JPS5817774B2 - Acrylic interpolymer deformation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an acrylic interpolymer encapsulated (e
The present invention relates to a novel pigment composition comprising an organic pigment (ncapsulated).

Colored pigments are widely used for various types of polymeric media.

The efficiency with which pigments are used as coloring materials in such applications depends on their dispersibility and the degree to which they remain finely dispersed in the final product.

In many cases, pigments, for example, even after repeated intensive milling of polymer and pigment, end up with agglomeration of the pigment, reducing the quality of the product.

The problem of agglomeration of pigments is particularly
This is particularly true in the case of automotive enamels and lacquers consisting of solvent solutions of acrylic polymers containing metal particles such as aluminum flakes to provide the poly-chromatic finish of d).

These finishes create a rich and attractive decorative effect because the finish emphasizes the curvaceous beauty.

This phenomenon is known as geomtric metamerfsm, and is known in the automotive industry as the one-two-tone "effect" (tw).

-tone effect) or 1 flip-flop (fl 1p-f 1op).

Changes in color depth and tone as a function of viewing angle are observed.

This becomes clear when comparing parts of different shapes of the car body in a single car.

On flat surfaces, this effect is observed when the painted board is rotated from vertical to obtuse angle <V.

The depth of color increases as the viewing angle changes from vertical to either direction.

In any case, this effect caused by the mirror-like reflection of flaky pigments is impaired if the colored pigment diffuses the light.

So-called transparent pigments (trans parentpfgm)
cnt) are pigments that do not contain particles large enough to cause diffuse light reflection.

To be suitable for this purpose, organic pigments must generally have a crystalline size of less than 0.1 micron and must resist particle agglomeration during the period from pigment manufacture to paint finish.

According to the invention, an acrylic interpolymer consisting essentially of 45 to 75% ethyl methacrylate, 25 to 55% n-butyl methacrylate, and 1 to 5% acrylic acid or methacrylic acid by weight. The interpolymer of 250 to 0.1 to 0.6 was measured at 25°C by dissolving it in 50 cc of chloroform.
A particulate composition is provided comprising organic pigment particles encapsulated with an organic pigment having a logarithmic viscosity of .

The particulate compositions of the present invention are highly compatible with the solvents and acrylic polymers typically used in automotive paint finishes today and can be mixed directly into the finish paint composition, typically without milling. can.

Because the individual pigment particles are encapsulated in the acrylic interpolymer, there is no tendency for the pigment particles to aggregate when it is mixed into the finishing composition.

The acrylic interpolymer encasing the particles is largely or completely dissolved in the final finish composition, by which time the pigment particles are dispersed to a sufficient degree that agglomeration is minimized.

This new encapsulated
The paint film formed from the pigments exhibits a high degree of transparency and a three-tone "effect."

In these aspects, it is convenient to compare the same paint films using pigments that do not contain such acrylic interpolymers.

The encapsulation of organic pigments to produce the granular compositions of the invention can be carried out in various ways.

It is convenient to mill the pigment and acrylic interpolymer, for example in a ball mill, sand mill, etc., with sufficient solvent to dissolve at least a portion of the polymer, thereby coating the individual particles.

The solvent is then removed, for example by steam distillation, and the particles are dried and optionally ground.

The use of a solvent for the polymer is not essential, and it is also quite practical to perform aqueous milling using an emulsion of the polymer.

The relative proportions of pigment and acrylic interpolymer can also vary widely depending on the intended use of the enveloping pigment; in many paint systems as little as 1% acrylic interpolymer by weight has been found to have a markedly advantageous effect. .

There is no harm in using a large amount of interpolymer, since it can remain as a binder in the final product.

For convenience, approximately 1
It is usually preferable to use 0 to 99%.

Solvents that can be used to prepare this particulate composition include acetone, ethanol, n-7'' propyl alcohol, isopropyl alcohol, 5ec-butyl alcohol, and dioxane.

Other solvents that can be used are water, ethyl acetate, n-propyl acetate, isopropyl acetate, 2-
These include nitropropane, ethylene tetrachloride, and 0-dichlorobenzene.

If desired, other additives such as stabilizers, antioxidants, etc. can also be mixed in when coating the acrylic interpolymer onto the pigment particles.

The organic pigments used in the practice of this invention must be substantially insoluble in common acrylic polymer solvents, but are otherwise selected from a wide range.

