JPH0326769A - High-brilliance flatting paint - Google Patents

Abstract

PURPOSE:To obtain the subject novel paint improved in hue, clarity, smoothness of a coating film, soft-feeling to the touch, crocking and color breeding by using a synthetic resin particle containing a pigment having a particle size of <= a specified value as a coloring component. CONSTITUTION:An objective paint the coloring component of which is a synthetic resin particle containing a pigment (e.g. carbon black, titanium dioxide, ultramarine or red iron oxide) having <=10mum particle size.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a new matte paint that has improved hue, clarity, smoothness of the coating film, soft feel, frictional color fading, color migration, etc. It is something.

[Conventional technology]

Various researches have been carried out to develop paints with deep and vivid colors, and one of the results of these efforts is the development of transparent color paints. However, although this paint is excellent in producing deep and clear colors, the paint film is glossy and various types of light are reflected on the surface of the paint film, making it feel dazzling to the naked eye. There were drawbacks.

In order to improve these points, matte paints were developed. In addition to coloring components such as pigments, conventional matte paints have a matting agent made of fine particles of synthetic resin such as silicic anhydride or acrylic resin mixed into the paint in order to diffusely reflect the light that reaches the paint surface. The majority of things.

On the other hand, some paints are colored by mixing relatively large urethane resin particles or acrylic resin particles of several tens of microns with pigments, etc., and mixing particles of different brightness and hue to create a mosaic-like hue effect. There is also a type of paint (hereinafter referred to as ``coarse particle paint'').

[Problem to be solved by the invention]

Conventional transparent color paints have the following problems.

■ The paint film is glossy and has a high reflectance to light, making it look dazzling to the naked eye.

■ Transfer of pigment to the object being contacted due to pressure or friction between the paint film and other substances, or frictional discoloration of the paint film, is likely to occur.

Furthermore, conventional matte paints have the following problems.

■ Since the matting agent is solid particles and is uncolored, it tends to cause uneven coating, which tends to cause uneven hue.

■ Light that is diffusely reflected by the matting agent particles on the surface of the paint film exits the paint film without passing through the paint film layer, resulting in a whitish color and poor clarity.

■ In order to remove the gloss, the surface of the paint film is roughened with a matting agent, which deteriorates the smoothness of the paint film.

■ Although it is not as bad as transparent color paint, the transfer of pigment to the object due to pressure contact or friction between the paint film and other substances, or t! ! Discoloration of the film due to friction is likely to occur.

Further, conventional coarse particle paints have the following problems.

■ The surface of the coating film is not smooth.

■ Insufficient soft feel.

■ Stains are easily generated due to static electricity and are difficult to remove.

■ Particles in the paint tend to settle.

The problem to be solved by the present invention is to solve such problems.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors provide a coating material in which a certain amount of colored synthetic resin fine particles containing a pigment of 10 microns or less are used as a colorant.

That is, the paint according to the present invention has the following structural features.

■ Most natural roses and other flowers have very deep and vivid colors, even though they are completely matte. Therefore, when we closely observe the surfaces of these flowers, we find that although they appear smooth to the naked eye, under a microscope they have a surface structure with minute irregularities made up of countless minute cilia. I understand.

Based on this knowledge, the present invention uses colored fine particles of 10 microns or less as a coloring component, which makes it look very smooth to the naked eye and touch, but when observed under a microscope, it looks like natural roses or other roses. For the first time, it has become possible to form a coating film with minute irregularities similar to those of a flower.

■ In conventional matte paints, coloring agents such as pigments and matting agents share their respective functions and are used separately, but in the present invention, synthetic resin fine particles containing pigments are used separately. By using this, we succeeded in providing a function as a coloring agent and a matte effect.

One method for efficiently producing synthetic resin fine particles containing such a dye is to incorporate a dye such as a pigment into the resin when the resin is produced by polymerizing monomers.

Conventional coarse particle paints have not been manufactured with particles of less than 10 microns. However, in the present invention, by adjusting the conditions during monopolymerization of monomers, it has become possible to produce dye-containing fine particles of 10 microns or less.

■ The synthetic resin used in the present invention is transparent so as not to impair the coloring effect of the pigment contained therein, and
Any dye may be used as long as it does not cause any trouble to the polymerization even if a dye such as the pigment shown below is present during monomer polymerization, and the most common ones are: Acrylic resin can be used.

■ The dye used in the present invention may be any dye as long as it can coexist during the polymerization of the above-mentioned transparent synthetic resin and can be mixed and sealed inside the resin.
Specifically, carbon black, titanium dioxide, ultramarine blue,
Inorganic pigments such as Bengara, organic pigments such as cyanine, perylene, quinacridone, azo, and indathrene, and dyes such as metal-containing dyes are included.

(2) The paint as used in the present invention includes not only paint in the narrow sense but also printing ink and the like.

