HU202900B - Coating material with improved properties - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to a coating material having improved mechanical properties with good weather resistance (reduced water absorption). The coating material of the present invention comprises 4.5 to 25 parts by weight of a copolymer of methacrylate, styrene, optionally acrylate monomer, and 12-52 carbonated chlorinated hydrocarbons, containing from 0 to 20 parts by weight of cellulose nitrate, 5-25 parts by weight. part of the pigment, 0.4-6 parts by weight of other additives, preferably a spreading agent, plasticizer, 0-14 parts by weight of filler and 100 parts by weight of organic solvent. EN 202 900 B Scope of description: 8 pages -1-

Description

BACKGROUND OF THE INVENTION The present invention relates to a coating material having improved mechanical properties with good weather resistance (reduced water uptake).

The coating agent of the present invention comprises a copolymer of vinyl monomers polymerized with chlorinated hydrocarbons having improved properties as binder, optionally cellulose nitrate, as well as pigment, additives and optionally filler.

In the paint industry, a number of coating materials are known which bind acrylate, methacrylate polymer.

Hungarian Patent No. 151,048 describes the preparation of an acrylate or methacrylate copolymer prepared from a partially transesterified monomer with a higher alcohol. In the Hungarian Patent No. 156,384, the coating binder used is a copolymer of acrylic acid, methacrylic acid, maleic chlorohydrin ester. According to Hungarian Patent No. 173,565, oligomers of maleic or fumaric acid are incorporated in the acrylate copolymer in the presence of an organotin compound catalyst. Hungarian Patent No. 178,860 discloses the preparation of a binder prepared by graft polymerization of vinyl chloride copolymers and acrylic acid esters.

In U.S. Patent No. 1,210,966, a linear acrylic copolymer containing a carboxyl group in a non-aqueous solution is prepared in the presence of an aluminum alkoxide complex catalyst.

British Patent 2,101,121 discloses an E-prolactone modified hydroxymethacrylate copolymer.

U.S. Pat. No. 4,107,235 discloses the preparation of two acrylate copolymers with different glass transition points, which are used as binders in admixture in specified amounts.

The copolymer of the copolymer disclosed in German Patent No. 2,851,613 is an addition product of a monoglycidyl compound of an alpha, beta, unsaturated monocarboxylic acid.

The acrylate copolymer of Swiss Patent No. 583 754 also contains a 2,3-epoxypropyl acrylate monomer.

The disadvantages of the known acrylate copolymers are that they are not metal-compatible with other film-forming agents, such as cellulose nitrate in particular, their elasticity, their adhesion is in many cases unsatisfactory and their pigment-wetting ability is inadequate.

It is an object of the present invention to provide a coating material which has a new acrylate or methacrylate graft copolymer base and improved mechanical properties, better weather resistance (reduced water uptake).

This object can be achieved by using a binder in the coating material which has a relatively smaller molecular weight distribution, a lower molecular weight and a lower viscosity value at the same dry matter content.

A further advantage of the binder used is that it is even compatible with cellulose nitrate.

Preferably, cellulose nitrate containing from 11% to 12.5% by weight of nitrogen and from 2.0% to 3.0% by weight of hydroxyl groups can be used in such a combination.

The binder of the present invention comprises 0.3-7% by weight of a chlorinated acrylate or methacrylate copolymer.

This is prepared by mixing methacrylate, styrene, and optionally acrylate monomer with an organic peroxide catalyst - 100 parts by weight of a monomer mixture - 0.5-10 parts by weight of C12-52, 50-70% by weight of chlorine hydrocarbons, and 0-. 01-3 parts by weight of a C15-18 organic aliphatic carboxylic acid zinc salt and 1.2-5 parts by weight of an epoxy compound are polymerized in an organic solvent medium at a temperature of 60-180 ° C.

The copolymer thus produced has a lower molecular weight or viscosity than known acrylate copolymers.

This is due to the fact that during the polymerization, the chlorinated hydrocarbon is grafted onto the resulting copolymer as a chain terminator and thus prevents the weight increase of the polymer chain. The molecular weight of the acrylate copolymers formed in the conventional process varies in a relatively wide range. In the process according to the invention, it is possible to obtain a relatively uniformly low molecular weight copolymer by grafting the chlorinated hydrocarbon chain terminator.