Particularly useful are polychloro, polybromo-1 partially chlorinated, and chlorine-free copper phthalocyanines.

Similarly, quinacridone in the γ- or β-crystalline phase, as well as 2,9-dimethyl-12,9-dichloro-12,9-
difluoro-12,9-dimethoxy- and 4,11
-Substituted quinacridones such as dichlorogynacridone can also be used.

Solid solution quinacridone pigments, such as U.S. Pat. No. 36,505
Pigments such as those described in No. 10 can also be used.

Other pigments that can be used are toluidine red, benzidine yellow, thioindigo red, azo yellow, permanent 1/tsudo, and watc.
hung red) and Flav Anthrone yellow (
f lavantthrone yellow).

As will become clear from the examples below, it is often advantageous to subject the pigment to a pre-milling treatment in the absence of the acrylic interpolymer.

This usually results in a finely divided powder of less than 0.1 part and is highly amorphous in nature.

The acrylic interpolymer should have a logarithmic viscosity of about 0.1 to 0.6, preferably about 0.2 to 0.35.

The logarithmic viscosities referred to herein are those measured at 25° C. in 5 cc of chloroform using an interpolymer of 25 rv.

As mentioned above, the acrylic interpolymers mentioned here have a high degree of compatibility (compatibility) with a wide range of acrylic resin-based coatings, including thermosetting enamels, thermoplastic lacquers, and non-aqueous dispersions. Highly advantageous.

The interpolymers are also compatible with non-acrylic paint systems and printing ink systems such as acrylic polymers, plastics such as polyvinyl chloride, polystyrene, and nitrocellulose.

This interpolymer also has a relatively high softening point so that the encapsulated pigment particles can be dried without undesirable sticking.

The method of making the acrylic interpolymer is not critical.

This interpolymer is most conveniently synthesized by well-known solution polymerization using a suitable solvent.

A suitable method for obtaining a terpolymer consisting of about 59% ethyl acrylate, 39% n-butyl methacrylate and 1.5% acrylic acid (all percentages are by weight) is as follows.

In a 41 resin kettle equipped with a stirrer, addition funnel, reflux condenser, thermometer and nitrogen purge, 600 g ethyl methacrylate, 400 g n-butyl methacrylate, 15 g acrylic acid, 20 g n-dodecyl mercaptan chain. chain transfer agent
agent) and 11209 n-propyl acetate solvent.

The mixture was stirred and heated to 93° C. and then 400 g of 6° Og azobisisobutyroni-I-Ryl free radical initiator was added.
of n-propyl acetate at 50% per minute.
It takes 75 minutes for 11Ll.

Maintain the temperature at 92-94°C, stop adding the initiator after 75 minutes, and keep the mixture at 92-94°C for 15 minutes.
Add the remainder of the initiator in one portion and bring the reaction temperature to 96-98°C.
Maintain for 60 minutes.

At the end of this time the polymer solution is cooled and drained.

40% strength resin solution (in n-propyl acetate)
The Brookfield viscosity of is 150 cps.

The logarithmic viscosity of the resin from which the solvent has been completely removed is 0.
25.9 when the polymer is dissolved in 50 ml of chloroform and measured using an A50 Cannon Fennuke Viscometer.

The isolated resin is soluble in 95% and 100% ethyl alcohol, and its 40% solids solution is clear and colorless.

If it is desired to encapsulate the pigment by an aqueous milling operation, it is preferred to prepare the terpolymer by standard emulsion polymerization techniques and use it in the form of an emulsion.

The invention is further illustrated in detail by the following examples, in which parts and percentages are by weight unless otherwise specified.

Although in the examples reference is made to automotive finishes of the thermosetting acrylic type, it will be understood that the important advantages of the invention are achieved in the production of acrylic or thermoplastic lacquers as well.

Similarly, the use of the novel particulate composition of the present invention is not limited to automotive finishes; the material can also be used in other types of finishing compositions, inks, plastics and textile pigments. It's practical.

Example 1 Add the following ingredients to the mill container.

600g 1/8 inch (3,2771W) steel ball.

12 g of finely ground crude polychlorocopper phthalocyanine.

1.2g sodium nitrite.

1.2 g of trisodium phosphate decahydrate.

79.0g of acetone.

8.9g of approximately 59% ethyl methacrylate, 39%
butyl methacrylate and 1.5% acrylic acid.