In addition to the pigment-containing transparent synthetic resin fine particles mentioned above, the paint used in the present invention includes, like ordinary paints and printing inks,
Paint or ink resins such as polyurethane, polyester, polyvinyl chloride, and polyacrylic; Ketone solvents such as MEK, aromatic solvents such as toluene, Alcohol solvents such as PA, ethyl acetate, butyl acetate, etc. Contains ester solvents, solvents such as DMF, THF, and ink solvents.

In order to completely confine the dye, it is preferable to further coat the outside of the dye-containing Hewei resin fine particles with the same synthetic resin. Such coated dye-containing synthetic resin fine particles can be easily produced by using freshly synthesized dye-containing synthetic resin fine particles as cores and once again polymerizing monomers on their surfaces.

[Effect]

Since the paint according to the present invention has the above-described structure, it is thought that the following effects work.

(2) Since the pigment-containing synthetic resin particles are as fine as 10 microns or less, the surface of the coating film is extremely smooth visually and to the touch.

■ Microscopically, the surface of the paint film has minute irregularities, just like natural roses and other flowers, so it has excellent anti-glare properties and has the same color tone and soft feel as roses and other flowers. It will be done.

■ When applied, since there is no matting agent, there is less white scattered light due to the matting agent near the coating surface, resulting in white blurring due to white scattered light. Therefore, colors appear very clearly.

■ When applied, there is no matting agent, so depending on the matting agent lol! 4 Unattenuated light reaches the internal pigment, and the light emitted from there leaves without being attenuated by the matting agent, giving the color of the paint film depth.

(2) Since the pigment-containing synthetic resin fine particles are less than 10 microns in size, the dispersion stability in the paint is high. Therefore, it does not easily settle during standing, unlike conventional coarse particle paints.

■ When applied, the pigment may come out into the coating film [1!
There is almost no seepage to the surface.

In addition, there is almost no possibility that the dye will transfer to the object to be contacted due to pressure contact or friction with other substances.

■ As a transparent synthetic resin, l! When a resin with high impact resistance strength, such as a bridge acrylic resin, is used, the coating film has high scratch resistance (resistance to scratches) and further improves friction discoloration.

■ When applied, since there is no matting agent, there is almost no white scattered light caused by the matting agent, so the base color is likely to appear. Therefore, the base color can be utilized.

〔Example〕

In a 500-liter reaction vessel, 90 kg of MEK, 10 kg of cross-linked acrylic monomer, 5 kg of regular acrylic monomer, 30 kg of monoazo red pigment dispersion, and 0.5 kg of peroxide catalyst.
kg was added, the temperature was gradually raised, and the reaction was carried out at 80°C for 8 hours. The obtained reaction product was taken out and prepared as a dye-containing crosslinked acrylic resin fine particle dispersion'/Ii (hereinafter referred to as rB).

On the other hand, a reactant was obtained in the same manner as above, and after cooling to 50°C without taking it out, 90 kg of MEK, 10 kg of crosslinked acrylic monomer, and 5 k of ordinary acrylic monomer were added.
g, add 0.5 kg of peroxide catalyst and heat at 80°C.
Allowed time to react. The obtained reaction product was taken out and used as a coated dye-containing crosslinked acrylic resin fine particle dispersion (hereinafter referred to as "b").

These dye-containing crosslinked acrylic resin fine particle dispersions
30% each for 30 kg of a and b
Polyurethane resin solution 1 3 kg, MEK, 13 kg of a solvent such as luene were blended and stirred, finely divided using a grinding mill, and then sieved with 150 mesh LII to obtain a paint (hereinafter referred to as
respectively referred to as "A" and "B").

Also, in the same way as resin a except for the pigment, MEK90k
g, 10 kg of cross-linked acrylic monomer, 5 kg of normal acrylic monomer, and 0.5 kg of peroxide catalyst were reacted, and 301 tg of monoazo red pigment dispersion was added.
For each 30 kg of the mixture at the ratio of 3
13 kg of 0% polyurethane resin solution, 13 kg of solvents such as MEK and toluene were blended and stirred, and the mixture was finely divided in a grinding mill, filtered through a 50-mesh sieve, and the paint (hereinafter referred to as R) was mixed and stirred.
．． (referred to as J).

Furthermore, a matte paint (hereinafter referred to as r]) J) containing a monoazo red pigment was produced using a conventional method.

The particle diameter distribution of the particles present in each of the conventional matte paint D1 thus obtained, the paint B1 according to the present invention, and a commercially available coarse particle paint was measured, and the results are shown in FIG. I got similar results. In this figure, the horizontal axis shows the particle diameter (μm), and the vertical axis shows the ratio (%) of particles falling within the constant particle diameter range shown in the figure.