Suitable monomers include ethyl acrylate, butyl acrylate, methyl methacrylate, isobutyl methacrylate, ethyl hexyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, styrene, methyl benzene, alpha at least two of the styrene monomers are used. The chlorine-containing hydrocarbon is suitably a hydrocarbon having from 16 to 32 carbon atoms and 50 to 70% by weight of chlorine.

The polymerization is carried out in the presence of 20-60% by weight of solvent at a temperature of 60-180 ° C. The solvent used is aromatic hydrocarbons, ketones, esters or mixtures thereof, which may also contain aliphatic hydrocarbons and alcohols.

Depending on the boiling point of the solvent mixture, the polymerization is t-butyl hydroperoxide, methylamyl ketone peroxide, acetyl poroxide, lauryl peroxide, cyclohexyl hydroperoxide, benzoyl peroxide, t-butyl peracetate, p-chlorobenzoyl peroxide, continued in the presence of tert-butyl peroxide catalyst.

According to our method, 0.01 to 3 parts by weight of a zinc salt of an organic acid having from 15 to 18 carbon atoms is added to the mixture to accelerate the polymerization.

Further, 0.2 to 5 parts by weight of epoxy compound (epoxy resin, epoxidized fatty acid ester, preferably fatty acid glycidyl ester) per 100 parts by weight of the monomer mixture are used as an acid acceptor.

The copolymer thus produced has the following advantageous properties:

- improved adhesion and flexibility,

- reduced molecular weight or viscosity,

- excellent pigment wetting capacity,

- rapid drying,

-2HU 202900 Β

- compatibility with other binders,

- versatile and easy to process.

The coating material of the present invention is 4.5-25 parts by weight of 0.3-7% by weight chlorine-containing copolymer of 1500-5000 molar above, 0-20 parts by weight of cellulose nitrate, 5-25 parts by weight of pigment, 0.4-6 parts by weight of other additives, preferably it contains a bulking agent, a plasticizer, 0-14 parts by weight of a filler and 100 parts by weight of an organic solvent.

The chlorine-containing acrylate or methacrylate copolymer binder 10 also has an excellent pigment wetting ability, while the cellulose nitrate binder pigment has an extremely poor wetting ability.

Therefore, if the coating material also contains cellulose nitrate, the pigment paste must be prepared using the chlorine-containing copolymer and mixed with the cellulose nitrate.

Commonly used materials can be incorporated into the coating material as a pigment or filler. Preferably, the pigment used is titanium dioxide, phthalocyanine blue, and quartz flour, talc, chalk, mica, slate are preferred fillers. As an additive, various spreading agents are preferably propylene glycol ethyl ether, isotorone, surface hardness enhancer, preferably polyethylene wax, plasticizer such as dibutyl phthalate, dibutyl adipate and the like. employed.

The preparation of the chlorine-containing copolymer and coating material used in the coating material of the present invention is illustrated by the following examples:

Example 1

The following solvents and monomers are weighed into a stainless steel autoclave with stirring:

tr. xylene 35 tr. methyl isobutyl ketone tr. butyl acrylate tr. methyl methacrylate tr. styrene tr. hydroxyethyl acrylate 40 tr. chlorinated hydrocarbon (carbon number: 16; chlorine content: 56% by weight)

0.5 tr versatic acid glycidyl ether tr. zinc octoate in 10% solution in xylene.

Running the mixer, starting the heater, 1 tr. benzoyl 45 peroxide 2 tr. slurried in xylene. The heating was continued until the reaction was continued for ca. 7075 'C. Steam heating is stopped and added as needed to raise the temperature to 90 ° C and maintain the temperature between 95-100 ° C with additional portions of the monomer mixture without heating. Under these conditions, the following monomer mixture is added:

tr. butyl acrylate tr. methyl methacrylate tr. styrene tr. hydroxyethyl acrylate tr. Benzoyl Peroxide

After the addition was complete, the temperature was maintained at 110-120 ° C for three hours. benzoyl peroxide 2 tr. xylene slurry was added to the reactor material and kept at 120-130 ° C for an additional two hours. The resulting polymer solution was treated with 30 tr. xylene and 10 tr. methyl isobutyl ketone. The solution has a non-volatile content of 50% by weight viscosity of 610 * 10 ' ³ Pa.s. The graft copolymer has a molecular weight of 4212

Example 2

Add the following solvents to a steam-autoclave equipped with a stirrer, reflux condenser:

tr. thence tr. ethyl acetate 5 tr. ethylene glycol acetate

The solvent mixture is heated to 80 'C and the following monomer mixture is added such that the reactant is spun at constant reflux.