The mill is run at 75% of critical speed for 68 hours.

A sufficient amount of acetone is also used to collect and drain all the pigment slurry from the mill.

Steam is passed through the slurry until its temperature reaches 95°C,
During this time, all the acetone is removed.

At this point a solution of 26 g of concentrated sulfuric acid in 333 g of water is added and the resulting green slurry is heated at 95'-100°.
Heat to C for half an hour.

The product is collected by straining, washed free of acid, dried at 80° C. and pulverized.

By standard sand milling operations, the pigments prepared above were prepared in an automotive thermoset acrylic enamel of metallized type, i.e., using a mixture of 90% terpolymer-encased organic pigment and 10% aluminum flakes. dispersed into

When applied to a metal surface as a paint film, the pigments of the present invention exhibit a higher degree of step drama compared to paint films prepared using similar but commercially available polychlorocopper phthalocyanine pigments that are not encapsulated with a terpolymer. One two tone “
Show effectiveness.

Example 2 A 58 gallon (219,21 capacity) ball mill is charged with the following materials.

938 lb (425,5 kg) portion 8 inch (3,
2mm) steel ball.

26.4 pounds (12 ky) of finely ground polybromo copper phthalocyanine.

16.4 pounds (7.4 ky) of the terpolymer used in Example 1.

130 pounds (59 kg) of acetone.

Following the procedure described in Example 1, the ball mill is rotated at 75% of critical speed for 48 hours.

The mill contents are drained, the acetone and pigment are recovered, and an automotive enamel is prepared as described in Example 1.

This enamel provides a finish that exhibits a much more pronounced one-tone "effect" than enamels similarly prepared using commercially available polybromo copper phthalocyanines.

Example 3 (a) Charge the following ingredients into a ball mill.

18 parts of 4-chlorophthalic acid, 4-sulfonate acid, phthalic anhydride, urea, and copper chloride.
A blister copper phthalocyanine pigment containing about 4.0% chlorine and about 0.27% sulfur, obtained by reacting chlorine (loride) in kerosene in the presence of ammonium molybdate.

5 copies of 1000 copies 8 inches x 1 inch (16 mm x 25
．． 4mm) steel rod.

The ball mill rotates for 6 hours at a speed of approximately 70% of critical speed.

The contents are discharged from the mill through a screen and the pigment is recovered.

(b) Charge the following ingredients into a ball mill.

One part of 600g is 8 inch (3.2) steel balls.

12. Partially chlorinated raw steel phthalocyanine pigment prepared in (a) of 0.9.

8.0 g of the same terpolymer used in Example 1 7.9g of acetone.

The ball mill is run for 68 hours to encapsulate the pigment and mixed into the automotive enamel with 10% flaked aluminum as described in Example 1.

This enamel paint film exhibits remarkable clarity and depth of color.

This enamel is significantly superior in these respects to an enamel similarly prepared but omitting the terpolymer envelopment.

Example 4 This example illustrates the preparation of samples with 1% and 10% terpolymer concentrations.

Charge each of two 1 quart containers with the following materials:

One portion of 1500 g 2 inch (12,7 mm) steel balls.

150g roofing nails.

``35g aluminum sulfate 18 hydrate.

15p crude chlorine-free phthalocyanine.

4.0 g of ethylene tetrachloride.

To prepare a final sample containing 10% resin, 1
．． Add 85 g of the terpolymer of Example 1 to one container.

Add 0.179 terpolymer to another container to prepare a sample containing 1% resin.

The mill charge is ball milled at 75% of critical speed for 66 hours.

Separate the steel ball and nail and add each dry powder separately to the next solution.

A solution of 2000 g of H2O, 81 g of concentrated sulfuric acid, and 1.679 g of copper phthalocyanine monosulfonate sodium salt (to improve rheology).

Each slurry is heated to 95-100°C, held for 2 hours, strained, washed until free of sulfate ions, and the product is dried and ground.

Nitrocellulose inks of these materials are prepared by standard ball milling operations.

This product with 1% terpolymer is much clearer (lack of light scattering) when applied to aluminum foil than a similarly prepared sample without the terpolymer.

The product containing 10% terpolymer showed much greater clarity in the nitrocellulose ink than the product containing 1% terpolymer.

Example 5 (a) The following materials were charged into a ball mill equipped with a water jacket.

