after cooling, more adhesive, tougher, more impact-resistant and more pressure-resistant than that from comparison product A.

"Table 3

Characteristic values of the hot climating compound

IK-ii oil X Collateral proilukl Λ Viscosity (l'as) at I Kl ( 70 200 150 ι. 2 (1 W) IX (I C 7th 18th 201) ( A. 8th 220 l 2 3 MiiulesUemneratur for processing in Snril / .verlahren 180 C 200 C Drawing process 130 C 150 Γ

Claims (1)

Claims; 1. Binder for road marking paint !! that from 60 to 90% by weight of at least one pigment and / or inorganic filler and 10 to 40 % By weight binder! exist, characterized that the binder is made of a copolymer