tr. ethyl methacrylate tr. styrene tr. hydroxypropyl methacrylate

4.5 tr chlorinated hydrocarbon (Carbon number: 12; chlorine content: 70% by weight) tr. epoxy resin (epoxy equivalent: 800)

0.5 tr 2,4-dichlorobenzoyl peroxide

0.6 tr zinc naphthenate (in a 10% solution in toluene)

After the addition was complete, the mixture was heated for a further three hours. Then another 0.2 tr. 2,4-Dichlorobenzoyl peroxide was added and reflux was continued for two hours. Incompatible material content: 50% by weight viscosity 540 * 10 ' ³ Pa.s. The graft copolymer has a molecular weight of 4088.

3-7. Example

Example Code:

Comparative

3. 4. 5. 6. 7.

methyl methacrylate ethyl acrylate butyl acrylate isobutyl methacrylate

2-ethylhexyl methacrylate hydroxyethyl acrylate hydroxyethyl methacrylate styrene

14 20

16

- - 8

- 4 6

14 16

20

16

HU 202 900 Β

Example Code: Third 4th Comparative 5th 6th 7th 16 hydrocarbons * - 1.5 - - - 12 hydrocarbons ** 1 - - - - 12-50 hydrocarbon mixture ' *** _ - 5 - - epoxy resin (epoxy equivalent: 2110) - 0.8 - - - versatiksav glycidyl ether 0.4 - 1.6 - - Benzoyl Peroxide - 0.5 0.6 - 0.6 di-t-butyl peroxide 0.4 - - 0.4 - zinc octoate (10% w / w solution) - 1.2 0.8 - - zinc naphthenate (10% w / w solution) 0.2 - - - - Solvent Mixture I (toluene / methyl ethyl ketone 3: 1 by weight) 50 50 - 48 - Solvent mixture Π. (Xylene: methyl isobutyl ketone 3: 1 by weight) - - 50 - 46.4 mw 4820 4942 4600 5215 6908 100 100 100 100 100

* Chlorine content: 52% by weight ** Chlorine content: 56% by weight *** Chlorine content: 70% by weight 25

The viscosity of the prepared 50% non-volatile copolymer solutions is as follows:

using it to produce a bright-drying white enamel,

Example 3 730 · 10 ′ ³ Pa.s.

Example 4 720 · 10 ′ ³ Pa.s.

Example 5 710 · 10 ′ ³ Pa.s.

Example 6 84ΟΊΟ ^'3 cps

Example 7 1050 · 10 ′ ³ Pa.s.

Example 8

Proceed as in Example 2, but adding the following mixture of material to the apparatus: butyl acrylate 18.0 tr. methyl acrylate 5.0 tr styrene 24.5 tr C16, 52% w / w chlorine-containing hydrocarbon 0.7 tr 12 carbon at 70% chlorine-containing hydrocarbon 0.5 tr epoxy resin (epoxy equ .: 440) 0.7 tr Benzoyl Peroxide 0.3 tr. di-t-butyl peroxide 0.2 tr zinc octoate (10% w / w xylene) solution) 0.1 tr. xylene methyl isobutyl ketone (3: 1) weight ratio) 50.0 tr.

100.0 tr.

The 50% solution of the copolymer solution has a viscosity of 490 · 10 · ³ Pa.s.

Example 9

The copolymer solution prepared according to Example 1 was dissolved in water

I. 38.5 tr.

20.0 tr. 1.0 tr

II. 5.0 tr 2.5 tr 1.0 tr

III. 32.0 tr.

Example 1 50% Copolymer Solution Titanium Dioxide (Rutile) Benzyl Alcohol Butyl Acetate Ethyl Acetate Dioctyl Phthalate Cellulose Nitrate (20% solution in isobutyl acetate / methyl isobutyl ketone 1 / 1 ratio)

Mixture I is homogenized with a high speed mixer and then dispersed in a pearl mill. To the resulting pigment paste was added II. materials. The mixture was homogenized and finally the reaction mixture was stirred for 3 hours. The cellulose nitrate solution according to FIG.

The property of the product is shown in Example 17.