5 parts of 1000 parts 8 inches (1,6cIrL) X 1
20 parts of crude β single-phase quinacridone.

1 part ethylene tetrachloride.

The mill rotates at 75% of critical speed for 60 hours while passing hot water at 90-100°C through the jacket.

At the end of this time, the dry powder is discharged from the mill and collected.

(b) The following materials were charged into a ball mill.

600g 1/8 inch (3,2) steel ball.

11.4. ! β single-phase quinacridone pigment prepared in 9.(a).

14.79 g of the terpolymer described in Example 1 in acetone.

An automotive enamel is prepared in the same manner as in Example 1.

This enamel exhibits a metallic one-tone "effect" that is better at spacing compared to metallic automotive finishes using pigments prepared in a similar manner but without the terpolymer.

Example 6 (a) To 100 parts of 98% H2SO4, add 60 parts of linear quinacridone and 40 parts of quinacridonequinone.

The resulting mixture is stirred at 5-10°C to ensure complete dissolution.

This solution is introduced continuously in turbulent conditions through a small orifice into the center of a stream of cold water flowing under pressure through a tapered tube.

The ratio of H2O to H2SO4 is about 10=1 and the temperature rise is about 15°C.

The resulting strongly acidic slurry was heated to about 70°C and
-80°C for about 2 hours.

The solids are strained, washed to remove acid, and dried at 60°C to obtain 100 parts of a dark red powder.

The X-ray diffraction pattern of this product shows that the quinacridone forms a solid solution dissolved in the quinacridone quinone.

(b) Charge the following materials into the mill container.

600g 1/8 inch (3.2mm) steel ball.

5.7 g of the solid solution of quinacridone and quinacridonequinone prepared in a).

0.3 g of ortho-carboxybenzamidomethyl quinacridone (prepared according to Example 1 of U.S. Pat. No. 3,275,637).

14.0 g of the terpolymer of Example 1.

799 acetone.

An automotive finish is prepared according to the procedure of Example 1.

This paint exhibits excellent one-two tone properties.

Example 7 Crude polychlorocopper phthalocyanine is used directly as an aqueous presscake as follows.

Charge the following items into the container.

600g 1/8 inch (3.2mm) steel ball.

12 g of crude chlorinated copper phthalocyanine presscake (in dry form).

8 g terpolymer (dry).

The composition of this terpolymer is similar to that used in Example 1, except in this case it was produced by emulsion polymerization.

5.3 g of 50% sodium hydroxide.

Enough water to bring the total amount of water from all sources to 1009.

The ball mill is run at 18 Orpm for 66 hours.

The pigment slurry is separated from the steel balls and a solution of 3.9 g of ortho-dichlorobenzene and 0.38 g of hydrogenated rosin in ortho-dichlorobenzene (28%) is added.

Ortho-dichlorobenzene is distilled off as quickly as possible by blowing out steam from a sparger.

Strain and collect the product, wash until the base is gone,
Dry at 0°C and grind.

Attractive 1 when dispersed in thermosetting acrylic enamel
Gives a metallic finish with a two-tone effect.

The present invention can be summarized as follows.

(2) consisting essentially of 25 to 95% by weight of ethyl methacrylate and 5 to 75% of n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate and 2-ethylhexyl acrylate; Acrylic monomer selected from 0
．． An organic pigment wrapped in an acrylic interpolymer containing 5 to 10% of an ethylenically unsaturated acid selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid and having a logarithmic viscosity of 0.1 to 0.6. A granular composition consisting of particles.

2. The granular composition of claim 1, wherein the acrylic interpolymer consists of 45 to 75% ethyl methacrylate, 25 to 55% n-butyl methacrylate, and 5 to 5% acrylic acid.

3. The granular composition according to item 1 or 2,
The organic pigment is a halogen-containing copper phthalocyanine pigment.

4. The granular composition according to item 1 or 2, wherein the pigment is a quinacridone pigment.

Claims (1)

Claims: 1. Essentially 45 to 75% ethyl by weight. An acrylic interpolymer consisting of methacrylate, 25 to 55% n-butyl methacrylate, and 1 to 5% acrylic acid or methacrylic acid,
The interpolymer of 250r11y was dissolved in 50cc of chloroform and measured at 25°C to give a concentration of 0.1 to 0.6.
A particulate composition consisting of organic pigment particles encapsulated with an organic pigment having a logarithmic viscosity of .