From this figure, it is considered that for the conventional matte paint D, the pigment particles appear as a particle distribution with a peak at 0.3 μm, and the matting agent appears as a particle distribution with a peak at 4.0 μm. On the other hand, for paint B according to the present invention, the pigment-containing synthetic resin fine particles appear as a particle distribution with a single peak at 4.0 μm and the majority (87.2%) occupying a particle size of 10 μm or less. This is thought to reveal that the particles are extremely fine.

On the other hand, commercially available coarse particle paints have a diameter of 40 μm.
This appears as a particle distribution in which the majority (90.5%) has a peak of 10 μm or more, which is considered to indicate that the colored resin particles are very large.

When these paints A, B, C, and D were applied to soft vinyl chloride resin test pieces and a comparative test was conducted, a matting effect was observed in all the samples.

The matting effect was also observed in C, probably because the crosslinked acrylic resin fine particles, which do not contain any pigment, acted as a matting agent. Further, color unevenness was observed in C and D, and color clarity was good in A and B. Furthermore, the smoothness of the coating film surface is A, B.
, C is good<N! 4! Color transfer to objects pressed against the membrane is C.
A and B are better than D, and the friction color fading resistance is better than A than C and D.
was better, and B was better than A.

Furthermore, when the surface of the coating film of the test piece coated with the above-mentioned paint B according to the present invention is observed under a microscope at 100x and 400x magnification, very fine ripples similar to the surface of a rose flower can be seen. However, when observing the surface of the coating film of a soft vinyl chloride resin test piece coated with a conventional coarse particle paint, it was found that there were large irregularities such as undulations. It was observed.

Furthermore, when the size of the pigment-containing synthetic resin particles of B was measured based on a scanning electron micrograph at a higher magnification, the size of the particles was several microns at most.

Furthermore, using an industhrene blue pigment instead of the monoazo red pigment, a paint E according to the present invention was manufactured in the same manner as B, and a conventional paint F was manufactured in the same manner as D, and each test piece was The coating was coated, and the optical properties of the coating film, such as anti-glare properties and hue clarity, were measured. The results are shown in Tables 1 and 2.
It was as follows.

Anti-glare properties are measured using a gloss meter! ! It can be expressed by the intensity of the light that is diffusely reflected from the coating when the coating is irradiated with light obliquely. In general, if a paint film reflects light like a mirror, the maximum intensity of the reflected light will appear at the same angle on the opposite side of the irradiated light beam, and if there is a blurred white or lack of depth in color, , the maximum intensity of reflected light tends to appear where it faces the coating film, that is, around 90°. From this point of view, as shown in Table 1, paints B and E according to the present invention do not exhibit strong reflected light peaks at specific angles, like conventional paints D and F. do not have. This means that r! ! 11t! J has no shine or blurring,
This is thought to indicate that the color has depth.

The table also shows the sharpness of the hue of the coating film *, a*, b* and C*.
It can be known by measuring the value. As can be seen from the measured values shown in Table 2, paints B and E according to the present invention have a higher L* value (lightness) than conventional paints D and F.
is low and the C value (chroma) is high, suggesting that the paint according to the present invention has less white blur and excellent hue clarity.

Table 2 Such tests were also conducted with other organic pigments such as azo, cyanine, berylene, quinacridone, indathrene, and metal-containing dyes, but similar results were obtained with all of them.

〔Effect of the invention〕

The matte, high-visibility color paint according to the present invention has the above-mentioned structure and function, and therefore solves the problems of gloss of conventional transparent color paints, sharpness, color unevenness, white blur, and smoothness of conventional matte paints. problems in the smoothness of conventional coarse particle paints,
The matte, high-definition color paint of the present invention solves problems related to soft feel, dirt and particle settling, as well as color migration and abrasion discoloration common to these paints. Because the resin is used in the form of fine particles, it has high dispersion stability in the paint and is resistant to sedimentation. When applied, the surface of the paint film is very smooth visually and to the touch, but microscopically it is Just like natural roses and other flowers, the surface of the paint film has fine irregularities, so it has excellent anti-glare properties, and the same color tone and soft feel as roses and other flowers can be obtained. Because there is no need to use a matting agent, there is no white blur caused by matting agents, a deep color that is not attenuated by the pigment appears, and because there is almost no white scattered light, the base color can be brought out. Since it is encapsulated in fine particles, it provides excellent effects such as good color migration and frictional color fading.

[Brief explanation of drawings]

Figure 1 shows a conventional matte paint D1 and a paint B according to the present invention.
1 and the particle diameter distribution of particles present in commercially available coarse particle paints, respectively. In this figure, the horizontal axis shows the particle diameter (μm), and the vertical axis shows the proportion (%) of particles falling within the constant particle diameter range shown in the figure. Figure 1 Particle diameter/L

Claims (1)

[Claims] Paint whose coloring component is synthetic resin fine particles containing a pigment of 10 microns or less