Example 10

Using the copolymer solution prepared in Example 2, a bright-drying white enamel was prepared as follows:

I. 38.5 tr. Example 2 50% Copolymer Solution 20.0 tr. titanium dioxide (rutile)

1.0 tr benzyl alcohol

II. 5.0 tr butyl acetate 2.5 tr. ethyl acetate 1.0 tr. Dioctyl phthalate

HU 202 900 Β

III. 32.0 tr. cellulose nitrate (20% solution in a 1/1 mixture of isobutyl acetate / methyl isobutyl ketone)

Mixture I is homogenized with a high speed mixer and then dispersed in a pearl mill. To the resulting pigment paste, we added Π. materials. The mixture was homogenized and finally a. The cellulose nitrate solution according to FIG.

The property of the product is shown in Example 17.

Example 11

Silk-gloss, fast-drying weather-resistant white enamel can be produced from the following material composition:

35.5 tr. Example 3 50% Copolymer Solution

18.5 tr of titanium dioxide (rutile)

23.0 tr. cellulose nitrate 20% solution (in the solvent of Example 9)

9.0 tr. Isobutyl acetate

3.5 tr methyl ethyl ketone 5.0 tr. toluene

0.5 tr isophorone

2.5 tr dibutyl adipate 2.0 tr. colloidal diatomaceous earth 0.5 tr. polyethylene wax

The enamel is prepared as described in Example 9.

Example 12

Example 9 is repeated, but the composition of the enamel is as follows and the preparation of the enamel in a fast mixer is carried out in a single step and the dispersion is carried out in a bead mill.

38.4 tr. 50% by weight copolymer solution of Example 4

5.5 tr. titanium dioxide (rutile)

5.0 tr titanium dioxide (anatase)

17.7 tr. quartz

5.5 tr chalk 5.3 tr. talc

5.5 tr. slate flour tr. aluminum stearate 11.9 tr. acetone

5.6 tr. toluene

Example 13

An abrasive sandwich patch can be used to eliminate surface irregularities and increase the thickness of the coating system, based on the following material composition:

42.0 tr. Example 5: 50% by weight copolymer solution

4.2 tr. aromatic gasoline 6.8 tr. propylene glycol ethyl ether

8.0 tr. horganyfehér

4.8 tr titanium dioxide (anatase)

14.0 tr. chalk

6.0 tr. slate flour

14.0 tr. talc

0.2 tr nail

0.4 tr polyethylene wax

The material homogenized with the fast mixer is dispersed on a rolling mill to a homogeneous product.

14-15. EXAMPLE (Comparative) The procedure of Example 9 was followed, but instead of the copolymer solution of Example 1, the copolymer of Examples 6 and 7, which did not contain a chlorinated hydrocarbon, was used.

Example 16

Matt blue enamel is prepared as described in 9. The composition of the enamel is as follows:

46.8 tr. cellulose nitrate 20% solution (in the solvent of Example 9)

10.2 tr. copolymer 50% by weight (Example 8)

7.7 tr. titanium dioxide (rutile)

3.3 tr phthalocyanine blue

9.0 tr. piasztorit

4.2 tr. benzyl butyl phthalate

0.3 tr. isophorone

0.4 tr organophilic bentons

7.6 tr. Ethyl glycol

Wed 3.7 isobutanol

8.1 tr. xylene

100.0 tr.

Example 17

9-16. Exemplary coating material was tested. The test results are as follows:

Hardness Flexibility Impact resistance Water absorption MSZ 9640/2 Erichsen mm MSZ 9640/9 MSZ 9640/11

Example

9th H 5.7 60 0.36 10th 2 H 7.4 90 0.91 11th H 6.1 55 0.42 12th 3B 3.2 30 - 13th 2B 3.4 25 1.00 16th H 5.4 74 0.85

Comparative example

14th 2 H 2.2 20 1.50 15th 3B 1.5 10 2.30

The test results show that the coating material according to the invention has improved elasticity, impact resistance and improved weather resistance due to lower water uptake.

Claims (2)

PATENT CLAIMS 1. Coating polymer, acrylate or methacrylate copolymer with improved mechanical properties and weather resistance, of a binder, a pigment, an additive and optionally a filler, characterized in that 4.5-25 parts by weight of chlorine-containing methacrylate, optionally styrene, optionally a copolymer of acrylate monomer and grafted C12-52 chlorinated hydrocarbon, having a molecular weight of 2500-5000, 0-20 parts by weight of cellulose nitrate, 5-25 parts by weight of pigment, 0.4-6 parts by weight of other additives, preferably spreading agent, softener, 0-14 parts by weight. filler and 100 Contains 5 parts by weight of organic solvent. Coating material according to claim 1, characterized in that it contains quartz flour, talcum, chalk, slate flour as filler.